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By Leonard C. Grimshaw

Diffusion of carbon from gases into iron has been the object of much research, because of its long recognized importance in carburizing processes, but the direct diffusion of carbon from steel into iron has received relatively little attention. Because of the increasing use of clad metals in industry, direct diffusion from steel into iron is becoming of practical importance. Therefore, the object of this investigation was to study the diffusion of carbon from several different kinds of steel directly into relatively pure iron, realizing that elements in the steels other than carbon might influence the rate of carbon diffusion. The previous work on diffusion of carbon into iron has been considerable, and includes many reports in foreign languages. This work has recently been well reviewed by Mehll and Krynitsky12 and the reader is referred to their excellent bibliographies. Methods of Study There are two main methods by which the direct diffusion of carbon from steel into iron may be studied. In one method, steel is first decar-burized in part, and diffusion of carbon then allowed to take place from the steel into the decarburized steel. This method is open to two serious objections: (1) the decarburized steel is not iron, but contains elements such as manganese, silicon, chromium or tungsten, which may be an essential part of the steel under study, and which may seriously influence the diffusion of carbon into the decarburized area; (2) there is from the start of diffusion an unknown carbon-concentration gradient between the steel and the decarburized area. Another method, which possesses neither of these disadvantages, is to study diffusion from steel into a thick plating of electrolytic iron. Herc the chief difficulty is to secure an electrolytic deposit of iron upon steel without introducing an oxide film at the interface that will interfere with diffusion. The author is able to deposit iron upon any kind of steel without introducing an oxide film at the interface, so that diffusion of elements from the steel into the iron is free to proceed unhindered.

Jan 1, 1938

By Leonard C. Grimshaw

Diffusion of carbon from gases into iron has been the object of much research, because of its long recognized importance in carburizing processes, but the direct diffusion of carbon from steel into iron has received relatively little attention. Because of the increasing use of clad metals in industry, direct diffusion from steel into iron is becoming of practical importance. Therefore, the object of this investigation was to study the diffusion of carbon from several different kinds of steel directly into relatively pure iron, realizing that elements in the steels other than carbon might influence the rate of carbon diffusion. The previous work on diffusion of carbon into iron has been considerable, and includes many reports in foreign languages. This work has recently been well reviewed by Mehll and Krynitsky12 and the reader is referred to their excellent bibliographies. Methods of Study There are two main methods by which the direct diffusion of carbon from steel into iron may be studied. In one method, steel is first decar-burized in part, and diffusion of carbon then allowed to take place from the steel into the decarburized steel. This method is open to two serious objections: (1) the decarburized steel is not iron, but contains elements such as manganese, silicon, chromium or tungsten, which may be an essential part of the steel under study, and which may seriously influence the diffusion of carbon into the decarburized area; (2) there is from the start of diffusion an unknown carbon-concentration gradient between the steel and the decarburized area. Another method, which possesses neither of these disadvantages, is to study diffusion from steel into a thick plating of electrolytic iron. Herc the chief difficulty is to secure an electrolytic deposit of iron upon steel without introducing an oxide film at the interface that will interfere with diffusion. The author is able to deposit iron upon any kind of steel without introducing an oxide film at the interface, so that diffusion of elements from the steel into the iron is free to proceed unhindered.

Jan 1, 1938

By E. T. Turkdogan, Klaus Schwerdtfeger, P. Grieveson

The rate of growth of "Fe4N" on a iron was measured by nitriding purified iron strips in flowing am -monia -hydrogen gas mixtures at 504" and 554°C. It is shown that a dense nitride layer is formed when a zone -refined iron is used in the experiments. With less pure iron, the nitride layer is found to be porous. Through theoretical treatment, the self-diffusivity of nitrogen is evaluated porn the parabolic rate constant, and found to be essentially independent of nitrogen actirlity, e.g., D* = 3.2 x l0-12 and 7.9x l0-12 sq cm per sec at 504" and 554?C. Some consideration is given to the mechanism of diffusion in the nitride phase. THERE is a great deal of background knowledge on the solubility and diffusivity of nitrogen in iron, and on the thermodynamics and crystallography of several phases in the Fe-N system. Although case-nitrided steels have many applications in practice, no work seems to have been done on the diffusivity of nitrogen in the iron nitride, ?', phase. The only work reported on the related subject of which the authors are aware is an investigation by Prenosil,1 who measured the growth rate of the e phase on iron by nitriding in ammonia-hydrogen gas mixtures. EXPERIMENTS Purified iron plates of approximate dimensions 1 by 0.5 by 0.03 cm were nitrided in flowing mixtures of ammonia and hydrogen, in a vertical furnace fitted with a gas-tight recrystallized alumina tube. After a specified time of reaction, the sample was cooled to room temperature by withdrawal to the water cooled top of the reaction tube. The furnace temperature was controlled electronically in the usual manner within *l°C; the temperature was measured using a calibrated Pt/Pt-10 pct Rh thermocouple. For each experiment the iron strip sample was cleaned with fine emery cloth and degreased with tri-chloroethylene prior to the experiment. The ammonia-hydrogen gas mixtures were prepared from anhydrous ammonia and purified hydrogen using constant pressure-head capillary flowmeters. The gas mixture flowed upward in the furnace with flow rate of 400 cc per min at stp. The composition of the gas mixture was checked by chemical analysis at regular intervals. In most cases, the compositions of the exit gas and metered input gas agreed within about 0.3 pct, indicating that cracking of ammonia did not pose a problem at the temperatures employed. Two series of experiments were carried out using two different types of purified iron samples. In the first series of experiments at 550°C, vacuum carbon deoxidized "Plastiron" was used. The main impurities present in this iron were, in ppm: 4043, 50-Cr, 20-Zr, 40-Mn, 20-P, 20-S, 20-C, 50-0, and 10-N. In these experiments the rate data were obtained by measuring the change in weight of the iron specimen suspended in the hot zone of the furnace by a platinum wire from a silica spring balance. The nitride layer formed in these experiments was found to be porous, particularly near the outer surface. In other experiments, high purity zone-refined iron (prepared in this laboratory) was used. The total impurity content of this iron was 30 ppm of which 20 ppm was Co + Ni, 4 ppm 0, other metallic impurities were less than 1 ppm. The zone-refined iron bar, -2.5 cm diam, was cold rolled to a thickness of about 0.03 cm and the specimens were prepared for the experiment as described earlier. After the nitriding experiment, the sample was copper plated electro-lytically and mounted in plastic for metallographic polishing. After polishing, the thickness of the ?' layer was measured using a metallographic microscope. The nitride layer formed on the zone-refined iron was essentially free of pores. RESULTS The different morphology of the nitride layers grown on "Plastiron" and zone-refined iron is shown in Fig. 1. Both samples were nitrided side by side for 55 hr. The holes in the less pure iron, Fig. l(a), are confined to a region about one half thickness from the outer surface. The dense layer grown on zone-refined iron, Fig. l(b), is thinner than the porous layer on the "Plastiron". The impurities in the iron are believed to be responsible for the formation of a porous nitride layer. The pore formation may be due to the high nitrogen pressures existing within the nitride layer, e.g., the equilibrium nitrogen pressure is 1.2 x l05 atm in the 38.6 pct NH3-61.4 pct H2 and 6.6 x l03 atm at the Fe-Fe4N interface at 554°C and 0.96 atm. It is possible that the oxide inclusions present in the electrolytic iron may facilitate the nuclea-tion of nitrogen gas bubbles within the nitride layer. Support for this reasoning is the fact that pores are only encountered in the outer range of the layer where nitrogen pressures are largest. The photomicrographs in Fig. 2 show the effect of reaction time on the thickness of the dense nitride layer formed on zone-refined iron. These sections are from samples nitrided in a stream of 29 pct NH3-71 pct H2 mixture at 554°C for 22, 70, and 255 hr. In all the sections examined the nitride-iron interface was noted to be rugged. These irregularities are be-

