Search Documents

By Fred P. Dewey

Early last March Mr. Jerome Coldren, an old miner add prospector, undertook a prospecting tour through the western part of Kansas, and discovered a very peculiar bed of rock, which yielded a white metal on fusion with soda. Mr. W. D. Church, city chemist at Topeka, examined the metal and found it to contain nickel. This discovery created much excitement, and was at first doubted. Many samples of the material, from a range of twenty miles, were sent to the Smithsonian Institution for examination ; and in every instance a qualitative test showed the presence of nickel, although the amount appeared to vary greatly. The ore is quite different from any other nickel-ore. It consists of a quartzose conglomerate from bean-size down, with much decomposed material between the pebbles, and the whole cemented by a more or less manganiferous limonite. In the qualitative tests, the nickel appeared to vary with the manganese. In all the tests, simple treatment with HCI dissolved a great deal of AI2O3. The principal deposit is near the top of a small hill on the divide between Smoky Hill river and Butte creek. The surface-rock is the conglomerate, and, at varying distances, stains of the limonite appear and gradually increase ; so that the ore is simply the lower portion of a bed of conglomerate which has been heavily charged with the manganiferous limonite. Below the conglomerate is a layer of selenite; below this, a soft sandstone, containing well-preserved fossils, and below the sandstone, a shale. From 2 to 6 per cent. of nickel in selected samples has been reported by different chemists; but the following two analyses on large samples show the average composition of the material:

Jan 1, 1889

By G. R. Brophy, A. J. Miller

The Grossmann principle1 for the calculation of hardenability of steel from composition is attractive because of its simplicity. It postulates that the hardenability of a steel for any particular grain size may be expressed in terms of an ideal critical diameter, which is the product of an ideal critical diameter for a "pure" iron-carbon base multiplied by a succession of factors for each element of composition contained, including the incidentals. It infers that the multiplying factor for a given quantity of an element is constant for all combinations of composition. Gross-mann has stated that in the great majority of cases the experimental values of hardenability are found to be well within 10 per cent of the calculated values. The validity of the scheme has been confirmed in principle by Crafts and Lamont2,3 and by Kramer et al.4 Their results differ from the original in the magnitude of the effect of some elements but, since they accepted the product concept and followed its direction, it is to be ex~ected that similar results would be obtained. Crafts and Lamont, in their second Paper, recognized that the factor relations for manganese and nickel were not continuously linear, but beyond certain critical amounts increase sharply. Austin, Van Note and Prater6 demonstrated nonlinear relations between hardenability and alloy contents. Their curves for chromium, silicon, manganese and nickel were all convex upward to show decreasing incremental effects. They concluded that Grossmann's factors under-evaluate the hardening effect of low percentage additions of these elements, and overevaluate the larger additions. More recently W. Stevens has found that the factor method fails when applied to complex steels containing two or three principal alloying elements other than carbon. Multiplying factors derived from his results bear a complex relation to composition and are not constant for a given amount of an element as the base composition varies. C. A. Liedholm7 found that, using either the Grossmann or the Crafts-Lamont multiplying factor values, not only were the relative hardenabilities of two heats of S.A.E. 6130 chromium-vanadium steel

Jan 1, 1947

By A. J. Miller, G. R. Brophy

The Grossmann principle1 for the calculation of hardenability of steel from composition is attractive because of its simplicity. It postulates that the hardenability of a steel for any particular grain size may be expressed in terms of an ideal critical diameter, which is the product of an ideal critical diameter for a "pure" iron-carbon base multiplied by a succession of factors for each element of composition contained, including the incidentals. It infers that the multiplying factor for a given quantity of an element is constant for all combinations of composition. Gross-mann has stated that in the great majority of cases the experimental values of hardenability are found to be well within 10 per cent of the calculated values. The validity of the scheme has been confirmed in principle by Crafts and Lamont2,3 and by Kramer et al.4 Their results differ from the original in the magnitude of the effect of some elements but, since they accepted the product concept and followed its direction, it is to be ex~ected that similar results would be obtained. Crafts and Lamont, in their second Paper, recognized that the factor relations for manganese and nickel were not continuously linear, but beyond certain critical amounts increase sharply. Austin, Van Note and Prater6 demonstrated nonlinear relations between hardenability and alloy contents. Their curves for chromium, silicon, manganese and nickel were all convex upward to show decreasing incremental effects. They concluded that Grossmann's factors under-evaluate the hardening effect of low percentage additions of these elements, and overevaluate the larger additions. More recently W. Stevens has found that the factor method fails when applied to complex steels containing two or three principal alloying elements other than carbon. Multiplying factors derived from his results bear a complex relation to composition and are not constant for a given amount of an element as the base composition varies. C. A. Liedholm7 found that, using either the Grossmann or the Crafts-Lamont multiplying factor values, not only were the relative hardenabilities of two heats of S.A.E. 6130 chromium-vanadium steel

