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By Herbert Dumont

Since 1947 Preussag AG Metal1 has used a process for fuming zinc- and lead-containing dump slags and residues from vertical retorts in a half-shaft furnace at their Hüttenwerk Harz at Oker. Contrary to the classic shaft furnace, only one side of the half-shaft furnace is fitted with tuyeres. The opposite side is a bricked slope. The upper shaft section is piped. There zinc vapor and combustion gases are burned by sucked-in air. Gases and fume enter a boiler located on the rear length of the furnace via a piped fire bridge. The gases are then cooled in an air preheater prior to dedusting in a bag filter. The furnace is charged with briquettes of metal-bearing materials, coal and pitch. The leaded zinc oxide fume is comparatively rich in both lead and zinc. The copper in the feed is recovered in low-copper matte. The slag can be discarded. The Oker plant comprises 13 furnaces of 2.9 to 4.9 m length in the tuyere area. Two other plants in Italy and Spain are processing zinc leach residues by this technique. Fuming of zinc-lead-oxide ores as well as partially roasted sulfide- zinc-lead-copper bulk concentrates will be possible.

Jan 1, 1970

By Donald B. Evans, Robert D. Pehlke

The solubility of nilrogen in liquid binary alloys of iron with Litanium. zivconium, columbium, vanndiurn, and tantalum was measured for alloy composiLions up to the solalbility limils of lhe alloy nitrides. All five alloying agents were found to decrease markedly the activity coefficient of nitrogen in liquid ivon. The metal/nitvogen mole ralios in the alloy nitrides formed were generally .found to be slighlly greater than 1.0, but in no case greater than 1.5. From the experimental data, the standard free energies of fortmation of titanium and zir-conium nitrides have been calculated for the Lemperaluve range 1550° to 1750 C. The solublily Products for columbium, tantalum, and vanadium nitrides are also reported. A number of research investigations have examined the effect of refractory metals on the solubility of nitrogen in liquid iron. Although data on zirconium are not available, investigators are in agreement that titanium, vanadium, columbium, and tantalum markedly increase the solubility of nitrogen in liquid iron. This fact alone makes desirable the acquisition of thermodynamic data for these elements in liquid iron. Since refractory metals are known to be stable nitride formers, they have been suggested as steel denitrifying agents, and some of their nitrides have recently been considered as containment materials for liquid iron and iron alloys. Most available thermodynamic data for these metals relate to their dilute concentrations, but effective thermodynamic treatment of these applications requires data at concentrations near the solubility limit of the alloy nitride. Although some work has been done at relatively high alloy concentrations in liquid iron (particularly for vanadium 2,3 and titanium 2,4), the results have been somewhat contradictory. Disagreement may be partly attributed to the fact that the compositions of most refractory metal nitrides have been shown to be nonstoichiometric, and to vary 2,5-8 depending on the temperature and nitrogen gas pressure with which the solid nitride phase is in equilibrium. One purpose of this study consequently has been to determine the compositions of the refractory metal nitrides precipitated from a liquid iron solution. EXPERIMENTAL PROCEDURE Rao and Parlee2 and Evans and Pehlke 9 have discussed the technique for measuring the solubility product of an alloy nitride phase in liquid iron by finding the point of departure of the nitrogen solubility from Sieverts' law. The method consists of measuring the solubility of nitrogen in a melt of iron containing a known concentration of a second metal as a function of the nitrogen gas pressure over the melt. In this study the second metal was one of the refractory metals titanium, zirconium, columbium, vanadium, or tantalum. When the nitrogen pressure at which the refractory nitride forms is reached, a deviation of the measured solubility of nitrogen in the melt from Sieverts' law is observed in the form of a "pressure halt." The concentration of nitrogen in the melt associated with this breakpoint in the nitrogen-absorption curve is then used to calculate the nitride solubility. The Sieverts method was used to measure nitrogen solubility as a function of nitrogen pressure and temperature. The experimental equipment for this technique has been previously described in detail. 1,9 Charge materials used were vacuum-melted high-purity iron (Ferrovac-E) and the best commercial grades of the refractory metals obtainable (in all cases at least 99.8+ pct pure). Recrystallized alumina crucibles were used to hold all melts except those containing zirconium, for which zirconia crucibles were necessary. Temperatures were measured by a disappearing-filament type optical pyrometer sighted vertically downward on the melt surface through a 1/4-in.-diameter sight hole in the crucible lid. By means of a technique previously described, 9 in which the refractory-metal nitride was precipitated at one temperature then redis-solved by raising the temperature 50°C and precipitated again at a higher temperature, it was possible to obtain data over a temperature range of up to 200°C on a single melt. It was found that this technique could not be used with melts containing zir-

Jan 1, 1965

By Howard A. Meyerhoff, J. Earl Frazier

It is not known when silica sand was first noticed along the north coast of Puerto Rico, but the first mention of its occurrence was made in 1922, by N. L. Britton,1 who described its presence in isolated patches extending from Loiza westward beyond Manati. Further observations were made in 1925 and 1926 by Meyerhoff,2 who extended the known occurrences still farther westward to the low hill belt in the Quebradillas limestone immediately south of Hatillo. The extraordinary purity of the sands, which in most localities exhibit no contamination from the non-siliceous materials surrounding them, was quickly appreciated, and the feasibility of utilizing them for the manufacture of glass was investigated, initially by the Committee on Mineral Resources3 and later (1936) by the Puerto Rico Recon-structionAdministration and by H. C. Ray, mining engineer of the Insular Bureau of Mines. In 1934 samples submitted to the Hazel Atlas Glass Co., of Washington, Pennsylvania, were reported to have the composition as shown in the table on column two. Appreciation of the quality of the sand prompted geological and quantitative studies of the deposits, as well as cornmercial investigations to determine the feasibility of utilizing it locally or on the mainland for the manufacture of glass containers. Distribution of the Sands The quartz sands consistently lie within the outcrop area of the Quebradillas limestone, the youngest of the Miocene formations in the Tertiary coastal plain that fringes the northern coast of the Island. Many of the deposits are closely associated with limestone outcrops, but some appear to be embedded in lagoonal sediments at some distance from rock exposures, and at least one deposit, near Dorado, has been reworked by waves and littoral currents. With this single known exception, the deposits consist of irregular, patternless patches of white sand, which have sharply defined contacts with the surrounding material. Although patches of sand are present in a 90-km. belt that is not more than 5 km. wide, extending from Loiza to Hatillo, they attain maximum size, purity and number in the north central coastal area between Dorado and Barceloneta. Fifty separate deposits have been mapped in Lago Tortuguero and to the south of it, some as small as 50 ft. in diameter but