Jan 1, 1970

By R. O. Williams

Analytical representation of the thermodynamics of solutions is highly desirable from the standpoint of accuracy, compactness, and numerical manipulations. In particular, computer calculations are greatly implemented. Mathematical considerations show that previous expressions have one or more serious defects. This investigation shows a Fourier series to be satisfactory but that it is also possible to derive a new series which fits certain additional conditions. Included examples show the value of analytical expressions in giving a simple characterization of each system using some two to five parameters, the elimination of the Gibbs-Duhem integration, and the es timation of the error for the experimental function as well as derived functions. It is further shown that the present characterization provides easy comparison between systems. IN the past, thermodynamic calculations have depended to a considerable extent on tabular and graphical methods. As the volume and precision of such data increase such methods become less satisfactory. Specifically, the selection of the optimum representation and the estimation of errors require statistical methods which in turn require analytical representation. The utilization of such data require further manipulations which are best done analytically for maximum precision. For example, phase equilibria are determined by common tangents to free-energy curves: a graphical determination is normally of low accuracy. As computers are increasingly used analytical representations become almost mandatory. Insufficient mathematical consideration has been given previously to the selection of empirical expressions. Those expressions having some theoretical justification are generally too inflexible and mathematically unattractive. We consider the problem in some detail and show that a Fourier series can be effectively used. Also a new series is defined which has certain advantages. ANALYSIS We wish to consider the analytical representation of the heat of mixing, AH, the excess free energy, ?Gxs, and the excess entropy, ?sXS, as a function of composition, X, for binary solutions relative to the pure components in the same state. When a distinction is not required, we use W to denote any one of the above functions. One may use a Taylor expansion around X = 0 to generate a power series. As the derivatives are un- known we represent the series as W = A + BX + CX2 + DX3 + EX4 + ... [l] where the constants A , B, C , ..- are to be selected to provide some optimum fit. For the extremes of composition W is necessarily zero so it follows that A = 0 [2a] B +C + D + E +••• = 0 [2b] Nonelectrolytes, which we are considering, appear to satisfy the condition that d3W/dx3 = 0 [3] in the terminal regions. This is the basis of the a, ß, and Q functions used by Hultgren et al.' and others. While this condition does not have a strong theoretical basis it does appear desirable that any analytical relation should satisfy this condition. Darken2 and Turk-dogan and Darken3 have shown that many systems exhibit this behavior over an extended range from each terminal region, departure being restricted to a limited intermediate region. Since we have no a priori knowledge as to where this transition occurs we can require that this condition be satisfied only as a limit at the extreme compositions as a general condition. We will show later how more restricted conditions can be included in specific solutions. Darken2 has called this behavior the quadratic formalism; we call our application the limiting quadratic formalism, LQF. This condition applied to the above power series requires that D = 0 [4a] 4-3-2E +5-4-3_F + 6 • 5 . 4G + ••• =0 [4b] The form of the power series normally used, due to Margules,4 is W=X(1-X)(A + BX + CX2 + DX3 + EX4 + •••) [5] where A, B, C, --. are a new set of constants. (Guggenheim5 has given a variation of this expression in a more desirable form. Since, however, it is contained in the above expression it does not require separate consideration.) This form is precisely what results by incorporating the conditions in Eq. [2] into the power series and regrouping the constants. The LQF requires that B =C [6a] and 4.3.2(D-C) +5-4-3(E-D) + ••• =0 [6b] Thus, the correct form of the Margules expression with two adjustable parameters is w =X(1-X)[A + B +X2-2/3x3)] 171 and the EX4 term must be included before three adjustable parameters are permitted.