Jan 1, 1947

By E. T. Turkdogan, P. Grieveson

Experimental results are presented for the rate of solution of nitrogen in a iron in the temperature range 750° to 873°C and in 6 iron in the temperature range 1410° to 1470°C. It is shown that the rate controlling process is diffusion of nitrogen into the iron. The diffusiting of nitrogen in a and 6 iron is derived from the results, and the temperature dependence of the diffusivity is represented by the equation D = 7.8 x e- 18,900/RT sq cm per sec. The solubility of nitrogen in a and 6 iron, in equilibrium with 1 atm pressure of nitrogen, has been measured. Using these results and other available data, it is found that the variation of the logarithm of nitrogen solubility with the reciprocal of absolute temperature is nonlinear. In an Appendix, some results of Darken and Smith are presented for the rate of solution of nitrogen in iron using ammonia + hyidrogen mixtures. These data also support the view that diffudsion of nitrogen in iron is the rate-controlling process when ammonia + hydrogen mixtures are used. A considerable effort has been made to obtain data on the solubility1-5 and diffusivity of nitrogen in a iron6-l2 because an understanding of the effect of nitrogen on the properties of steel must be based on an accurate knowledge of the properties of nitrogen in pure iron. However, no information is available concerning the kinetics of solution of nitrogen in a and 6 iron. Recently the authors13 have investigated the rate-controlling mechanism operating in the kinetics of solution of nitrogen in y iron. This study was directed to determine the rate-controlling processes for similar reactions with a and 6 iron as well as to establish values for the solubility of nitrogen in equilibrium with nitrogen gas in a and a iron. EXPERIMENTAL The procedure used in experiments to determine the rate of solution in cylindrical iron rods was the same as that described in a previous communication.13 Ferrovac E grade iron used in all experiments contained the following impurities in weight percent: C, 0.005; Mn, 0.001; P, 0.002; S, 0.006; Si, 0.006; Ni, 0.025; Cr, 0.002; V, 0.004; W, 0.02; Mo, 0.01; Cu, 0.001; Co, 0.01; 0, 0.007. After cleaning the surface, the iron rods were treated in an atmosphere of purified hydrogen for 17 hr before the reacting gas was introduced for known experimental times. After quenching, the samples were sectioned radially and analyzed for nitrogen. In addition to experiments using rods, iron foils were used in the measurements of solution rates of nitrogen in a iron. The foils of two different thicknesses were prepared by cold rolling Ferrovac E grade iron cylindrical rod to 0.051 and 0.152 cm. Foil samples were used in a rectangular form 5 cm long and 1.25 cm wide. The specimens were thoroughly cleaned of surface oxide with fine emery cloth and degreased with carbon tetrachloride immediately before entry into the furnace. The experimental procedure was the same as that used in the study with rods. At the completion of an experiment, the foil samples of the nitrogenized iron were analyzed for nitrogen after discarding 0.3 cm from the perimeter of the specimen. Iron foils were nitrogenized and denitrogenized in the a and 6 range with a gas mixture of 95 pct N and 5 pct H for times varying from 5 min to 2 hr. Results obtained for the average composition of nitrogen in iron for these experiments are presented in Fig. 1. Prior to the denitrogenization experiments, the samples were saturated with nitrogen at 1000°C and 0.67 atm N, giving a uniform nitrogen concentration of 0.0204 pct. According to the known a-y phase boundary in the Fe-N system,14 this composition lies within the ferrite region at temperatures 750" to 850°C. Use of this initial nitrogen content insured that reaction occurred between the gas and a single solid phase, a iron. Examples of the results for the mean concentrations of nitrogen in cylindrical iron rods, 0.356 cm radius for both the a and 6 ranges are given in Fig. 2. Typical examples of the results obtained for the radial distributions of nitrogen in rods are presented in Fig. 3. It appears that the results for radial distributions can be extrapolated to constant surface compositions which agree with the equi-

Jan 1, 1964

By William Y. Holland, Roger M. Cook

In view of the increasingly widespread deterioration of concrete structures as the result of the interaction of the alkalies sodium and potassium released by hydration of portland cement and susceptible rocks and minerals in aggregates, it is believed that a paper summarizing the geographic distribution of these aggregates will be of interest to producers and users of concrete, concrete products, and concrete-making materials. THIS paper reviews the problem of alkali-aggre-gate reaction in concrete and describes the geologic and geographic occurrence and distribution of alkali-reactive sand and gravel in western United States. It includes no discussion of crushed stone or synthetic aggregates. Most deposits of sand and gravel are accumulations of particles of rocks and minerals from a variety of sources, and it is not unusual for at least one or two varieties of the rocks to contain some form of reactive material. Examination by petro-graphic methods of many sands and gravels, as well as manufactured aggregates, has shown that a comparatively high proportion of the deposits does contain, in greater or lesser degree, rocks and minerals known to be deleteriously reactive with the alkalies of cement. Fortunately the amount of reactive materials is commonly less than that necessary to cause deleterious effects in concrete. As investigation of unsound concrete structures progresses, it becomes evident that the alkali-aggre-gate reaction is even more widespread than supposed, Figs. 1 and 2. Even though some parts of the country appear at present to be immune, further investigations will probably show that the effects of alkali-aggregate reaction can be seen in many structures in these areas, although only on a small scale in most of them. Many concrete structures will, of course, have lived their useful life before disintegration from this cause is serious, and in others the alkali-aggregate reaction may never become significant even though the microscopic evidence of reaction is present. The alkali-aggregate reaction first was reported to be a cause of deterioration of concrete in 1940 when Stanton1 described expansion of concrete pavements in California. Similar expansion and deterioration of concrete was recognized during succeeding years in concrete structures located in many parts of the country, but particularly in the western states. A number of concrete laboratories2 became interested in the problem. It was soon determined that only certain combinations of aggregate and cement caused the alkali-aggregate reaction to take place, and moreover that the reaction progresses only in the presence of water. Further research proved that cements containing more than 0.60 pct total alkalies (pct Na,O + 0.658 x pct K2O), when used with aggregates containing appreciable amounts of reactive ingredients, caused the reaction to take place, usually with subsequent deterioration of the concrete. During the last few years this limitation has been adhered to in both government and private construction as the maximum allowable alkali content of cement to be used with aggregates of known alkali reactivity. Because of this limitation, it appears that deleterious reaction either has been reduced or eliminated in many recently built structures in which it probably would otherwise have occurred. Recent tests have shown that the degree of expansion obtained with any particular cement-aggre-gate combination depends not only on the alkali content of the cement but also upon the relation of this alkali content to the amount and degree of reactivity of reactive constituents in the aggregate.' In laboratory mortar bars, opal and cements with alkali content of as low as 0.2 pct (as equivalent of Na2O) have produced deleterious expansion as the result of alkali-aggregate reaction. These experiments demonstrate that aggregates containing even 0.1 pct of opal are deleteriously reactive. It was soon determined that alkali-silica gels were formed by the interaction of the alkalies of the cement and the reactive aggregate, Figs. 3 and 4. Osmotic or swelling pressures produced by the continued hydration of these gels cause expansion of the concrete with resulting cracking, warping, and dislocation. Evidence of the alkali-aggregate reaction can be seen by a petrographic study of the deteriorated concrete. Among the first structures studied by this method was Parker Dam on the Colorado River, California-Arizona. In the concrete from this dam pebbles of rhyolite, andesite, siliceous limestone, and chalcedonic chert were found to be reactive.

