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By H. LeRoy Scharon, A. B. Cleaves

THE application of geophysical techniques in the A engineering surveys of the Philadelphia and Western Extensions of the Pennsylvania Turnpike System is unique inasmuch as this is the first time, (to the authors' knowledge), that such studies have been employed on a large scale on a major highway system. These investigations were confined to specific areas along the center line of the proposed Philadelphia Extension between Carlisle and King of Prussia, and the Western Extension between Irwin and the State line near Youngstown, Ohio, as shown in Fig. 1. Along the 100 miles of the philadelphia Extension, the geophysical surveys were confined to 137 individual cuts and comprised a total length of 37.4 miles of line. The Western Extension, 66 miles in length, has 108 individual cuts. The accumulated length covered by electrical resistivity studies was 17.3 miles. The depth of the cuts varied from a minimum of 10 ft to a maximum of 62 ft. The geophysical investigations were made for the purpose of determining depths to bedrock in the 245 proposed cuts and at the sites of various structures. The 'data also served as a basis for geological interpretations of the condition of bedrock, contact zones, rock types, water table, and other factors significant in highway construction. The geophysical method of investigation employed the use of the electrical resistivity principle using the Gish-Rooney type electrical resistivity meter and the Wenner electrode configuration.* Apparent resistiv- ities were determined for constant intervals to various depths and were correlated with surface geological observations and subsurface geological conditions revealed by key diamond drill holes situated within a given cut interval. From these correlations, depths to bedrock were postulated with notations on other geological features that might be pertinent to modern highway construction. Geology The bedrock underlying the areas of the extensions of the Turnpike afford an excellent academic study of the electrical resistivity depth method as well as a practical application to modern highway engineering. The rocks encountered on the Philadelphia Extension vary in age from pre-Cambrian to Triassic and Quaternary, whereas in the Western Extension, bedrock is confined to relatively flat-lying strata in the Allegheny, Conemaugh, and Monongahela formations of the Upper Paleozoic, Pennsylvanian. Glacial and Recent stream, valley, and terrace deposits are common. Philadelphia Extension The oldest bedrock encountered in this extension are igneous and metamorphic. These, encountered chiefly in Chester County, consist of the strongly

Jan 1, 1952

By T. R. Braithwaite

The brief comments made in this chapter deal mainly with shaft sinking, but don't assume that freezing techniques apply only to shaft sinking. They can be used on tunnel work, on such things as liquid gas storage in sediment, and I think you will probably see other applications for it as we go along. The method was first developed in 1883 and was used to sink shallow shafts through water-bearing overburden in Germany and in England. One of the early shafts was in Germany and was sunk by freezing to 310-ft depth. The project required 17 months for drilling, roughly 5 1/2 months for freezing, and another 7 months for sinking, giving an average progress of 10 ½ fpm. Fortunately there have been numerous improvements and new developments in this technique through the years. With equipment and techniques available today, we can take a 20-ft-diam shaft down through 2000 ft of water-saturated overburden and the time schedule runs roughly 4 months for site preparation, freeze-hole drilling, installing the casings, and setting up the plant; 4 ½ months for freezing; and 6 months for excavating and installing permanent linings. This gives a progress rate of about 140 fpm, on average. I might qualify that a little in that the special linings that are required for some formations can affect the time. If it's straightforward sinking where one can use a heavy concrete lining, up to 630-640 fpm may be achieved in a shaft; but with special cast-iron tubbing or types like that, 5 fpd is pretty good progress, so the lining does affect the time. The freezing method is used mainly for sinking shafts through unstable water-bearing formations which cannot be grouted either effectively or economically and which are too deep to enclose in pile casing. Even with overburden, grouting methods available today can handle roughly 100 lb water pressure; in the range of, say, 100 to 150 ft from the surface, it's very often best to grout 40 or 50 ft. You normally drive a pile casing and go through it. Below that range, freezing is very often the economical

Jan 1, 1970

By F. W. Bloecher, A. M. Gaudin

THIS paper describes the results of a series of tests carried out to determine the partition of dodecylamine between distilled water and the surface of quartz at various concentrations of dodecylamine acetate in solution. An adsorption-column technique was utilized for this purpose. Ralston and Harwood, of Armour and Co., had synthesized marked dodecylamine acetate for us.' In their preparation which we employed, 0.0007 pct of the total carbon was the radioactive isotope, carbon fourteen. Unmarked dodecylamine acetate of high purity was also prepared by them for our use. The presence of carbon fourteen in the dodecylamine enabled us to analyze quantitatively for dodecylamine on the surface of quartz, using a radioactive-tracer technique. The method used was that known as internal gas counting of carbon dioxide, formed by oxidation of the amine. This method has already been described, "3 ' and the reader is referred to these papers for details of the analytical method and procedures. and surrounding liquor, a technique analogous to chromatographic columns was utilized. The experimental setup is shown in fig. 1. The dodecylamine-acetate solution was made up in a volumetric flask and poured into the glass funnel shown. It was allowed to drip slowly onto the quartz bed, the rate of flow from the funnel reser- voir being controlled by a hose clamp. The quartz column was contained in a small, fritted-glass filter (size 20 mm, C). The beaded top edge of the filter was cut off to enable the holder and contents to fit into the open end of the 30/45 joint on the combustion tube. This combustion tube is used in the analytical train described in a previous paper.' A piece of gum-rubber tubing joins the bottom of the fritted-glass filter to a filter flask, which in turn is connected to a vacuum line, or water aspirator. The rate of flow of amine solution through the bed was