Jan 1, 1970

By William R. Rumbold

When I was in South Africa during the latter part of 1904, there were three known tin-fields, which may be called the Cape Town, the Bushveld, and the Swaziland fields. The Cape Town Tin-Field. This district is situated near Kuils river, 20 miles west of Cape Town, and 5 miles from Kuils River station on the Cape Town & Stellenbosch railway. The deposits are in granite, intrusive in the Malmesbury beds, which are supposed to be of Silurian or Cambrian age. The granite, resisting denudation better than the surrounding shales, has formed low-lying hills, the highest of which, the Bottlelary Berg, is 1,510 ft. above sea-level. The rock consists of quartz, orthoclase feldspar, and biotite mica; tourmaline is also present. The feldspar occurs in large crystals. The rock is generally decomposed on the surface, and the decomposition sometimes extends as deep as 100 ft. This formation—granite intrusive in Silurian shales— extends for many miles to the northeast, but so far as I know the Kuils River deposits are the only ones now known to occur in it, though probably further prospecting will reveal other deposits. This particular discovery was accidental; alluvial tin being found in the course of boring for oil. The Kuils River Deposit. This deposit comprises both lode and alluvial tin. The lode strikes N-S., and dips about 30' E. into the hill. It is 5 ft. wide, and composed of dense white quartz, in which pinkish-gray cassiterite is distributed in large crystals. The vein also contains considerable quantities of wolframite. Fig. 1 is a rough plan of the relative positions of the lode and the alluvial deposit, the latter, as shown, following the course of a stream, while the lode crops out on the hillside ,

Jan 1, 1909

By B. L. Averbach, M. Cohen, C. H. Shih

The isothermal formation of martensite is studied in Fe-Ni-Mn and Fe-Mn-C alloys under conditions where the athermal transformation is completely avoided, there being no martensite present at the beginning of the isothermal reaction. The initial rate of martensite formation is extremely low under these conditions, but it increases greatly as soon as some martensite is formed. It appears that true initial characteristics of the isothermal reaction can be studied only in samples wherein the formation of martensite on cooling is completely eliminated. THE phenomenon of isothermal martensite formation is well established1 -" but the observations have been made in the presence of varying quantities of athermal martensite. Complete avoidance of athermal martensite and the formation of martensite under pure isothermal conditions have been reported by Kurdjumov and Maksimova2 in an Fe-Ni-Mn alloy (23 pct Ni, 3.4 pct Mn, and the balance Fe) and have been confirmed by recent experiments of Cech and Hollomon in a similar alloy. In each case, the isothermal transformation rate was a maximum at the beginning of the transformation and decreased as the reaction proceeded. These initial transformation rates were used by Fisher7 for the confirmation of calculated nucleation rates based on classical nucleation theory extended to include the effect of elastic strain energy. Cech and Hollomon have admitted, however, that up to 3 pct martensite formed on cooling in their samples and thus was present at the initiation of their isothermal runs. In this paper, experiments on similar alloys are described, except that care was taken to remove the incidental martensite developed at the surface prior to the isothermal reaction. It is shown here that the reaction rate at the beginning of the strictly isothermal reaction is very low. As soon as some detectable amount of martensite is produced, the transformation rate increases rapidly but ultimately decreases as the reaction proceeds. When martensite is allowed to form isothermally in the presence of about 2 pct of prior martensite, the apparent initial reaction rate is a maximum and corresponds to the observations of Kurdjumov and Maksimova and Cech and Hollomon. It is evident that the cooperative nature of the martensitic reaction results in a significant stimulating or autocatalytic effect on the isothermal reaction rate. Experimental Procedure The chemical compositions of the alloys used in this investigation are listed in Table I. The Fe-Ni-Mn alloys A and B were melted in an induction furnace, cast into ingots 2 in. diam by 4 in. long, and forged into % in. diam rods. The manganese steel (alloy C) was melted in an arc furnace and cast into ceramic molds 1/4 in. diam by 5 in. long. The rods were sealed in evacuated Vycor tubes and homogenized at 1175" to 1200°C for 50 hr. The long homogenization resulted in some manganese loss from the surface, producing a thin layer of transformed material. This surface layer was removed by grinding and the specimens were then swaged to 0.050 in. diam wire. Measurements of electrical resistance were made with a Kelvin double bridge to follow the course of the martensitic transformation. A small permanent magnet was also useful in scanning an entire specimen for small localized quantities of martensite. This test is almost as sensitive as the electrical resistance method in detecting the presence of martensite (which is ferromagnetic in these alloys) and it was especially useful in deciding whether a specimen was completely free of martensite. The wire specimens (0.050 in. diam by 2.5 in. long) were sealed in evacuated tubes and austenitized for 5 min at 1150°C. The specimens were quenched into water and, unless otherwise stated, stress-relieved for 1 hr at 650 °C in order to induce greater uniformity in the subsequent martensitic transformation. As dem-

Jan 1, 1956

By C. S. Matthews, M. J. F. Rosenbaum

The purpose of thir work wax to lcarn it~lzut infori~lation could he obtained from various typs of pilot water floods and to attempt to find the optunum pilot patter11, for a revervoir which had previously been depleted by a solution gas drive. The study was made in the laboratory with mathemetical methods a dynamic analog and a potentiotnetric analog. Results werp tested against the field llistorics of a nrrnlber of pilot water floods. At a reasonable valrre of currzulative injection, the total production rate for the one-injector five-spot should reach about 6.5 per cent of injection rate, and for a four-injector five-spot, about 9 per cent. Accurate estimates of ultimate recovery cannot be made on the basis of such snzall prorluction rates. However, with a pilot composed of nine ir1jector.s and 16 producers the production rate is approximately 50 pcr cent of injection rate at a reasonable value of camulative injection. Sonle inforn~ation for extended performance predictions might he obtained from such a large pilot. These conclusions were drawn on the basis of results obtained for unit mobility ratio, and a sturly using tlre potentiometric analog was made of the effect of other mobility ratios to determine the range of applicability of these predictions. For the four-injector, five-spot pilot with the ratio of production to injection rate (before water breakthrough) is about twice that for with it is about two-thirds; and with M0= 10, it is about one-third For high mobility ratios, it was found that the production rate increased considerably as water-cut increased. These result can be used to modify, qualitatively, the inter.pretntions based on curves for the unit rnobilit\. ratio CaSeS. It was found that the maximum ratio of production rate to injection rate obseriled in field pilot floods was of rhe scime order as that prerdicted by these methods. The time required to reach thisr maximum did not generally agree with the time predicted for a homogeti~orir reservoir. The differcrlce between predicted and observed time of response gives an indication of the permeability profile and of the condition of the producin,g wells. Pilot water floods of the pattern type are generally carried out in reservoirs which have been depleted by solution gas drive and are at low pressure. Under these conditions, oil and water can be considered incompressible. It is assumed that, as the water is injected, an oil bank forms ahead of it and that there is a distinct interface between the water zone (or bank) and the oil zone (or bank) and between the oil zone and the region ahead of the oil zone. It is further assumed that only gas is mobile in the unflooded (gas) region, only oil is mobile in the oil bank and only water is mobile in the water bank. The saturations and the mobilities associated with each zone are assumed uniform. We idealize our reservoir to be homogeneous, horizontal and of constant thickness. Effects of gravity within the producing layer are assumed negligible. If the actual time-dcpendent flow problem is approximated by a acries of steady-state problems. the potential and stream function in the oil bank and water hank satisfy Laplace&apos;s equation in two dimensions. We can therefore use a poteiitiometric analog of this system. Potentiometric models have yielded uscful results in this laboratory&apos; and clsewhere in the study of a variety of secondary recovery problems. For the case where M = I, we generally prefer to use theoretical mcthods as well as a simpler dynamic analog. Except where otherwise noted, the ratio, side of five-spot/wellbore radius. is taken to be 3,600. a figure which corrcsponds to a normal-size wellbore in a 10-acre well spacing. THEORETICAL EVALUATION OF VARIOUS PILOT PATTERNS, Mw0 = 1 <&apos;he theoretical models which we used to examine the performance of various pilots are shown in Fig. 1. Image theory was used to determine the ratio of production rate to injection rate as a function of the volumc of the flood. The ratio of production rate to injection rate was chosen because this is an easily measurable quantity which is characteristic of a pilot