Jan 1, 1954

By W. M. Weigel

The rapid advance, during recent years, in the manufacture of articles that have been in common use for generations and the development of new materials entering into appliances and devices unheard of fifty years ago have created a demand for some of the more common non-metallic minerals. To supply this demand there has quietly developed a branch of the mining industry of which little is known by most mining engineers —the mineral-filler industry. In this paper, and generally in the trade, the term mineral filler is applied to a mineral used in its natural state after mechanical preparation only (such as grinding, milling and washing), without undergoing any chemical change and without exerting any chemical action on the substance with which it is incorporated. The consumption of mineral fillers is confined chiefly to large manufacturing centers in the Eastern and Northern Statcs. Where available, materials originating near the place of consumption are used, as most fillers bring a comparatively low price and, frequently, the freight may equal the cost of the finished filler at the mine. The Southern States have abundant deposits of non-metallic minerals suitable for fillers, which supply the manufacturing industries in adjacent states. Many of these deposits are equal to, or superior, in quality to those mined in the North, but they can not compete with them because of the freight rates. The mineral-filler industry has felt the present depression, but it has suffered less than most mining industries, for as a rule the mills are simple, the overhead expenses are low, and the labor is entirely local and can revert to farm work when the plant closes down. Many other deposits in the southern district will undoubtedly be developed when business revives and freight rates are adjusted. Most of the non-metallic mines are small and the tonnage handled is low in comparison with the tonnage involved in modern large-scale mining of coal, iron, copper, etc. On the other hand, at nearly all non-metallic

Jan 1, 1923

By W. M. Weigel

The rapid advance, during recent years, in the manufacture of articles that have been in common use for generations and the development of new materials entering into appliances and devices unheard of fifty years ago have created a demand for some of the more common non-metallic minerals. To supply this demand there has quietly developed a branch of the mining industry of which little is known by most mining engineers —the mineral-filler industry. In this paper, and generally in the trade, the term mineral filler is applied to a mineral used in its natural state after mechanical preparation only (such as grinding, milling and washing), without undergoing any chemical change and without exerting any chemical action on the substance with which it is incorporated. The consumption of mineral fillers is confined chiefly to large manufacturing centers in the Eastern and Northern Statcs. Where available, materials originating near the place of consumption are used, as most fillers bring a comparatively low price and, frequently, the freight may equal the cost of the finished filler at the mine. The Southern States have abundant deposits of non-metallic minerals suitable for fillers, which supply the manufacturing industries in adjacent states. Many of these deposits are equal to, or superior, in quality to those mined in the North, but they can not compete with them because of the freight rates. The mineral-filler industry has felt the present depression, but it has suffered less than most mining industries, for as a rule the mills are simple, the overhead expenses are low, and the labor is entirely local and can revert to farm work when the plant closes down. Many other deposits in the southern district will undoubtedly be developed when business revives and freight rates are adjusted. Most of the non-metallic mines are small and the tonnage handled is low in comparison with the tonnage involved in modern large-scale mining of coal, iron, copper, etc. On the other hand, at nearly all non-metallic

Jan 1, 1923

By James Douglas

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

Jan 1, 1910

By J. C. Fisher, J. H. Hollomon, David Turnbull

Understanding of the diffusion problem has recently been furthered by the analysis of Birchenall and Meh1.l They pursued the problem of the variation of the diffusion coefficient with composition for non-ideal solid solutions. Their analysis follows the tradition of Wagner,l Jost, Dehlinger, and Darken & who assumed the net flux of diffusing material to be proportional to the gradient of a quantity related to free energy. The basic assumption in Birchenall and Mehl's formulation of the problem is that the net flux of diffusing material is proportional to a thermodynamic activity gradient. To estimate the applicability of the derived relations, they corrected the diffusion coefficients of carbon in austenite by utilizing Smith's6 activity data for carbon, and the diffusion coefficients for zinc in copper with activity data computed from the vapor pressure measurements of Har-greaves.' The corrected coefficients for carbon were virtually independent of carbon concentration. For the diffusion of zinc in copper a moderate variation of diffusion coefficient with concentration remained after the correction. The problem of diffusion can be formulated in another way than that used by Birchenall and Mehl. The method is that of chemical rate theory and has been used by Eyring and his coworkers8,9 as well as by Eyring and Zwolinskilo in a discussion to Birchenall and Mehl's paper. As yet the method has not been applied to substitu-tional solid solutions. On the basis of their assumptions, Eyring and Zwolinski derived a relation between the diffusion coefficient and activity that is identical with that of Dehlinger and Darken but which does not correct for the variation of the diffusion coefficient with concentration as well as does the relation derived by Birchenall and Mehl. It was thought that the theory of diffusion would be more complete if the inconsistency between the two analyses could be rationalized and if diffusion in substitu-tional alloys were analyzed on the basis of the concepts of the chemical rate theory. Chemical Rate Theory According to the theory of absolute reaction ratess the reaction +..... +X, Eq I is viewed as taking place in two steps. First the reactants A1, A², . . . A; combine to form an activated complex M with which they are in equilibrium: A1 + A1+ . . . + A=M. Eq 2 Second the activated complex decomposes to give the products XI, XZ, . . . Xi: M?X, + X²+ . . . +Xi Eq g It has been showns that the number of activated complexes decomposing per unit volume per unit time is given by the expressiont kT -h CM † The transmission coefficient has been taken as unity.

Jan 1, 1949

By David Turnbull, J. H. Hollomon, J. C. Fisher

Understanding of the diffusion problem has recently been furthered by the analysis of Birchenall and Meh1.l They pursued the problem of the variation of the diffusion coefficient with composition for non-ideal solid solutions. Their analysis follows the tradition of Wagner,l Jost, Dehlinger, and Darken & who assumed the net flux of diffusing material to be proportional to the gradient of a quantity related to free energy. The basic assumption in Birchenall and Mehl's formulation of the problem is that the net flux of diffusing material is proportional to a thermodynamic activity gradient. To estimate the applicability of the derived relations, they corrected the diffusion coefficients of carbon in austenite by utilizing Smith's6 activity data for carbon, and the diffusion coefficients for zinc in copper with activity data computed from the vapor pressure measurements of Har-greaves.' The corrected coefficients for carbon were virtually independent of carbon concentration. For the diffusion of zinc in copper a moderate variation of diffusion coefficient with concentration remained after the correction. The problem of diffusion can be formulated in another way than that used by Birchenall and Mehl. The method is that of chemical rate theory and has been used by Eyring and his coworkers8,9 as well as by Eyring and Zwolinskilo in a discussion to Birchenall and Mehl's paper. As yet the method has not been applied to substitu-tional solid solutions. On the basis of their assumptions, Eyring and Zwolinski derived a relation between the diffusion coefficient and activity that is identical with that of Dehlinger and Darken but which does not correct for the variation of the diffusion coefficient with concentration as well as does the relation derived by Birchenall and Mehl. It was thought that the theory of diffusion would be more complete if the inconsistency between the two analyses could be rationalized and if diffusion in substitu-tional alloys were analyzed on the basis of the concepts of the chemical rate theory. Chemical Rate Theory According to the theory of absolute reaction ratess the reaction +..... +X, Eq I is viewed as taking place in two steps. First the reactants A1, A², . . . A; combine to form an activated complex M with which they are in equilibrium: A1 + A1+ . . . + A=M. Eq 2 Second the activated complex decomposes to give the products XI, XZ, . . . Xi: M?X, + X²+ . . . +Xi Eq g It has been showns that the number of activated complexes decomposing per unit volume per unit time is given by the expressiont kT -h CM † The transmission coefficient has been taken as unity.

