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By Zay Jeffries

From the title of this chapter the reader could expect an attempt to out- line the anticipated shape of things to come, mineralwise. We have no crystal ball and if we possessed one we could claim no expertness in its use. In the first place no one can tell the future status of man. No one has any way of knowing to what extent peace will prevail, nor to what extent changes may occur in national sovereignties or forms of government or in international relationships. So future man is an uncertainty. Nor can we predict new developments that may result in significant changes in man's status or in the mineral industry or both. If, for example, this chapter had been written in the middle 1930's, nearly everything that has happened since in the fields of atomic energy and space technology would have been missed. Yet what vast changes these I have made in the status of man! Also the changes in the mineral industry have been important. A writer would have been bold indeed had he prophesied that uranium would play such an important role. But we need not confine our foggy vision to these fields. The steep rise in the use of aluminum, titanium, and germanium reflects the unpredictable in what may be thought of as the more normal pursuits. This should not discourage one from using the past and currently observable trends as bases for limited predictions. To do this, however, it is desirable to make certain assumptions about man's status without pretense that these assumptions have a high probability of fulfillment: 1. Only minor changes will occur in the geographical boundaries of the nations of the world. 2. World War III will not take place in the near future. 3. As a consequence of (2), man will not destroy himself by wanton use of atomic weapons. 4. Disarmament will take place, if at all, gradually rather than all at one time. Under the above assumptions the world will enjoy a period of relative peace even though the status may be one of an armed truce. The assump-

Jan 1, 1964

By Arthur F. Taggart

The quality of aggregate materials is. of major importance in governing durability and permanence of concrete structures. The problem of selecting suitable aggregate materials is two-fold. Geological factors include the type and character of the aggregate source, presence of known or suspected reactive constituents, and presence of thermally incompatible materials. Laboratory investigations include petrographic studies, soundness and reactivity tests, and tests of thermal properties. The importance of each factor in the selection of satisfactory aggregate material is considered in detail.

Jan 1, 1950

By A. L. Moore

KAISER Bauxite Co., a subsidiary of Kaiser Aluminum & Chemical Corp., has been mining and shipping Jamaican bauxite for over a year. On Feb. 10, 1953 the first boat load of bauxite left Port Kaiser, Jamaica, for the company's alumina plant at Baton Rouge, La. To provide its own source of the aluminum ore, a Kaiser Aluminum & Chemical Corp. exploration party started initial reconnaissance in 1947. This work, and subsequent exploration, led to the acquisition of reserves sufficient to warrant a full-scale mining operation for several decades.

Jan 3, 1954

By W. J. Tait, A. E. Craig, E. P. McCurdy

C. M. Marquard—The problem of the automatic control of a grinding-classification circuit is not nearly as simple as has been indicated and it cannot be universally solved through the application of this device. The sound emanating from a ball mill such as the metallic clink of the balls against the liners can at times be misleading. The fact that the sound level due to the balls hitting the liners may be at a minimum does not necessarily mean that the mill is properly loaded. I have in mind an ore we treat that has a soft talcy gangue. The soft fluffy nature of this material makes the sound from the ball mill a most misleading parameter that is worthless as a means for controlling the amount of ore fed to the mill. In every milling plant there are transportation lags due to the time it takes the ore to travel from the mill bins to the ball mill. In many plants there may be several different transportation lags due to varying distances of bins from ball mill. These transportation lags can most seriously affect the operation of a controller. It has been found that under many circumstances the transportation lags can be so bad as to cause the controller to hunt seriously. Hunting can and in many cases does become so serious as to render automatic control impossible because of the surges it causes. While it is possible to compensate for this type of lag, this apparatus does not lend itself readily to accomplish the required compensation. Further, if there are groups of bins at various distances from the ball mill, compensation for one may not be sufficient or may be too great for another. Each milling plant presents a separate problem. The apparatus as presently described does not appear sufficiently flexible to accomplish this. It should be noted that the load on the classifier rakes is determined by measuring the current input to the rake drive motor. Variations in line voltage will

Jan 1, 1951

By E. P. McCurdy, W. J. Tait, A. E. Craig

C. M. Marquard—The problem of the automatic control of a grinding-classification circuit is not nearly as simple as has been indicated and it cannot be universally solved through the application of this device. The sound emanating from a ball mill such as the metallic clink of the balls against the liners can at times be misleading. The fact that the sound level due to the balls hitting the liners may be at a minimum does not necessarily mean that the mill is properly loaded. I have in mind an ore we treat that has a soft talcy gangue. The soft fluffy nature of this material makes the sound from the ball mill a most misleading parameter that is worthless as a means for controlling the amount of ore fed to the mill. In every milling plant there are transportation lags due to the time it takes the ore to travel from the mill bins to the ball mill. In many plants there may be several different transportation lags due to varying distances of bins from ball mill. These transportation lags can most seriously affect the operation of a controller. It has been found that under many circumstances the transportation lags can be so bad as to cause the controller to hunt seriously. Hunting can and in many cases does become so serious as to render automatic control impossible because of the surges it causes. While it is possible to compensate for this type of lag, this apparatus does not lend itself readily to accomplish the required compensation. Further, if there are groups of bins at various distances from the ball mill, compensation for one may not be sufficient or may be too great for another. Each milling plant presents a separate problem. The apparatus as presently described does not appear sufficiently flexible to accomplish this. It should be noted that the load on the classifier rakes is determined by measuring the current input to the rake drive motor. Variations in line voltage will

Jan 1, 1951

By John Henry Harden

WITH imperfect instruments it is impossible to make accurate surveys; the results are inaccurate maps, with their attendant consequences. The design of the writer is to describe an improved form of tripod head, and certain defects in an English transit and a miners' dial, with the method taken to remedy the defects of the transit. When the present transit superseded the surveyor's compass, there was one special objection brought against it, and with some show of reason ; namely, that the tripod of the compass with its ball and socket motion, allowed a quicker levelling-up (and, consequently, more work) than was possible with the transit. To this objection it was replied, that the ball and socket would not allow the instrument to be levelled with the same degree of precision that could be attained with the levelling screws, and that if time was sacrificed greater accuracy was attained. Nevertheless, it is a well-known fact that in this country, and especially in England, the compass or miners' dial holds its ground solely from its rapid adjustment. Ever since the introduction of the transit, efforts have been made to give to this instrument the same facility of levelling possessed by the compass or dial, and the same means have been tried, i. e., a . ball and socket motion, since a modification of this in some form was the only method that would answer. The upper part of a transit is, however, much heavier than the corresponding parts of a compass, and, therefore, requires more binding power, which cannot be ob¬tained with an ordinary ball and socket joint. It has been a study with instrument-makers to combine the facility of these two tripods -the quickness of the ball and socket with the steadiness and accuracy of the screws; but in all attempts in this direction the ball and socket of the compass has been literally followed, the entire stability of the instrument depending upon the friction of the ball in its socket. There is great need for a tripod that can be more easily manipulated than the present form, for it rarely happens that an engineer has a level surface on which to set his instrument, and very often

Jan 1, 1879

By James Aston

A proper consideration of this subject is not confined to the technical channels of production and metallurgy. It concerns an industry, and should cover economic aspects which are of material importance in any program of development. The discussion may logically be treated under three subdivisions, as follows: (1) manufacture, (2) characteristics related to quality of material; (3) adaptability and exploitation of product. Manufacture of Wrought Iron The manufacture of wrought iron is the most ancient art of the ferrous metal industry. The eighty years or less of existence of processes identified with our modern "Age of Steel" is a relatively brief interval compared with the several thousand years associated with the production of wrought iron by man. From the primitive early methods of production, manufacture for many centuries followed the line of direct reduction. There were developments as experience was gained through the years; but man's needs for a strong, ductile, forgeable product were met by reducing the ore to metallic iron in a single-stage operation. Following the development several centuries ago of what has become our modern blast-furnace operation, manufacture of wrought iron was gradually transformed into a two-stage method of first producing cast iron and then refining this to the desired degree of forgeability; the forerunner in principle of today's scheme of manufacture of steel. The product retained the essential characteristics of highly refined base metal with iron-silicate slag incorporation, which were associated with the material resulting from direct reduction methods. Cort's invention of the puddling process in 1784 is a landmark in wrought-iron manufacture. It consisted essentially in adapting a coal-fired reverberatory furnace to the refining operation; thus lifting the industry out of the slough of