By E. H. Rennhack, J. F. Libsch

Definite transition behavior was found in unalloyed titanium at 0.13 pct 0 equivalent. The addition of 0.5 Sn, 1.0 Al, 0.5 Al, and 1.0 Sn lowers the tvansition temperature of titanium at oxygen equivalents exceeding 0.22, 0.29, 0.40, and 0.51, respectively. Metallographic evidence indicates that progressive amounts of oxygen restrict deformation at low temperatures resulting eventually in brittle fracture. The presence of tin or aluminum is thought to alter the atomic distribution of oxygen within the titanium lattice in such a manner as to facilitate some degree of slip and twinning. 1 ITANIUM-like iron and zinc experiences a transition from ductile to brittle fracture with decreasing temperature. The presence of sufficient quantities of the interstitial elements, carbon, oxygen, and nitrogen in solid solution, has been shown to progressively lower the room-temperature impact resistance of titanium with increasing interstitial content.1"1 Ogden,et al,2 reported finding no transition from ductile to brittle fracture with decreasing temperature in iodide titanium. However, a definite transition was found to occur at 0.36 pct 0 equivalent in an alloy containing 0.47 pct carbon in solid solution. The oxygen equivalent in this case was obtained by assuming the effects of carbon, oxygen, and nitrogen in combination on the impact properties of titanium to be additive on the same basis as their separate effects on tensile strength, namely: Oe = 2/3 (pct C) + pet 0 + 2 (pet N) They concluded that the tendency toward transition behavior is dependent on the total interstitial content in solid solution and not on any one particular interstitial element. Rennhack,4 however, recently found transition behavior in iodide titanium at an oxygen equivalent of 0.17 pct. Ogden, etal3, reported that the strengthening effects of carbon, oxygen, and nitrogen in titanium decrease with the addition of tin. They showed that tin additions increase the tolerance of titanium for the interstitials, that is, 10 pct Sn permitted individual additions of up to 0.4 wt pct of the interstitial elements without any significant loss in ductility. Aluminum tends to decrease ductility and impact strength of titanium for a given interstitial ~ontent.3 Van Thyne and Kessler5 found that the solid solubility of carbon in titanium doubled in the presence of 10 pct Al. The precise effects of tin and aluminum in the nrespncp of rorvfen nn the impact properties of titanium had previously not been determined. The high oxygen tolerance of titanium containing tin may provide a suitable means for improving the impact properties of titanium containing the interstitial elements, particularly oxygen. Unlike tin, however, aluminum has a high affinity for oxygen and will reduce rutile titanium dioxide (TiO2)by a thermit-type reaction.6 Thus, the atomic distribution of oxygen in titanium might be different in the presence of aluminum. The present work was undertaken to: 1) Determine the effect of oxygen on the transition behavior of unalloyed iodide titanium. 2) Determine the effect of small amounts of tin and aluminum on the transition behavior of iodide titanium in the presence of oxygen and other interstitial~. EXPERIMENTAL Three different lots of iodide titanium were employed to prepare the alloys studied in the present work. Their chemical composition is presented in Table I. The compositions of the tin and aluminum used for alloying are shown in Table 11. Oxygen additions were made using calcined rutile titanium dioxide (TiO2)of 99.7 pct purity. Alloy Preparation—Four titanium-base alloys containing separate additions of 0.5 and 1.0 pct each

Jan 1, 1960

By C. L. Mantell

Although so common and well known a metal, tin is really a less abundant element than many of those less familiar and usually ranked with the scarce or rare elements, such as cerium, yttrium, lithium, beryllium, titanium, zirconium and vanadium. The color of tin is white, with a slightly bluish tinge. When it is compared with nickel, the latter metal is brown. When placed alongside of tin, chromium is definitely blue. Tin is whiter than silver or zinc. Exceedingly thin films of tin show various shades of brown by transmitted light. The metal has a brilliant luster, and when mirror-polished, has high light reflectivity. The luster depends to a large extent upon the pouring temperature at which the metal is cast. If the temperature be too high, iridescent colors may show on the surface. These are the result of oxide film formation. If the pouring temperature be too low, the surface is dull. Small amounts of foreign metals, such as lead, arsenic, antimony and iron, decrease the luster of tin and impart a yellowish tinge to the metal. The structure is decidedly crystalline. The cast metal is a mass of crystals. When a bar of tin is bent, it emits a characteristic creaking sound. This is called the "cry" of tin, resulting from the grinding of the crystals one against the other during the bending of the metal. Tin metal may lose its crystalline structure by cold working, but grain growth occurs rapidly under the influence of heat. Metal which has been cast at a low temperature may become amorphous as the result of mechanical work. If such material be heated to temperatures well below the melting point, say at 110° C. for a half hour or for a few minutes at 150" C. recrystallization occurs. If the surface of tinned plate, tin foil, or tin meta1 in cast form be etched with hydrochloric acid containing a little free chlorine, attack occurs at the intererystalline faces. The surface shows patterns resembling the frost flowers on window panes in winter. The etched appearance is called moire metallique. Fine dendritic surface crystals of tin may be obtained by casting the metal on a surface of polished steel. In commercial tin plate, the intercrystalline boundaries are shown by fine grooves or channels, .which result from the method