Jan 1, 1949

By F. H. Deily, Jean M. Quets, Milton E. Wadsworth, John R. 222-000-000-012 Lewis, D. S. Rowley, R. J. Howe

Samples of synthetic magnetite were reduced in hydrogen-water vapor atmospheres in the temperature range 450o to 900oC. The reaction was always surface controlled, indicating the final products of reaction are nonfirotective. Three separate cases have been identified from the kinetic results: Case I, reduction of magnetite to iron below 570°C; Case II, reduction of magnetite to iron above 570°C; and Case 111, reduction of magnetite to wustite above 570 oC. In Cases I and 111 the kinetics have been explained by the formation of oxygen anion vacancies in the magnetite surface followed by associated diffusional processes. In Case 11 the observed kinetics have been related to the concentration of iron cation vacancies in the wustite layer formed, followed by associated steady-state diffusional processes. The concentration of cation vacancies in the wustite is maintained constant by the magnetite-wustite equilibrium. THE reduction of the oxides of iron has been a subject of study and interest for many years. However, few attempts have been made to interpret the results in terms of the mechanism of reduction of an iron oxide by either hydrogen or carbon monoxide. Stalhane and Malmberg' using CO, H2, and CO-Hz mixtures, developed the rate expression: where m = mass of oxide reduced, t = time, k = a constant, s = surface area, P = partial pressure of of CO or H,, and P, = partial pressure of the reducing gas at equilibrium. The rate of reaction per unit area was proportional to the difference between the partial pressure of the reducing gas and its pressure at equilibrium. Hansen, Bitsianes, and Joseph2 studied the reduction of pellets of hematite to magnetite with mixtures of CO-CO,. They concluded that below 450°C the reaction proceeded according to a model in which CO reacts with the hematite surface producing an oxygen ion vacancy. The rate controlling step was then assumed to be oxygen ion diffusion through vacancies resulting in the formation of magnetite. They derived an expression giving the rate of reduction proportional to the cO/CO, ratio. Recently McKewan3 published results for the reduction of magnetite spheres in atmospheres below 570°C. He explained his results by an equation of the form where K, is the equilibrium constant for wustite-iron equilibrium attributed to the formation of wustite as an intermediate in the reduction of magnetite. According to McKewan, Kp is an equilibrium constant for H, -HO adsorption in which oxygen is deposited on the surface from the H,Oand subsequently acts as a poison for reduction by hydrogen. Sample Preparation and Experiments. In this work the authors used the same apparatus and experimental procedure employed in the hydrogen reduction of magnetite. Sintered disk samples weighing approximately 1.5 g and measuring 1.2 cm in diameter and 0.25 cm in thickness were prepared by a method described previously.4 Partial pressures of hydrogen and water vapor were controlled by bubbling hydrogen through a series of flasks containing distilled and deionized water maintained at constant temperature in an oil bath. The total flow rate of the reacting gases—hydrogen and water vapor—was approximately 0.5 liter per min. The entire external system was maintained at a temperature above the oil bath to prevent condensation of water vapor. This was accomplished by wrapping electrical resistance elements over all surfaces. The glass column containing the weighing system-a McBain balance suspended from a gold chain-was enclosed in an aluminum tube heated by nichrome resistance wire enclosed in an insulating material. The temperature of the glass column was held constant by means of a series of thermocouples connected in parallel to a Leeds and Northrup temperature controller. This was necessary since variations in temperature resulted in expansion and contraction of the glass column and could be readily observed with the cathetometer. The spring extensions were measured through a window with a gaertner cathe-

Jan 1, 1962

By W. M. Parris, P. D. Frost, H. A. Robinson

The effects of hydrogen content and strain rate on the static tensile and notch-rupture properties of the Ti-3Mn-complex alloy heat-treated to differed strength levels were investigated. The extent of embriulement was found to be proportional to the amount of hydrogen present and the strength to which the specimens were heat-treated. The research suggests the possible necessity of specifying lower hydrogen limits than are now allowed when titanium alloys are heat-treated to higher strengths than are presently used. The research also supports a hypothesis advanced earlier for a mechanism of hydrogen embrittlement. MUCH attention has been focused on the effects of hydrogen in in Most of the published in- formation has dealt with the effects of hydrogen on alloys in the annealed or lowest-strength condition. The work of Kotfila and Erbin3 is one of the few exceptions. In view of the fact that heat-treatments are now being used to produce high strength in titanium alloys,' it is necessary that more attention be given to the effects of hydrogen on these alloys in the heat-treated condition. Research was initiated to establish the effects of hydrogen on the properties of the Ti-3Mn-complex alloy at various strength levels. This research, which supplemented that of Kotfila and Erbin, was started because it was found that high-strength tensile specimens of this alloy were strain-rate sensitive. The essential results of the research are summarized in this paper. MATERIALS AND EXPERIMENTAL PROCEDURES Material for this investigation was a 41/2-in.-diam bar forged from a single commercial heat of the Ti-3Mn-complex alloy having the composition given in Table I. The as-received forging was reduced further by forging at 1750°F to 3/4-in. square bars. About one fourth of this material was vacuum annealed at 1400°F for 24 hr to obtain a base hydrogen content of 25 ppm. The remaining bars were hydrogenated to levels of 90, 140, and 260 ppm in a large Sievert's apparatus in the following manner: Four 3/4-in. square bars, 5 in. long, were placed in the reaction chambzr. The chamber was evacuated, heated to 1400°F, and a measured amount of hydrogen was introduced. When absorbtion was complete, as indicated by the drop in pressure, the reaction tube was cooled and the bars removed. Each batch of bars was then sealed in individual evacuated Vycor containers and heated for 24 hr at 1400°F in order to distribute the hydrogen homogeneously. After vacuum-annealing or hydroge nation, the bars were rolled at a temperature (1400°F) below the ß-transus to 1/2 - in. - diam rounds. Groups of the rolled specimens representing each of the hydrogen levels were given the following heat-treatments: 1) One hr at 1300°F, water-quenched. 2) One hr at 1300°F, water-quenched, and aged 8 hr at 1100°F. 3) One hr at 1300°F, water-quenched, and aged 4 hr at 1000°F. 4) One hr at 1300°F, water-quenched, and aged 48hr at 800°F. Heat-treated bars were machined into standard 0.250-in.-diam tensile specimens having 1-in. gage lengths. Throughout the processing and testing of this material, hydrogen analyses were made by vacuum-fusion methods to check for accuracy of hydrogen additions, homogeneity, and possible losses during processing. A summary of these analyses is given in Table II It may be seen that the actual hydrogen contents were reasonably close to the desired levels. In addition, it was noted that the variation in hydrogen content within any one bar did not exceed