Jan 1, 1935

By G. R. Speich

The distribution of carbon and the type of substructure in iron-carbon martensites containing 0.02 to 0.57pct C has been studied in the as-quenched condition and after tempering at 25" to 700°C by using electrical resistivity, internal friction, hardness, and light and electron microscope techniques. in marten-sites containing less than 0.2 pct C, almost 90 pct of the carbon segregates to dislocations and to lath boundaries during quenching; in martensites containing greater than 0.20 pct C, appreciable amounts of carbon enter normal interstitial positions located far from defects. Tempering martensites with carbon contents below 0.20 pct at temperatures below 150°C results in additional carbon segregation to dislocations and to lath boundaries but no carbide precipitation whereas -carbide precipitation occurs in martensites with carbon contents exceeding 0.2 pct. Above 150°C, a rod-shaped carbide (either Fe3C or Hagg) is precipitated in all cases. At 400°C, spheroidal Fe3C precipitates at lath boundaries and at former aus-tenite grain boundaries. At 400" to 600"C, recovery of the martensite defect structure occurs. At 600" to 700°C, recrystallization of the martensite and Ost-waW ripening of the Fe3C occur. The effects of the carbon segregation that occurs during quenching and the subsequent substructural changes that occur during tempering on martensite tetragonality, hardness, and precipitation behavior are discussed. A mathematical analysis of carbon segregation during quenching is presented. RECENT studies of the strength of low-carbon martensitel-4 emphasize the importance of carbon segregation to the martensite lath boundaries and to the dislocations contained between them during quenching. Unfortunately, very few studies of the tempering of low-carbon martensites have been conducted, so the exact nature of this segregation is poorly understood. In fact, most early tempering studies5,6 were restricted to carbon contents greater than 0.20 pct. Moreover, these studies did not determine the amount of carbon segregated to the martensite substructure during quenching so that the initial state of the martensite was not established. Aborn7 studied the precipitation of carbide in low-carbon martensite during quenching but did not establish whether carbon segregation occurs prior to carbide precipitation, nor did he study the subsequent tempering sequence in detail. In the present work we have used electrical resistance and internal friction measurements, supplemented by electron transmission microscopy to establish the carbon distribution in as-quenched specimens. Specimens thin enough to avoid carbide precipitation (but not carbon segregation) were employed. The redistribution of carbon on subsequent tempering below 250°C was followed by measurements of elec- trical resistance. Additional studies were made on specimens tempered at 250" to 700°C to elucidate the overall tempering behavior of low-carbon martensites, including the formation of cementite and recrystalli-zation of the martensite. EXPERIMENTAL PROCEDURE Eight iron-carbon alloys with 0.026, 0.057, 0.097, 0.18, 0.20, 0.29, 0.39, and 0.57 wt pct C were prepared as 8-lb ingots by vacuum melting. Typical impurities in wt ppm were 40 Si, 20 Mn, 30 S, 10 P, and 10 N. These alloys were hot rolled to 3 in. plate at 1095°C) (2000°F). The hot-rolled plates were surface ground to remove scale and the decarburized layer, then cold rolled to 0.010 in. sheet. Specimens cut from the sheet were austenitized for 30 min at 1000°C (1830°F) in a vacuum tube furnace in which the pressure did not exceed 2 x 10-3 torr. Chemical analysis of specimens after austenitization indicated no decarburization at this pressure. Immediately before quenching, the furnace was filled with prepurified helium. The specimen was then pushed rapidly through an aluminum foil gasket, which sealed the bottom of the furnace, into an iced-brine bath (10 pct NaC1, 2 pct NaOH). The quenching rate at the M, temperature is about 104'c per sec for 0.010 in thick specimens, as calculated from Newton's law of heat flow2 using a heat transfer coefficient of 25 ft-'. This quenching rate is sufficiently high so that all the alloys transformed completely to martensite throughout the entire 0.010 in thickness and no carbide precipitation occurred in the martensite. All specimens were immediately transferred to liquid nitrogen after quenching and stored there until needed. Tempering below 250°C (480°F) was done in silicone oil baths thermostatically controlled to *;"C. Tempering above 250°C was done in circulating air furnaces or lead pots with the specimens contained in evacuated silica capsules. Electrical resistance was determined by measurement of the potential drop across both a standard resistance and the specimen, connected in series. All resistance measurements were made in liquid nitrogen (77K, -196°C) to minimize thermal scattering of electrons and thus maximize the contribution of impurity scattering to the resistance. Specimen dimensions were 5.10 by 0.19 by 0.025 cm. Although the precision in the electrical resistance measurements was +0.1 pct, the electrical resistivities could only be measured with an accuracy of +5 pct because of uncertainty in the specimen dimensions. Internal friction measurements were performed in an inverted pendulum apparatus at vibration frequencies of either 1.9 or 66 Hz. The specimen dimensions were 5.10 by 0.375 by 0.025 cm. Hardness measurements were made with a Leitz-Wetzlar microhardness machine with loads of 100 g. Specimens were examined by light microscopy after etching in 2 pct Nital and by electron transmission microscopy after preparation of thin sections by electrolytic thinning in a chromic-acetic acid solution.