Jan 1, 1929

By C. L. Mantell

Although so common and well known a metal, tin is really a less abundant element than many of those less familiar and usually ranked with the scarce or rare elements, such as cerium, yttrium, lithium, beryllium, titanium, zirconium and vanadium. The color of tin is white, with a slightly bluish tinge. When it is compared with nickel, the latter metal is brown. When placed alongside of tin, chromium is definitely blue. Tin is whiter than silver or zinc. Exceedingly thin films of tin show various shades of brown by transmitted light. The metal has a brilliant luster, and when mirror-polished, has high light reflectivity. The luster depends to a large extent upon the pouring temperature at which the metal is cast. If the temperature be too high, iridescent colors may show on the surface. These are the result of oxide film formation. If the pouring temperature be too low, the surface is dull. Small amounts of foreign metals, such as lead, arsenic, antimony and iron, decrease the luster of tin and impart a yellowish tinge to the metal. The structure is decidedly crystalline. The cast metal is a mass of crystals. When a bar of tin is bent, it emits a characteristic creaking sound. This is called the "cry" of tin, resulting from the grinding of the crystals one against the other during the bending of the metal. Tin metal may lose its crystalline structure by cold working, but grain growth occurs rapidly under the influence of heat. Metal which has been cast at a low temperature may become amorphous as the result of mechanical work. If such material be heated to temperatures well below the melting point, say at 110° C. for a half hour or for a few minutes at 150" C. recrystallization occurs. If the surface of tinned plate, tin foil, or tin meta1 in cast form be etched with hydrochloric acid containing a little free chlorine, attack occurs at the intererystalline faces. The surface shows patterns resembling the frost flowers on window panes in winter. The etched appearance is called moire metallique. Fine dendritic surface crystals of tin may be obtained by casting the metal on a surface of polished steel. In commercial tin plate, the intercrystalline boundaries are shown by fine grooves or channels, .which result from the method

Jan 1, 1929

By A. S. Adams

A GLANCE at the list of papers1 that have been published since 1920 on the general subject of flotation suggests the variety of ideas that exist regarding the underlying cause of the phenomenon.&apos; Among these ideas, we find several coherent theories, but none that adequately and completely explain the phenomenon. Ralston2 and Bains3 suggested an electrical theory which has to do with the attachment of mineral particles to a bubble by the attraction of unlike electrical charges. This theory has its root in the fact that a bubble of air in pure water is electrified in such a way that the surface is negatively charged while the body of the water is positively charged. This result, which was first discussed by Helmholtz, also obtains when the water contains anything except a high concentration of hydrogen ions, or ions which are trivalent or tetravalent. The theory also holds that the mineral particles have positive charges on their surfaces, and so there is attachment between bubble surface and mineral particles by the old law of electrostatics, which states that unlike charges attract. CONTACT ANGLE AND OIL ATTRACTION The contact angle-the angle formed by a fluid-fluid boundary when both are in contact with a solid-has been indicted several times for complicity in the phenomenon of flotation. This angle is supposed to indirectly measure the surface energy of a solid. Thus if we have two fluids in contact with a solid, we may express the difference between the two fluid-solid tensions as equal to the fluid-fluid tension times the cosine of the angle between the two fluids.4 If the two fluids are in contact with the solid, this is, no doubt, an excellent way of establishing relative surface energies. However, in flotation, we deal with substances which are not wetted by water. What assurance have we, then, that the angle

Jan 1, 1928

By Earl F. Hanson

Fires in heavily timbered mines are disastrous, involving danger to both life and property. Some mines have been completely ruined or so heavily damaged that reopening them would not pay. Though few mines are entirely free from danger of fire, the risk is minimized by proper care and good design of plant. The Tintic Standard mine is at Dividend, Utah, in the famous Tintic mining district, about 60 miles south of Salt Lake City. The development of the mine was begun in 1907 by the late Mr. E. J. Raddatz and his associates. From the beginning, the work was hampered by high rock temperatures and the presence of high concentrations of rock gases such as carbon dioxide and nitrogen. Development work was carried on with great perseverance for nine years, and resulted in the discovery of ore in 1916. The total production of the Tintic Standard mine to Jan. 1, 1936, amounted to 1,664,388 tons of ore, having a gross value of $61,996,719. General Layout of the Mine The No. 2 shaft, which is the main working shaft of the Tintic Standard, is within the main orebody and is connected with the five other shafts. Their respective positions with respect to the No. 2 shaft are as follows: North Lily, 2770 ft. northwest with drift connections on the 700 and 900-ft. levels; No. 3 shaft, 670 ft. east connected through the 700-ft. level; Eureka Standard, 4550 ft. south, connected on the 900-ft. level; No. 1 shaft, 1470 ft. southwest, with connecting drifts on the 900 and 1250-ft. levels; Eureka Lilly, 2000 ft. southwest, with connecting drift and raise through the 1250-ft. level. The Tintic Standard orebody consists essentially of one continuous oreshoot extending from the 600-ft. level to the 1450-ft. level, with a cross-sectional area of approximately 70,000 sq. ft. at both top and bottom, reaching a maximum area of 215,000 sq. ft. between the 1100