Jan 1, 1951

By F. W. Bloecher, A. M. Gaudin

THIS paper describes the results of a series of tests carried out to determine the partition of dodecylamine between distilled water and the surface of quartz at various concentrations of dodecylamine acetate in solution. An adsorption-column technique was utilized for this purpose. Ralston and Harwood, of Armour and Co., had synthesized marked dodecylamine acetate for us.' In their preparation which we employed, 0.0007 pct of the total carbon was the radioactive isotope, carbon fourteen. Unmarked dodecylamine acetate of high purity was also prepared by them for our use. The presence of carbon fourteen in the dodecylamine enabled us to analyze quantitatively for dodecylamine on the surface of quartz, using a radioactive-tracer technique. The method used was that known as internal gas counting of carbon dioxide, formed by oxidation of the amine. This method has already been described, "3 ' and the reader is referred to these papers for details of the analytical method and procedures. and surrounding liquor, a technique analogous to chromatographic columns was utilized. The experimental setup is shown in fig. 1. The dodecylamine-acetate solution was made up in a volumetric flask and poured into the glass funnel shown. It was allowed to drip slowly onto the quartz bed, the rate of flow from the funnel reser- voir being controlled by a hose clamp. The quartz column was contained in a small, fritted-glass filter (size 20 mm, C). The beaded top edge of the filter was cut off to enable the holder and contents to fit into the open end of the 30/45 joint on the combustion tube. This combustion tube is used in the analytical train described in a previous paper.' A piece of gum-rubber tubing joins the bottom of the fritted-glass filter to a filter flask, which in turn is connected to a vacuum line, or water aspirator. The rate of flow of amine solution through the bed was

Jan 1, 1951

By K. L. Clark, Nicholas Kowall

MAXIMUM furnace efficiency and close control of final steel composition demand that the steel melter be able to follow closely the variations in the carbon content of the bath. For many years, the fracture test has been used by melters for estimating carbon, because it requires only a very short time to pour a sample into a chill mold, cool it in water, break it with a sledge hammer, and observe the fracture. After long experience gained from the observation of such fractures, most melters are able to estimate the carbon content of steel with amazing accuracy, particularly in the lower carbon ranges. Notwithstanding the utility of the fracture test, there has been widespread interest in other methods for rapid carbon determination to supplement it and to ensure against possible errors in human judgment. Several methods, based upon measurement of magnetic properties as functions of carbon content, have been described in the literature1-6 and have been found to give reasonably reliable results in plant practice when scrap composition is known and controlled. A difficulty encountered in the use of analyzers of the magnetic type is that alloying elements do change the relationship between carbon content and magnetic properties and it becomes necessary to establish calibration curves for all the expected combinations of alloy residuals that are not oxidized in the bath. The work reported here is of an investigation of a method that is independent of alloying elements normally present in constructional steels, being based upon the relatively well-known fact that in plain carbon and low-alloy steels martensitic hardness is a function of carbon content alone. WORK OF OTHER INVESTIGATORS In 1938, Burns, Moore and Archer published a curve7 that showed that the hardness of martensite is a function of carbon from 0.10 to 0.50 per cent and is independent of grain size or alloy content, at least within the range found in constructional S.A.E. compositions. Some of the deeper hardening types investigated, however, contained carbon to a maximum of only 0.20 per cent. Using this principle, Kern8 developed a method of rapid carbon determination for S.A.E. 43xx steels. His procedure consisted of chill-casting a test bar that was large enough to give a surface that could be prepared for Brinell indentations. The test piece was quenched immediately after solidification was complete and hardness readings were taken, so that the carbon content could be read from an experimentally determined curve giving the relationship between as-quenched hardness and carbon. EXPERIMENTAL WORK Although Kern's work had been done with a relatively deep-hardening steel, it

