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By RALPH HAYES SWEETSER

ONE per cent. of ash in a ton of coal has been so little considered that in many circles it has been positively ignored. Even P. T. Barnum had never heard of it, or he would have had one on exhibition alongside the Cardiff Giant and the White Elephant. One per cent. of ash is closely related by both those freaks of Barnum in that it is "stone" and, in its aggregate, it is the greatest "White Elephant" that the American public now supports. Some of you may have paid Mr. Barnum for a look at the "petrified man" (named the Cardiff Giant by the gullible wise men of the early seventies); but it is certain that everyone of you is now paying for the support of the great White Elephant that is being constantly carried by our railroads all over the country-at the public's expense. " One per cent. of ash in a ton of coal" requires 120,000 open-top railroad cars each year to transport this use- less stone giant from its native bed in the coal seams of the bituminous regions to the coal bins of the consuming public.

Jan 1, 1924

By R. S. MACPHERRAN

TRENDS in the manufacture and use of cast iron are decidedly toward specialization, alloy iron, and increased strength. Old handbooks list only one kind of cast iron, with a tensile strength of 15,000 lb. Recent A.S.T.M. specifications show that from 50,000 to 60,000 lb. per sq. in. can now regularly he guaranteed. The use of alloy iron, heat-treated iron, and even nitrided cast iron, is rapidly growing and all kinds are improving in quality. Iron for operation at high temperature and corrosion-resisting irons have also been developed. Only a few years ago cast iron was "cast iron," but now there are almost as many kinds of cast iron as there are foundries making it

Jan 1, 1936

By C. G. Dunn, F. Lionetti

The energy associated with grain boundaries in polycrystalline aggregates is believed to play a major role in grain growth processes and, when growth ceases, to determine the final equilibrium grain boundary angles. Further, the energy of grain boundaries of recrystallization nuclei is a factor in nucleation processes. It is important to know, therefore, how the energy per unit area of a grain boundary, that is, the grain boundary surface tension y, depends on the difference in orientation of the two lattices of the grains producing the boundary. Although the problem is important, surprisingly little has been done toward a quantitative evaluation of the effect of orientation difference on grain boundary energies. C. S. Smith1 recently has discussed this problem and in addition to showing effects of orientation difference on equilibrium angles has shown a variety of interesting effects of surface tension on the appearance of microstructures. Fig 1 and the following relations expressed in Eq 1, which connect equilibrium grain boundary angles and surface tensions, illustrate equilibrium conditions which are believed to hold true in metals. ?l2 _ ?23 _ ?l3 [1] sin ?3 sin ?1 sin ?2 Clearly any two of these surface tensions can be expressed in terms of the third when the equilibrium angles ?1, ?2, and ?3 are known. Applied to the present problem for solid state equilibrium of three grains, the angles ?1,?2 and ?3 must be measured in a plane perpendicular to the line of junction of the three grains. Normally a direct determination of these angles from random microsections is impossible. Consequently Harker and Parker2 and Smith1 (except for some measurements on flat specimens) resorted to a statistical method to determine equilibrium grain boundary angles. Smith reported that grain boundaries meet the surface of a piece of metal nearly perpendicularly. He reported also, in connection with direct angle measurements on flat specimens with grains extending through the thickness, that angles varied appreciably from 120" and concluded that there was a measurable effect of orientation difference on surface tension. Another direct way of determining equilibrium angles and a method adaptable to studying particular configurations, recently suggested by Dunn,³ is to use a three-grain flat specimen with orientations of grains so chosen that the junction line of the three grains will be straight throughout the thickness and perpendicular to the surface of the specimen. Choice of orientations is possible when individual grains of each group can be grown to predetermined orientations through the reorienting and growth of " seed crystals " as described.³ Not only is it possible, for example, to have grains with the same crystallographic plane in the plane of the specimen, but a given orientation difference between two grains can be made a common factor to an unlimited number of three-grain groups while a series of orientation differences is investigated. Any effect of anisotropy of gas-solid surface tension due to grain orientation should be minimized by having all gains oriented the same with regard to crystallographic plane in the plane of the specimen. Another feature of the three-grain group is the notched grain boundaries as shown in Fig 2 for one specimen (S4). The notches serve to anchor the end positions of the grain boundaries (especially at high temperatures) while the central and junction point of the grains moves toward an equilibrium position. Final equilibrium should produce straight grain boundaries if the notches are very narrow and if changes in orientation* of the grain boundary do not alter the surface tension.† If one assumes the straight line condition and no change of surface tension with small changes in grain boundary orientation and finds the equilibrium configuration by a minimization of the grain boundary energy, one obtains the relations given in Eq 1. The approach to straight line boundaries or to minimum energy configurations in specimens containing large grains, such as those used in the present investigation, may be very slow compared with the approach to equilibrium conditions for the grain boundary angles. It may be desirable, as proved to be the case in the present investiga-