Jan 1, 1948

By J. Earl Frazier, Howard A. Meyerhoff

It is not known when silica sand was first noticed along the north coast of Puerto Rico, but the first mention of its occurrence was made in 1922, by N. L. Britton,1 who described its presence in isolated patches extending from Loiza westward beyond Manati. Further observations were made in 1925 and 1926 by Meyerhoff,2 who extended the known occurrences still farther westward to the low hill belt in the Quebradillas limestone immediately south of Hatillo. The extraordinary purity of the sands, which in most localities exhibit no contamination from the non-siliceous materials surrounding them, was quickly appreciated, and the feasibility of utilizing them for the manufacture of glass was investigated, initially by the Committee on Mineral Resources3 and later (1936) by the Puerto Rico Recon-structionAdministration and by H. C. Ray, mining engineer of the Insular Bureau of Mines. In 1934 samples submitted to the Hazel Atlas Glass Co., of Washington, Pennsylvania, were reported to have the composition as shown in the table on column two. Appreciation of the quality of the sand prompted geological and quantitative studies of the deposits, as well as cornmercial investigations to determine the feasibility of utilizing it locally or on the mainland for the manufacture of glass containers. Distribution of the Sands The quartz sands consistently lie within the outcrop area of the Quebradillas limestone, the youngest of the Miocene formations in the Tertiary coastal plain that fringes the northern coast of the Island. Many of the deposits are closely associated with limestone outcrops, but some appear to be embedded in lagoonal sediments at some distance from rock exposures, and at least one deposit, near Dorado, has been reworked by waves and littoral currents. With this single known exception, the deposits consist of irregular, patternless patches of white sand, which have sharply defined contacts with the surrounding material. Although patches of sand are present in a 90-km. belt that is not more than 5 km. wide, extending from Loiza to Hatillo, they attain maximum size, purity and number in the north central coastal area between Dorado and Barceloneta. Fifty separate deposits have been mapped in Lago Tortuguero and to the south of it, some as small as 50 ft. in diameter but

Jan 1, 1948

By G. W. Binkley, R. E. Collins, G. K. Dumbauld

A mathematical analysis has shown that the primary factors affecting the deposition of cement in unfractured perforations during squeeze-cementing operations are: the properties of the cement slurry, the geometry of the perforations, and the filtration time. The validity of the analysis has been substantiated by laboratory investigations. The information presented in this paper makes possible the prediction of the rate of deposition of cement in and about unfractured perforations under given squeeze-cementing conditions, the proper filtration time to control the amount of deposition to any desired value, and the deposition properties needed in cement slurries to restrict to any desired degree the formation of nodes of cement .Solids inside the casing. INTRODUCTION The deposition of solids against a permeable medium by the process of filtration is an important property of a cement slurry. General recognition of the role of filtration in the use of cement in wells is evident in view of the fact that several patents on low-water-loss cements have been issued during the past few years. In the conventional, high-pressure squeeze-cementing technique, a large volume of cement slurry is usually displaced into the area surrounding the perforated interval after the formation has been fractured hydraulically.&apos; Near the end of the job, the pumping rate is slowed or stopped intermittently in an effort to obtain a high pressure in the wellbore. The way in which a high pressure is obtained is not understood thoroughly. but it is be- lieved to be caused by the deposition of a rigid mass of compacted cement particles either in the fractures of the formations or inside the casing opposite the perforated interval. In a method of squeeze-cementing introduced several years ago, a small amount of cement slurry is squeezed into the perforations at a low pressure to avoid fracturing the formation. The filling of the unfractured perforations with cement particles by the process of filtration is important to the success of this technique. Early in the development of this low-pressure squeeze-cementing technique, laboratory and field-size experiments showed that conventional, neat cement slurries were unsatisfactory if the tubing was extended into or through the perforated section of the casing. The extremely high filtration rate of neat cement slurries caused the deposition of a compacted mass of cement inside the casing and made it impossible to remove excess cement by reverse circulation and difficult to withdraw the tubing. Because the need for cements with a reduced filtration rate was obvioils and urgent, modified cements containing 12 per cent bentonite were used until research was completed on modified cements containing 25 per cent bentonite.< These modified cements were useful in the solution of the immediate problem, but the following questions remained unanswered: (I) what is the optimum filtration rate of cement slurries for this application, (2) how long should the squeeze pressure be applied. and (3) how great are the effects of squeeze pressure and well temperature on the rate of deposition? Furthermore, the relationship of the filtration properties of cement slurries to the dimensions of the perforations and the wellbore was unknown. In order to obtain information relative to these basic considerations, a systematic evaluation of all the factors involved in the deposition of Cement during low-pressure squeeze-cementing operations was initiated. Although the work was directed toward an evaluation of the factors influencing the deposition of Cement in the low-pressure squeeze-