Jan 1, 1937

MINING, to be precise, ends when the ore is delivered to a bin outside the mine. Usually the next step is concentrating; or, as it is more often called, milling. A few elementary definitions will help make clear the discussion that is to follow. A rock is an aggregate of minerals; copper ore is rock that contains copper-bearing minerals in quantity sufficient to make it profitable to mine and recover the copper in the form of marketable metal. Manifestly, under a literal interpretation, a mass of material might be copper ore one day and merely copper-bearing waste rock a week later, if the price of copper happened to drop in the interim. Emphasis already has been placed on the expansion that took place in the ore reserves of the Porphyry companies as a consequence of the great strides made in the technique of mining and ore treatment. So, even if one inserted a qualifying phrase, "at an average price for the metal," after the word "profitable," the definition would still be open to criticism. Place is another factor. It is evident that a body of excellent ore in Arizona might cease to be ore in the economic sense if it were moved intact to the interior of China. However, it is with ore in its technical and scientific aspect that this chapter is concerned. Speaking in general terms, the ton of Porphyry ore as it arrives at the surface contains 25 to 70 lb. of copper minerals in the form of disseminated particles or thin coats along fracture planes. When subjected to appropriate treatment this ton yields 12 to 40 lb. of metallic copper. These ranges take into account conditions of today and of 25 years ago. Two procedures are available: (1) concentration, followed by smelting of the concentrate, or (2) leaching and precipitation, usually by electrolytic deposition. Smelting and leaching are metallurgic processes in that they involve chemical change; concentration

Jan 1, 1933

By H. J. Snyder

Both the room-temperature and 600°F (315°C) primary solid-solution phase boundaries for the silver comer of the Ag-Cd-In temary system have been determined using X-ray diffraction and metallo-graphic techniques. Solid solubility of indium in silver at room temperature and 600°F (315°C) is shown to be between 20.3 and 21.7 wt pct, and corrects the previously extrapolated value of 18 wt pct appearing in the literature. The solid solubility of cadmium in silver at room temperature, not previously established, is shown to be between 34.9 and 41.3 wt pct. The solid solubility of cadmium in silver at 600°F (315°C) is confirmed as 43.2 wt pct. The shape of the primary phase boundary line for the subject temary system appears straight at room temperature and curves con-vexly towards the solvent (silver) comer at 600°F (315°C). THIS investigation was undertaken to initiate development of the Ag-Cd-In ternary diagram by establishing the primary solid-solution phase boundary in the silver corner of the diagram. At the present time, a diagram for this ternary system is not available, while this system appears to offer potential for a variety of uses. One alloy in the system has already proven to be useful as a control rod material in nuclear reactors.1"3 To encourage additional exploration of the potential of the system an understanding of its ternary diagram would be beneficial. It is towards this end that the present study is directed. LITERATURE SURVEY In undertaking this study, a comprehensive literature survey was first conducted to find information that would be useful for guidance. Useful knowledge did result from investigating the respective solubilities of indium and cadmium in silver as indicated in the binary constitutional diagrams of the systems Ag-In and Ag-Cd and also reviewing possible shapes of ternary primary phase boundaries. Weibke and Eggers~ used metallographic techniques to establish the system In-Ag as illustrated in Fig. Is This diagram shows that silver in the solid state is capable of dissolving approximately 18 wt pct In. This solid solubility of indium in silver holds true from room temperature up to 1276°F (691°C), then decreases continuously up to 1&apos;761°F (960.5"C), the melting point of the silver. The solid-solubility limit of indium in silver established by Weibke and Eggers has been confirmed by Hume-Rothery and Reyno1ds. G Durrant&apos; used a method which consisted of microscopic examination of quenched specimens to establish the Cd-Ag system as displayed in Fig. 2.&apos; The primary phase boundary of Fig. 2 proved to be in good agreement (ie., within 1 wt pct) with other studies*&apos;1&apos; of the Ag-Cd system made using X-rays and metallog-

Jan 1, 1968

By R. E. Reed-Hill, W. H. Hartt

High-purity magnesium single crystals, oriented with basal plane parallel to stress axis, were deformed in tension at room temperature so as to form second-order (1011)- (1012) twins. Investigation by optical and replica electron microscopy revealed that these twins can support very large internal strains approaching 1000 pct and that fracture follows as a direct consequence of these strains. At low strains the basal plane within (10i1)- (10i2) twins rotates with increasing deformation until it becomes approximately parallel to the twin boundaries. This rotation is not consistent with deformation by basal slip in the double twin, but may be rationalized in terms of nonbasal slip. Observations also indicate that basal slip in the primary (1011) twin, prior to second-order twinning, may contribute to this rotation. Deformation markings that are difficult to interpret in terms of slip on previously observed systems were noted in the twin bands. A possible means of rationalizing these markings is to relate them to grain boundary shear. The fracture associated with these twins is thought to initiate by formation of voids at the twin boundaries. These grow into microcracks, with ultimate fracture occurring by tearing of the interconnecting regions. THE significance of deformation and fracture along second-order (10i1)-(10i2) twins in polycrystalline magnesium1-&apos; and many magnesium alloys4 was discussed in a previous paper.5 It was noted that this double twinning mode effectively controls the room-temperature deformation and fracture of magnesium single crystals, oriented with the basal plane parallel to the tensile axis. Reed-Hill and Robertson6 observed that, although these crystals may fracture at a macroscopic strain of less than 1 pct, shear strains up to 1000 pct could occur within (1011)- (10i2) twin bands. They concluded that the fracture was "ductile" and resulted from concentrating the deformation into a very small volume. The present research was undertaken to obtain a better understanding of the deformation and fracture associated with these twins. EXPERIMENTAL TECHNIQUES The experimental procedure involved straining high-purity magnesium single crystals in tension at room temperature. Specimens were oriented so that the applied stress direction was within 2 deg of the [1010] crystal axis. The specimen cross section was rectangular with faces closely parallel to (1210) and (0002). The specimen preparation and testing procedures have been described in detail elsewhere.5 Second-order (1011)- (1072) twins nucleated during straining were studied using optical and replica electron microscopy techniques. For the latter, cellulose acetate-carbon double replicas were employed. Observations were made on the (1210) crystal surface, which is the plane of shear for twins of this type. In addition to the single crystals, some investigations were carried out on longitudinal polycrystalline specimens. These were obtained from high-purity magnesium plate with a texture in which the basal planes of the grains tended to be nearly parallel to the specimen axis. All. polycrystalline specimens were annealed prior to testing in order to produce a coarse grain structure, permitting Laue back-reflection X-ray photographs to be obtained from grains of interest. EXPERIMENTAL RESULTS a) Deformation Within ( 101 l )-( 1072) Twins. Fig. 1 is an optical micrograph demonstrating the extent of the plastic deformation that can occur in (1011)-(10i2) twin bands. Notice at the lower left corner of the photograph the large displacement of the dark band (a polishing step) where it crosses the twins. The shear strain in the twin band at this position was computed to be 700 pct, using the ratio of step width to twin thickness. It was previously shown5 that (1011)- (1012) twin bands are often composed of small, separate twins aligned close to the macroscopic habit plane. Fig. 2 is an electron micrograph from near the upper end of the twin band in Fig. 1. This illustrates that the twin habit often does not coincide exactly with the macroscopic band habit, but may be inclined at a slightly smaller angle to the matrix basal plane. Figs. 3 through 6 are electron micrographs of the twin band in Fig. 2 illustrating successive steps in the development of deformation inside the band. A twin band such