Jan 1, 1950

By M. J. Marcinkowski, K. S. Raghavan, A. S. Sastri

A detailed transmission electron microscopy investigation was carried out in connection with a manganese Hadfield Steel. At small plastic strains, numerous individual intrinsic stacking faults are observed. With increased plastic deformation, the stacking faults thicken into twin lamellae which in turn subdivide the original austenite matrix into smaller domains. The twin boundaries act as strong barriers to subsequent dislocation motion and is in a sense equivalent to grain refinement. It is this "grain refinement" which is believed to be the cause of the very high work hardening rates in the Hadfield Steels. In many cases, especially where an hcp phase is the stable one at low temperatures, the stacking fault energy in fcc metals and alloys decreases with decreasing temperature.' Since stacking faults of the intrinsic type are precursors of both twins as well as the hexagonal close packed structure, both of these entities should become more frequent as the temperature of a fcc crystal is lowered. In the case of the twin, there is no chemical driving force for its formation and it is generally necessary to provide the required driving force by an applied stress, i.e., strain energy. In the case of the hcp structure the transformation from the fcc modification can occur spontaneously (marten-sitically) since a decrease in chemical energy does in fact occur; however, an applied stress will provide an even greater driving force toward complete transformation. Since the transformation products mentioned above occur in an inhomogeneous manner throughout the crystal and since these can act as potential barriers to further plastic deformation2 marked strengthening effects can be anticipated. Also because metal and alloy strenghening is in general proportional to the shear modulus, these effects should be greatest in steels of the austenitic type (y), i.e., the fcc types. Perhaps the two most important steels in this category are the austenitic stainless steels and the Hadfield manganese steels. Both may be quenched from elevated temperatures so as to retain the austenitic states characteristic of those temperatures. The effect of subsequent deformation at lower tem- peratures has a profound effect on the stress-strain curves of these alloys. In particular Fig. 1 shows the compressive stress-strain curves obtained with an 18-8 stainless steel which was quenched from 1850°C after annealing for 1 hr so as to produce all y. As the temperature is lowered, the work hardening rate increases markedly. Although some hcp or c mar-tensite can be generated by plastic deformation as the temperature is lowered,~ it is believed to be a transition phase4 and most of the martensite produced is of the bcc or a variety.3 It is this stress induced martensite which gives rise to the very low initial work hardening at 77°K as can be seen in the stress-strain curve in Fig. 1. Similar low initial work hardening rates have been observed in the stress induced Ni-Ti martensites.5 Fig. 2 shows that an even more rapid rate of work hardening occurs in the Hadfield steels treated in the same way as that described for the 18-8 stainless steels a; the temperature is lowered. It is this ability to work harden to such high stress levels that makes the Hadfield steels particularly suitable for armor plate and heavy construction equipment. However, unlike the case of Fig. 1, no initial low rate of work hardening is observed in any of the curves in Fig. 2. Thus the stress induced formation of any low energy martensite phase in any significant quantity must be ruled out. This observation is in accord with the X-ray findings of Otte.~ On the other hand, small quantities of the E phase have been observed by other investigators using transmission electron microscopy (TEM) above Even more significant was the fact that large numbers of deformation twins were observed in the deformed Hadfield steels,678 which were postulated to be one of the reasons for the high work hardening ability of this class of steels.8 It is the purpose in what follows to discuss a series of experimental observations pertaining to the stress induced transformation in a Hadfield steel and to formulate a dislocation mechanism which adequately accounts for the observed results. EXPERIMENTAL PROCEDURE The stainless steel used to obtain the curves shown in Fig. 1 was of the AISI Type 303 containing approximately 18.0 pct Cr and 8 pct Ni. On the other hand, the Hadfield manganese steel used to obtain the curves shown in Fig. 2 contained between 1.00 to 1.25 pct and 11.5 to 13.5 pct Mn. In all cases the samples were in the form of compression cylinders 0.220 in. in diam and 0.370 in. long. Prior to testing the samples were annealed for a hr at 1050°C and rapidly quenched into a brine solution. This treatment was sufficient to preserve the y phase for subsequent testing at lower temperatures. All samples were compressed in an Instron testing machine using a cross head speed of 0.02 in.

Jan 1, 1970

By Victor R. Cabrera

Expansion of Marcona Mining Co.'s operations in Peru several years ago increased the number of laborors and the variety of required jobs at the Company's facilities. This change made the former wage administration outdated, becoming evident by the increase of inequity grievances which threatened tile Company's good labor relations. Such a situation led Marcona to design a new wage plan based on a thorough job evaluation of all its laborer positions. The iron ore deposits, 15 miles inland from the ports of San Juan and San Nicolas, Peru, supply ore to steelmakers in the U.S., Europe and Japan. Marcona Mining Co. operates the mines under a long-term lease agreement with Peru.

Jan 7, 1964

By F. G. Jones, R. D. Pehlke, H. E. Gardner

The solubility of nitrogen in liquid Fe-18 pct Cr-8 pct Ni-0. 7 to 2.3 pct A1 alloys has been measured up to the solubility limit for the formation of aluminum nitride in the temperature range 1600° to 1700°C uszng the Sieverts' method. The solubility of nitrogen in 18-8 stainless steel increases with increasing aluminum content. Based on a nitride composition, AlN, the standard free energy of formation of aluminum nitride from the elements dissolved in liquid 18-8 stainless-steel alloys has been determined to be: ?G° = -42,500 + 20. IT in the range from 1600° to 1700° C. EVANS and pehlke1 have measured the equilibrium conditions for the formation of aluminum nitride, AlN, in liquid Fe-A1 alloys. The present study extends that work to the more complex solvent, liquid 18 pct Cr-8 pct Ni (18-8) stainless steel. Recent work by Small and pehlke2 has dealt with the effect of fourth-element additions on the solubility of nitrogen in 18-8 base alloys. They found the effect of aluminum additions, up to 0.74 pct, on the solubility of nitrogen to be small. The present study covered the range from 0.74 to 2.28 pct aluminum, and by extending the composition range may be used to better define the effect of aluminum on the nitrogen solubility in these alloys. EXPERIMENTAL PROCEDURE The Sieverts' method was used to measure the equilibrium solubility of nitrogen gas in liquid 18-8 stainless steel alloys containing 0.74, 1.49, 1.93, and 2.28 pct Al. The solubility was measured as a function of the nitrogen gas pressure at temperatures of 1600°, 1650°, and 1700°C. The apparatus used is the same as described by Small and Pehlke.2 The 100-g melts were made from Ferrovac-E high-purity iron, Crucible Steel Co.; 99.95 pct Cr, Union Carbide Corp.; 99.9 pct Ni, International Nickel Co.; and 99.99+ pct Al, Aluminum Co. of America. The aluminum was charged at the bottom of the crucible, surrounded by nickel and iron. The chromium was packed into the interstices to minimize vapor transport of the aluminum during initial melting. The hot volume of the system, measured for each melt with argon, ranged from 45 to 55 standard cu cm with a temperature coefficient of —8 x 10-3 cu cm per °C. The melt temperature was measured with a Leeds and Northrup disappearing-filament type optical pyrometer sighted vertically downward on the center of the melt surface. The temperature calibration of the system by Small and pehlke2 was assumed. Two problems are involved in determining the solubility product of a solid, metal nitride phase in liquid iron alloys. These are: 1) establishing the point of departure from Henrian behavior at the solubility limit of the metal nitride phase; and 2) determining the composition of the solid nitride which is precipitated. Determination of the solubility product of AlN was made by admitting small amounts of nitrogen into the reaction bulb until the deviation from Sieverts' law was clearly evident in the form of a pressure halt. To obtain the solubility product at several temperatures during one run the following procedure was used: 1) add increments of nitrogen to determine the Sieverts' law line at the lowest desired temperature; 2) continue to add nitrogen to precipitate a small amount of the nitride phase; 3) increase the melt temperature 50°C to dissolve the precipitated nitride; 4) repeat step 2 until either a nitride formed or the system reached ambient pressure; if a nitride formed at 1650°C, the sequence was repeated at 1700°C. The composition of the precipitated phase was checked by an X-ray diffraction pattern obtained from powder scraped from the surface of the solidified 1.93 pct A1 melt. RESULTS AND DISCUSSlON Solubility Measurements. Fig. 1 is a typical nitrogen-absorption curve obtained from measurements on a 1.93 pct A1 alloy. Since the initial absorption of nitrogen follows Sieverts' law the nitrogen solubility is plotted as a function of the square root of the pressure of nitrogen gas in the reaction bulb. The results of the solubility measurements for all alloys studied are summarized in Table I. The slope of the Sieverts' law line for each alloy was determined. Since this is also the solubility of nitrogen at 1 atm pressure of nitrogen gas, the latter designation is used for the data. It should be noted. however, that in most cases the value lies above the solubility limit for AlN. Fig. 2 shows the effect of aluminum on the solubility of nitrogen at this reference pressure and as a function of melt temperature. The solid portions of the lines represent attainable solutions; the dashed regions lie above the limit for precipitation of AlN.