By L. E. Murr, P. J. Smith

A study has been made by transmission electron microscopy of thin foils of 304 stainless steel fatigued external to the electron microscope in reversed bending, and of thin foils fatigued directly within the microscope in alternating tension. The build-up of stacking faults in the thin foils during fatigue zoas correlated with the dislocatirm structures found in thin films prepared fror fatigued bulk specimens. The performance of the special devices designed for fatigue of thin foils so outlined and the importance of alternative methods of preparation of more uniform fatigue specimens bY vapor deposition are emphasized. INVESTIGATIONS on fatigued bulk aluminum1,&apos; and stainless stee13j4 have revealed the existence of dislocation substructure on examination by transmission electron microscopy of electrolytically thinned foils representative of these bulk specimens. While this technique has proved extremely valuable, it has several shortcomings. First, the method of fatiguing bulk specimens and then thinning to foil for electron-transmission observation allows only one observation of internal structure at any one portion of the fatigue life. Second, thinning the bulk fatigued specimens to foil results in the loss of at least one original surface. Thus, what one sees in the remaining electron-transparent sections is an internal dislocation or fault structure which in many cases cannot be correlated with the original surface markings. This is an undesirable feature, since it is well-known that metal surfaces play an important part in the fatigue process.5 An obvious third undesirable feature of the thinning-from-bulk technique is the fact that static observations have difficulty (in the case of fatigue) explaining the mechanism of a dynamic process. What is required then is a method whereby a selected thin area can be continuously observed either while undergoing cyclic deformation or at various fixed stages of fatigue deformation. While Murr and wilkov6 have reported some success with an apparatus designed to fatigue thin metal foils directly within the electron microscope, the nature of the specimen-mounting procedure and the mechanical features involved in the adaptation of the fatigue device to the electron microscope make this method difficult to operate. It was not possible, for example, to make frequent observations of a selected area because of difficulty in maintaining a chosen area in a stable viewing position inside the electron microscope. Except for the build-up of a dislocation substructure and what are commonly referred to as "slip striations", little else has been reported from observations on thin-foil sections prepared from bulk fatigue specimens. segal17 has found "slip striations" in stainless-steel fatigued specimens which were electropolished from both sides, but gave no explanation as to their origin or identity in terms of lattice imperfections. The research to be reported in this paper was undertaken with the following objectives in mind. First, an attempt was made to devise a technique or techniques whereby thin metal foils could be fatigued and repeatedly observed by transmission electron microscopy. Second, it was hoped that some correlation could be made between deformation striations found in fatigued thin transmission specimens and thin foils prepared from bulk fatigued specimens. These investigations illustrate quite convincingly that a feasible method is available for the direct study of the fatigue mechanism and similar dynamic phenomena in thin transmission specimens inside the electron microscope. I) EXPERIMENTAL METHODS Three modes of specimen fatigue and observation of fatigue damage were used. These involved fatigue of thin-foil specimens in a special arrangement external to the electron microscope and observation of a selected area at various stages in the fatigue life, the fatigue of thin-foil transmission specimens inside the electron microscope, and the fatigue of bulk specimens external to the electron microscope followed by thin-foil preparation for direct observation at predetermined stages. Design of the External Fatigue Clip and Specimen Holder for the Hitachi H.U.11 Electron Micro-scope. The purpose of the fatigue clip was to provide a reversed bending fatigue stress to a thin-foil transmission specimen outside the electron microscope. In order to accomplish this, a flat-bottomed, U-shaped brass clip was made as shown

Jan 1, 1965

By D. K. Das, P. A. Beck, S. P. Rideout

IN a previous publication1 1200°C isothermal phase diagram sections were given for the Cr-CO-Ni, Cr-Co-Fe, Cr-Co-Mo, and Cr-Ni-Mo ternary systems, in which the a phase formed narrow, elongated solid solution fields. The present investigation is concerned with the 1200°C isothermal sections of the Co-Ni-Mo, Co-Fe-Mo, and Ni-Fe-Mo ternary systems. A prominent feature of these systems is the presence of narrow, elongated µ phase fields. The crystal structure of the phase designated as µ both here and in the previous publication1 was determined by Arnfelt and Westgren.2 For the (CO, W)µ phase, named by them Co,W, (and also frequently designated as a), these authors found that the crystal system is hexagonal-rhombohedra1 and the space group is D53d — R3,. Westgren and Mag-neli3 later found that isomorphous phases exist in the Fe-W and the Fe-Mo systems (these phases are often referred to as < and E, respectively). Henglein and Kohsok4 stated that the phase described by them as Co7Mo,; (otherwise frequently designated as c) is also isomorphous with the above three. The Co-Fe-Mo system was investigated at 1300°C by Koester and Tonn,5 who found a continuous series of solid solutions between (Co, MO)µ and (Fe, MO)µ Koester6 also indicated similar uninterrupted solid solutions in the Ni-Fe-Mo system. However, since the Ni-Mo binary system does not have a phase isomorphous with F, Koester&apos;s diagram is expected to be erroneous. No data appear to be available in the literature concerning the Co-Ni-Mo system. The face-centered cubic (austenitic) solid solut,ions of iron, nickel, and cobalt, which are quite extensive in all three systems at 1200°C, are here designated as the a phase. The body-centered cubic (ferritic) solid solutions, based on iron, are designated in this report as the ? phase, in conformity with the nomenclature used previously.&apos; Experimental Procedure The alloys were prepared by vacuum induction melting in zirconia and alumina crucibles. The lot analyses for the metals used have been given.&apos; The number of alloys prepared was 46 for the Co-Ni-Mo system, 65 for the Co-Fe-Mo system, and 113 for the Ni-Fe-Mo system. The compositions of these alloys were selected with due regard to maximum usefulness in locating phase boundaries. The alloy specimens were annealed at 1200°C in an atmosphere of purified 92 pct helium and 8 pct hydrogen mixture. Alloys consisting almost entirely of the face-centered cubic austenitic a phase, or of the body-centered cubic ferritic c phase were double-forged with intermediate annealing. The double-forged specimens were then final annealed for 90 hr at 1200 °C and quenched in cold water. Alloys containing considerable amounts of any of the other phases could not be forged. Such specimens were annealed for 150 hr at 1200°C and quenched. Microscopic specimens of all alloys were prepared by mechanical polishing, in many cases followed by electrolytic polishing. Description of the polishing and etching procedures used and tabulation of the intended compositions of the alloys prepared are being published in two N.A.C.A. Technical Notes.7,8 , Many of the alloys were analyzed chemically and, in general, the results are in excellent agreement with the intended compositions. X-ray diffraction samples were prepared by filing or crushing homogenized alloy specimens and by reannealing the obtained powders in evacuated and sealed quartz tubes. After annealing for 30 min at 1200°C the tubes were quenched into cold water. X-ray diffraction patterns were made with unfiltered chromium radiation at 30 kv, using an asymmetrical focusing camera of high dispersion. X-ray diffraction and microscopic methods were used jointly to identify the phases present in each specimen. The amounts of the phases in each alloy were estimated microscopically. The phase boundaries were located by the disappearing phase method. The results were used to construct 1200°C isothermal sections for the three ternary phase diagrams. The accuracy of the location of the phase boundaries determined in this manner is estimated to approximately ±1 pct of each component. The portion of the three phase diagrams lying between the µ, P, and 6 phases on the one hand, and the molybdenum corner on the other, has not been investigated. Recently Metcalfe reported0 a high temperature allotropic form of cobalt on the basis of dilatometric results and of cooling curves. In the present work no attempt was made to search for the new phase in the cobalt corner of the Co-Fe-Mo and Co-Ni-Mo systems. No alloy was prepared with more than 80 pct Co; the alloys used were intended to locate the boundary of the a phase saturated with cL. The microstructures of the quenched a alloys near the cobalt COrner gave no suggestion of an in-suppressible transformation On quenching. The location of the boundaries of the a + ? two-phase fields in the Fe-Ni-Mo and Fe-CO-MO systems was determined entirely by the microscopic method. The face-centered cubic a alloys near the ? field transform partially or wholly into the body-centered cubic ? phase on quenching from 1200°C to room temperature. The ? formed in this manner has an