Jan 1, 1969

By S. Stutz

Coal, like most other minerals, only exceptionally occurs in a sufficiently pare state to he directly available for general manufacturing purposes. And even where this is the case, the small coal or slack is usually more impure than the lump coal, as the slate, clay, etc., from the roof and bottom of the vein become mixed with it in the handling it undergoes. These impurities often exceed ten or more per cent. in addition to the impurities of the coal itself. The most common impurities of the coal are slate, or shale, clay, and sulphur. The latter occurs in different forms, but moat frequently as bisulphide of iron, or iron pyrites, and as sulphate of lime, or gypum. In both cases the impnrities add greatly to the amount of ash, and where they are present in considerable quantities the raw coal, and still more the coke made from it, is unfit for the manufacture of iron. Coke will coutain on an average at least fifty per cent. more ash and sulphur than the ram coal from which it is made. To the manufacturer of iron every additional per cent. of ash which his coal or coke contains is a source of additional expense, seemingly small, and yet very important in the aggregate. In the blast-furnace, for instance, the ash must be heated up to the melting-point, and, since it is composed largely of refractory substances, the consumption of carbon in melting it will be equal to at least one-half of its weight; that is, a certain part of tile coke is consumed for the melting and fluxing of the ash and is lost. Besides this, it is well enough known to the iron-master that coke containing lees ash makes the &lag or cinder more liquid and less incliner1 to stick to the walls of the furnace. Fuel containing much sulphur produces generally a white iron, poor in carbon, while from the same ore arrd flux, with a pure fuel, a good foundry iron might be obtained. The work of separating slate, sulphur, etd, from the coal has as yet only been successfully accomplished by the washing process. This process depends for its success on the differences in the specific

Jan 1, 1881

By American Institute of Mining Engineers

David J. Mack (University of Wisconsin, Madison, Wise.)—Have the authors considered that the effects reported in their paper are readily explainable on the basis of equilibrium grain boundary segregation rather than ordering? It seems to the writer that all of their experiments and observations correlate well with known behavior associated with equilibrium grain boundary segregation. Although at first glance one would tend to dismiss such a possibility because of the similarity of the gold and copper atoms, their sizes differ by 12.8 pct which is in the range where segregation at grain boundaries would be expected. Then, too, the electrochemical differences between the copper, the Cu3Au, and the gold strongly suggest that a segregation mechanism is involved in the corrosion of the Cu-Au alloys. R. Bakish and W. D. Robertson (authors&apos; reply)—The authors would like to thank Dr. Mack for his consideration of the problem of grain boundary segregation as an explanation of the observed phenomena. We had considered the problem in the following terms: Assuming a pure binary Cu-Au alloy and an ideal solid solution, the surface excess, T2= N25 — N2, of the second component (gold) may be expressed in the following way20 1 —exp (—da/kT) where 8 is the difference in surface tension of copper and gold, and a is the surface area per atom. In the present case, 6 is positive which implies that the component in excess at the boundary is gold. Since the only chemically active component in ferric chloride is copper, it does not appear that the segregation of gold is likely to increase the boundary activity. A small concentration of a third component could profoundly affect the situation. Analysis indicated only spectrographic traces of impurities, all of which are soluble in both copper and gold. Quenching experiments, reported in the paper, also tended to eliminate significant effects attributable to a third component.

Jan 1, 1958

By R. A. Stauffer

THE chief ore of lithium is spodumene, a lithium-aluminum silicate containing up to 3 pct lithium. The preparation of lithium salts from spodumene is costly because of the low concentration of the metal and the difficulty of separating it from the other alkali metals present. Dr. Kroll&apos;s and Dr. Schlecten&apos;s recent paper&apos; has reviewed various methods proposed for preparation of lithium. It will be seen from this paper that the methods proposed to date have required one or another of the lithium salts as a raw material. The high cost of these salts has been the chief item of expense in the lithium metal produced. This situation has made it interesting to investigate the possibility of producing the metal directly from spodumene. When spodumene is calcined at 1000°C in the presence of lime, lithium oxide is replaced in the ore as is evidenced by the fact that it may be leached from the reaction mixture with water.2 Free energy calculations suggested that lithium oxide might be reduced with aluminum or silicon and the lithium produced distilled from the reaction mixture by heating to about 1000°C in a vacuum. These facts taken together suggested that it might be possible to prepare lithium metal directly from spodumene by heating a mixture of the ore, lime, and a suitable reducing agent in vacuum and distilling off the lithium metal as formed. THE REPLACEMENT OF Li20 IN SPODUMENE A series of experiments were undertaken to determine the ratio of lime to spodumene necessary to free substantially all the lithium oxide present in the ore. The spodumene used in these experiments was supplied by Foote Mineral Co. in the form of powder of about 200 mesh. Analysis of the spodumene was as follows: [ ] Lime (cp -200 mesh) was added in various ratios to spodumene and thoroughly mixed in a ball mill. Two hundred gram samples of spodumene-lime mixtures were charged loosely in fireclay crucibles and held at 1000°C in a gas-fired furnace for 5 hrs. The product in each case was ground to pass 140 mesh and then placed in a thimble in a soxhlet extractor. Extraction with water was carried on for 6 hrs. After this period the extract was reduced in volume by evaporation in order to precipitate dissolved lime and was then filtered and titrated with 1/4 normal hydrochloric acid. After correcting for residual calcium oxide in solution, the alkali present was calculated as lithium oxide. The results of these experiments are shown in Table I and Fig I. At lime-spodumene ratios less than 1.5, the products were invariably fused. At the ratio of 1.5 and above, the product was loosely sintered with little evidence of fusion. When the ratio of lime to spodumene was three, replacement of alkali oxides in the