Jan 1, 1970

By David L. Holt

The contribution of grain boundary shear to total elongation, CS/E&apos;, has been measured in an Al-Zn eu-tectoid alloy that was quenched from above the invariant temperature, then annealed at 250° C to a grain size of&apos; 1.8 p. At 250°C, ks/E&apos; is low at both high and low strain rates, but reaches a maximum, estimated as 60 pct at an intermediate rate of 5 X 10 per rnin. Rate sensitivity, as measured by the index m = a log a/a log E&apos;, follows the same trend, and furthermore the maximum values of m and -cur at approximately the same strain rate. This result, combined with the metallographic observation that boundary migration enhances boundary shearing, is interpreted as supporting a previous suggestion that the high rate sensitivity characterizing super-plasticity is the result of combined boundary shearing and migration. It is suggested that the latter event relieves stress concentrations at triple points, and smoothes boundaries so that stress is governed largely by a viscous boundary shear. GrAIN boundary shear has been considered in relation to superplasticity in several recent papers.&apos; The problem has been to explain the high strain rate sensitivity of flow stress, and the variation of rate sensitivity with strain rate (E&apos;) and grain size (L). The requirements for superplasticity, small L and high T, suggest the reasonableness of an approach to high rate sensitivity involving grain boundary shear. Further support came from experiments on the A1-Cu eutectic alloy,&apos; where it was found that strain rate sensitivity of cast material annealed to produce an equiaxed, micron-size grain is always low; taking as an index of rate sensitivity m = a log a/a log <, m < 0.3. However, m in hot-worked alloy of comparable grain size can be as high as 0.7. In the cast and annealed material, each phase is a single crystal, the only boundaries are interphase boundaries, and it is, consequently, geometrically impossible for boundary shear to contribute to deformation in any major way. Other observations (for hot-worked material) were a-L at constant (low) strain rates and indications that the rate of recrystallization was enhanced as strain rate increased. As a result of this work, it was proposed that high rate sensitivity arises from a deformation mode of boundary shear associated with boundary migration. Migration serves to relieve stress concentrations at triple points, and smoothes boundaries so that they assume properties of fluid films. On the other hand, the low rate sensitivity observed at high and low strain rates reflects deformation of bulk material. Measurement of the variation of grain boundary shear with strain rate and m have not yet been made. Such measurements are important, especially in view of a proposal, differing in detail from the above, that high m arises merely from a transition between a grain boundary shear mode of deformation at low rates to a transgranular mode at high rates.2&apos;4 In the present work, the contribution of boundary shear to total deformation is measured and in addition metallographic observations are made on surfaces of deformed specimens to look at the interaction between boundary shear and migration. The Al-Zn eutectoid alloy was chosen for its homogeneous, fine-grained structure, which is obtained readily without hot-working. It has also been the subject of a previous phenom-enologically directed study. EXPERIMENTAL Material. Compression specimens, cross section 4 by + in., length \ in., were machined from a sand-cast ingot of composition 77.5 wt pct Zn, 22.5 wt pct Al. (The melt was prepared from 99.9 pct Zn and 99.99 pct Al.) After homogenization at 375°C for 50 hr, the specimens were quenched in brine and removed before the heat evolution that accompanies de -composition of the high-temperature phase.5&apos;6 The resulting microstructure, see Fig. l(a), was too fine for grain boundary sliding to be easily studied; coarser structures were obtained by annealing for various times at 2 50°C. Annealing was terminated by a brine quench. Final average intercept lengths between all grain boundaries (both interphase and those lying in a phase), L, were: 0.5 p [annealed for 15 min, Fig. (a)], 0.8, 1.1, and 1.8 p [Fig. l(b)l. Testing Procedure. An Instron machine was used for most of the compressive deformation. Tests were of two types: those in which crosshead velocity was changed in steps to measure m as a function of strain rate15 and tests at constant velocity to a fixed (engineering) strain of -0.2 (20 pct). Stress reached a steady-state value (a) which was plotted, on a logarithmic scale, against log strain rate (E&apos;). An alternate and equivalent evaluation of m was to take the slope of the log o vs log 6 curve. Time at temperature before testing was 15 min. Strain rates covered by the Instron (4 x lo-&apos; to 4 x 10&apos; per min) were insufficient; at a higher rate of 5 x lo2 per min a gas-operated testing machine was used, the gas driving a piston to compress the specimen at a controlled velocity.&apos; To obtain points on the log a vs log E&apos; curve at low rates, specimens were compressed by a dead weight. strain rate was an average value computed by dividing strain at the end of test by loading time. In some tests strain was measured at fractions of the loading time; creep rate was found to be reasonably constant.

Jan 1, 1969

By W. A. Backofen, D. L. Holt

Push-pull fatigue tests have been carried out at 4.2°K, 77oK, and room temperature on two poly crystalline materials of widely different stacking-fault energy (?): pure copper (? - 70 ergs per sq cm) and the Cu-8 wt pct A1 alloy (? - 2.8 ergs per sq cm). Constant stress-amplilude was imposed and measurement was made of the plastic-strain amplitude (ep) at saturation. Lives extended from 104 to 106 cycles. Designating lives at the various temperatures by NRT, N77, and N4.2. the ratios N77/NNT and N4.2/N77 ranged from 3.5 to 18 under the condition of common Ep . Metallo-graphic examination revealed different crack morphology in Cu-8 Al fatigued at room temperature, and at 77" and 4.2oK. At room temperature, cracks lay in or near grain and lain boundavies; at 77o and 4.2oK. cvacks were transcrystalline. Tests on single crystals of Cu-8 A1 showed that such a change in the cracking mode in polycrystallitle material accounted for a factor of- about 3.25 in N77/NRT . The longer life at lower tewperatztre (conslant cp) has heels attributed to two deuelopinents: a reduced production of the dislocation tangles and subgrain boundaries which serve as paths of rapid cracking, and suppression of oxygen chetni-sorption at the crack tip It was concluded that in both materials the luller accounted for an extension of the life at 4.2oK beyond that at room temperature by a factor of 15. XV ECENT experiments on the fatigue of Cu-A1 alloys in the so-called high-cycle range (greater than lo4 cycles) have emphasized the importance of stacking-fault energy (y) as a quantity affecting crack propagation rate and fatigue life.1,2 It was found in comparisons at essentially fixed plastic-strain amplitude that crack growth rate decreased by a factor of about 5 over the composition range from copper (? - 70 ergs per sq cm) to Cu-8 wt pct Al (? - 2.8 ergs per sq cm). The argument was made that, when stacking-fault energy is high, cross slip and climb are favored, so that dislocation tangles and/or subgrain boundaries form more readily under cyclic loading. Since the boundaries and tangles act as paths of rapid crack propagation ,3, 4 life is shortened as a result. However, when stacking-fault energy is reduced (as by alloying), cross slip and climb become more difficult, with the result that substructure formation is retarded and growth rate is also reduced. A purpose of the present work was to investigate the substructure effect in relation to temperature. As temperature is lowered, ? is varied only slightly (if at all), but decreased thermal activation can interfere with cross slip and climb. Thus substructure formation could be curtailed and life increased. Fatigue life in the high-cycle range is also known to be strongly influenced by environment. Working with copper, Wadsworth and Hutchings observed that life in a vacuum of 10-8 mm Hg exceeded life in air by a factor of 20.5 They isolated oxygen as the agent that furthered cracking. While the details are still unclear, a requirement in any mechanism of oxygen-accelerated cracking is that there be chemisorption at the crack tip. That could prevent welding on the compression half cycle,= interfere with reversal of slip,1, 6 or aid in breaking metal-metal bonds at the crack tip.5&apos;7 In the work being reported here, temperature was lowered by immersion in liquid nitrogen and helium, which also served to reduce both the oxygen concentration and chemisorption rate. A possible effect upon life, i.e., a lengthening, had to be recognized. Several researchers have determined fatigue lives at low temperatures presenting their results in the form of stress amplitude (S) vs cycles in life (N) curves.8-11 Such curves reflect, primarily, the fact that metal is strengthened by lowering temperature; effects of substructure and changing environment tend to be masked. The difficulty can be overcome by comparisons based on identical plastic-strain amplitudes, and in the present work the dependence of life on both plastic strain and stress amplitude was established. EXPERIMENTAL Materials. The principal materials were polycrystal-line copper (? - 70 ergs per sq cm)" and the Cu-8 wt pct Al alloy (? - 2.8 ergs per sq cm),I3 the latter being near the limit of solubility of aluminum in copper and having, therefore, the lowest stacking-fault energy in the CU-Al system. Specimens were machined from 0.118-in.-diam cold-swaged rods of high-purity (99.999 pct) copper and the Cu-8 Al alloy, the latter produced initially in a graphite boat by induction vacuum melting a mixture of 99.999 pct Cu and 99.99 pct Al. The machined specimens were annealed to produce mean grain diameters of about 0.070 mm in copper and 0.190 mm in the alloy. Specimen dimensions are given in Fig. 1. Values of the tensile yield stress, ultimate strength, uniform strain (determined by the Considgre construction), and reduction of area, for both materials at 4.2oK, 77oK, and room temperature, are listed in Table I. The tensile apparatus in which these results were obtained has already been described.14 Apparatus. Specimens were fatigued in push-pull with a machine that is illustrated schematically in Fig. 2. The specimen is first soldered into the top grip (1) with Woods metal, and the grip is then screwed into the inner tube (2) which is connected to the drive rod of the Goodmans vibration genera-