Jan 1, 1953

By K. R. Carson, J. Weertman

An attempt is made to ascertain the mechanism of tangle and cell formation and its dependence upon dislocation-interstitial carbon interactions. The strain-hardening behavior of single crystals of 3.25 pct Si-Fe was determined at 300° and 425°K and under conditions of both continuous and interrupted tensile strain. Significantly enhanced hardening was observed in crystals deformed at the elevated temperature, and it was further accentuated by interrupted straining. Transmission electron microscopy was used to study the resultant dislocation structures. Strain aging was found to aid tangle and cell formation at 425°K, but at both temperatures embryo tangles formed solely from primary glide dislocations, presumably by a process involving cross slip and "mushrooming". IN the course of plastic deformation all bcc metals and alloys develop a dislocation structure characterized by loose-knit groups of tangled dislocations. With increasing strain the tangles become more tightly knit and grow larger; finally a three-dimensional cellular substructure is formed:1 This process has been observed with the transmission electron microscope.&apos;-l7 However, most investigations were confined to the study of nearly pure polycrystalline metals at relatively low temperatures. At intermediate temperatures, 0.17 to 0.14 Tm where T, is the melting temperature in degrees absolute, the mobility of interstitial impurities such as carbon is high enough to permit migration to nearby glide dislocations but is still low enough so that a significant drag force is exerted.18,19 it is also in this temperature range that a hump occurs in the curve of work-hardening rate vs temperature for iron. Analogous plots for tantalum" and columbiumzo show a definite upward trend in the work-hardening rate. Keh and Weissman1 have pointed out that this behavior may be explained solely on the basis of changes in the dislocation configuration: at low temperatures the dislocations tend to be relatively straight and uniformly distributed, but at intermediate temperatures tightly knit tangles and cellular substructure appear. The interference of these tangles with glide dislocations causes the observed increase in the work-hardening rate. This explanation appears reasonable, yet one might ask what factors cause tangle formation to be so favorable at intermediate temperatures. It seens likely that the strong dislocation-interstitial interactions which are known to occur in this temperature range are at least partly responsible," with the magnitude of the effect being proportional to the interstitial concentration. The purpose of the present work is to study the relationship between tangle formation and strain hardening in a bcc metal in the temperature range 0.17 to 0.4 Tm. Particular emphasis was placed upon a study of the effects of interstitial-dislocation interactions. Single crystals of 3.25 pct Si-Fe containing about 200 ppm of C in solid solution were used in the investigation for the following reasons: 1) The mobility of interstitial carbon in 3.25 pct Si-Fe is negligible at 300°K but increases rapidly at slightly elevated temperature22. Hence, differences between the flow curves and dislocation structures of crystals deformed at 300°K, 0.17 T,, and crystals deformed, say, at 425°K, 0.24 Tm, should be appreciable because of the enhanced dislocation-carbon interactions at the elevated temperature. This effect was accentuated in some samples by interrupted straining, thereby introducing a certain amount of aging. 2) Near room temperature, slip in suitably oriented 3.25 pct Si-Fe single crystals is largely confined to the (110) planes.23&apos;24 Dislocation structures formed under conditions of single glide are the least complicated and their method of formation is the most easily discernable. 3) Dislocations in Si-Fe can be tightly locked with carbon atmospheres by a low-temperature aging treatment. The subsequent thinning of samples to foil thicbess causes little or no rearrangement in the dislocation structure.25 EXPERIMENTAL PROCEDURE Large single-crystal sheets of 3.25 pct Si-Fe were donated by Dr. C. G. Dunn of the General Electric Research Laboratory, Schenectady, N. Y. The orientations of the sheets were determined and slabs 1.0 by 0.25 by 0.05 in. were cut such that the desired tensile axis corresponded to the long dimension. The slabs were mechanically polished and subsequently decar-burized by heating at 1000°C for 3 days in a flowing wet-hydrogen atmosphere. A carbon content of about 200 ppm was introduced by heating at 805°C for 25 min in a flowing atmosphere of dry hydrogen containing heptane vapor. Shaped copper tools were then used to spark-machine at 0.125 by 0.50 in. gage length onto each slab. Vacuum annealing at 1225°C for 2 days followed by a quench into the cold end of the furnace to retain carbon in solid solution concluded the soecimen preparation. Continuous tensile flow curves for crystals of severa1 orientations Were obtained both at 300&apos; and 425°K. A strain rate of 6.67 x 10-4 Per set was used in these and all other tests. Crystals oriented for single glide, B and D in Fig. 1, were subjected to a 3.5 pct plastic elongation to insure uniform slip along the gage length; they were then immediately subjected to interrupted strain cycling as indicated in Fig. 2(a). Each cycle consisted of unloading to 1.5 kg per sq mm, holding