Jan 1, 1969

By Frank C. Kelton

It is perhaps not widely realized that extraction and saturation processes carried out on oil well core samples alter the properties of these samples to varying degrees. On the other hand it is felt by some that quick-freezing of core samples increases their permeability and porosity significantly. Accordingly, laboratory tests were carried out on 49 pairs of horizontally adjacent samples in order to differentiate between the effect of quick-freezing per se on permeability and porosity of the samples, as distinguished from the effect of the identical saturation treatment on permeability and porosity of the companion samples. Also, additional field data were obtained on comparison of frozen vs unfrozen companion samples. LABORATORY INVESTIGATION OF FREEZING us SATURATION EFFECTS Procedure The samples used in these tests were two-cm cubes cut in horizontally adjacent pairs from cores from eight Gulf Coast and Mid-Continent wells, which cores had not previously been frozen. These samples were extracted with carbon tetrachloride, dried, and air permeabilities run in the conventional manner. They were then evacuated and saturated with brine of 25,000 ppm sodium chloride content, and porosities determined by gain in weight. The samples were partially desaturated by evaporation down to an average brine saturation of 68 per cent. One sample from each pair was quick-frozen by covering with dry ice after wrapping in a single layer of paper, and allowed to remain frozen for about two hours; the companion sample from each pair was not frozen. After thawing the frozen sample, all samples were immersed in tap water overnight in order to leach out most of the brine. Air permeabilities were re-run, and the samples were again saturated with brine to determine a second porosity value. For purposes of averaging of data, the samples were grouped according to four permeability ranges, from 0 to 10, 10 to 100, 100 to 1,000, and 1,000 to 3,840 md. Average permeability and porosity changes for the frozen vs the unfrozen adjacent samples are shown in Table 1. Discussion As may be seen from Table 1, the averages of the per cent permeability increases for the quick-frozen samples ranged from 3.8 to 12.9 per cent among the four permeability groups. The average changes among the four groups of unfrozen companion samples ranged from a decrease of 0.2 per cent to an increase of 9.3 per cent. There was no particular correlation of these changes with magnitude of permeability; however, the increase for each group of frozen samples paralleled the increase for the corresponding unfrozen samples. The differences between the two sets of values are believed to be a valid indication of the effect of the quick-freezing in itself, since the treatment of the two samples in each pair was identical except for freezing. The permeability changes which are strictly the result of the quick-freezing are shown in the sixth column of Table 1. These range from a decrease of 0.9 per cent to an increase of 4.0 per cent; the overall weighted average is 1.2 per cent, as compared to an average increase of 6.8 per cent caused by the saturation treatment of the samples not frozen. The average porosity changes are in general smaller than the changes in permeability, and range from a decrease of 2.3 per cent to an increase of 3.3 per cent. The overall weighted average change ascribed to the quick-freezing is 1.0 per cent of porosity. Many factors can contribute to the changes in permeability and porosity observed when subjecting cores to the simple processes used in these tests. Such are: hydration and swelling of clay, adsorption of ions, changes in surface structure and wettability, expansion and compression effects due to ice formation, shrinking and cracking, leaching of salts and colloids, displacement of particles resulting in either blocking or enlarging of pore openings. Whatever particular mechanisms are involved. however, it is apparent not only from this study but also from other investigations in the literature' not directly concerned with quick-freezing, that the effects produced by commonly used extraction, saturation and drying techniques may be of considerable magnitude The results of this study indicate that for the particular samples and techniques used, such effects are of the order of five to six times the effect of quick-freezing. insofar as changes in permeability are concerned. It may be argued that these samples might not include extremely shaly material where the effect of freezing upon permeability may be much greater. However, had such material been available for these tests, it would undoubtedly have been very susceptible also to alteration by the extraction and saturation treatment used. To investigate this point further, the individual sample data were re-grouped according to the magnitude of the average per cent permeability increases for the pairs of samples, irrespective of permeability. The results

Jan 1, 1953

By WILLIAM J. LINNEY

MAGNETITE ore from Lyon Mountain, so- called "Low Phos Chateaugay," has long been known to the iron and steel industry for its almost complete absence of impurities. These magnetites occur along the northern foothills of the Adirondacks in several parallel and folded stringers which are continuous for several miles, striking generally northeast-southwest and dipping usually over 45° to the northwest, or roughly toward the St. Lawrence River. Ore of minable thickness is found in shoots of various sizes as to length and breadth, but of undetermined and possible great depth.

Jan 1, 1943

By J. C. METCALF

MORE than 80 per cent. of the iron produced in the United States and over 30 per cent. of the world's annual production is obtained in the Lake Superior district. Though iron ore was discovered on the Marquette range in 1844, the poor transportation facilities retarded the development of this region for many years. The structure of the Lake Superior basin is essentially an east-west synclinorium with steep dips on the south side of the lake and considerably flatter ones on the north and west. The Upper Huronian series, which -is the iron-bearing one of the formation, on the south side of the lake dips north from 55' to 80°, and on the north side dips south from 8" to 200. The series has been subjected to local folding and faulting, which have influenced the development of the mining systems used.