Jan 1, 1968

By A. H. Larson, R. J. McClincy

Laboratory-scale decopperizing experiments with multiple sulfur addifions were conducted at 330°C on ternary Pb-Cu alloys containing, as the third elenlent, Sn, Ag, As, Sb, Bi, Zn, and Au, common impurities in lead blast-furnace bullion. For silver and tin, an increased rate and extent of &apos;cofifier removal was obsert3ed. The elements As, Sb, Zn, Au, and Bi had no effect or less effect as compared to sulfur additions with no i)npurily additions. THE production of primary lead in the blast furnace yields an impure lead frequently containing such impurities as copper. antimony. arsenic. tin, gold, silver iron, oxygen. and sulfur. By cooling this lead to a temperature near its melting point. most of the iron, sulfur, and oxygen and part of the other impurities are removed in the form of a dross. With incipient solidification of the lead, the copper concentration wil have been reduced to 0.02 to 0.05 pct. depending upon the concentration of the other impurities. according to Davey.&apos; Since copper interferes with the treatment of silver after the desilverizing process, it is desirable to decrease the copper content of the lead still fur-ther before the lead is desilvered. The decopperizing of the lead is accomplished by stirring a small quantity. approximately 0.1 pct. of elemental sulfur into the lead at a temperature near its melting point, 330" to 360°C. The copper is removed as a copper sulfide which constitutes a small fraction of a voluminous dross consisting mostly of lead sulfide and entrained metallic lead. The residual copper concentration following the decopperizing operation is frequently as low as 0.001 to 0.005 pct. Thi fact has aroused considerable interest because the equilibrium copper concentration of lead in contact with solid PbS and solid Cu2S is at least an order of magnitude greater, 0.05 pct Cu at 330C. 1, 2 Most investigators have suggested that various impurities in the lead bullion are responsible for the very low copper concentrations frequently encountered in practice. There is little agreement, however? as to which of the impurities are helpful and which are not.3"11 Also. few investigators have sought to explain the mechanisms responsible for the removal of copper to very low concentrations. Willis and Blanks9 have proposed that a nonstoichiometric copper-deficient cuprous sulfide forms in place of the supposed Cu2S. Being copper-deficient, this sulfide phase would possess a low copper activity, and the diffusion of copper dissolved in the liquid lead into this phase would be greatly facilitated. Pin and wagner2 have investigated the removal of copper from liquid lead by studying the effect of impurity-doped lead sulfide on the decopperizing of pure Pb-Cu alloys. Samples of the doped PbS were held in contact with copper-saturated lead for 1 week at 33&apos;7°C. They reported a beneficial effect on decopperizing with bismuth and antimony and no effect with tin or silver. which is directly opposite to the results observed in practice and those reported by Davey 3 and this studv. The purpose of this paper is to describe the effects of certain additive elements on the extent to which copper can be removed fro111 liquid lead by successive additions of sulfur. The impurity elements were added individually to prepared Pb-Cu alloys. The resulting ternary alloys as well as a binary Pb-Cu alloy were then decopperized with repeated additions of sulfur. EXPERIMENTAL Materials. Granulated test lead with a purity of 99.999 pct and the additive elements Cu. Ag. Sb. Bi. Zn. Sn. and Au with purities of 99.99 pct were American Smelting and Refining Co. research-grade materials. The major impurities in the lead were 1 ppm each of iron and copper. all others being less than 1 ppm. The arsenic used was a technical-grade arsenic of 98+ pct purity. Reagent-grade flowers of sulfur were melted under argon to provide small pieces free of fines. Apparatus. The decopperizing experiments were carried out in a 25-mm-OD by 375-mm-long Pyrex tube sealed at one end. The tube was mounted vertically in a resistance-heated. hinge-type tube furnace controlled to within ±lcC. Temperature measurement was accomplished by means of a standardized chromel-alumel thermocouple sealed into the base of a silica. paddle-type stirring rod. All decopperizing experiments were carried out under an argon atmosphere. Procedure. A Pb-Cu starting alloy containing 0.05 pet Cu was prepared under carbon and poured into cold tap water to produce shot. The ternary alloys were prepared by melting together 100 g of the starting alloy and a sufficient amount of the impurity element to yield the desired concentration. The resulting alloy was then homogenized in a Pyrex tube at 450C with continuous stirring. The furnace temperature was then lowered to the operating temperature of 330°C. When thermal equilibrium had been obtained at the operating temperature, individual additions of 0.2 pct (0.2 g) of solid sulfur were added to the melt and stirred in. Stirring was continued for a period of 3 min. discontinued for 5 min. and resumed for the remaining 2 min of a 10-min cycle. This cycle was repeated for as many sulfur additions as desired. When the decopperizing experiment had been completed the lead bullion was quenched and samples of the bullion and dross phases were taken for analysis. Results. The results obtained in the decopperizing

Jan 1, 1970

By A. U. Seybolt, V. A. Phillips

Binary iron alloys containing 1 pct of Al, Cr, Mn, Mo, Si, Ti, or V, and 0.4 pct C, 1 pct Cr steels with and without 1.2 pct A1 or 2.0 pct Ti additions, were ion-nilrided at 550° to 600° in N-H mixtures. Nitriding increased the inicrohardne ss of all the binary alloys except those containing manganese or molybdenutn, and also hardened the heat-treated steels if aluminum or titanium urns present. Transmission electron microscopy revealed particle formation in all casts where hardening occurred. Electron diffraction gare positive identifications for ALN, CrN, and a, Si3N4 in the binary alloys, and AlN and CrN in the aluminum- cold chromium-bearing steels, respectil&apos;uly. Cubic VN with a, = 4.13A was tentatively identified. Particles, apparently of CrN, also formed in the base steel but did not increase the hardness very much. Chromium and vanadium formed nitride platelets on {001}° matrix planes, while titanium gave clusters <15A diam. Aluminum nitride precipitated at grain and subgrain boundaries, and within the grains. Silicon gave profuse precipitates of several Morphologies at grain boundaries and cubical particles within the grains. No effect of the alloy carbides on nitride precipitation was observed in the heat-treated steels. THE nitriding of steel has been a well-established commercial process for about 40 years, but in spite of this comparatively long period of use there have been few studies aimed at understanding the process. Most studies, like the early but very competent work of Jones and organ&apos; and nones.&apos; were concerned with establishing the pertinent engineering variables of steel composition, gas composition, temperature, and time. As far as the present authors are aware, there have been no studies of the composition, size, shape, or distribution of the nitrides formed in the nitriding of steel. Noren and Kindbom3 did, however, examine a few nitrided steels by surface replica electron microscopy, and were able to show the presence of car-bonitrides and AlN and TiN nitrides. pitsch4,5 and Hrivnak6 examined nitrided pure iron by transmission electron microscopy. Baird7 found manganese nitrides in Fe-1.6 pct Mn when nitrided at 650°C, using the same technique. In the present work, emphasis was placed on transmission electron microscopy because of its inherently better resolution, using principally binary alloys of iron containing 1 pct of alloying element. In addition, a few simple 0.4 pct C steel compositions were examined to investigate possible carbonitride formation. It was not anticipated that all of the added elements would form nitrides under the conditions used, but it was considered desirable to obtain direct experimental evidence on this point. It would be considerably easier to ascertain the presence of alloy nitrides by examining appropriate binary alloys in preference to relatively complex steels. The work reported here could have been done using orthodox ammonia-nitriding procedures, but an operating ion-nitriding equipment was available, and was therefore used for specimen preparation. EXPERIMENTAL DETAILS 1) Materials. Binary alloys were made up from vacuum-melted electrolytic iron with 1 wt pct additions of Cr, Ti, V, Al, Mn, Mo, and Si of about 99.9 pct purity. In addition, three steels were similarly made up—a basis steel with 1 wt pct Cr and 0.4 wt pct C and two steels with further additions of 1.2 wt pct A1 or 2.0 wt pct Ti, respectively. The materials were vacuum-melted and cast as 11-lb heats into tapered square molds of about 2 by 2 in. average cross section. The castings were forged and hot-rolled to 11/4 in. rounds. Discs of 4 in. thickness by about 1 in. diam were machined from the rods. Some of these discs were hot-forged and hot-rolled to about 0.020 in. thick, sand-blasted, and then cold-rolled to about 0.003 in. thick. At this point, the surface was cleaned by light etching with HC1, then washed, dried, and vapor-degreased prior to nitriding. 2) Ion-Nitriding Procedure. The type of ion-nitriding equipment used here is similar to that described by Jones and Martin.8 Briefly, a mixture of nitrogen and hydrogen at 5 mm total pressure is placed in a vacuum chamber with a dc potential of 450 to 500 v applied between the work (cathode) and the grounded metal vacuum enclosure (anode). Nitrogen ions are accelerated to the work where a thin layer of Fe4N forms on the surface and thus sets up a nitrogen concentration gradient. This causes nitrogen atoms to diffuse into the surface layers of the alloy forming a finely divided dispersion of alloy nitrides, causing hardening of the surface. In the work to be reported here. the nitriding was carried out at 550° to 600°C to be consistent with commercial nitriding practice. The temperatures cited are those measured by a thermocouple located under a platform on which the work was sitting. Except where otherwise stated, the mixture used in nitriding the binary alloys contained -2.0 pct N, balance hydrogen. The nitrogen concentration in the nitriding gas mixture used for the binary alloys was purposely kept lower than normally used in nitriding steels. 10 to 20 pct, in order to minimize Fe4N formation. In this way only the alloy nitrides would be present as a second phase. However, in the case of steels which would contain a- carbide phase along with as