Jan 1, 1969

By Pol Duwez

The effect of the rate of cooling on titanium, zirconium, and thallium has been measured. For titanium-molybdenum alloys, it has been shown that for molybdenum concentration up to 8 pct the rate of cooling has no effect on the transformation temperature, but this temperature decreases progressively with increasing molybdenum content. HIGH strength to weight ratio and remarkable corrosion resistance have often been advanced as the main reasons for the present widespread interest in titanium. For the physical metallurgist, the existence of an allotropic transformation in titanium is another important factor. As in the case of iron, an allotropic transformation may be the fundamental property upon which the response of Ti-base alloys to heat treatment will depend. It is therefore important to study the mechanism of the allotropic transformation in pure titanium and the effect of alloying elements on this transformation. The existence of an allotropic transformation in titanium was reported in 1931 by Schulze.&apos; Later, De Boer et al.&apos; determined the transformation temperature from a discontinuity in the electrical resistivity at 882"42O°C. According to recent work," the transformation temperature is 882.5"&1°C. The crystal structure of the room temperature a phase is hexagonal close-packed and the high temperature fi phase is body-centered cubic.&apos; It is well known that the high temperature /3 phase of pure titanium cannot be retained by quenching to room temperature. Several investigators&apos;-&apos; have shown that in alloys of titanium with metals which are soluble in the @ phase (for example, nickel, molybdenum, chromium, or manganese), the /3 structure can be retained, providing the concentration of the alloying element is greater than a certain critical value. Below this critical value, the alloys transform during quenching, at least partially, into a supersaturated solid solution having the a. structure. This behavior is very similar to that found in some iron binary alloys (Fe-Ni and Fe-Mh, for example) and is an indication that the transformation might occur by means of a shear mechanism analogous to that observed in the austenite-martensite reaction. The present investigation is mostly concerned with the effect of the rate of cooling on the /3 to a transformation. In the first portion of this paper, the results obtained on pure titanium are described. Two other pure metals, zirconium and thallium, were also investigated, because they both have an allotropic transformation like titanium, from an hexagonal close-packed to a body-centered cubic structure. For purposes of comparison, the effect of rate of cooling of the y to a transformation of iron was included in the experimental program. The second part of this paper deals with Ti-Mo alloys. The equilibrium phase boundaries involving the solid state reactions on the Ti-rich side of the system were determined and a study was made of the effect of the rate of cooling on the transformation of the high temperature /3 solid solution. Experimental Procedure Since the main object of the present investigation was the determination of the effect of the rate of cooling on a transformation temperature, the best technique available was that used by Greninger" in his study of the martensite arrest in carbon steels. This method consists of heating a very small sample of metal to which fine thermocouple wires are .attached, cooling the sample rapidly by means of a blast of helium, and recording the temperature vs. time curve on an oscillograph. The apparatus used in the present experiments was very similar to that described by Greninger, except that the heating coil was made of molybdenum wire (0.040 in. in diam) and the assembly was placed in a bell jar under vacuum of 10" mm Hg or less. The specimen con-

Jan 1, 1952

By P. Crowther, G. J. Lamprecht

The solubilities of silver, zinc, and cerium in liquid sodium, in the temperature ranges 100 to 270°C, 190° to 550°C, and 120" to 460°C, respectively, have been determined. From the solubility data the heat the entropy the partial molal enthalpy of mixing the excess entropy and the partial molal free energy of solution for the systems Nu-Ag and Na-Zn have been calculated. For the system Na-Ce the observed negative is discussed in terms of the solubility of the oxide Ce2O3. In an earlier publication the results obtained in the study of the solubility of tin&apos; in liquid sodium are presented, as well as the detailed analytical procedures used. 1) REAGENTS Spectroscopically pure metals as supplied by Johnson Matthey and Co, were used to produce the following tracers: 253-day Ag110, 245-day zn65, and 325-day ce141. The tracers were prepared by irradiation in a thermal neutron flux of 4 x 10 13 neutrons cm-2 sek-1. To obtain a uniform amount of the required specific activity, needed for each solubility experiment, the radioactive metal was diluted with the corresponding inactive metal, by melting them together in an inert atmosphere. The liquid sodium used contained 11 ±2 ppm of O,1 determined by the vacuum distillation method.&apos; The oxygen was assumed to be present as the oxide NaD. 2) THE SYSTEMS: SODIUM-SILVER AND SODIUM-ZINC Plots were made of the log of the mole fraction of silver, Fig. 1, and of zinc, Fig. 2, dissolved in the liquid sodium vs reciprocal absolute temperature. The equations for the solubilities, based on the least-squares fit to each plot, are: where Xi is the mole fraction metal dissolved in sodium, T is the absolute temperature, and s is the standard deviation in the value of log Xi. The heats and the entropies lution were calculated from the solubility data by In neither of the two cases was any intermetallic compound formed between sodium and the solute metal as was the case for tin.&apos; Thus, for the silver and zinc systems the pure metal was taken as the reference phase. Since the solids in equilibrium with the liquid sodium were the pure metals, one can calculate the partial molal enthalpy of mixing and

Jan 1, 1969

By N. S. Kenny, A. A. Burr

THE purpose of this note is to present evidence that vacancies, which have been produced by quenching from a high temperature, alter the rate of strain-hardening of an hep single crystal. The majority of investigations of the effects of quenched-in vacancies on the yield stress of metals have been made using fee samples in the form of thin wires. However, there is an inherent disadvantage in using such wires to study the effects of vacancies on the rate of strain-hardening of metals because fee wires begin stage II slip either immediately upon yielding or very shortly thereafter. When stage II slip occurs, very rapid strain hardening also occurs, masking the effects of vacancies on the rate of hardening. In this investigation single crystals of magnesium hep were studied since magnesium has only one slip plane at low temperatures and has, therefore, an extensive easy glide region. In addition, the effect of both static and dynamic recovery on the rate of hardening were eliminated by testing in liquid nitrogen. Both forms of recovery occur in hep metals by dislocation climb, which is a diffusion controlled mechanism and is negligible at liquid nitrogen temperatures. Finally, the dependence of the strain-hardening rate on the crystal orientation was eliminated by using the equations of Schmid and Boas.&apos; Variations in the strain-hardening rate could, therefore, be attributed to the presence of vacancies. Single crystals in the form of rods approximately 5 mm in diam and 6 cm long were grown by a modified Bridgman technique from commercial high-purity magnesium (99.97 pet) supplied by the Dow Chemical