Jan 1, 1959

By F. A. Schaufelberger

METAL can be recovered from a leach solution either indirectly by precipitation as a compound that is later reduced or directly by electrolysis, cementation, or chemical reduction, for example, with hydrogen. The widely used electrowinning processes suffer from the inefficiency of converting fuel to low voltage dc and from low current efficiency when complete recovery is attempted. With the batch hydrogen reduction methods outlined here, a unit of fuel converted to hydrogen in modern gas reform plants will make two to three times as much metal as can be obtained with electrolysis. With continuous hydrogen reduction, four to six times as much metal is obtained. Precipitation by reducing a metal salt solution with H, has been known for almost 100 years.' Commercial use of the process, however, awaited the research and development program initiated by Chemical Construction Corp. Within the last few years this program has brought about construction of commercial plants, listed on page 545. Ideal hydrogen reduction will precipitate a pure metal from a solution obtained by commercial leaching methods at a rapid rate without excessive temperatures and pressures. The metal precipitate will be of desired size and density, less than a percent left in the vessel being deposited on the wetted parts. The present discussion will outline Chemical Construction Corp.'s early development program and will discuss the chemistry and mechanics of reducing copper, nickel, cobalt, and cadmium from solution by H2. Work on selective reduction of nickel from cobalt has been described earlier.' The article is not concerned with precipitation of copper by disproportionation of cuprous solutions where yield is limited3 to 50 pet.* It does not discuss use of gaseous reducing agents other than hydrogen, such as SO2,4 which may lead to contamination with sulfur, or C0,5 which is considerably more expensive than hydrogen and produces a gaseous reaction product, CO2.† The article does not include use of other nongaseous reducing agents,7 which are far more expensive than CO. Also, notes on the history, engineering design, and performance of commercial plants have been given elsewhere.' It will be shown that a pure metal can be precipitated by reduction with hydrogen from solutions obtained by commercial leaching methods when the solution composition is controlled and proper acidity, proper metal ion concentration through controlled complex formation and hydrolysis, and adequate agitation for suspension of metal and for transfer of reducing gas are maintained. Reasonable temperatures and pressures are used which are less excessive than those used by previous workers, although they are maintained at above equilibrium values because of process kinetics.' It has also been found necessary to induce nuclea-tion and to control growth and agglomeration in order to get a powder product of suitable physical properties. Review of the Literature Muller, Schlecht, and Schubardt of I. G. Farben10 claimed a successive reduction of silver, copper, nickel, cobalt, and zinc from ammoniacal solution by applying progressively higher temperatures and hydrogen pressures. Metals produced by this technique were not pure, since no attempt was made to adjust the solution composition between the different reductions. It is doubtful that the zinc product contained any metallic zinc. The major contribution to the literature" was made by the Ipatiews,12 who prepared platinum, iridium, copper, nickel, cobalt, lead, tin, arsenic, antimony, and bismuth at often extreme conditions, up to the critical temperature of water (373ºC), at 1500 to 7500 psi, for as long as several days. Even cadmium and zinc were claimed to have been observed in trace quantities precipitated together with basic salts. In the early experiments solutions were not stirred. Extensive formation of oxides and basic salts occurred, probably long before sufficient hydrogen could be supplied in the unstirred liquid to decrease the metal concentration in solution by reduction. The importance of hydrogen pressure was

Jan 1, 1957

By P. B. Mee

The secondary re crystallization behavior of two vacuum-melted, nominally 3 pct Si-Fe alloys has been studied, one alloy being produced from pure electrolytic iron and semiconductor-grade silicon and the other from commercial-purity hot band. The vacuum-melted and vacuum-remelted alloys were found to develop {110}(hhl) and {lll)(hkl), respectively, on annealing in high vacuum and {100}(0kl) and {11l}(hkl), respectively on annealing in pure hydrogen of dew point, < — 60°C. H2S doping of the hydrogen or annealing in commercial argon was found to effect a reversal for the vacuum-remelted alloy from (111) to (100) secondary recrys-tallization, while prolonged vacuum annealing at 2 x 10-6 Tow resulted in a tertiary re crystallization from (111} to (110). The growth selection of the {lll}(hkl) component was found to be governed predominantly by the {111}/planar misorientation, the maximum deviation of the resulting secondaries being 5 deg. It is considered that the driving force for {111}(hkl) secondary recrystallization arises from the preferential lowering of ?111, possibly by phosphorus or nitrogen diffusion, just as oxygen and sulfur under certain conditions have been found to preferentially lower ?100. When heavily cold-rolled metals are annealed at high temperatures, primary recrystallization usually occurs rapidly and may be followed by considerable grain growth. However, in the presence of a fine dispersion of inclusions1"3 or with a strong matrix preferred orientation4&apos;&apos; the matrix may be stabilized and a secondary recrystallization may then be effected. Also, in vacuum-melted Si-Fe it has been shown possible to develop {100}(001) and {110}(001)6 surface energy driven secondary recrystallization textures. Further, it has been found that, on annealing very pure metals, grain growth normally ceases when a grain size approximately twice the strip thickness is acquired, due to the formation of V-shaped thermal grooves which result in an equilibrium being set up between surface and grain boundary stresses. If, however, a surface energy difference ??s, exists between adjacent grains (of the order of a few percent of the grain boundary energy ?b), then according to Mullins8 a secondary recrystallization may be effected, since the grains having lowest ?s would grow at the expense of their higher-energy neighbors. For clean bee metal surfaces ?110 should be lowest; however, for 3 pct Fe-Si (100) secondary structures have frequently been developed and have been attributed by Walter and Dunn9 to an alteration of the relative surface energies due to the preferential chemisorption of oxygen on (100) planes. Kohler,10 however, indicated that this reversal may be achieved by employing minute quantities of highly polar compounds in the annealing atmosphere, i.e., sulfur compounds, in par- ticular H2S being beneficial in (100) growth. This work has been verified by Kramer" using {100)/{110} bicrystals, while Mager12 demonstrated the importance of sulfur diffusion within the strip. Detert13 has intimated that carbon may be responsible for the preferential lowering of ?110 although no direct evidence has appeared yet to support this supposition. It must , be appreciated that the above-mentioned examples of surface energy driven secondary recrystallization were obtained with very pure vacuum-melted materials with oxygen contents (which is now known to be a critical factor") less than 35 ppm. During the course of a textural study on Si-Fe it has been found that under certain conditions (111) secondary recrystallization can be obtained by what is believed to be a surface energy growth selection mechanism. The purpose of the present paper is to briefly describe this result and to try and postulate the possible causes. EXPERIMENTAL Two vacuum-induction-melted, nominally 3 pct Si-Fe alloys were produced, one from pure electrolytic iron and semiconductor-grade silicon designated A and the other from commercial-purity hot band, designated B.