Jan 1, 1921

By P. R. Sperry, A. P. Beck

It has been shown1 that in poly-crystalline strips of high purity aluminum with a fairly random orientation distribution, grain growth progresses gradually until the average grain diameter reaches a value approximately equal to the strip thickness. Recent work at this laboratory led to the realization that grain growth might be impeded to a considerable extent in the presence of a sharply defined texture, where orientation differences between neighboring grains are small. In order to investigate this effect the following experiment was carried out with the same lot of high purity aluminum previously used for grain growth studies in randomly oriented material.' Very large grain size was developed by grain growth at 650°C in specimens of 0.200 in. thickness. These specimens were then rolled to a thickness of 0.050 in. or 1.25 mm—a reduction of 75 pct. In the rolled strip each large grain corresponded to an elongated area easily identified by etching. After annealing for 1 to 25 min at 600°C and re-etching, these elongated areas were again recognizable. Within each area, corresponding to a single large grain before annealing, there formed by recrystallization a multitude of new grains with a fairly well developed preferred orientation. The orientation and the size of the new grains formed in areas corresponding to different large grains, varied widely depending on the orientation of the parent grains with respect to the rolling direction and the plane of rolling. Many areas were found where the average grain size was considerably smaller than the specimen thickness. Such an area occurred in a specimen cut in half before annealing. One half, containing a portion of the area in question, was annealed 1 min at 600°C, the other half, with the remaining portion of this area, for 25 min at the same tempera-Aluminum killed low carbon steel, § which is now used extensively for severe deep drawing or other difficult forming operations, is unusual in that its grain structure, after cold reduction and box annealing in accordance with conventional continuous sheet or strip mill practice, often is elongated, although at times it is equiaxed. Since this unusual structure has been found superior for many, but not all, severe forming operations, recrystallization of the steel, both at constant temperature and on continuous heating, was investigated and compared with that of rimmed steel in the hope that something might be learned about the mechanism of, and the factors controlling, the formation of such elongated grains. In this structure, the grains are elongated both in the lengthwise direction of the strip and transverse to this direction, even though nearly all of the extension in both hot and cold rolling is in the lengthwise direction. The grains are thus roughly pancake-shaped, being longer and wider than they are thick, as observed also by Burns and McCabe,1 and as illustrated by the typical structures shown in Fig 1. Fig la, representing a conventional longitudinal section, shows the length and thickness of the grains, whereas Fig Ib shows their length and width as seen by examining a section parallel to the sheet surface. Both illustrate the very irregular grain boundaries usually associated with the elongated grain shape. A finer equiaxed grain structure in this same grade is shown in Fig Ic. Either the elongated or the equiaxed structure may be present in the annealed product, and in rare instances the two types may coexist in a single specimen, as shown in Fig 1 d. Isothermal Recrystalliza-tion of Rimmed and Alamimum Killed Steel An aluminum killed steel known to have an elongated grain structure after conventional processing (Steel B, Table l), was selected for the initial recrystallization studies; for comparison, a rimmed steel, A in Table 1, was used. Samples of each in the form of hot rolled strip 0.075 and 0.095 in. thick, respectively, were cold rolled on a small laboratory mill in steps of about 0.010 in. per pass to obtain total reductions of 40 and 60 pct. Small pieces of the cold reduced strip were heated in lead at selected constant temperatures for one of several periods of time, then cooled in air. Rate of heating in the lead was, of course, very fast. Hardness of the cooled specimen was measured and a longitudinal section examined metallographically. Isothermal recrystallization curves for these two steels at 1050°F, based on hardness of the air cooled specimens, are shown in Fig 2 in which the amount of recrystallization corresponding to each plotted point is indicated. The marked difference in the behavior of these two types of steel is evident. After a corresponding amount of cold reduction, the rimmed steel recrys-tallizes in a much shorter time than the killed steel and the shape of its recrystallization curve, (plotted on a logarithmic time scale), is very different. The curve for rimmed steel indicates that recrystallization is analogous to isothermal transformation of aus-i.enite in that it proceeds at a progressively faster rate up to some 50 pct recrystallization, then at an increasingly slower rate. For the aluminum killed steel, however, the start of

Jan 1, 1950

By C. H. Bowen

NDUSTRY needs a generally applicable means of defining average grain size and grain size distribution. Students of sediments hade explored this field, employing methods that might also prove useful in engineering problems. Before attempting to solve specific problems it is well to review the derivation of commonly used grade scales and the reasons for their selection. This aspect of the problem seems largely to have been lost, and a review of basic factors may suggest causes for failures in using size analysis data. Three facts are implicit in selection of a grade scale: 1) Most particulate mixtures are continuous distributions of sizes, and any grade scale that may be employed is an arbitrary means of visualizing that distribution. 2) For purely descriptive purposes, any grade scale, regardless of the rationality of the class intervals, will be satisfactory if it is accepted by a sufficient number of workers. 3) For analytical purposes, class intervals must be small enough to define the continuous distribution accurately. Further, where statistical studies are involved, a fixed relationship should exist between classes or grades. An argument in favor of geometrically related size grades lies in the fact that most particulate mixtures contain such a wide range of sizes that use of an arithmetic diameter scale is practically impossible. Udden, who recognized this fact in 1898,' proposed one of the first grade scales based on a regular geometrical interval. Udden used 1 mm as his basic diameter and a ratio of 2 (or 1/2) between classes. In 1922 Wentworth2 re-examined Udden's grade scale, retaining the same class interval and basic diameter, but extending the scale in both directions and renaming the classes. In 1930 (Ref. 3, p. 82) the American Society of Testing Materials proposed what is now known as the U.S. Standard fine sieve series, also based on the 1 mm diam, with a v2 ratio between sieves. This, then, is a one fourth Udden-Wentworth series in the sizes below the 4 mesh sieve. The U.S. Standard coarse sieve departs from the 1 mm base and uses inches; hence it is not a direct continuation of the fine series. The U.S. Standard series would thus seem to possess all the attributes of a good grade scale, which it is. It has a large number of classes (sieves). in fact too many for practical use in its entirety. This v2 subdivision of the Wentworth grades has led to the common use of two v2 sieve series, the half-Wentworth and the engineers' series. Geologists and sedimentologists favor the half Wentworth, or 18, 25, 35, 45 sieves, etc., whereas the engineers, preferring round numbers, utilize the other half of the U.S. Standard grade scale in the 16, 20, 30, 40 sieves, etc. The fixed geometrical ratio between classes is an advantage in statistical analysis, but the unequal classes cause some complications in calculations. This is especially true when moment measures are used. It was to simplify these calculations that Krumbein in 1934 devised the phi scale. Phi is defined as being equal to —log2 of the diameter in millimeters. Selection of logarithms to the base 2 relate the phi scale directly to the Wentworth grade scale in such a manner that the whole or fractional diameter values 2, 1, 1/2, 1/4 mm, etc., become rational whole numbers, —1, 0,1, 2, etc. Since this is an arithmetic rather than geometric series, calculations are facilitated. When the logarithm is multiplied by —1 the phi values below 1 mm become positive, those coarser than 1 mm negative. Because of its relationship to the Wentworth grade scale (and in turn to the U.S. Standard fine sieve series) it is not necessary to use the transformation equation to calculate the phi value for each individual sieve; this can be done graphically as shown in Fig. 1. It should be noted that this graph may be extended in either direction to include the range of sizes most commonly used by the individual worker. Application to Statistical Analysis Any attempt at systematically relating size analysis data to properties involves a statistical study whether it is recognized as such or not. Since this is true it would seem more logical to use measures and devices related to the general body of statistical theory. Several methods are available for studying particulate mixtures. One of the most commonly employed, and also the most often misused, is the histogram or block diagram. If its limitations are recognized and provided for, the histogram is a very useful tool. According to conventional practice, the bars of equal width are plotted and the values noted in terms of diameters, when in point of fact, log diameter is implied by such notation. Further, the histogram is sensitive to choice of grade scale and size of class interval, either of which may color the result. Grade scales whose classes are not related by fixed intervals are particularly difficult. Another basic weakness of the histogram is that it pictures a continuous distribution as a series of discrete grades.