Jan 1, 1962

By Sylvan Cromer

The need for a clear understanding of the physical nature of the flow of gas-liquid mixtures in vertical pipes is ever becoming more apparent. This type of flow is encountered when gas and oil are produced from a well; when water is removed from gas wells with siphon lines and when liquids are elevated by means of air or gas lift. Although a number of investigator1-7 have published data on the flow of gas-liquid mixtures, in only a few cases has the experimental setup been devised to permit visual study. In the fields of heat transmission, such as the boiling of liquids and the study of the critical phenomena of the hydrocarbons, researchers have been able to throw additional light on heretofore unexplainable happenings through actual observation in glass apparatus. This investigation was therefore undertaken in order to obtain qualitative as well as quantitative results for air-water flow. Experimental Apparatus and Procedure The flow column used in these tests was made of standard 2-in. pipe and was approximately 98 ft. in height. Pyrex observation sections 2 ft. long having the same internal diameter as the wrought-iron pipe were placed at 14-ft. intervals in the column. The bottom of the tube was cut off square and terminated in the mixing chamber. No perforated nipple or footpiece of any kind was used. To the top of the column was fastened a semicircular return bend having a 4-ft. radius. The flow column was supported by a standard cable-tool drilling derrick (Fig. 1) into which were built observation platforms at each Pyrex section.

Jan 1, 1940

By Sylvan Cromer

The need for a clear understanding of the physical nature of the flow of gas-liquid mixtures in vertical pipes is ever becoming more apparent. This type of flow is encountered when gas and oil are produced from a well; when water is removed from gas wells with siphon lines and when liquids are elevated by means of air or gas lift. Although a number of investigator1-7 have published data on the flow of gas-liquid mixtures, in only a few cases has the experimental setup been devised to permit visual study. In the fields of heat transmission, such as the boiling of liquids and the study of the critical phenomena of the hydrocarbons, researchers have been able to throw additional light on heretofore unexplainable happenings through actual observation in glass apparatus. This investigation was therefore undertaken in order to obtain qualitative as well as quantitative results for air-water flow. Experimental Apparatus and Procedure The flow column used in these tests was made of standard 2-in. pipe and was approximately 98 ft. in height. Pyrex observation sections 2 ft. long having the same internal diameter as the wrought-iron pipe were placed at 14-ft. intervals in the column. The bottom of the tube was cut off square and terminated in the mixing chamber. No perforated nipple or footpiece of any kind was used. To the top of the column was fastened a semicircular return bend having a 4-ft. radius. The flow column was supported by a standard cable-tool drilling derrick (Fig. 1) into which were built observation platforms at each Pyrex section.

Jan 1, 1940

By W. A. Barrows

Mesabi ores differ from all other soft hematite-ores of the Lake Superior region in having but little or 110 binder. When exposed to heat, instead of baking into lumpy masses as do the Gogebic, Menominee or Marquette fine ores, they are changed to a sandy powder; and the finer particles, having little or no tendency to adhere together in the furnace, are carried by the ascending gas-currents into the down-comers and gas-mains forming flue-dust of a fine gritty nature. The term " finer particles " is used in this paper to mean ore fine enough to pass through a sieve with 80 meshes to the linear inch. Ore coarser than this is not likely to be carried over except in case of a slip, or an explosion in the furnace. The higher the percentage of fine particles in an ore from this range, therefore, the greater the amount of dust likely to result from its use. This statement, however, does not hold good in case of fine ores from the other ranges, and ores from the older ranges, carrying as high as 20 per cent. of material fine enough to pass through a 100-mesh sieve, have been in successful use for years, and have left no records of their causing trouble in furnace-practice by dust, slips, or explosions, so common since the introduction of Mesabi ores. Mesabi ores containing less than 12 per cent. of material which will pass through an 80-mesh sieve are considered of good structure; from 12 to 18 per cent., fair structure; and more than 18 per cent., poor structure. It was at first supposed that all these fine particles were carried over when the charge was lowered into the furnace, or during a slip, but the presence of partly reduced iron oxides in the flue-dust, even when no slip has occurred, proves that a part of the dust at least must have been low enough in the

Jan 1, 1905

J. T. Pullon, Rowangarth, Roundhay, Leeds, England :— In discussing Mr. Lee&apos;s paper, I wish to call attention to the fact that Mr. B. II. Thwaite (who was heard here yesterday on the subject of the application of blast-furnace gas for the production of power, of which he was undoubtedly the pioneer) read, at the Engineering Congress in Glasgow in 1901, a paper on the profitable utilization of power from blast-furnace gases,&apos; in which he suggested the diversion and cleaning of the whole of the waste gases coming from the blast-furnace and their utilization for power-production, so as to obtain, with proper manipulation, from 4 to 6 times the efficiency of present methods. He suggested also the heating of the stoves with producer-gas of a higher and therefore more suitable calorific value, so as to maintain them in a constant state of maximum efficiency, free from dust, and to avoid the irregular working of the furnace, besides obtaining a maximum supply of air-blast, of 15 or even 20 lb. pressure, by means of internal-conibustion blast-engines driven by the cleaned waste furnace-gases, with a surplus of gas left for other uses. Since that time, in view of the necessity of having a stand-by plant, immediately available, in case of strikes or other reasons causing the banking or blowing-out of the blast-furnace, he has developed, as an addition to his other types of producer, a high blast-pressure gas-generator, producing a gas identical with, or somewhat superior to, blast-furnace gas; and in which all the ash of the fuel is turned into fluid slag, which is available for, the production of slagwool. The gas is a little richer in carbon monoxide than average blast-furnace waste gas, and has only from 1 to 3 per cent. of hydrogen. Fig. I, drawn from a photograph, shows a plant containing this generator, now in operation at Leeds. It is made in units of from 1,000 to 10,000 h.p. capacity for each vessel, and coupled,