Jan 1, 1947

By W. N. Logan

WHAT is mineral wool? This question is frequently asked by those unacquainted with its manufacture. The word "mineral" suggests that it is of mineral origin; the word "wool" suggests that it is of animal origin; but the only similarities it has to wool are its fibrous character and its white fleecyness. Mineral wool is a fiber produced by melting rock to a glasslike condition and blowing the glass into fine white, wool-like threads. A -number of the products fabricated from-mineral wool are used for some form of insulation, but mineral wool is adaptable to many other uses. It is used in the manufacture-of pipe covering designed to with; stand the high temperatures produced in steam pipes. In a similar form of insulation it is used to cover boilers and furnaces. It is used in ,the fabrication of upholstery tow for sofas and car seats: In acoustics it has many uses, such as acoustifibroblock, which is used in floors to destroy sound and vibration, and acoustic mat, which is used under carpets to destroy sound. In the insulation of houses, loose wool and granulated wool are used beneath attic floors and between the studding in frame buildings to prevent the escape of heat in winter and the entrance of heat in summer. Mineral wool is used also in fabrication of linofelt, which is a quilted form of insulation; in fibrofelt, which is an insulating board; in the fabrication of lith, which is an insulating block; in anti-fibroblock ,which is used in insulation and refrigeration; in flexfelt; in loose wool; in pressed block; in heavy oiled wool; in dark oiled block; and for many other purposes. The materials used in the manufacture of mineral wool are of two kinds. The first is a rock which contains silt, clay and silica, with smaller amounts of lime and magnesia. The second is a more highly calcareous rock which may carry a small amount of magnesia. The latter is used as flux to assist in the melting of the former. The relative proportion of the alumina-iron-silica content to the lime-magnesia content is normally as fifty to fifty but a considerable range is possible.

Jan 1, 1932

By G. G. Hancock, H. H. Johnson

Hydrogen gas at atmospheric pressure is shown to cause substantial embrittlement in a martettsitic high-stretzgth steel. Subcritical crack growth is observed at very lom stresses and with high growth rates. It is suggested that an adsorbed layer of hydrogen atoms at the crack-tip surface provides the damaging hydrogen. Oxygen in small quantity, as little as O.7 pct by volume, is shown to eliminate subcritical crack growth in gas environments caused by hydrogen or water vapor. However, dissolved oxygen in water has little or no influence upon crack-growth rates. Oxygen-stopped cracks may be restarted by water, or by hydvogen or water vapor if oxygen is removed from the environment. These observations are interpreted in terms of preferential adsorption of oxygen at the crack tip and the formation of an oxide barrier. RECENT investigations1-3 have demonstrated that environmental factors are frequently responsible for delayed failure in martensitic high-strength steels. The environment causes crack initiation from preexisting cracklike flaws at unexpectedly low stresses, often far below the uniaxial yield strength. The crack then propagates at a rate controlled by the environment and the crack-tip stress-field intensity; during this period crack propagation will cease if either the stress or the aggressive environment is removed, and this may be considered a definition of subcritical crack growth. Fracture occurs when the crack has grown to a critical length, such that the fracture toughness of the steel is exceeded. Several liquids are known to cause delayed failure, but water and water vapor are the most severely damaging of the environments investigated to date.&apos;-3 It has been suggested that hydrogen produced during corrosion reactions may be the actual embrittling agent2 The severe embrittlement caused by water vapor inevitably raises the question as to whether other gas environments are damaging. Previous work4&apos;5 has demonstrated that high-pressure hydrogen (2250 psi or greater) is an effective embrittling medium, as measured by such criteria as reduction in area, notch tensile strength, and time to failure. Moreover, the embrittlement was eliminated by the addition of small quantities of air or oxygen to the high-pressure hydrogen, but it was not influenced by additions of nitrogen or argon.4 In the present study attention is focused upon gas environments at atmospheric pressure, in particular hydrogen and oxygen. The influence of these constituents upon the initiation and growth of a crack from a pre-existing cracklike flaw in a high-strength steel was determined directly by the electric-potential method of monitoring crack growth. MATERIALS AND PROCEDURE The H-11 steel was supplied by the U.S. Naval Research Laboratory as 3 by 12 by 0.065 in. sheet specimens with 1-in. transverse center slots. The slot tips were finished by Elox machining to a radius of 0.001 in. or less. The yield strength was 230,000 psi; chemical composition and heat-treatment schedule are given in Table I. The experimental apparatus, precracking procedure, and incremental loading sequence have been described previously.3 In the only significant change, precracking was sometimes carried out by a hydrogen embrittlement and baking technique. All experiments were conducted at room temperature; the hydrogen gas environment was purified by a commercial palladium purifier. Crack initiation and propagation were followed by the electric-potential method,&apos;-3 using a calibration that has been recently dicussed. Stress-field intensities at the crack tip were computed by the conventional Irwin frmula; the plasticity correction was negligible and therefore not included. EXPERIMENTAL RESULTS A striking brittleness associated with molecular hydrogen at atmospheric pressure is demonstrated by the data in Table I1 and Fig. 1, which indicate that subcritical cracks in hydrogen initiate at lower stress-field intensities and propagate more rapidly than in fully humid argon. Ki and Kf are the crack-tip stress-field intensities at initiation and termination of subcritical crack growth, respectively. Termination, of course, corresponds to fracture. In both hydrogen and humid argon Ki is less than Kf

Jan 1, 1967