Jan 1, 1957

By AIME

TITANIUM-RICH ilmenite deposits, situated in the Allard Lake area in Quebec some 400 miles down the St. Lawrence River from Quebec City and 28 miles north of Havre St. Pierre on the north shore of the Gulf of St. Lawrence, are undergoing an intensive development program by the joint efforts of the Kennecott Copper Corp. and The New Jersey Zinc Co. Easily accessible ore, amounting to about 125 million long tons and carrying from thirty to forty per cent titanium oxide, has been delimited. Plans are being made for construction of an electric smelter at Sorel, on the south bank of the St. Lawrence midway beween Montreal and Three Rivers, which will produce 650 long tons of high-grade titanium slag and 500 long tons of iron per day from 1500 long tons of ore. Occurrence of ilmenite ore in this area has been known since J. A. Retty reported his geological work in the lower Romaine River area for the Quebec Bureau of Mines in 1941. In this report Dr. Retty mentions the presence of anorthosite rocks, some of which were rich in ilmenite. Claims were staked by several interests but the small showings and complex metallurgy were too formidable for any organization not adequately equipped with capital, metallurgical knowhow, and market outlets. However, Kennecott became interested and through a newly formed Canadian subsidiary, Kennco Explorations Ltd., options were taken up under the direction of A. H. Robertson. An area of 300 square miles was traversed in the summers of 1945 and 1946. During 1946 and 1947 geophysical and diamond-drill prospecting disclosed a num-

Jan 1, 1948

By A. W. Schlechten, Ernest J. Breton Jr.

Experiments on the separation of copper and zinc ions by selective action of ion exchange resins showed the carboxylic type to be more effective than the sulphonic resins. The latter demonstrated a greater capacity over a wider pH range. Data show the effectiveness of resins as a means of concentration. IN recent years the restrictions of stream pollution laws and the high price of metals have created an interest in ion exchange as a means for metal recovery. Some applications have proved successful. In Germany during World War 11, 17 tons of copper per day were recovered from rayon mill wastes by means of ion exchange resins;' and for some time in this country a large ion exchange unit has been in operation for the recovery of copper from rayon waste water. The possibilities of applying ion exchange to the recovery of metals occurring in plating rinse water is particularly promising. In most of these applications only the metal being recovered occurs in the waste. The ion exchange resins act merely as a means of concentrating the metals to a point where they can be recirculated. It would be highly desirable to use ion exchange as a means of not only concentrating but also of separating metals. With the exception of the impressive separations accomplished in connection with the atomic energy program, very little has been done on metal separations.' Therefore, an investigation was undertaken at the Missouri School of Mines and Metallurgy to determine if either of the two main types of ion exchange resins could be used to separate metal ions in solution. The selective removal of copper ions from a mixture of copper and zinc on carboxylic and sulphonic-type resins was investigated as a function of flow rate, pH, copper-zinc ratio, and concentration. It was shown that zinc can be separated from copper and that very large ratios of concentration can be obtained using ion exchange resins. Since ion exchange is relatively new to the field of metallurgy, a brief review of the subject will be included. Theory of Ion Exchange A comprehensive theory for ion exchange has not been developed as yet, but the mechanisms are analogous to metathetical reactions: R Na + Cu++ *=? K(SO3)2 Cu + 2Na+ R is the designation for the ion exchange resin. If a copper solution is passed over a resin bed in the sodium form, two ions of sodium will be released for every ion of copper removed. For the most part this reaction follows the laws of mass action and of electrical neutrality. Consequently, if an excess of sodium ions is passed over a bed containing copper, the reactions will be reversed, and the resin will be regenerated to its original form. A few empirical rules governing the exchange reaction have been set forth: 1—In general ions with a high valence will replace ions with a lower valence. 2—Ions having higher activity coefficients have a higher replacement potential. 3—In a series of mono-valent ions, those with the smallest radii of hydra-tion will tend to replace those having larger radii of hydration. 4—Where ions are similar in most respects, those with the higher atomic weight sometimes will take precedence. This last rule is not as definite as some of the others. These rules apply to rather dilute solutions at moderate temperatures and assume all ions to be present in about equal concentrations. Higher concentrations and temperatures may in some cases reverse the normal exchange reactions. Ion exchange materials are unique in that their efficiency increases as the concentration of the solution decreases. For many exchangers, most efficient operation is obtained at concentrations in the order of one thousandths of a percent. Most applications, though, are made in solutions containing considerably higher concentrations than this. Coste9 as shown that ion exchange resins will remove aluminum and iron effectively' from solutions of up to 10 pct chromic acid. Ion Exchange Resins Ion exchange resins are insoluble, porous, resinous structures to which active groups have been attached. Active groups such as (—SO,,)- and (COO)- pick up cations; hence structures saturated with groups such as these are called cation exchangers. Structures saturated with groups such as (—NH,)' which pick up anions, are referred to as anion exchangers. The resinous structure of necessity is resistant to strong acids, bases, oxidizing, and reducing agents, and most of the common organic solvents. An idea of the stability can be gaged from the fact that resins last for many years under constant use without detectable chemical or physical breakdown. The ion exchange reaction is not confined to the surface of these synthetic resins. Its porous structure permits active groups in the center of a particle as well as those on the surface to remove ions. A high capacity resin such as Amberlite IR-120 will remove up to 3.3 lb Cu per cu ft of resin. In this investigation several approaches to the problem of separating copper from zinc by ion exchange were considered. First, if a reagent could be found which would complex one of these metals and not the other, then by passing this reagent through a bed of exchanger containing copper and zinc, the