Jan 1, 1907

By Walter S. Lutz, J. T. Griffith

The rainfall during the last six months of 1942 in Scranton and vicinity was 24.06 in.—only 4.35 in more than the average for this district in any equivalent period—yet that rain forced The Hudson Coal Co. to handle 38.8 tons of water for every ton of coal mined. It filled to overflowing, or to a higher level, 14 flooded mine areas holding, in total volume, 8.3 billion gallons of water in storage; brought about a pumpage of 11.4 billion gallons in the months of December 1942 and January, February and March 1943 Half of the total energy generated or purchased (44,322,980 kw-hr.) was required to keep the mines sufficiently free of water to permit the mining of coal during a period of much needed output. Fig. I shows the extent to which this flooding of exhausted and idle properties has proceeded, and is known to be proceeding further, at the upper end of the Northern field. This rainfall (24.06 in.) means 80,559,444 tons of water on approximately 46.2 sq. miles of area tributary to the pumping plants. During the high rainfall period, 72,687,661 tons went underground, being pumped at the stations in this territory. This means an inflow of 88per cent, a runoff of 12 per cent compared with 64 per cent during normal conditions in a normal region. During this period no floods, either surface or underground, had to be dealt with, although the streams and rivers were high on several occasions. In general, the rainfall for the first three months of 1943 can be described as heavy but not abnormal.9 These figures not only indicate the large volumes of water to be handled but, by their very size, they also emphasize that the mine-water problem is not to be conquered, at least from an economical standpoint, by merely buying and installing more and more pumps. Into the solving of this water problem must go much planning, adhering to the principle of keeping the highest percentage of water at the highest possible level for the longest period of time; the storage of huge volumes in sumps capable of being reduced after the flood inflow and at rates less than the inflow; plans for prevention of surface inflow; provision of the minimum of pumping capacity arranged to as nearly 100 per cent pumping load factor as is possible; intercompany joint pumping plants; the conducting of water from one plant to another and from one property to another over distances measured in miles; priorities in power to the threatening situations; and. balance of the necessities and dangers existent in one colliery over another, day by day, when quantities of water are running high. Despite these astronomical figures of water volumes, their disposal to the surface is accomplished reasonably cheaply because, although the annual cost of $575,020 is a large sum, the cost per ton is about 0.1168 cents. Credit for this goes

Jan 1, 1947

By J. T. Griffith, Walter S. Lutz

The rainfall during the last six months of 1942 in Scranton and vicinity was 24.06 in.—only 4.35 in more than the average for this district in any equivalent period—yet that rain forced The Hudson Coal Co. to handle 38.8 tons of water for every ton of coal mined. It filled to overflowing, or to a higher level, 14 flooded mine areas holding, in total volume, 8.3 billion gallons of water in storage; brought about a pumpage of 11.4 billion gallons in the months of December 1942 and January, February and March 1943 Half of the total energy generated or purchased (44,322,980 kw-hr.) was required to keep the mines sufficiently free of water to permit the mining of coal during a period of much needed output. Fig. I shows the extent to which this flooding of exhausted and idle properties has proceeded, and is known to be proceeding further, at the upper end of the Northern field. This rainfall (24.06 in.) means 80,559,444 tons of water on approximately 46.2 sq. miles of area tributary to the pumping plants. During the high rainfall period, 72,687,661 tons went underground, being pumped at the stations in this territory. This means an inflow of 88per cent, a runoff of 12 per cent compared with 64 per cent during normal conditions in a normal region. During this period no floods, either surface or underground, had to be dealt with, although the streams and rivers were high on several occasions. In general, the rainfall for the first three months of 1943 can be described as heavy but not abnormal.9 These figures not only indicate the large volumes of water to be handled but, by their very size, they also emphasize that the mine-water problem is not to be conquered, at least from an economical standpoint, by merely buying and installing more and more pumps. Into the solving of this water problem must go much planning, adhering to the principle of keeping the highest percentage of water at the highest possible level for the longest period of time; the storage of huge volumes in sumps capable of being reduced after the flood inflow and at rates less than the inflow; plans for prevention of surface inflow; provision of the minimum of pumping capacity arranged to as nearly 100 per cent pumping load factor as is possible; intercompany joint pumping plants; the conducting of water from one plant to another and from one property to another over distances measured in miles; priorities in power to the threatening situations; and. balance of the necessities and dangers existent in one colliery over another, day by day, when quantities of water are running high. Despite these astronomical figures of water volumes, their disposal to the surface is accomplished reasonably cheaply because, although the annual cost of $575,020 is a large sum, the cost per ton is about 0.1168 cents. Credit for this goes

Jan 1, 1947

By L. D. Fetterolf, G. T. Mahler, W. M. Peirce, R. K. Waring

Until recently, the only commercial method of producing magnesium has been fused salt electrolysis, despite a considerable amount of experimental work on the direct reduction of magnesium oxide. In this early work, a number of investigators demonstrated that magnesium oxide would react with any one of several reducing agents to produce magnesium vapor, but that the mixture of magnesium oxide and reducing agent must be heated to a high temperature even in a vacuum. In particular, it was demonstrated that silicon and aluminum are effective reducing agents and that when either of these is used the magnesium vapor can be condensed to massive metal. In spite of this knowledge, no successful commercial reduction process was developed, at least in this country, because of the operational difficulties imposed by the requirement of high temperature and vacuum and because of the high cost of the reducing agent. The outstanding experimental work done by Pidgeon, who carefully reviewed all of the known methods of making magnesium and then selected ferrosilicon reduction, overcame some of the operational difficulties. The process developed by Pidgeon comprises briquetting a mixture of calcined dolomite and reducing agent, preheating the briquets to about 600°C. in an externally heated alloy retort, reducing the MgO with silicon in an evacuated horizontal alloy retort heated externally to about II50 C., and condensing the magnesium vapor to a solid in a cold extension of the retort projecting beyond the front of the furnace. A major advantage of Pidgeon&apos;s process is that the retort is not cooled down between charges. Earlier investigators had used apparatus that necessitated cooling and reheating of the retort between charges. Early in January 1942, when the War Production Board was considering the Pidgeon process for quickly increasing the production of magnesium, The New Jersey Zinc Co. offered to have a research investigation of the process carried on, with the hope of assisting in its further development. This offer was accepted, and a two-retort pilot plant was built at Palmerton and put in operation on Jan. 29,1942. An intensive investigation of certain phases of the process was carried out in the ensuing four months. This investigation was completed in the last part of May 1942) and the pilot plant was then shut down. Subsequently, The New Jersey Zinc Co. was requested to have further development work done on the process, and a more extensive investigation was undertaken in August 1942 under contract with the War Production Board and under the supervision of the War Metallurgy Committee. This paper describes the ,phases of the investigation that are thought to be of sufficient general interest to merit publication.