Jan 1, 1969

By J. Lindbo, B. Vigeholm

IN transmission electron microscopy, specimen thicknesses quoted are frequently based upon either traditionally familiar values or a few evaluations representing the whole material. Taking aluminum in 100 kv TEM as an example, average and maximum values are widely accepted as being 2000 to 2500 and 6000 to 7OOOÅ, respectively. It is the purpose of this note to revise these figures and to point out the importance of evaluating individual specimens carefully. All evaluations have been based upon slip trace widths and lattice orientations as determined from diffraction patterns. In many cases where two or more slip systems have been operating the geometrical method described by Crocker and Bevis1 has been applied as a check. The foils were usually oriented to within 2 deg from the exact Bragg angle. Kikuchi patterns were used as indications of correct orientations but not applied in the evaluations. The tilt of the foil surface relative to the beam normal may with certain geometrical relations between the tilt axis and the operating slip plane lead to substantial errors.2&apos;3 Where these geometries were inevitable the samples were omitted in the investigations. Various measures were taken in order to overcome ambiguities, e.g., comparison with neighboring grains, tilts, evaluations based upon two or three slip systems,&apos; and comparison with extinction contour evaluations where s = 0 conditions were obtained. Errors caused by misinterpretation of the slip traces on a micrograph are easily avoided by considering the bright-dark sequence on opposite surfaces and by taking into account the tapering of the foil usually leading to a distinguishable divergence of the pair of traces. In the investigations described here the interpretation was further facilitated as the slip trace formation was observed on the microscope screen and sketches taken down. In a few observations slipping was so violent that the distinction of pairs was considered dubious and consequently given up. To assess average values, thickness evaluations carried out in two independent investigations were analyzed: I) 99.998 pct A1 extruded, cold-drawn, and recrys-tallized to grain sizes between 35 and 500 um were deformed in tension at room temperature. In order to determine the dislocation densities as a function of strain,4 specimens prepared by spark machining and electropolishing in a PTFE holder were analyzed in the electron microscope at 100 kv. Thicknesses were evaluated for 569 selected areas. Histogram I in Fig. 1 shows the results, the average thickness being 4900Å. II) Electropolished specimens prepared from 99.9999 pct A1 with magnesium contents from 0.005 to 0.5 pct rolled to foil and annealed were subjected to fission fragment irradiationa2 For volumetric dose and defect concentration determinations thickness evaluations were performed on 123 areas. Histogram II in Fig. 1 shows the thicknesses of these areas averaging 4250Å. Whereas in investigation I no selection related to thickness has been made, some thin as well as thick areas have been omitted from I1 for experimental reasons. This and the application of two different microscopes although of the same type may account for the difference in average thickness. Assuming a mean error of 10 pct for a single evaluation, the error of the average should be negligible. In order to investigate the maximum transmissible foil thickness in aluminum, specimens were prepared from single crystals with (111) and (110) orientations parallel to the beam, and from polycrystalline material. Maximum values of thickness that could be measured were given by the stopping of the dislocations. The visibility often extended far beyond the end of the slip trace, but with no means of knowing the

Jan 1, 1970

By Y. Kondo, A. M. Gaudin

A combined method for sizing in the sub-micron range was developed using centrifugation and gamma emission. Its essential features are: 1) Centrifugation of suspended mineral in water carried out at 4°C where water has its maximal density and zero temperature gradient of density 2) Gamma activition of the sample suspension induced by irradiating it in a nuclear reactor prior to centrifugation 3) Measurement of the activity of a beam of suspension as it is sedimenting in the centrifuge, using a scintillation counter provided with a discriminator. Albite, the sodium feldspar, was used as feed to the comminution step, and the induced gamma activity of Na24 was measured. Dissolved sodium ion caused a a non-settling activity in the measurement. Other "noise" is due to scattered gamma radiation from albite particles in the centrifuge outside of the line of sight. These two activities were obtained sep arately and subtracted from the total activity counted. The relative solid concentration in the suspension under the collimating slit is proportional to this net activity. The cumulative weight per cent of undersize particles was calculated and plotted against size on logarithmic scales. The relationship was found to be linear down to about 30 mµ. The specific surfaces calculated from particle size distribution agree with those measured by krypton gas adsorption. The measurement of particle size distribution of comminution products has been of interest in clarifying the mechanism of the process. The Gaudin-Schuhmann equation1,2 relates the cumulative percentage undersize, y, to relative particle size x/k. The particle size, x, and the size modulus, k, together with the distribution modulus, m, characterize the particle size distribution, m is the slope of a plot of log (y) against log (x/k). This equation has been verified for ground particles down to 1 micron in size.3&apos;4 For particle sizes smaller than a few microns, the precision and facility of sedimentation and microscope techniques become questionable. Use of a centrifuge which shortens settling time from weeks to hours is attractive. Many centrifugal methods have been proposed; however, determination of the solid concentration of the suspension at a reference level as a function of time is difficult, and sampling the suspension is likely to introduce errors. Measurement of particle size distribution by X-ray absorption in gravitational5 and in centrifugal6 sedimentation have also been tried. In these methods, the absorption coefficient for the solid is independent of size, since the wave lengths of the X-rays and gamma-rays are orders of magnitude smaller than the particles. Radiometric techniques7 in size distribution measurement have been developed within the last several years. They offer advantages over usual gravimetric and optical methods. PRINCIPLE OF METHOD The combined method of centrifugation and gamma emission for sizing in submicron range described in the present paper has the following essential features. 1) Centrifugation is carried out at 4 ± 0.1°C. Convection currents in the water phase due to density changes caused by temperature variation may disturb completely the settling system. To avoid this difficulty, the unique property of water having zero temperature gradient of density at 4°C is used. 2) Prior to size measurement the sample suspension is irradiated in a nuclear reactor and gamma activity induced. The gamma activity of the particles sedi-mented radially is measured by a scintillation counter provided with a discriminator. By this method, interruption of centrifugation by withdrawing samples is avoided and the counting rate at any time represents the solid concentration in the suspension at the level of the collimating slit of the centrifuge at the particular time at which the measurement is made. 3) By proper selection of the feed material and of the comminution device, gamma activities of foreign