Jan 1, 1944

By J. L. Walter, W. R. Hibbard

A GREAT deal of work has been done on the rolling of single crystals of iron. Barrett and evensoon studied end orientations of heavily cold-rolled iron crystals and found that some crystals maintained a sharp single orientation during rolling. Others rotated into two or more orientations, and some fragmented and approached the entire polycrystalline texture depending on the original orientation of both the normal and rolling directions. Barrett, Ansel, and Mehl2 studied iron-silicon alloys and found that the addition of silicon to the iron had little effect on heavily rolled polycrystalline material. Dunn3 has extensively studied the cold-rolling and recrystallization of silicon-iron single crystals. Dunn found that for single crystals having initial orientation between (110) [001] and (111) [112], the principalcomponent of the cold-rolled texture is (111) [112]. Koh and Dunn4 studied the cold-rolled textures of single crystals having initial orientations in the range (001) [110] to (111) [IT01 and found that these are stable end orientations. They also found that all orientations having a [110] direction parallel to the transverse direction rotate to either the (001) [110] or the (111) [112] stable end orientation except for orientations near (112) [11], which divide and produce a final texture consisting of (001) [110]and (111) [112] components. Crystals having a (111) <112>-type texture re-crystallized to a (120) [001] or (110) [001]-type texture. Crystals having orientations with a range of (001) to (335) in the rolling plane and [110] in the rolling direction recrystallized5 to a wide spread of the initial orientations resulting from a multiplicity of 30-deg rotations about several (110) poles. The present study was undertaken to relate other orientations of crystals of silicon-iron to their cold-rolling and recrystallization textures, so that one might rationalize polycrystalline recrystallization data on the basis of the known deformation texture and the behavior of single crystals in these orientations. PROCEDURE Samples were obtained from a cylindrical ingot of 3 pct silicon iron prepared as follows: Armco iron was melted with high-purity silicon flakes under an atmosphere of argon to minimize oxidation. The alloy was poured into a special mold to form an ingot which consisted partially of large columnar crystals. Plates were cut from the columnar portions of the ingot with the longitudinal direction parallel to the columnar axes and ground to 0.040 in. thick. The plates were heavily etched to a thickness of 0.032 in. to remove the cold-worked surface. Orientations of seventeen crystals were determined by Laue back-reflection techniques keeping the mean columnar axis as the reference direction. The plate was then cut in two, parallel to the columnar axis. One portion of the plate was rolled at room temperature parallel to the columnar axis to a reduction in thickness of 84 pct. The remaining portion of the plate was rolled also at room temperature across the columnar axis to a reduction of 66 pct, at which point the crystals began to separate at the boundaries. After rolling, nine individual crystals were removed from the strip by cutting along the crystal boundaries with a jeweler&apos;s saw. Fig. 1 shows the original orientations of the six crystals that were straight-rolled and of the three crystals (4, 7, and 8) that were cross-rolled. Each rolled crystal was carefully etched to approximately 0.002 in. thick. Textures of the cold-rolled crystals were determined by use of the diffractometer with a non-integrating sample holder. The pole figures were made for the (200) poles using molybdenum Ka radiation and were plotted by an automatic stereographic projection recorder.&apos; Spurious poles were determined by rerunning portions of the pole figures using strontium oxide to filter out the Ka radiation. The central portions of the pole figures have not been determined. The pole figures were completed to about 55 deg from the periphery at which point the sample holder interfered with passage of the beam. Following the determination of the cold-rolled

Jan 1, 1959

By E. E. Schumacher, G. S. Phipps, H. M. Bouton

The seriousness of the present tin scarcity has stimulated large consumers of this vital metal to develop drastic conservation measures in order to extend the available supplies to cover the emergency period. By devising new soldering methods and alloys the Bell System has contributed a substantial share in the tin conservation effort. Fortunately, the changes, as far as can be determined now, have not introduced weakness into the soldered joints. Some of the new procedurcs were already in the process of development at the onset of the emergency, while others were devised under its stress. In some instances, the newly developed solders were found to be more difficult to use than the alloys previously available, and would not have been introduced under normal conditions. One major change made that previously had been under consideration will result in large savings of tin. Unless service difficulties are encountered, this modification gives promise of remaining after the emergency has passed. The change involves a reduction in the amount of solder placed on a wiped joint between the cable sheath and the sleeve. Instead of the customary full sized wiped joint, a wipe of fillet proportions is formed. Through this change, a solder saving of more than 60 per cent per joint can be realized. Plumbers and cable splicers for many years have joined lead pipes and cable sheath by a soldering process called " wiping." The name is an apt description of the operation. For a wiped joint, the sections to be united are heated by molten solder poured over their surfaces, and the resulting semiliquid mass is manipulated by wiping with cloth pads to a well rounded symmetrical form like the one shown in Fig. I. The operation requires considerable skill on the part of the splicer and close control of the composition of the solder. At first consideration, the problem of tightness in such joints seems simple but experience shows that even under the best conditions the fissures frequently found in the solder occasionally link and form a path that allows leakage to occur. In telephone cables not maintained under gas pressure, such leaks permit the entrance of water, which wets the paper-covered conductors and thereby impairs the insulation value and causes service interruptions. Ry going to an extreme and wiping off all the solder in excess of a fillet, it has been found that many causes of porosity are eliminated. Figs. 2 and 3 show cross sections of joints wiped in the old and the new ways. The saving in solder, and consequently in strategic tin, is evident. The field splicing forces find that joints are easier to make by the new method and are less likely to be porous. The metallurgical considerations that are responsible for the success of the fillet wipe are of interest. Much has been written about the wiping process of soldering cable joints and the many requirements of a good wiping solder have frequently been listed. The success of the procedure described