Jan 1, 1952

By T. B. Counselman

WHEN one thinks of Minnesota iron ore, one thinks of big open pits, where high- grade ore is simply scooped up with a power shovel, loaded into cars, and hauled away for shipment to the blast furnace. On the western end of the Mesabi range, however, are large tonnages of iron ore which contain too much silica to be used directly in the blast furnace, and these ores must first be concentrated to a purer form. The Mesabi range is about 100 miles long and a maximum of 3 miles wide. The iron formation, which in its unaltered form is called taconite: consists of a banded iron- bearing chert. Where the high-grade ore bodies occur, these have resulted from folding and cracking with sub- sequent leaching out of the silica, leaving the iron oxide behind. The big open pits and the underground mines are situated in these concentrations.

Jan 1, 1941

By William O. Hotchkiss

IN COMMON with every other good citizen I long for conditions that will make perpetual peace a reality throughout the world. I have studied the statements of our public men relating to what we must do to bring this about after this war is over. In most of these I find one common error. They always build their plans on the unstated, subconsciously accepted premise that there can be such a thing as an ideal nation whose citizens are possessed of infinite wisdom and actuated only by motives that are above reproach. This heavenly vision fails to correspond with the facts. We wish it could be true but we are forced sadly to admit that the human beings that will live here after this war is over are going to be much like the fallible race that has occupied our planet for the past centuries.

Jan 1, 1943

By J Price, M. R. Geer, H. F. Yancey

COAL mine operators recognize coal as an abrasive material, because the wear of drilling, cutting, and conveying equipment is reflected as a cost item for replacement of parts. Similarly, industrial consumers of coal experience abrasive wear on all coal-handling equipment. Operators of pulverized fuel plants are doubtless most keenly aware of the abrasiveness of coal, because under the high contact pressures developed between coal and metal in pulverizers, abrasive wear is increased many fold. Moreover, experience in operating pulverized fuel plants has demonstrated that some coals are much more abrasive than others. Hardgrove' stated that maintenance costs entailed by the wear of grinding elements is often a more important variable than the cost of the power required to pulverize different coals. Craig2 also reports that one coal may cause pulverizer parts to wear several times faster than another. It is apparent, therefore, that those concerned with pulverizing coal could profitably employ a method for estimating the abrasiveness of different coals, just as they utilize standard tests for thermal value, grindability, and ash-fusion temperature to assist in selecting the most suitable and economical coal to use in a particular plant. The objective of this investigation was to develop a test procedure that would be suitable for general use in estimating the abrasiveness of coals. However, few, if any, of the standard tests now used for evaluating the properties of coal are the product of a single investigation or the result of a single investigator's efforts. Rather, in each case, a testing procedure was devised by one investigator, used by others on a wider variety of coals, and finally refined completely as the result of the joint efforts of a number of interested people. Thus, the test procedure for estimating abrasiveness developed in the course of this work may not be refined sufficiently in its present form for general use, but it may serve as the starting point from which an acceptable test procedure can be developed. The method has been used thus far on only about a dozen coals, and there has been no opportunity to attempt a correlation between experimental results and actual plant experience. Only wider use of the procedure by other investigators and correlation with plant experience can determine to what extent the method will have to be modified to render it suitable for general application. Test Method Although the literature contains no record of an attempt to devise a method for estimating the abrasiveness of coal that could be used industrially, several investigators have tested properties of coal that are closely related to its abrasiveness. The abrasiveness of a material generally is considered to be related to its hardness, and hardness tests for coal have been employed by Heywood,' O'Neill," and Mathes. Also, the resistance of coal to abrasion, a property that presumably is related to the abrasiveness of coal, was measured by Heywooda and by Simek, Pulkrabek, and Coufalik.2 11 these investigators tested only individual pieces of coal. Since coal is a heterogeneous material having components of varying properties, tests of this type can yield results having little more than academic interest. Only a test method that utilizes a representative sample of coal can give results that are useful industrially. The abrasion tests used for various other materials have been considered for adaptation to testing the abrasiveness of coal. The tests used for metals,7-9 paving and flooring,'" and rubber," cannot be used because coal is not sufficiently abrasive.~ The present experimental work was begun before World War II and was conducted by three research fellows"'" working under a joint agreement between the University of Washington and the Bureau of Mines. After a great deal of preliminary work with a variety of apparatus and materials, a test procedure was developed which consisted of rotating a test disk 2Yz in. diam in a steel mortar containing the coal sample. The shaft carrying the test disk at the lower end and a 100-lb load on the upper end was free to move vertically. The bed of coal in the mortar was kept fluid by low-pressure air admitted through a port near the bottom of the mortar. Measurable wear on an Armco iron disk could be obtained in this test procedure, but, despite extensive efforts to eliminate them, several major disadvantages remained in this test method. First, with most coals the amount of wear on the iron disk did not exceed a few milligrams. Second, a single type of disk was not applicable for all coals. A smooth iron disk gave satisfactory results with both bituminous and sub-bituminous coals, but hardly any wear with anthracite or coke. A disk having studs or projections gave more satisfactory abrasion losses with anthracite and coke and presented no operating difficulties with free-burning bituminous and sub-bituminous coals. It could not, however, be used with caking coals because these coals formed a