Jan 1, 1964

By B. A. Wilcox, A. H. Clauer

The tensile and creep deformation characteristics of fiber reinforced composites have been studied, primarily at room temperature. The matrix was an alloy of Mg-14 wt pct Li-1 wt pct Al (LA141A alloy) and the reinforcing fiber consisted of continuous wires of a high strength precipitation hardening stainless steel (AFC-77 alloy). The ultimate tensile strength and strength-to-density ratio of composites were much improved over that of the mmix, both at room ternperatwe and up to 200°C. Creep studies at room temperature revealed logarithmic weep behavior for wires and composites and steady state creep for the nonreinforced matrix. It was concluded that creep of the fibers controlled composite creep. The instantaneous logarithmic weep rate of the composite, 6, was related to the average tensile stress on the fibers, where n = 3.4. Mg-Li alloys are the lightest structural metals commercially available, e.g., the alloy LA141A (Mg-14 wt pct Li-1 wt pct Al) is 27 pct less dense than beryllium Although Mg-Li alloys have moderate tensile strengths at normal strain rates and ambient temperature, their creep strength is relatively poor, even at room temperature. Reinforcement by fibers offers a means of increasing the tensile strength as well as overcoming the limitations of low creep strength. With a proper choice of reinforcing filament, composites could be designed with higher strength-to-density and modulus-to-density ratios than the matrix alloy. This communication reports a study on the tensile and creep characteristics of alloy LA141A reinforced with continuous wires of a high-strength precipitation hardening stainless steel (AFC-77 alloy). The matrix has a bcc structure, with possible precipitates of AlLi and MgLi2A1,3 and is ductile at room temperature Stainless steel wire was chosen as the -reinforcing filament since previous work at Battelle4 showed that a good bond between wire and matrix could be produced in this system. For all volume fractions of reinforcing wire, the theoretical composite strength-to-density ratio is greater than that of the matrix and the modulus-to-density ratio is somewhat lower than that of the matrix. EXPERIMENTAL PROCEDURES The 0.004-in. diam AFC-77 wire was obtained from two suppliers: National-Standard Co.* and Crucible 0.13 Si, 0.18 V, 0.011 P, 0.012 S, balance Fe. In the as-received condition, wires from both sources had room-temperature ultimate tensile strengths of 585,000 to 590,000 psi with approximately 2 pct total elongation and 40 pct reduction in area. Composite preparation was accomplished by the vacuum infiltration technique. This involved placing the continuous wires in a mild steel tube (1/8-in. ID), capping one end of the tube with a sheet of the matrix alloy, and evacuating the other end of the tube. When the capped end was placed in a crucible of the molten matrix alloy and held for 31/2 min at 70O°C, the liquid metal was drawn up the tube approximately 7 to 8 in. A cross-sectional view of a typical composite is shown in Fig. 1. This preparation technique promoted excellent bonding between the matrix and wires, and porosity was rarely observed. Test specimens for both creep and tension studies were prepared by machining off the steel tube. Tensile tests on the wires and composite specimens were made in an Instron using a cross-head speed of 0.01 in. per min. The composite specimens had no reduced section and were held in self-tightening grooved serrated grips. Most of the specimens broke in the effective 1-in. gage section. Even though several tests fractured in the grip section, their ultimate strengths were essentially the same as those of specimens which fractured in the gage section. Creep specimens of the composite were gripped in a similar manner, and

Jan 1, 1970

By Paul A. Farrar, Harold Margolin

The system Ti-Cr has been re investigated From 40 to 100 pct Cr. The high-temperature modification of TiCr, was found to exist in the temperature range from 1365 where it terminates in the eutectoid reaction TiCr,(TI)* — HE chromium-rich region of the Ti-Cr system was investigated by Vogel and Wenderott,&apos; Mc Quillan,&apos; Van Thyne et dl.,&apos; and Cuff Duwez and Taylor determined the crystal structure of the low-temeperature modification of TiCr, to be fcc a = 6.943A and Levinger&apos; discovered the existence of a second (high-temperature) modification of TiCr, and determited its crystal structure to be hexagonal a = 4.932A, c/a = 1.617i. No information was obtained as to the temperature range over which each modification of TiCr? existed; therefore the present investigation was initiated. I) Experimental Techniques Alloys employed for the delination of this system were prepared from iodide titanium and high-purity chromium. The purity of these materials is as follows: Iodide titanium: purity 99.99 pct; major impurities—carbon 0.0001 pct; oxygen 0 to 0.002 pct; nitrogen 0 to 0.002 pct; silicon 0 to 0.005 pct; manganese 0.001 pct; copper 0.001 pct (Foote Mineral Co., Lot 609-29). Chromium #1: metallic purity 99.997 min.; interstitial content—oxygen 0.27 to 0.46 pct; hydrogen 0.028 to 0.038 pct; nitrogen 0.0002 pct (Ave-quipo Inc.). Chromium #2: purity 99.9 pct; major impurities—carbon 0.01 pct; oxygen 0.013 pct; nitrogen 0.02 pct; silicon 0.01 pct; sulfur 0.03 pct; iron 0.01 pct (Fulmer Research Institute Ltd.). A total of sixteen alloys of thirteen different compositions was prepared in the range from 40 to 95&apos; *All percentages are given in weight percent. pct Cr. The compositions of the alloys prepared were as follows: Ti-40, 45, 50, 60, 62, 64, 66, 68, 70, 80, 85, 90, and 95 pct Cr. Two buttons were prepared of the 66, 90, and 95 pct Cr alloys. The 40 pct Cr and one of the 66 pct Cr alloys were prepared from the chromium # 2. All the other alloys were prepared from chromium #1. The alloys were arc-melted as 25-g buttons in a copper-hearth glass-walled furnace7 under an inert atmosphere of high-purity helium. The alloys were sintered at 250 amp and melted twice at 350 amp for 30 sec with the buttons being turned over between melts. Weight losses during melting were determined and in the range 45 to 68 pct Cr they were found, in all cases, to be less than 1.25 pct of the total alloy weight. A number of the high-chromium alloys shattered during cooling from either the first or second melt, which made the weight loss considerably larger than usual. The 70 and 80 pct alloys lost approximately 5.7 pct of their total weight, the 85 pct alloys 1.5 pct, the 90 pct alloy 2 pct, and the 95 pct alloy 3 pct. However, it is felt that the actual composition of the alloys in this region is probably within approximately 1 pct of the intended composition, as a large portion of the material lost was that due to shattering after melting. Nominal compositions were therefore used in plotting data and referring to the alloys. The alloys were cut into specimens, wrapped in molybdenum sheet, and encapsuled in argon-filled quartz or Vycor tubes for heat treatment. The heat-treatment times and temperatures are given in Table I. The specimens were quenched in iced brine (I.B.Q.) following heat treatment. The standard techniques of grinding, polishing., and etching were used in preparing the specimens for metallo-graphic examination. For alloys below 68 pct Cr