Jan 1, 1943

By H. M. Bouton, G. S. Phipps, E. E. Schumacher

The seriousness of the present tin scarcity has stimulated large consumers of this vital metal to develop drastic conservation measures in order to extend the available supplies to cover the emergency period. By devising new soldering methods and alloys the Bell System has contributed a substantial share in the tin conservation effort. Fortunately, the changes, as far as can be determined now, have not introduced weakness into the soldered joints. Some of the new procedurcs were already in the process of development at the onset of the emergency, while others were devised under its stress. In some instances, the newly developed solders were found to be more difficult to use than the alloys previously available, and would not have been introduced under normal conditions. One major change made that previously had been under consideration will result in large savings of tin. Unless service difficulties are encountered, this modification gives promise of remaining after the emergency has passed. The change involves a reduction in the amount of solder placed on a wiped joint between the cable sheath and the sleeve. Instead of the customary full sized wiped joint, a wipe of fillet proportions is formed. Through this change, a solder saving of more than 60 per cent per joint can be realized. Plumbers and cable splicers for many years have joined lead pipes and cable sheath by a soldering process called " wiping." The name is an apt description of the operation. For a wiped joint, the sections to be united are heated by molten solder poured over their surfaces, and the resulting semiliquid mass is manipulated by wiping with cloth pads to a well rounded symmetrical form like the one shown in Fig. I. The operation requires considerable skill on the part of the splicer and close control of the composition of the solder. At first consideration, the problem of tightness in such joints seems simple but experience shows that even under the best conditions the fissures frequently found in the solder occasionally link and form a path that allows leakage to occur. In telephone cables not maintained under gas pressure, such leaks permit the entrance of water, which wets the paper-covered conductors and thereby impairs the insulation value and causes service interruptions. Ry going to an extreme and wiping off all the solder in excess of a fillet, it has been found that many causes of porosity are eliminated. Figs. 2 and 3 show cross sections of joints wiped in the old and the new ways. The saving in solder, and consequently in strategic tin, is evident. The field splicing forces find that joints are easier to make by the new method and are less likely to be porous. The metallurgical considerations that are responsible for the success of the fillet wipe are of interest. Much has been written about the wiping process of soldering cable joints and the many requirements of a good wiping solder have frequently been listed. The success of the procedure described

Jan 1, 1943

By R. K. Waring, E. C. Truesdale

The Research Division of The New Jersey Zinc Company (of Pa.) has conducted, over a period of years, numerous tests of the reducibility of various zinc ores and the reactivity of various kinds of coal, using a number of different experimental methods. Most of these tests have involved the reduction of mixtures of ore and coal. In such cases the following simultaneous reactions are believed to be mainly responsible for the production of zinc, as was shown by Bodenstein1 some years ago: ZnO+ CO = Zn + CO2 [1] C + CO2 = 2 CO [2] Each of these reactions is dependent upon the other for the supply of CO and CO2 , respectively, and the over-all rate of formation of zinc vapor will be determined by the slower of these two reactions. An analogous pair of reactions sometimes of importance is: ZnO + H2 = Zn + H2 O [31 C + H2O = CO + Ha [4] While it is possible to obtain an indication of the relative reducibility of various ores, or of a fine versus a coarse ore, by testing them with a given coal, and while coal reactivities may be measured in a corresponding manner, a more direct determination of relative reaction rates is possible by carrying out the desired reactions, such as I and 2, separately and under reproducible conditions. It is one purpose of this paper to present some of the results that have been obtained by the latter method. C. G. Maier2 discusses the relative rates of reactions I and 2 and concludes that while at relatively low temperatures reaction I is faster than reaction 2, this difference becomes less with increasing temperatures, although at smelting temperatures reaction I is still the faster. He also says (p. 48), "At temperatures . . . between IIOO° and I3oo°C., . . . the zinc oxide reduction reaction is intrinsically more rapid than its physical limitations; that is, it is limited by gas diffusion rates." In the course of numerous reactivity tests involving the separate use of reactions and I and 2, we have obtained data that show by direct experiment, we believe for the first time, the correctness of Maier&apos;s statements concerning these reactions. We also include data on the relative rate of reaction 3, involving reduction by hydrogen. Finally, some interesting results obtained by carrying out the reduction of a zinc ore-coal briquet in streaming atmospheres of nitrogen, carbon monoxide and hydrogen, respectively, are presented. *

Jan 1, 1943

By E. C. Truesdale, R. K. Waring

The Research Division of The New Jersey Zinc Company (of Pa.) has conducted, over a period of years, numerous tests of the reducibility of various zinc ores and the reactivity of various kinds of coal, using a number of different experimental methods. Most of these tests have involved the reduction of mixtures of ore and coal. In such cases the following simultaneous reactions are believed to be mainly responsible for the production of zinc, as was shown by Bodenstein1 some years ago: ZnO+ CO = Zn + CO2 [1] C + CO2 = 2 CO [2] Each of these reactions is dependent upon the other for the supply of CO and CO2 , respectively, and the over-all rate of formation of zinc vapor will be determined by the slower of these two reactions. An analogous pair of reactions sometimes of importance is: ZnO + H2 = Zn + H2 O [31 C + H2O = CO + Ha [4] While it is possible to obtain an indication of the relative reducibility of various ores, or of a fine versus a coarse ore, by testing them with a given coal, and while coal reactivities may be measured in a corresponding manner, a more direct determination of relative reaction rates is possible by carrying out the desired reactions, such as I and 2, separately and under reproducible conditions. It is one purpose of this paper to present some of the results that have been obtained by the latter method. C. G. Maier2 discusses the relative rates of reactions I and 2 and concludes that while at relatively low temperatures reaction I is faster than reaction 2, this difference becomes less with increasing temperatures, although at smelting temperatures reaction I is still the faster. He also says (p. 48), "At temperatures . . . between IIOO° and I3oo°C., . . . the zinc oxide reduction reaction is intrinsically more rapid than its physical limitations; that is, it is limited by gas diffusion rates." In the course of numerous reactivity tests involving the separate use of reactions and I and 2, we have obtained data that show by direct experiment, we believe for the first time, the correctness of Maier&apos;s statements concerning these reactions. We also include data on the relative rate of reaction 3, involving reduction by hydrogen. Finally, some interesting results obtained by carrying out the reduction of a zinc ore-coal briquet in streaming atmospheres of nitrogen, carbon monoxide and hydrogen, respectively, are presented. *