Jan 1, 1952

By A. J. Williams

THE province of Saskatchewan, situated in the center of the Great Plains region of Canada, has, like most prairie areas, an essentially agricultural economy. Most of its population of about 860,000 is located in the southern half of the province in the farming and ranching areas. To the north of the prairie is a broad forested belt supporting a considerable timbering industry, and the northern one third of the province is glaciated pre-Cambrian rock formation. This latter area is relatively barren of vegetation, but the presence within it of a considerable variety of radioactive, noble and base metals, and industrial minerals has been shown by prospecting in recent years.' Glacial Geology The Keewatin ice sheet, considered to have accumulated in the country to the west of Hudson Bay in Pleistocene time, covered at its maximum advancement almost all of Saskatchewan and extended south of the international boundary. Only in the Cypress Hills in the southwest and around Wood Mountain in the south central portion of the province did the preglacial formations escape the action for this glacial period. The bedrock of the plains and forest areas therefore is overlain by moraines and modified glacial drift, which vary in thickness from a few feet to 400 or 500 ft.' Glacial action in the pre-Cambrian area of the province was largely erosional, most of the more recent formations and some of the pre-Cambrian rock being transported out of the area to the south and west. It has been estimated that about 13 pct of this area is composed of lakes and rivers not too adaptable to rail or water transportation, so that until the use of aviation for exploration purposes became general, development of the area was slow. To the south, the heavy mantle of glacial drift has to some extent deterred the discovery of industrial minerals in the bedrock underlying the forest and prairie regions3 At the same time, this drift contains numerous deposits of those most elementary and necessary industrial minerals, sand and gravel. Sedimentary Basin The major feature of the sedimentary deposits underlying the plains regions is the basinal structure known as the Moose Jaw syncline, which runs from the southeast corner of the province in a northwesterly direction. To the west of this syncline the formations curve upward, then have been faulted and further upthrust to appear at the surface in the foothills of the Rockies in Alberta; to the east and north they curve upward into Manitoba and northern Saskatchewan, but the surface contacts are covered mostly with glacial drift.238 The axis of the syncline dips to the southeast, so that there is also an upward trend of the formations along the axis to the northwest. In illustration of the regional structure underlying the province, the pre-Cambrian basement has been logged in drillholes at the following depths in several locations: Ogema (south central), 9390 ft; Gronlid (northeast), 2599 ft; Vera (northwest), 4422 ft; Big River (north northwest), 2348 ft. Fig. 1 indicates the general surface geology of the province, ignoring such glacial overburden as may overlie many of the bedrock formations. Also indicated is the approximate location of the axis of the Moose Jaw syncline.' Industrial Minerals Clays: The province is fortunate in possessing a widespread distribution of clays of ceramic value, ranging from those used for heavy structural products to the high grade pottery and china clays. Shales suitable for brick and tile production are found in the Upper Cretaceous and Tertiary formations across the south of the province where the glacial drift is thin or nonexistent. Many deposits of glacial lake clays suitable for such wares are found scattered over the rest of the province south of the pre-Cambrian area. The Whitemud formation of the Upper Cretaceous is a narrow sedimentary band of secondary clays found intermittently at points across the south of the province where glacial action did not disturb or remove them.' In the southwest corner of the province, around Eastend in the Frenchman River valley, the refractory clays of this formation are contaminated somewhat with iron compounds or other alteration products of basaltic rocks. This eliminates the use of those clays in true whitewares, as they fire to creamy buff shades at the lower temperatures and to a blue-specked grey at cone 8 to 12, (2280°F to 2390°F), the range commonly used in firing whiteware. However, for use in the production of colored artware, caneware, stoneware or crockery, and sewerpipe, this type of clay makes an excellent body that requires little or no addition of flint, feldspar, or other fluxing materials such as are required in the higher class of ware.' It is not a grade of clay that can be shipped great distances to the manufacturing centers, but a market for considerable tonnages has developed at nearby Medicine Hat, where cheap natural gas is available for the firing of the ware. Farther east in the south central portion of the province, the clays of the Whitemud formation are generally more refractory and white burning. The formation is divided into three zones, consisting of white clays, brown shale, and white sandy clays.

Jan 1, 1953

By D. T. Peters

To better understand the Co-Mo interaction in maraging steels, the precipitate reversion behavior of two alloys closely related to the 18 Ni-250 grade has been studied. The reversion experiment is carried out by aging at a low temperature, T1 (preaging temperature), for some period of time and then aging at a higher temperature, T2, called the reversion tetnperature. Aging and reversion tmzperatures used were in the range 679 to 1050°F. Reversion is marked by an increase in resistivity and a decrease in hardness. It teas found that some reversion took place at all cornbinations of T1 and T2 but that pronounced rei3ersion resulfed for an Fe-18 pct Ni-5 pct Mo-8 pcl Co alloy exposed to preagz'ng' temperatures at or below 850°F. A similar alloy not containing cobalt exhibited no such discontinuity in reversion behazior with TI. The results are interpreted in terms of two types of molybdenum-rich precipitates, one nucleated at dislocations and the other in the matrix. The increased supersaturation resulting from the presence oj- cobalt evidently provides sufficient energy to nucleate the matrix phase. Anotnalies in the temperature dependence of the resistivity decrease and peak hurdness in the Fe-18 pct Ni-5 pct Mo-8 pct Co alloy as a junction of aging temperature noted in an earlier study are explained on this basis. SEVERAL investigatorsl-9 have studied the details of the precipitation-hardening reaction of the maraging steels. The great majority of conclusions have been drawn from transmission electron microscopy. Although much has been learned by this method, alternate techniques which will give information earlier in the aging process are needed for a more complete understanding of the series of precipitation steps probably involved in the aging reaction. Peters and cupp'' have recently shown, by measurements of the kinetics of precipitation, that an 18 pct Ni-Co-Mo maraging steel shows a distinct change in precipitation behavior at aging temperatures below 850°F. The results were interpreted in terms of the existence of two types of precipitates at low aging temperatures. Only one precipitate type is present at higher aging temperatures. The low-temperature precipitate was found to be a particularly effective strengthener. No evidence for the additional low-temperature precipitate was found in the 18 pct Ni-5 pct Mo ternary alloy. The object of this investigation was to study further the characteristics of the two types of precipitates and the interaction between cobalt and molybdenum characterizing this system. Some preliminary experiments indicated a difference in reversion behavior in specimens aged above and below 850°F. This suggested that knowledge of the reversion behavior might shed some light on these two questions. Hardy and Heal11 have defined reversion as the loss of hardness, electrical conductivity, or other properties caused by heating for a very short time at temperatures above the aging temperature. The precipitate reversion referred to in this paper is entirely distinct from "austenite reversion" often referred to in maraging steel literature. This latter phenomenon could more accurately be called the diffusion-controlled formation of austenite. Much has been written about reversion in several of the aluminum-base binary and ternary alloys.'2-16 Two explanations for reversion have been advanced. Based on the classical nucleation theory of Volmer-Weber-Becker-Doring,17 Konobeevski18 suggested that reversion was due to the size of the precipitate particles