Jan 1, 1944

By J. Nutting, D. H. Kirkwood

The oxidation of lead sulfide in air between 200° and 350°C has been investigated by electron diffraction from thick sulfide films and from galena surfnces. It has been demonstrated that sulfate is the stable reaction product up to 570°C. Sulfate is HAGIHARA has investigated&apos; single crystals of galena roasted in air by the reflection electron-diffraction technique, which owing to the very limited penetration of the beam into the crystal gives information of the nature of the surface only. He has shown that up to 280°C the first oxidation product is lead sulfate, followed by lead mono-oxysulfate (PbO . PbS04). At longer times and higher temperatures more complex patterns appeared which could not be analyzed. All of these patterns were of streaks or spots arising from crystals oriented on the galena surface, and it is probable that these crystals are lead compounds whose structures have not been determined, such as the other oxysulfates (2Pb0 • PbS04 and 4Pb0 . PbS04) or a number of oxides. Certain lead sulfide films, formed chemically, give ring patterns in transmission electron diffraction2 because they are polycrystalline, and should also give ring patterns of the products after oxidation. It was thought that a diffraction study would reveal the sequence of phases produced in the reactions at different temperatures, since X-ray powder patterns are available for many lead compounds. PREPARATION OF FILMS The films were prepared by passing H2S over a saturated solution of lead nitrate in water. Once a silvery film had formed on the solution surface, no further thickening was apparent. The films were transferred by a gauze to a bath of distilled water for washing and pieces of film were caught on small discs on which they were dried. The discs were formed initially on galena up to temperatures of 300°C, followed by oxide and oxysulfates in turn at longer times. The appearance of- these phases is believed to result from an inadequate rate of supply of sulfur to the top surface 01. the crystal. standard Siemens mounts, made of platinum alloy, and had seven 20-p apertures drilled through them. The parts of the film which had dried onto the disc surface were light blue in color, which is the interference color of a film about 600A in thickness. A strong pattern of lead sulfide was obtained in transmission electron diffraction through the apertures but slight broadening indicated a crystallite size of around 200A. Tilting a sulfide film in the beam produced arcing of the rings, increasing the intensities of the (Ill), (3111, and (222) rings and reducing (200) and (220). This arises from preferred orientation in the film, a [loo] direction of the crystallites being normal to the plane of the film. These specimens were oxidized in an oven maintained at the required temperature. The reported times include that taken to heat the film to the reaction temperature. STABLE PHASES FORMED IN OXIDATION The conditions in which various oxidation products of lead sulfide are stable have been considered by the authors in a previous paper.3 It was shown that in a normal atmosphere, taken as containing lo-&apos; atm of SOs, lead sulfate would be stable up lo about 570°C. This was confirmed by oxidizing thin films of sulfide for several days, and the analysis of the transmission-diffraction pattern is given in Table 1. The fit with the patt$rn from X-rays is good, except for the missing 3.62A ring. Some disagreement in intensities of reflections given by X-rays and electrons is to be expected. Up to 570°C a spotty pattern of sulfate was still obtained, indicating grain growth, but above this temperature the film disintegrated. Probably this is associated with the decomposition to PbO . PbS04. It needs to be emphasized that the atmosphere

Jan 1, 1965

By S. F. Frederick, W. A. Bailey

The relationship between microstructure and mechanical properties of cast 356-type aluminum alloys was studied to determine the cause of the variations in properties resulting from differences in solidification rate. It was found that variations in strength are a consequence of variations in ductility and that ductility is inversely proportional to the dendrite cell size. A mechanism is proposed to account for this correlation based on the fracture strain of the inter-dendritic silicon particles and the differential strain across dendrite cell boundaries. IT has long been assumed that permanent mold castings of aluminum are superior to sand castings because of their finer grain structure and reduced porosity.&apos; A systematic variation of static properties was noted during unpublished studies of fatigue-strength variations with solidification rate of A356-T6. Of particular interest was the observation that for a given composition and heat-treatment, both ductility and the ultimate strength increased with higher solidification rate. Because the A1-Si system forms the basis of many alloys used for castings and welding wire, a study was initiated to determine the details of how higher cooling rates improved mechanical properties of these alloys. The results of this study are presented here. EXPERIMENTAL PROCEDURE Specimens were prepared from 356-T6 to supplement the A365-T6 alloy data from earlier studies. This allowed a comparison of behavior of alloys with substantially different strengths but with only small differences in alloy composition. The composition and heat treatment of both alloys are given in Table I. The specimens were cut from a chill plate casting,&apos; which is a 6 by 9-in. plate, 1 in. thick, which has one end heavily chilled, and a large riser at the other so that solidification is essentially unidirectional from the chill end to the riser. Although not measured here, solidification times measured on similar specimens by embedded thermocouples are a few seconds at the chill end and up to 5 min near the riser. Specimens were obtained by cutting slabs from the plate, parallel to the chill; these represented different cooling rates, with essentially the same composition. For the tests, either 0.125 or 0.250-in. thick slabs were cut for standard 2-in. gage length specimens. The thicker specimens were tested to failure at 2000 lb per min while the thinner specimens were tested in an Instron machine at a constant cross-head speed of 0.02 in. per min. These thin specimens were intended for trans- mission electron microscopy. Some thin specimens were tested to failure while the remainder were given various amounts of prestrain. Dendrite cell sizes were measured by the linear intercept method on photomicrographs at either X100 or X50, depending on the cell size. It was assumed that the dendrite cells were outlined by the silicon particles. Determinations were made on two mutually perpendicular planes and an rms average taken. Electron fractographs of representative tensile specimens were made in the conventional manner using the two-stage replica technique.3 Samples for transmission electron microscopy were prepared by chemical milling followed by electropolishing. RESULTS AND DISCUSSION The results of the tensile tests and the dendrite cell-size determinations are given in Figs. 1 and 2. All data show the same trends, namely, a decrease in ultimate strength and elongation with increasing distance from the chill (and solidification time), and a corresponding increase in dendrite cell size. The yield strength remains essentially constant. The constancy of the yield strength was particularly significant since it indicated that variation in the solidification rate does not affect the stress required to initiate plastic flow. By plotting true stress-true strain curves as in Fig. 3, it can be seen that both

Jan 1, 1969