Jan 1, 1943

By J. E. Spruiell, F. H. Patterson, B. F. Shuler

The microstructures and textures developed by the working of high-purzly thermochemically deposited tungstem sheet have been inuesligated. Greater than 60 pct reduction was required to deslroy the columnar grain structure which existed in the as-deposited sheet. With increasing reductions the texture gradu-ally charged from the initial as-deposited orientation with (100) parallel to the sheet normal to a (100}(011) ideal ovienlation with some spread about the rolling direction. This texture was retained after recrystalli-zation a1 2000°C. THE processes for depositing tungsten by hydrogen reduction of tungsten hexafluoride have been under development for the past several years.1,2 The nature of the deposition process is such that the as-deposited material contains a highly oriented columnar grain structure perpendicular to the deposition substrate. This well-defined columnar structure may be useful in certain applications293 but a wrought or equiaxed structure may be desired for some components such as tubing. Knowledge of the effects of working ther-mochemically deposited (TCD) tungsten is therefore necessary in order to establish the feasibility of obtaining worked and recrystallized microstructures and textures. The details of a recently developed technique for thermochemically depositing flat, uniformly thick tungsten sheet are presented with emphasis on the effects of deformation by rolling on the microstructure and texture. Although no work has been previously reported on the rolling and the annealing textures of TCD tungsten, there have been some determinations of textures for cold-rolled tungsten foil prepared from powder-metal -lurgy billets.4-8 The general description is that of a predominantly lurgy{100}(011) texture, with some spread about the rolling direction as an axis. pugh5 reports data both for cold-rolled and for annealed foil having about 96 pct initial cold work. He observed no change in texture, except for a decrease in the spread, for annealing treatments of 30 min at temperatures up to 1800°C. On annealing at 1900°C, both the low-temperature components plus new components which were described alternately as {001}(320) plus {001)(230) or as {100}(011) ± 12 deg about the sheet normal were observed. Above 1900°C, the new orientation existed alone, and it was stable up to 2500°C, the highest temperature that Pugh investigated. THERMOCHEMICAL DEPOSITION OF TUNGSTEN SHEET High-purity tungsten sheet was reproducibly deposited on the inner walls of a molybdenum mandrel by the thermochemical reaction WFs(g) + 3H2(g) - W(s) + 6HF(g). The mandrel was heated by a five-zone tube furnace which afforded a controllable fixed-temperature profile. Sheets measuring 1+ by 12 in. have been deposited with uniform thicknesses of up to 0.145 m. As shown schematically in Fig. 1, the purified reaction gases were metered into a mixing chamber at a Hz-to-WF6 ratio of 15 and preheated to 350°C. The flow rate of the WF6 was 300 cu cm per min at stp. These gases were directed through a conical injector into the deposition chamber. Inside this chamber hydrogen reduction of the WF6 to pure tungsten metal occurred on the hot walls of the molybdenum mandrel at a total pressure of 5 Torr. Typical temperatures for the five zones in the chamber were, respectively, 565", 540", 550°, 570°, and 590°C. The hydrogen fluorlde generated from the reaction, the excess hydrogen, and some un-reacted WF6 were pumped on through the scavenger

Jan 1, 1968

By W. W. Anderson, D. G. Girton

The photoluminescence of Pr, Nd, Ho, Er, Tm, and Yb in CdS, and Ho, Er, Tm, and Yb in ZnSe has been observed from crystals Prepared by diffusion using rare earth metals and an excess chalcogen pressure. For a given temperature, time, and chalcogen pressure the spectral characteristics were very reproducible from run to run, and the emission intensity for Nd, Er, and Yb in CdS was as high or higher than the best vapor phase doped crystals we have grown. For a few rare earths it was found that certain conditions of diffusion tend to yield optimum rare earth emission intensity with respect to the background lattice emission. Photoluminescence measwements of Yb in CdS as a function of depth gave a profile which was neither a Gaussian nor complementary error function. Part of the profile appears to arise from a fast component of the diffusion and the other part from a slow diffusing component. At 960°C and 33 atm S pressure, a com -plimentary error function approximation of the slow diffusing component gave a diffusion coefficient of D = 1.3 x 10-9 sq cm per sec. MOST of the studies of emission from rare earth ions in II-VI compounds have been reported on crystals doped during growth,1,2 although Kingsley and Aven prepared ZnSe:Er by diffusion for paramagnetic resonance and fluorescence studies. Pappalardo and Dietz prepared CdS:Yb by diffusion, but they made optical absorption measurements., We know of no study on the properties of rare earth diffusion in the II-VI compounds. To date we have diffused Pr, Nd, Ho, Er, Tm, and Yb into CdS, and Ho, Er, Tm, and Yb into ZnSe and observed the rare earth emission spectra. For a given temperature and chalcogen pressure, the emission characteristics are very reproducible from run to run and for Yb, Nd, and Er in CdS, as good as the best crystals we had prepared by doping during vapor phase growth.2 The emission of Pr, Ho, and Tm has been observed in CdS prepared by diffusion for the first time. Previous attempts2 to prepare these later three materials by vapor phase growth were unsuccessful. The problem of obtaining reproducible characteristics in II-VI semiconductor compound work is well known.5 Not only is it difficult to reproduce results from one laboratory to another but it is sometimes difficult to reproduce results from one growth run to another under ostensibly identical conditions within one laboratory. This situation has been particularly bothersome in research on the luminescence of rare earth activated ZnS1 and Cds2. Crystals from one vapor phase growth run would show very strong rare earth line emission while crystals from a nearly identical run would show no rare earth emission. It was also observed on occasion that the intensity of the rare earth emission was not constant over the entire volume of a single crystal. MATERIAL PREPARATION AND INSTRUMENTATION Vapor phase grown boules of CdS were supplied by Dow Corning. This material was characterized by a free electron concentration of n - 3.5 x 1015 cm-3 and Hall mobility of 350 sq cm per v sec at room temperature. There were microscopic voids and decorated precipitates in some samples. The precipitates annealed out at diffusion temperatures but the voids remained. Single crystal rectangular samples of mm dimensions were sawed from the boules. The ZnSe was polycrystalline, UHP grade from Eagle-Picher. Poly-crystalline samples were sawed from the ingots. The samples were lapped, polished on one side, etched in a solution of 0.5 M K2Cr2O7 in 16 N H2SO4, and thoroughly washed in distilled water. A sample, excess sulfur (or selenium), and 5 mg of rare earth metal (turnings) were sealed in a 3.6 cm3 quartz ampoule at about 2 X 10-5 torr. The high chalcogen pressure used (1 to 30 atm) prevented thermal etching of the crystals and affected the diffusivity and solubility of the rare earth ions in the crystal lattice. For meaningful or reproducible results, it is thus necessary to specify the vapor pressure at which the diffusion was carried out. It is assumed that a negligible amount of the chalcogen was used in the formation of rare earth sulfides or selenides Our sulfur vapor pressure calculations are based on data assuming S2, S6, and S, molecules only in which case the equilibrium constants are given by6 where the pressures are expressed in torr. Selenium vapor consists of a mixture of Se2, Se4, Se6, and Se6 molecules. The selenium vapor pressure was calculated using equilibrium constants given by The status of the rare earth source during diffusion is unknown, i.e., the partial pressures of the rare earth metal and of the rare earth chalcogenides has not been determined. All emission spectra were recorded at 77°K on a Perkin-Elmer model 98-G spectrometer using a 640 line per mm grating. No correction was made for the spectrometer and detector spectral sensitivity. Excitation was by means of an XBO 1600 w xenon arc