Jan 1, 1968

By W. A. Tiller, W. C. Johnston

The solute distribution ahead of an advancing solid-liquid interface is controlled by varying the momentum boundary layer thickness in the liquid adjacent to the interface. Single pass zone-melting experiments on Pb-Sn alloys are described in which the liquid is caused to rotate in the plane of the solid-liquid interface due to the influence of a magnetic .field rotating in this plane. The variation of the diffusion boundary layer thickness with field strength is determined. DURING the freezing of an alloy a partitioning of solute occurs at the solid-liquid interface, the magnitude depending upon the difference in the solid and liquid solubilities at the interface temperature. Because the diffusion coefficient is so small in the liquid relative to normal freezing rates, either a pileup or a depletion of solute occurs at the interface when the partition coefficient, kO, is either less than or greater than unity, respectively. This solute distribution is completely characterized by i) the solute concentration in the liquid far from the interface, C) the ratio of freezing velocityf, to diffusion coefficient, D, iii) the partition coefficient, ko, and iv) the thickness of the diffusion boundary layer, 6,, at the interface (this assumes that an electric field is not applied across the interface). For a particular system, C ko and D are fixed so that the character of the solute distribution can be changed only by a variation of either f or 6c. As is well known, the freezing velocity can be changed by varying the thermal environment of the alloy. Whereas, the thickness of the solute rich layer can be changed by varying the fluid flow conditions in the liquid. It is the purpose of this paper to describe a technique for controlling the fluid flow conditions in the liquid. During most solidification experiments the driving force for fluid flow arises from either mechanical mixing, thermal convection or electromagnetic mixing. The momentum boundary layer thickness, 6m at the solid-liquid interface, within which negligible movement of the liquid occurs, has been calculated for the special case of mechanical mixing where crystals are solidified by the Czochralski technique.l,2 The calculation of 6m for the case of thermal convection has also been made.3 In some calculations it has been assumed that the momentum boundary layer thickness, 6,, may be equated to the thickness of the diffusion boundary layer 6c, at the interface. However, as may be seen from Appendix I this is only true in very special cases and in general where a is a constant of magnitude determined by the particular liquid alloy. Neither calculations nor experimental data exist for the dependence of upon electromagnetic mixing. In this paper experiments are described in which the liquid is caused to rotate in the plane of the interface due to the torque developed on it by a magnetic field, H, rotating in this plane. The variation of is controlled by the variation of H. A magnetic field rotating in a plane perpendicular to the interface has been used for the purification of aluminum. Experimentally, we determined the variation of 5C with H by using the zone-melting technique of pfann5and a theoretical relationship of Burton et a1.2 pfann5 has shown that, after the passage of one molten zone through a long cylindrical charge of uniform concentration, CO, the solute distribution, C,, in the solid is as shown in Fig. 1. The equation describing this distribution is

Jan 1, 1962

By N. J. Grant, K. M. Zwilsky

A series of copper-alumina dispersion strengthened alloys were prepared using three different copper and two different alumina powder sizes. Improvements in strength of up to ten times that of pure copper were found in room-temperature as well as elevated-temperature stress-rupture tests. Conductivity values remained from 70 to 90 pct that of pure copper. The best alloys were based on the finest metal powder (1 p) and contained from 7.5 to 10-0 vol pet of 0.018 or 0,033 p alumina. DISPERSION strengthening of metals consists of strengthening a metal matrix by the addition of oxides or other refractory constituents, followed by strain hardening, in order to reinforce the base material and extend its temperature range of application. Since the discovery of SAP by lrmannl and Von zeerleder2 in 1949, many investigators have reported data obtained on a variety of metal-inert oxide alloys.3-7 The present work deals with the mechanical mixing of copper and alumina powders. While several techniques of introducing the second phase have been investigated to date, mechanical mixing so far has been recognized as the simplest, least expensive, and most universally applicable technique that can be used to obtain an ultrafine dispersion of inert particles. In the present case, the effects of changing the metal particle size, the oxide particle size and the volume percent of oxide were investigated. This work is an extension of a previous study.6 EXPERIMENTAL PROCEDURE The starting materials were three different grades of copper powder and two different alumina powders. The three metallic powders were -74 µ(- 200 mesh) electrolytic copper powder consisting of irregular equiaxed particles having a normal screen distribution and analyzing 99.5 pct Cu, and two powders having a 5-µ and 1-µ particle size, average, respectively. The latter powders were produced by the hydrogen reduction of purified sulfate solutions at elevated temperature and pressure and were furnished by the Sherritt Gordon Mines, Ltd. The alumina used was obtained from Godfrey L. Cabot Co., under the trade name of Alon C, one batch of powder having a particle size of 0.018 µ, the other a particle size of 0.033 µ. The crystal structure of these alumina powders was found to be cubic gamma. Each batch of powder was mixed in a Waring Blendor for a total of 15 min, followed by a low-temperature reduction in hydrogen and vacuum compacting in cylinders which were hydrostatically pressed at 35,000 psi to give a compact that could be handled conveniently. Six of the compacts were hydrogen sintered at 900°C while the remaining four were sintered at 1000°C. Subsequently, all compacts were hot extruded at 760°C with a reduction of area ratio of approximately 20 to 1. Evaluation of alloys included density and resistivity measurements, room-temperature tensile tests, stress-rupture tests at 450°C plus one other temperature per alloy, hardness tests, microstruc-tural examination, X-ray analysis of the dispersed phase after dissolving the metal phase, and oxidation studies on two of the alloys. A vacuum-melted, wrought copper rod was tested together with these alloys for comparison purposes. RESULTS Table I is a summary of the compositions, sintering temperatures, densities and conductivity values of the ten alloys prepared. All alumina additions are given in volume percent, and will be referred to as

Jan 1, 1962