Jan 1, 1969

By H. C. Fiedler

Heats of high purity iron containing 3.1 pct Si and be -tween 0.0003 and 0.0295 pct N were prepared by vacuum melting ad then pouring while in a nitrogen atmosphere with the pressure between 0 and 90 psi. Strip from a heat with 0.0184 pct N underwent complete secondary recrystallization during the final anneal. Heats with less nitrogen had too few Si3N4 particles to restrain normal grain growth, and the heat with higher nitrogen had too many particles to allow complete secondary recrystallization. In the hot-rolled structure, Si3N4 precipitates only at the grain boundaries, with the consequence that annealing after hot-rolling diminishes the ability to subsequently undergo secondary recrystallization. In contrast to this behavior, ALNprecipitates uniformly in the hot-rolled structure. Under 1 atm of nitrogen, Si3N, in 3.1 pct Si-Fe dissociates between 900" and 950°C; the solubility of nitrogen increases from 0.0010 pct at 900" to 0.0030 pct at 1200°C. The solubility of nitrogen in Si-Fe has been the subject of many investigations. Corney and Turkdogan1 heated a 2.83 pct Si alloy in nitrogen and found the solubility, under 1 atrn of nitrogen, to be 0.0019 pct at 900°C. They claimed that Si3N4 did not form in the alloy above 705°C in 1 atrn of nitrogen. Fryxell et al.2 heated samples of 3.25 pct Si-Fe containing 0.0025 pct N over a range of temperatures and then analyzed for total nitrogen by vacuum fusion and for nitrogen in solution by a modified Kjeldahl technique. At 900°C, they reported the solubility of nitrogen in equilibrium with Si3N4 to be 0.0011 pct. pearce9 found the solubility of nitrogen at 900°C under 0.95 atrn of nitrogen to be 0.0017 pct in a 3.06 pct Si alloy. He reported that Si3N4 does not form above 770°C in 1 atrn of nitrogen. Although internal friction measurements have given somewhat higher values for the solubility,4-6 if the solubility of nitrogen is as low as has been reported by most investigators, and if Si3N4 is stable up to at least 945°C at 1 atrn pressure of nitrogen as reported by Seybolt,7 a small amount of nitrogen in properly processed Si-Fe should be effective in promoting secondary recrystallization. The requirement is that in the final heat treatment there be enough small, well-dispersed particles of Si3N4 to restrain normal grain growth. Fast8 has obtained secondary recrystallization by nitriding high-purity 3 pct Si-Fe after hot-rolling to a thickness of 0.118 in., followed by processing to 0.012 in., and annealing. A large amount of nitrogen, 0.076 pct. was introduced during the nitriding heat treatment, but he has since reported9 that "a few hundredths of a percent" is sufficient. Small amounts of aluminum10 or vanadium" nitride are capable of promoting secondary recrystallization. Heats containing as little as 0.010 pct A1 or 0.042 pct V and from 0.006 to 0.009 pct N underwent complete secondary recrystallization at final gage, whereas heats with lesser amounts of aluminum or vanadium did not.l2 To be reported is the behavior of nitrogen in high-purity 3.1 pct Si-Fe, and the relation of this behavior to the ability to undergo secondary recrystallization. PROCEDURE Ingots weighing 1 lb were made by vacuum melting high-purity electrolytic iron (A104, Glidden Co.) and high-purity silicon (Monsanto Co.). The latter was used in preference to ferrosilicon to insure a low aluminum content. The design of the melting furnace permitted pouring with the furnace atmosphere either below or above atmospheric pressure. Accordingly, at the completion of melting, nitrogen was admitted to the desired pressure and the heat then immediately poured. The ingots were sound, with no indication of porosity. In Table I are listed the heats investigated, the nitrogen pressure at pour, and the nitrogen and oxygen contents as determined by vacuum fusion with a platinum bath at 1850°C, a procedure which insures measurement of the total nitrogen.13 In addition, all heats contained 3.1 pct Si and not more than 0.002 pct C, 0.003 pct S or 0.005 pct Al. It was subsequently found that the quantity of nitrogen contained in the heats in Table I does not necessarily represent that obtained under equilibrium conditions. For example, the ingot poured immediately after 1 atrn of nitrogen was admitted to the chamber contained 0.0093 pct N, whereas an ingot poured 3 min after the nitrogen was admitted contained 0.021 pct N and another poured after a 6-min delay contained 0.029 pct N. While some bleeding of the hot top occurred in the latter instance, the ingot when examined in cross section appeared sound. The ingots were heated to 1325°C in hydrogen and rapidly rolled to 0.080 in. in 3 passes. The roll speed of the final pass was reduced so as to increase the quenching effect of the rolls. The hot-rolled pieces were processed both as-hot-rolled and after heating for 3 min at 900°C in hydrogen. After cold-rolling to 0.026 in., the strips were heated for 2 min at 900°C in hydrogen, then cold-rolled to the final gage of 0.012 in. The loss of nitrogen in going from the ingot to cold-rolled strip was no more than 10 pct. The final heat treatment, which was for the purpose of develop-