Jan 1, 1970

With the signing of the armistice on Nov. 11, the direction of the main concentration of effort of the United States was changed. In order to win the war, all industrial efforts had to be organized and centralized. With the war won and peace in sight, this centralization of effort stopped and the full play of individual initiative was allowed to resume its sway in the community. During this period of reversal of direction of effort, there was a natural loss of momentum and the United States, as well as the rest of the world, is in for a period of readjustment. The immense progress that was made in one direction under the stress of the necessities of war, which focused the energies of a nation in one direction, is an outstanding example of what can be accomplished if a community with many varying interests can be united on one objective which it desires to attain. The realization that the fusing of many interests into one stream of effort is difficult should not prevent us from taking the long view ahead that is necessary in order to be able to measure the progress made. If we don&apos;t have a mountain peak to guide us, we are very likely to run in circles in the plain without reaching the goal to which we strive. The most efficient development of natural resources is an ideal that, from a material point of view, appeals to the engineer. This ideal includes giving of opportunities to everyone to take a share in the development of these resources.. It also contemplates rewarding foresight

Jan 4, 1919

By J. D. Livingston, H. E. Cline

Cu-Pb alloys in the vicinity of the monotectic composition have been directionally solidified under a high temperature gradient at rates up to 2 X l0-&apos; cm per sec. Over a wide range of compositions, high growth rates yield a composite structure consisting of continuous rods of lead in a copper matrix. This range of compositions increases with increasing growth rate, in agreement with arguments based on the relative velocities of composite growth and the growth of copper dendrites or lead drops. The breakdown of the composite structure at slow growth rates is explained in terms of the relative interphase surface energies. The observed interrod spacings of the composite structure are large compared with the predictions of the Jackson-Hunt equations of eutectic growth. ThE directional solidification of many eutectic alloys produces fine composite structures of parallel lamellae or rods. There has been considerable interest not only in the fundamentals of this two-phase solidification process,&apos;-3 but also in the interesting physical properties produced by such regular and aniso-tropic microstructures. Composite structures can be grown only over a limited range of composition, beyond which coarse primary dendrites of one phase appear. In organic eutec-tics, this composition range of composite structures has been shown to increase with increasing growth rate.7"10 These results were explained in terms of the relative velocities of composite (coupled) growth and dendritic growth. Although similar arguments should apply to metallic eutectics,11-13 suitable experimental results are lacking. In contrast to the work on eutectics, the directional solidification of monotectic alloys has received little attention. (The monotectic reaction is similar to the eutectic reaction, except that one of the resulting phases is a liquid, which subsequently solidifies in a separate reaction at a lower temperature.) Directional solidification of some monotectic alloys&apos;4715 yields regular rodlike microstructures, whereas in other cases macroscopic separation of solid and liquid phases occurs.16 chadwick17 rationalized these results in terms of the probable relative magnitudes of the various interphase surface energies. A recent study of chill-cast Cu-Pb alloys18 revealed a fine rodlike microstructure in alloys near the monotectic composition. It was decided to investigate the directional solidification of such alloys, and to determine the range of composition and growth conditions yielding composite structures. The Cu-Pb system is convenient for such a study, both because it is simple metallurgically, with no compound formation and negligible solid solubilities, and because its basic properties are well-documented. Recent literature on the Cu-Pb system includes studies of bulk thermo-dynamic properties,&apos;g surface energies,20"21 densi-ties,25 and diffusion constants.a6 A similar study of the directional solidification of Cu-Pb alloys was recently undertaken, independently, by Kamio and Oya." EXPERIMENTAL Alloys were prepared by melting 99.999 pct Cu and 99.999 pct Pb in a graphite crucible, stirring well, and pouring into a cold graphite mold. Rods 0.175 in. in diam were machined from the ingots. Alloy compositions studied ranged from 25 to 55 wt pct Pb. Samples were placed in graphite crucibles 5 in. long with 4 in. OD and 0.035-in. walls. They were melted under flowing argon in a vertical, two-zone. platinum -wound furnace. A voltage stabilizer was used to minimize fluctuations in input power. The narrow specimen diameter minimized convection. Directional solidification was achieved by driving the crucible downward into a +-in. hole in a water-cooled copper toroid. The toroid was located immediately below the narrow end zone of the furnace. The end zone was separately powered to maintain high local temperature. Therefore a high temperature gradient (approximately 300 deg per cm) was maintained in the specimen throughout the run. The crucible motion was screw-driven. and a wide range of drive speeds were