Jan 1, 1963

By K. Takahashi, I. Iwasaki

The methyl stretching vibrations for a series of normal xanthates, isoxanthates and normal amines were determined with the aid of an infrared spectro-photometer, and the results were compared with published information on the corresponding alcohols. The frequency shifts of methyl stretching vibrations may be attributed to the inductive effect of polar groups. The hydrogens in the shorter chain alkyl groups are somewhat polar and can be expected to interact with water molecules by hydrogen bonding. Contact angle, surface tension lowering, solubility, and critical micelle concentration appear to be related to the induced polarity of the alkyl groups. Traube&apos;s rule states that in homologous series of compounds solubility decreases and surface activity increases regularly with the size of the hydrocarbon group. Analyzing the work of transfer of a solute from solution to surface, Langmuir&apos; interpreted this rule to mean that each CH2 group added to a molecule produced its effect independently of the others. It is also well known2 that the maximum equilibrium contact angle with sulfhydryl collectors is independent of the polar groups and of the sulfide minerals, and that it increases to a certain limit with the number of carbon atoms in the alkyl group. This observation is thought to demonstrate the orientation of the collector molecules at the sulfide surfaces. The dependence on the hydrocarbon chain length is usually explained as due to the screening of the force field of polar mineral surfaces.3-5 Here again, Langmuir&apos;s principle of independent surface action appears to be implied. Heteropolar compounds consist of nonpolar and polar groups, the former being the hydrocarbon group and the latter containing such electronegative atoms as O, N, S, P, or halogens. According to Palit6 the hydrogens in the alkyl groups are more electroposi- tive than in the paraffins owing to the negative inductive effect of the polar groups and a possibility that a hydrogen bond with water molecules ensues. Goto and Takenaka7 provided direct evidence of the inductive effect by measuring the shift of the C-H stretching vibrations of alcohols, acids, and alkyl bromides with an infrared spectrophotometer. Their approach appeared to be directly applicable to the studies of surface activity both at air-water and water-mineral interfaces encountered in flotation systems. The present article attempts to relate the C-H stretching vibrations of alkyl xanthates, alcohols, and amines with such flotation chemistry parameters as contact angle, surface tension lowering, solubility, and critical micelle concentration. MATERIALS AND METHODS Normal xanthates from methyl to octyl inclusive and the isopropyl, isobutyl, and isoamyl xanthates used in this investigation were prepared in the usual manner.8 Normal amine hydrochlorides with carbon chain lengths of 1, 2, 4, and 6 were from Distillation Products Industries, of 8 from Archer-Daniels-Midland Co., and of 10, 12, 14 and 16 from Armour and Co. Normal propylamines, pentylamines and heptylamines from Distillation Products Industries were used both as received and as hydrochloride formed by converting the amines according to the procedure described by Li9 Perkin-Elmer Model 521 and 621 infrared spectro-photometers were used to investigate the spectra in the frequency region of 3050 to 2800 cm-&apos; with frequency scale expansion. The accuracy of the frequency readings was within + 1 cm-1. The KBr micropellet technique was used to prepare the xan-thate samples for measurements, and the halocarbon mull technique was used for amines and amine hydrochlorides. EXPERIMENTAL RESULTS Fig. 1 shows the CH3 asymmetric stretching vibrations as a function of the number of carbons in the alkyl group for normal xanthates, isoxanthates and amines. Also included in the figure are data for normal alcohols and isoalcohols taken from the article

Jan 1, 1970

By J. E. Hilliard

AS is well-known, the length per unit volume, Lv, of any lineal feature (such as grain edges in a polycrys-talline specimen) can be estimated from a count of the number of point intersections with a random plane of polish. Specifically:&apos; Lv = 2NA in which NA is the expected number of intersections per unit area of the plane. As with all other measurements in quantitative metallography, the estimation of Lv is subject to a sampling error, the magnitude of which will depend on the number of observations. The analysis is usually performed by counting the number of intersections falling within a closed test figure of known area applied to a succession of different areas on the plane of polish. The test figure can be drawn directly on the screen of a projection microscope or else superimposed on the image of the structure by means of a reticule in a focusing eyepiece of an ordinary microscope. The use of micrographs is very inefficient unless, as in the present study, these are also needed for some other purpose. Consider an analysis in which n applications are made of a test figure within which the expected number of intersections is N. The expected total number of intersections counted is then given by NT = nN If (N) is the standard deviation in N for one application of the figure and if the latter is applied to non-overlapping regions so that the N&apos;s are independent in the statistical sense, then the standard deviation in Nt is given by: a(NT) = a(N)vn Eliminating n from Eqs. [2] and [3] we obtain: Thus, k will be a constant for a given specimen and test figure. From Eqs. [ I] and [4] we find As is to be expected, therefore, the fractional error in the estimation of Lv is inversely proportional to the square root of the total number of intersections counted. It is very desirable to have at least a rough estimate of k before starting an analysis, since it will then be possible to decide in advance by use of Eq. [5J how many counts should be made in order to achieve the desired accuracy in Lv. Without such information the investigator, unless lucky, will either do needless (and tedious) work or else obtain a result with too large an error. It is very easy to calculate k for the limiting case of N — 0, i.e., when the test figure is vanishingly small. In this case there is a negligible probability of two or more intersections falling within the figure. There are therefore only two possible outcomes: a count of one with a probability of, say, p and a zero count with a probability of (I-p). Thus and Therefore: We might expect k to depend on N and therefore on the size of the test figure. Such a dependence was observed2 in the analogous case involving the estimation of grain-boundary area per unit volume by a count of the number of intersections of a test circle with traces of the boundaries on the plane of polish. In this case the theoretical value of k at the limit N — 0 was 1.41. It was also predicted that k would display an initial sharp decrease with increasing N. Experimentally, k was observed to decrease to a value of 0.62 at N - 6 and thereafter remain approximately constant. Furthermore, the value of k for N > 6 was found to be insensitive to the form of the structure provided no pronounced anisotropy or grain-size variation was present. In order to determinewhether k would exhibit a similar dependence on N in the estimation of grain-

Jan 1, 1967