Jan 1, 1970

By N. S. Stoloff, J. N. Mushovic

Age hardening response of a Mg-Th-Zr alloy has been studied at temperatures in the range 60° to 450°C. Transmission microscopy revealed clustering of thorium atoms at low aging temperatures, supporting a previous report of GP zone formation. Peak strengthening, which is observed at 325°C, is due to the formation of a coherent, ordered, DO19 type superlattice structure, of Hobable composition Mg3Th, as plates parallel to the matrix prism planes. These plates later reveal a Laves phase structure of composition Mg2Th. The equilibrium Mg4Th phase begins to precipitate in two different forms at an early stage, competitively with the Mg2Th plates. RECENT work on the Mg-Th system indicated that, unlike most magnesium-base alloys, complex precipitation phenomena may be occurring. The partial phase diagram of the Mg-Th system indicates that an equilibrium phase, Mg5Th, is the sole intermediate phase.&apos; sturkey,&apos; however, has reported, using X-ray and electron diffraction techniques, that a metastable fcc Laves phase, Mg2Th, precedes the formation of the equilibrium compound, which he identified as closer in composition to Mg4Th. Murakami et al.3 reported that the equilibrium phase precipitates preferentially on grain boundaries and dislocations in a Mg-1.7 wt pct Th alloy; Kent and Kelly4 aged a more dilute alloy, Mg-0.5 wt pct Th, for 4 days at 220°C and found similar results. In addition, they reported that a platelike phase with a structure close to that of the magnesium matrix forms perpendicular to the basal plane and is probably ordered. Research on a Mg-4 wt pct Th alloy by electrical resistance measurements and transmission electron microscopy has suggested that GP zones may form at low aging temperatures.3 However, the electron micrographs purporting to show this phenomenon were not conclusive. In view of the fragmentary evidence concerning the nature of the precipitation processes in the various Mg-Th alloys, an aging study was undertaken to clarify the characteristics of the various precipitates which form and to correlate the mechanical properties of the system with the direct precipitate-dislocation interactions. The latter results are presented elsewhere.&apos; The purpose of this paper is, therefore, to discuss the precipitation sequence in this system. EXPERIMENTAL PROCEDURE Sheet stock (0.060 and 0.010 in. thick) of a commercial Mg-3.93 wt pct Th-0.42 wt pct Zr alloy (designated HK3lA) similar to that studied by sturkey2 was supplied through the courtesy of Dr. S. L. Couling of Dow Metal Products Co. Zirconium does not enter into any precipitation reactions,&apos; but is present primarily as a grain refiner. The alloy was chill cast, warm rolled to 0.090 in. thick stock, and then finally reduced by a combination of hot and cold rolling. The alloy chemistry is given in Table I. This material was solution treated at 580°C for 4 hr in a dry CO2 atmosphere, and then water quenched. Material in this condition was fairly clear of precipitate particles and was fully recrystallized. Aging at temperatures less than 200°C was accomplished by immersing the alloy in a silicone oil bath; for higher temperatures, aging was done in a salt pot. Age hardening treatments were conducted at 60°, 80°, 105°, 135°, 160°, 250°, 325°, 350°, and 450°C for times ranging from 5 min to 400 hr. Hardness tests were performed on chemically polished 0.060-in.-thick blanks of solution treated material which were aged at the various temperatures for increasing lengths of time. For aging temperatures above 150°C the Rockwell Superficial 30T scale was employed, while samples hardened at temperatures below 150°C were monitored with the 45T scale. Each data point consists of at least three separate readings. Yield stresses also were measured at room temperature on both 0.060 and 0.010 in. sheet specimens aged at 325°C. The aged foils were thinned by the window method in a solution of 80 pct absolute alcohol and 20 pct concentrated perchloric acid (70 pct) maintained at 0°C. A stainless steel cathode was used and the applied voltage was 10 to 15 v. Thinned samples were rinsed in distilled water and pure methanol. After the me-thanol rinse the thin foils were quickly dried between filter paper. Foils prepared by the above method were examined in a Hitachi HU11B electron microscope operating at 100 kv. RESULTS A) Hardness. The hardness data are depicted in Figs. 1 and 2. Peak strengthening occurs at 325°C after aging about 6 min, see Fig. 1. Significant strengthening is achieved also at 350°C, but aging at 450°C produces only softening. The stepped curve at 250°C indicates that a complicated precipitation process may be occurring at that temperature. Fig. 2 suggests that at least two hardening mechanisms exist since the lowest temperature hardness peaks are displaced to the left of the peaks obtained at 135° and 105°C. A great deal of scatter is observed at long times in all cases due to magnesium surface degradation caused by the silicone oil bath. B) Identification of the Strengthening Precipitates. The structure formed atlowagingtemperatures (c10O°C) was not clearly resolvable by transmission microscopy. The only bright-field evidence for a change in structure was a mottled appearance which could be observed at extinction contours, as shown in Fig. 3(a), and the disappearance of this effect when dislocations produced under the influence of the electron beam passed through the matrix, as noted in

Jan 1, 1970

By A. D. K. Laird, John A. Putnam

This paper describes the application of x-ray theory to design procedures in connection with fluid saturation determinations during fluid flow experiments with porous media. A reliable and rapid method for calibrating the x-ray apparatuy is described. Extension of the method to fluid saturation determinations in three-fluid systems is described. INTRODUCTION In rerearch on oil production problems a method is required which will give quickly the quantity of each component of a fluid flow system present at any cross-section of a porous medium. The sample of porous medium under investigation is usually referred to as a core. The ratio of the volume of one component to the total fluid volume is defined as the saturation of the porous medium by that component. This ratio is generally given as per cent saturation. Some means of measuring saturation which have received consideration include: electrical conductivity of the fluids;1,2 emissions from radioactive tracers dissolved in the fluids; the radioactivity of silver caused by reflection of neutrons from hydrogen atoms in the fluids;&apos; the attenuation of a microwave beam. the diminution and phase shift of ultrasonic wave trains.4,5 and the reduction in intensity of x-ray beams in passing through the fluids. X-rays have already been used with some success. Since every material has a different power to absorb x-rays, the reduction in intensity of an x-ray beam as it passes through a core depends on the fluids present. The strength of the emergent beam can be found by converting its energy into a measurable form such as heat or ionic current. or by its effect on a photographic plate or fluorescent screen. The beam strengths could be interpreted as quantities of known fluids in the core if, previously, these beam strengths had been identified with a known combination of the same fluids. With some fluid cornbinations it might be desirable to dissolve powerful x-ray absorbing materials in one or more of the fluids, to increase the differences in the beam strengths for various fluid saturations. Boyer, Morgan and Muskat6 have described a method of measuring two component fluid saturation. One component was air or water; the other. minerat seal oil in which was dissolved 25 per cent by weight of iodobenzene to increase its absorbing power. The x-ray source was a tungsten target tube operated at 43 kv potential. The beam emerging from the core was measured as ionic current flowing across an air-filled ionization chamber by means of an amplifying circuit and galvanometer. Another portion of the beam from the x-ray tube was passed through a metal plate and measured in another ionization chamber. This portion, called the monitor beam, was used as an indication of the performance of the x-ray tube. The galvanometer readings were calibrated against air-oil core saturations, gravimetrically determined. The method was apparently established by experimental means. In the present investigation the available theory of x-radia-tion was surveyed with a view to extending the usefulness of the method and to developing design procedures for its application to measurement of fluid saturation in porous media. Application of the theory permits prediction of relative meter readings to be expected for any combination of porous matrix, various saturating fluids and auxiliary filtering media. It is thus possible to calibrate the equipment in terms of fluid saturation by an indirect but rapid technique. The results of calculations based on x-ray theory indicate. and results of the saturation calibration technique confirm. that a valid measurement of the saturation of the core can be made for any two components and in some cases for three components. THEORY The strength of an x-ray beam, after it has passed through a distance. 1, of matter of density, p, and mass absorption coefficient, µ at a given wavelength, A, may be expressed by the absorption formula I = I0 e ...........(1) where I, represents the intensity of the incident x-ray beam and I is the intensity of the emergent beam. The expression e is called the transmission factor of the material. The variation of I,, with wavelength depends upon the materials through which the x-ray beam has previously passed and upon the spectral distribution of energy at the source of the x-radiation. A group of curves. called spectra. which show the variation of intensity with wavelength and x-ray tube voltage are given in Fig. 1. These curves represent the general radiation from a tungsten target tube. When the tube voltage is greater than 69.3 kv, the characteristic radiation of the tungsten is emitted and is superposed on the general radiation. At a given voltage the minimum wavelength A,,,,, at which energy can be emitted by an x-ray tube is given by the formula 12,340 xml. = ——..........(2) volts where A,.,,.. is in Angstrom units. The wavelength at which the spectra have maximum intensity a1so decreases with increasing x-ray tube voltaue. The area under each curve represents to an arbitrarv scale the total energy emerging from the x-ray tube for that voltage. The variation of µ with wavelength has been determined for many substances and may be found in such references as those by Compton and Allison7 and by Hodgman.8 The phenomenon of absorption is composed chiefly of the capture of photons by the atoms of the absorbing material with associated displacement of electrons, and of the scattering, or the deflection, of the photons by the atoms. Curves of these mass absorption coefficients show jump discontinuities. or absorption edges. at wavelengths which are short enough for the photons,