available. The limited rate of heat removal caused a thermal lag in the specimens at high drive rates. However. temperature-time curves from thermocouples imbedded in a representative sample indicated that the average growth rate still approximately equaled the drive rate. Although the specimens were initially homogeneous, melting and re solidification redistributed the lead. producing composition variations of several percent along the specimen length. (During melting. lead melted first and ran down the sample surface. Rapid freezing tended to reproduce the resulting composition gr~dient, but slow freezing did not because a slow-moving interface tended to reject lead. as discussed later.) To determine local composition. ;-g samples were cut from regions exhibiting various microstructures and were chemically analyzed for lead content. Micrographs were taken on as-polished or lightly etched surfaces. Three-dimensional structure of the lead network was viewed with a scanning electron microscope after removal of some of the copper matrix with nitric acid. RESULTS Several different microstructures are observed, depending on composition and drive rate. Because melting and resolidification produced composition gradients, results are best presented in t&ms of final local composition, rather than initial or average composition. The ranges of local compositions and drive

Jan 1, 1970

By W. C. Hagel, J. H. Westbrook

THERE has been a recent revival of interest in the intermetallic compound AgMg as an experimental material for study of the physical and chemical properties of simple ordered structures. Studies of mechanical behaviors,1-4 diffusion,5,6 and thermo-dynamic properties7&apos;8 have been reported. In several of these studies, heat treatments have been carried out in argon-filled silica capsules at temperatures as high as 750°C with no apparent adverse effects. The present authors were, therefore, startled to discover in the course of some yet unpublished work, that gross melting of near-stoichio-metric AgMg compositions occurred in such samples more than 100 deg below their melting point of about 800°C. This note is to report a brief series of experiments carried out to establish the reason for this behavior. Gross errors in sample composition and failure of furnace temperature controls were quickly eliminated as causes of melting. The first tangible lead came from chemical analysis of an AgMg sample which had melted during treatment at 750°C. A silicon content of 3.3 wt pct was found. Since satisfactory analyses had been obtained on the original as-cast ingot, contamination by diffusion and/or reaction with the fused silica capsule seemed a distinct possibility. A perplexing fact, however, was the apparently capricious incidence of the effect. Not only was it previously unknown, even in the experience of the present authors; but, in the early part of the present study, melting sometimes occurred and sometimes not with specimens treated under constant conditions. Indeed, one sample successfully survived a 750°C heat treatment and yet melted completely during the course of a subsequent anneal in an identical capsule at a lower temperature. To obtain evidence that silicon contamination could lower the melting point to the extent observed, the following experiment was performed. A series of ternary alloys was made up with a stoichiometric AgMg base and containing 0.1, 0.2, 0.4, 1, 2, and 4 wt pct Si. Melting was done in MgO crucibles under a cover of argon gas. After holding 10 to 20 min in the temperature range 850° to 900°C, the alloys were allowed to solidify in the crucible and the temperature during cooling automatically recorded with a Pt/Pt-10 Rh thermocouple. Results from the cooling curves are shown in Fig. 1. Checks within 2 to 5C° were obtained upon repeated melting, cooling, and freezing. The whole series of cooling curves as well as metallographic examination of the melted alloys established that the AgMg rich portion of the AgMg-Si quasibinary is an eutectic-type system. The melting point of AgMg is lowered from approximately 820°C in the pure stoichiometric binary9 to about 710°C in the saturated intermetallic phase. Since second phase was observed in all samples on cooling to room temperature, the solid solubility of AgMg for silicon evidently falls rapidly with decreasing temperature as indicated schematically by the dashed solvus in Fig. 1. It is thus established that a silicon content

Jan 1, 1963

By Richard D. Call

Predicting the performance of a waste embankment requires an estimate of the properties of the waste and foundation materials. The performance characteristics and the associated material properties are: [ ] Methods for obtaining estimates of the material properties include: laboratory and field testing, back analysis, and indirect estimates from other material properties. The most critical technical need is the development of indirect methods for use in feasibility studies and mine planning, prior to production when actual samples of waste material are not available. Material properties are not unique, single values; they are probability distributions. There are two components to these distributions: the uncertainties in testing and the inherent variability of the material. The objectives of a material properties evaluation should be to obtain an unbiased estimate of the property distributions rather than the average or the minimum value. Whether the current trend to a probability design analysis is followed or a simple sensitivity analysis is conducted, the unbiased probability distribution is preferable to single values.

Jan 1, 1985

By James P. Kimball

Jan 1, 1885

By G. A. Beiswenger

The application of the law of supply and demand to the sale of crude oil is generally conceded, but the motives underlying the buyer&apos;s (refiner&apos;s) demands are not always obvious to the seller (producer). In some cases this obscurity has led to the conclusion that the refiner may be unnecessarily particular when he selects one crude and rejects another. This preference, however, is very largely the reflection of the refiner&apos;s product demands and the quality of the stocks obtainable from the selected crude. The purpose of this paper is to point out critical characteristies of the major classes of refined products and to show how crudes vary in their suitability for such products. With relatively few exceptions, available processing methods and addition agents make it theoretically possible to produce any type of refined product from any crude source, although it may not be economically sound to do so. The widespread application of thermal cracking for converting higher boiling stocks into gasoline is well known. More recently cracking and refining in the presence of catalysts9 have been developed, as well as various processes for polymerizing lighter hydrocarbons into gasolines having desirable characteristics.6 For several years, selective solvents have been applied commercially to refining inferior quality kerosene, Diesel fuel and lubricating oil distillates.3 Improved methods for refining lubricating oils from crude residual4 formerly suitable only for fuel, are now in use and a number of special solvent processes are available for dewaxing lubricating oils to low pour point.5 These improved refining methods have been developed not only to meet the demand for improved product quality but also to enable the refiner to obtain quality products from crude sources that would not yield such products by the older refining methods. In many cases, the utilization of these modern refining tools necessitates an appreciable expenditure for equipment as well as added manufacturing costs, and their application therefore must be justified economically. Despite the availability of such tools, the added processing costs involved and yields obtainable may render their application entirely impractical. To illustrate this point, inspections of typical cuts from various crudes

Jan 1, 1940

By Albert J. Phillips

LEAD is an inexpensive metal produced and consumed in large quantities with certain chemical and physical properties that permit handling the molten metal in bulk. These properties are its low melting point, resistance to oxidation, and its negligible solvent action on iron and steel. Thus, lead is almost always melted in large iron or steel kettles, heated from beneath, and is seldom melted in either directly or indirectly fired furnaces or electric induction or arc furnaces. Even with a modest operation a kettle holding 2 or 3 tons is employed, and the size will range up to 215 tons in the large lead refineries. The methods of handling tin and its alloys are essentially the same as for lead because of the similarity in melting point and resistance to oxidation, although because of the cost of the metal the scale is more modest. In melting lead and its alloys preliminary to a casting operation it is seldom that the melting unit is completely drained of its contents. The usual procedure is to continuously charge solid metal and continuously remove small amounts of liquid metal, so that the kettle is maintained essentially full at all times. For type metals, linotype machines usually employ automatic means of adding the solid alloy to the melting pot in proportion to the removal of the liquid metal in casting slugs of type. In the casting of grids for storage batteries, frequently automatic means of charging solid metal in direct proportion to the consumption of liquid metal in the casting is used. In the manufacture of bearing alloys, new alloy is charged in direct proportion to the consumption of metal in the bearings being cast, so that at no time does the level of the metal in the melting pot lower to any great extent. Even in the manufacture of bulky commodities such as pipe, cable. sheathing, and slabs for rolled sheet, it is the practice to employ a melting kettle of several times the capacity of the casting being made. A substantial level of liquid metal in the melting kettle is thus maintained even after the casting is poured and the original metal level is quickly restored by promptly charging new metal, even though there is no immediate need to proceed with additional casting. This procedure is permissible because the amount of fuel consumed in keeping the lead molten and immediately available for use is negligibly small and the cost is more than offset by the convenience. However, this convenient procedure necessitates study and control of certain properties of lead and tin alloys that are not of serious consequence in most other alloys and for that reason are not well known. These properties are "drossing rates" and "melting segregation." DROSSING RATE Users of lead long ago observed that the rate of dross formation on the surface of the lead in their kettles or pots varied greatly from time to time. This was particularly common in places where both antimonial lead alloys and commercially pure lead were being handled.

Jan 1, 1946

Illustrated guidebooks treating in a popular descriptive way of the geology and other features of the Western United States have been issued by the U. S. Geological Survey. They will be of much interest to mem¬bers in connection with the Arizona Meeting of the Institute and espe¬cially the guidebook of the Santa Fe Route, with side trips to the Grand Canyon, containing as it does relief maps, topographical and geological maps, covering the entire route of the railroad, illustrations from photo¬graphs and other interesting descriptions of this great country. The method of treatment is adapted to the lay-reader, although it includes much valuable and interesting technical information concerning the geographical and other features. The books are well indexed. These volumes sell for 50 c. each and may be obtained from the Superintendent of Documents, Washington, D. C. These guidebooks originally sold for $1 each, but the reprint edition has been reduced to 50 c. A list of the different guidebooks follows: Bulletin 611. Guidebook of the Western United States, Part A, The Northern Pacific Route, with a Side Trip to Yellowstone Park, by M. R. Campbell, and others. 1915. 212 pages, 27 route maps, 27 plates, 39 text figures.

Jan 6, 1916