Jan 1, 1951

By John A. Putnam, A. D. K. Laird

This paper describes the application of x-ray theory to design procedures in connection with fluid saturation determinations during fluid flow experiments with porous media. A reliable and rapid method for calibrating the x-ray apparatuy is described. Extension of the method to fluid saturation determinations in three-fluid systems is described. INTRODUCTION In rerearch on oil production problems a method is required which will give quickly the quantity of each component of a fluid flow system present at any cross-section of a porous medium. The sample of porous medium under investigation is usually referred to as a core. The ratio of the volume of one component to the total fluid volume is defined as the saturation of the porous medium by that component. This ratio is generally given as per cent saturation. Some means of measuring saturation which have received consideration include: electrical conductivity of the fluids;1,2 emissions from radioactive tracers dissolved in the fluids; the radioactivity of silver caused by reflection of neutrons from hydrogen atoms in the fluids;&apos; the attenuation of a microwave beam. the diminution and phase shift of ultrasonic wave trains.4,5 and the reduction in intensity of x-ray beams in passing through the fluids. X-rays have already been used with some success. Since every material has a different power to absorb x-rays, the reduction in intensity of an x-ray beam as it passes through a core depends on the fluids present. The strength of the emergent beam can be found by converting its energy into a measurable form such as heat or ionic current. or by its effect on a photographic plate or fluorescent screen. The beam strengths could be interpreted as quantities of known fluids in the core if, previously, these beam strengths had been identified with a known combination of the same fluids. With some fluid cornbinations it might be desirable to dissolve powerful x-ray absorbing materials in one or more of the fluids, to increase the differences in the beam strengths for various fluid saturations. Boyer, Morgan and Muskat6 have described a method of measuring two component fluid saturation. One component was air or water; the other. minerat seal oil in which was dissolved 25 per cent by weight of iodobenzene to increase its absorbing power. The x-ray source was a tungsten target tube operated at 43 kv potential. The beam emerging from the core was measured as ionic current flowing across an air-filled ionization chamber by means of an amplifying circuit and galvanometer. Another portion of the beam from the x-ray tube was passed through a metal plate and measured in another ionization chamber. This portion, called the monitor beam, was used as an indication of the performance of the x-ray tube. The galvanometer readings were calibrated against air-oil core saturations, gravimetrically determined. The method was apparently established by experimental means. In the present investigation the available theory of x-radia-tion was surveyed with a view to extending the usefulness of the method and to developing design procedures for its application to measurement of fluid saturation in porous media. Application of the theory permits prediction of relative meter readings to be expected for any combination of porous matrix, various saturating fluids and auxiliary filtering media. It is thus possible to calibrate the equipment in terms of fluid saturation by an indirect but rapid technique. The results of calculations based on x-ray theory indicate. and results of the saturation calibration technique confirm. that a valid measurement of the saturation of the core can be made for any two components and in some cases for three components. THEORY The strength of an x-ray beam, after it has passed through a distance. 1, of matter of density, p, and mass absorption coefficient, µ at a given wavelength, A, may be expressed by the absorption formula I = I0 e ...........(1) where I, represents the intensity of the incident x-ray beam and I is the intensity of the emergent beam. The expression e is called the transmission factor of the material. The variation of I,, with wavelength depends upon the materials through which the x-ray beam has previously passed and upon the spectral distribution of energy at the source of the x-radiation. A group of curves. called spectra. which show the variation of intensity with wavelength and x-ray tube voltage are given in Fig. 1. These curves represent the general radiation from a tungsten target tube. When the tube voltage is greater than 69.3 kv, the characteristic radiation of the tungsten is emitted and is superposed on the general radiation. At a given voltage the minimum wavelength A,,,,, at which energy can be emitted by an x-ray tube is given by the formula 12,340 xml. = ——..........(2) volts where A,.,,.. is in Angstrom units. The wavelength at which the spectra have maximum intensity a1so decreases with increasing x-ray tube voltaue. The area under each curve represents to an arbitrarv scale the total energy emerging from the x-ray tube for that voltage. The variation of µ with wavelength has been determined for many substances and may be found in such references as those by Compton and Allison7 and by Hodgman.8 The phenomenon of absorption is composed chiefly of the capture of photons by the atoms of the absorbing material with associated displacement of electrons, and of the scattering, or the deflection, of the photons by the atoms. Curves of these mass absorption coefficients show jump discontinuities. or absorption edges. at wavelengths which are short enough for the photons,

Jan 1, 1951

By H. B. Huntington

Some of the basic problems in understanding elec-tromigration in metals are discussed, along with the attempts that are being made to handle them. One such problem is the effect of the electrostatic forces. It is now acknowledged that the momentum exchange with charge carriers plays generally a dominant role in the driving force but the question remains to what extent the electrostatic force may still be effective. The electromigration of interstitial impurities is also an area which presents some intriguing questions. For the substitutional impurity, moving by the vacancy mechanism under the influence of an electric field, the correlation considerations are somewhat more complex than have been previously recognized. Another problem of basic importance in the calculution from first principles is the strength of the "electron friction" force, say for a simple one-band metal. A related problem growing out of the preceding is the prediction of the direction of the "electron wind" force for metals with band structure involving both holes and electrons. THE term electromigration has come to be used to describe the flow of matter in condensed phases carrying high electronic currents such as metals and alloys, whereas one usually reserves the term electrolysis for situations where the current is largely ionic, particularly in the liquid state such as molten salts. It follows that the mass transport number in electromigration is always very small, of the order of 10-7. Studies of electromigration date back some 30 years but the modern period would appear to date from the work of Seith and Wever1 who in the mid 1950&apos;s first incorporated markers to display mass motion relative to the lattice and first suggested that the direction of the mass flow was primarily determined by the sign of the charge carriers. Since that time interest in the field has grown steadily and more rapidly recently as certain technological applications became apparent. Chief of these is certainly the deleterious effects that electromigration can cause, even at relatively low temperature, to current-carrying elements in integrated circuitry.2 These phenomena have been the subject of intense study and considerable ingenuity. On the constructive side electromigration has proved a useful tool in the purification of certain metals.3 The interest of this paper is, however, centered more on the basic aspects of the subject than on its technological applications. That high electric currents should give rise to mass flow in metals and that the driving force should be more directly associated with momentum exchange with the charge carriers than with the electrostatic field are ideas that no longer cause surprise or particular interest. The field has matured to the point where the general concepts are widely accepted and continued progress in basic understanding rests on more detailed and quantitative exploration. It is the purpose of this paper to point out what are some of the current problems. As a result, we expect to raise more questions than we answer. The first of these will be the role of electrostatic forces, if any, in electromigration. A second section will deal with the electromigration of interstitials. A third and final section treats with electromigration of substitutional impurities or of the matrix atoms themselves. ELECTROSTATIC DRIVING FORCE In the conceptual treatments of electromigration it has been customary to write the driving force in terms of an effective charge number Z* and to divide it into two terms F = e£Z* = e£[Zel- z(pd/Nd)(N/p)(m*\m*\)] [1] The first of these represents the electrostatic force under immediate consideration in this section and the second and usually dominating term for metals arises from momentum exchange with charge carriers, commonly called the "electron drag" term. As can be seen it is set proportional to the electrons per atom, z, and the ratio of the specific resistivity of the moving entity to the corresponding resistivity per matrix atom. The (m*/Im*I) factor takes into account the fact that the sign of the charge carrier determines the sign of the driving force. The specific resistivity of the moving entity is averaged over its path. In the case of motion of the matrix atoms by vacancies this gives rise to approximately one-half the resistivity at the saddle point since the scattering power of the atom at its equilibrium position bordering the vacancy differs only slightly from that of a normal matrix atom. Although the formulation of the "electron drag" term in Eq. [I] is based on a highly simplified model for electron defect scattering, the essential features implicit in the expression are common to all the theoretical approaches that have so far appeared in the literature.4-6 As for Zel, most treatments of electromigration have included the quantity as the parameter which measures the direct interaction of the electrostatic field with the ion and equated it to the nominal valence of the latter. However, there has been considerable discussion whether this interaction may not be 0 in many cases.6 If the moving ion is always enveloped by the same distribution of shielding charge, then clearly its motion will not involve any work done by the electric field and one can expect there will be no electrostatic force exerted on such a neutral composite. From this point of view the shielding charge around the ion would be said to be complete and hence the entity within the Debye shielding sphere would be unaffected by the electrostatic field per se. There is, however, the prospect that, as the moving ion progresses, new charge comes in to participate in the shielding action

Jan 1, 1970

By Karl F. Peterson, H. K. Najarian, Robert E. Lund

PRIMARY products of the Josephtown smelter are zinc metal of various grades, lead-free zinc oxide pigments, cadmium metal, and sulphuric acid. Zinc concentrates of domestic and foreign origin are blended and desulphurized at the roaster plant. The equipment includes five, 12-hearth Herreshoff roasters and two modified Trail-type suspension roasters. The sulphur dioxide containing gases from the roasting operation are diverted to a four-unit contact acid plant for the manufacture of sulphuric acid. The roasted calcines are agglomerated by sintering on Dwight-Lloyd-type sintering machines; the sinter is crushed and sized within required limits; and the sized sinter is smelted in vertical shaft-type electro-thermic furnaces. Of the 13 electrothermic furnaces of various sizes now in operation, four are designed to produce American process zinc oxidc of various specifications; and the remaining nine furnaces are equipped with vacuum-type condensers and produce zinc metal. Papers describing the general smelting practice at Josephtown have been published by AIME. Since both High Grade zinc metal and lead-free zinc oxide pigments are produced direct from the electrothermic furnaces without need for subsequent refining, the elimination of impurities such as lead and cadmium has to be accomplished during roasting and sintering operations. To effect the producing of both High Grade and Prime Western zinc products, the roasting and sintering operations are on two separate circuits. A High Grade circuit produces finished sized sinter low in lead, cadmium, etc., for the High Grade furnaces; and the Prime Western circuit produces finished sinter destined for the furnaces producing Prime Western metal. Sintering at the Josephtown smelter differs in many important respects from the sintering practice in smelters operating horizontal retort zinc furnaces. Requirements of the electrothermic smelting furnaces define the physical characteristics of the sinter, while the chemical composition of the sinter is controlled according to the grade of metal and oxide to be made as final products. Three principal objectives in the sintering process at Josephtown smelter are: 1. To transform the zinc calcine from the roasting operations into a hard, yet porous agglomerate that will not crumble in the smelting furnace. 2. Crushing and sizing of the sinter to obtain a proper screen analysis which is normally —% in. down to +1/4 in. particle size. 3. To eliminate, particularly in the High Grade circuit, as much of the impurities such as sulphur, lead, and cadmium as possible. The sintering plant as originally built in 1930 was equipped with three standard 42 in. x 44 ft Dwight-Lloyd sintering machines. Each machine was equipped with a 15x60 in. sintering corporation fan driven by 150 hp, 900 rpm synchronous motor through a magnetic clutch and capable of delivering 30,000 cfm of air at 15 in. of water and 150°F. Each sintering machine was driven by 7½ hp dc motor with controllers for varying the speed of the machine from 8 to 32 in. per min. The pallets were cast iron and the grates of the herringbone type. The charge was mixed in a 4 ft diam x 8 ft Stehli pugmill and transported by belt conveyor, elevator and tripper conveyor to a small bin over each machine. Shortly after the start of operations the following changes were found necessary: 1. The herringbone grates which plugged very quickly and were difficult to keep clean were replaced by straight, narrow cast-iron grate bars running at right angles to the travel of the pallets. These grate bars are held in place by a center bar extending across the pallet on the 24 in. dimension and by removable retaining plates which form the sides of the pallets. 2. Mechanical grate knockers were developed in conjunction with new grate bars for continuously and automatically cleaning the grates. 3. As the cast-iron pallets cracked, they were replaced with cast-steel pallets. In 1938, the capacity of the sinter plant was increased with the installation of two 42 in. x 22 ft machines which were brought from the company&apos;s Herculaneum lead smelter. With a circulating load of some 250 to 300 pct, production of finished sinter on the 42 in. x 44 ft machines at this time amounted to about three tons of sized sinter per machine hour. In 1945, one of the 42 in. x 22 ft machines was replaced by a 60 in. x 44 ft machine of our own design. In 1948, as part of the plant-wide expansion program, the sinter plant not only was expanded but also divided into two separate plants; namely, Prime Western and High Grade circuits. The sinter destined for furnaces producing Prime Western zinc metal is made in a new plant comprising two 60 in. x 44 ft Dwight-Lloyd-type sintering machines, each having a 45,000 cfm Sturtevant fan at 18 in. water static pressure and served by an 8 ft diam x 12 ft long rotary charge pclletizer and auxiliary crushing and sizing equipment. The sinter destined for furnaces producing High Grade zinc metal and zinc oxide pigments is produced in the old sinter plant which was expanded to accommodate four of the 60 in. x 44 ft sintering machines, replacing the old sintering units. In the High Grade sinter circuit, two units of the 60 in. x 44 ft machines are used as preliminary soft sinter machines; and the remaining two units of the 60 in. x 44 ft machines are used to make finished hard sinter. Purification Theory Partial elimination of lead and cadmium in the sintering of zinc ores is common knowledge. However, by some manipulation and by taking advantage of the double circuit, it is possible to make zinc sinter which is nearly free of contaminators. Lead

Jan 1, 1952

By John Goodell

CIVIL engineers seem to number in their ranks more advocates of licensing than are found among the practitioners of other branches of the pro-fession. Licensing was not originated by civil engineers but it was forced upon them in two ways. In the first place, the civil engineering profession has hangers-on like every other profession. The first legislative result of their imperfect accomplishments with which I am familiar occurred in the far West. It was found that early irrigation works were so badly planned in some cases that not only were water rights made very uncertain but considerable sums were invested in structures and ditches which proved inadequate and occasionally complete failures. Water was too valuable to be wasted in that way and money too hard to obtain. In those sections, therefore, laws were passed many years ago which made it obligatory for the design of irrigation works and other structures utilizing water to be made by engineers who had satisfied a board of examiners that they possessed the technical qualifications to plan such works properly. The basic thought on which such laws rest is the same as that on which laws governing the licensing of boiler operators rest, namely, the safety and welfare of the public. While boiler explosions still occur and irrigation works are built which are not wholly satis-factory, these laws have helped the, public, it is gener-ally agreed.

Jan 4, 1922

By CHARLES COURT

I must tell you at the outset that I come to this conference deeply disturbed at the &apos;role of Government in international dealings in mineral and energy resources&apos;. I am disturbed by- the confusion that now passes for policy. I am disturbed by the short- range view of critical problems taken by a majority of Governments. I am equally disturbed by the even shorter range of view taken by a growing army of industries. Many of them clamour for Governments to solve their problems in a specific way, with little regard for any other sector but their own-and with even less regard for the fact that every time a Government takes over some of their responsibilities they surrender some of their freedom. I would not say that longer range views don&apos;t exist. But I would say that they don&apos;t prevail at the present time. Instead, we are seeing the constant development of many policies for individual problems which don&apos;t tackle the fundamental causes. We must get back to basics without delay.

Jan 1, 1978