Search Documents

By Luther Wagoner

HAVING given in a former paper1 the results of assays of sea-water, bay-mud, dredgings from San Francisco bay, etc., and' believing it might be interesting to extend the work to include' some deep-sea dredgings, I procured from the Smithsonian Institution six samples taken by the U. S, steamer Albatross, and marked as follows

Jan 9, 1907

By S. Shapiro, R. G. Ames

Background Research on the respiratory health of coal miners has focused predominately on the relationship between coal mine dust exposure and ventilatory function impairment (Lapp et al., 1972; Jacobsen, 1976), on the prevalence of coal workers' pneumoconiosis (Lainhart et al., 1969; Morgan et al., 1973), and on coal miner mortality (Ortmeyer et al., 1974; Rockette, 1977). Lesser attention has been paid to the effects of other mining exposures. For example, underground exposure to diesel exhaust emissions (Reger et al., 1980; Ames et al., 1982,1984). An omission in US coal mining research, however, has been identified by the US Office of Technology Assessment (OTA) as the failure to study the effects of inhaled polyvinyl chloride (PVC) thermal decomposition and combustion products (Seltzer, 1979). These products may be released in the mine environment by cable fires, cable explosions, smoldering cables, and conveyor belt fires. In addition to the OTA concern, recent findings of chronic respiratory conditions and other health complications resulting from exposure to PVC decomposition and combustion products in firefighters (Peters et al., 1974; NBS, 1980; NIOSH, 1982; Wallace, 1982), and in survivors of several large scale PVC-fueled fires (Dyer and Esch, 1976; Wallace, 1981, 1982), add immediacy to the concerns. PVC decomposition and combustion PVC decomposition is initiated at temperatures far below ignition (Hartstein and Forshey, 1974; Wallace, 1981). Hence, exposures to decomposition products from smoldering cables may be important health hazards in addition to cable insulation combustion products. Hydrochloric acid (HCL) appears to be the principle toxic substance from the thermal decomposition of PVC since up to 60% by weight is released as HCL (Barrow et al., 1979). HCL is released both as a gas and as an adsorbant on soot particles (Stone et al., 1973), thus allowing penetration of respiratory defenses. In addition, laboratory results indicate that phosgene (carbonyl chloride), a potentially lethal gas, may be produced in significant quantities from electrical arcing of wires covered with PVC insulation (Woolley, 1971; Brown and Birky, 1980). Health concerns related to PVC Toxic effects resulting from high level exposures to PVC pyrolysis and combustion products in animals (Cornish and Abar, 1969) and in humans (Wallace, 1981) is beyond question. Analyses have reported acute, or short-term, health effects resulting from exposure to PVC decomposition and combustion products (Peters et al., 1974; Polakoff et al., 1975). Recently, however, several studies have found that acute effects are often followed first by apparent healing, and then by delayed chronic effects. This pattern of consequential respiratory involvement among persons involved in major PVC-fueled fires has been noted in firefighters, specifically the 1975 New York Telephone Exchange fire (Dyer and Esch, 1976; Wallace, 1982), and the survivors of the 1977 Beverly Hills Supper Club fire (Wallace, 1981). An obstructive syndrome (low FVC and FEV1) was seen in 15% of workers three months following fighting a PVC-fueled fire (Colardyn et al., 1976). Long-term respiratory symptoms seen in studies of survivors of PVC-fueled fires include the bronchitis symptoms of cough and phlegm, and lung dysfunction (Wallace, 1981). Additional support for the thesis of longer-term respiratory effects resulting from PVC-fueled fires is derived from the finding that four persons who initially survived the Beverly Hills Supper Club fire died within nine months of the fire of severe respiratory impairment (Wallace, 1981).

Jan 1, 1986

By C. W. Hazelett

This paper is a resume of some of the accomplishments in direct rolling of strip from molten metal, and a description of some experimental developments in recent years. In all the early developmental work, we used a pair of rolls with a bath of metal between them, maintained by flanges or plates at the ends of the rolls. These flanges produced an excess cooling of the metal and built up enormous pressures at this point as the metal went through the bight of the rolls. Many means were tried for compensating for this excess cooling, such as thickening the strip at the edges, heating the end dams directly or by flowing more of the molten metal against them, leaving an open crotch below the end dam and above the bight of the roll, where the excessive pressures built up could be relieved by some of the metal squeezing out at this point, and so forth. All of these helped somewhat to solve the problem, so that very large heats of many metals melting up to 200°F., having commercially uniform gauges, could be rolled up to 24 in. in width. The rolls were made by mounting heavy rings on heavy shafts, and pressures up to 75,000 lb. per inch in width were used. Cooling of the rolls was generally done by spraying water on the outside surface of the rolls that came in contact with the molten metal. Roll life was commercial with brass, barely satisfactory with copper, and totally impractical with steels. The greatest difficulty encountered in all this work was caused by lack of uniformity in the product, owing to a folding action in the mill. Those who are familiar with the operation of a rolling mill know that a bar entering a mill moves at a lower speed than the peripheral speed of the roll. However, the metal solidifying from a bath in a direct rolling mill is cast at exactly the peripheral speed of the roll. This results in irregular folding of the metal, some irregular remelting of the previously solidified sections, and it is difficult, if not impossible, in some cases to exert enough pressure to weld these folded sections sufficiently into a sound product. In addition to this melange of solid, semisolid and liquid metal in the bath, we know that pressure near the freezing point of any alloy in which the constituents have different melting points—and I believe all of them have—causes the lower-melling-point constituent to be squeezed back until it becomes cold enough to solidify and go through the mill. This segregates all alloys, the segregation increasing with the pressures and the freezing ranges of the metals. Add to these problems the excessive roll-maintenance costs with high-melting-point metals and then, the greatest difficulty of all, the vanity of homo sapiens where a matter of possibly large importance is being considered, and the problems seemed almost insuperable. It was long ago obvious to me that something much more than the size of a corporation's money and self-assuradce was necessary if this process was to be made commercial. I should like to show you first the performance of the only mill we ever really designed and built, to see what might be done with a well constructed mill. We accomplished something new in history with this prccess, first, by producing at Scovill Manufacturing Co. coils of brass

Jan 1, 1945

By HORACE V. WlNCHELL

Location. THE St. Helens mining-district, indicated in sketch-map, Fig. 1, is chiefly in Townships 9 and 10 North, Ranges 5 and 6 East, of the Willamette meridian, in Skamania county, Wash. There is no railroad or even a wagon-road at present connecting it with any base of supplies; access is usually by wagon-road for FIG. I.-SKETCH-MAP OF THE STATE OF WASHINGTON. about 50 miles from the town of Castle Rock to Spirit lake, and from that point by pony-trail from 6 to 10 miles farther. History. Nearly 20 years ago two German farmers, totally inexperienced in prospecting, penetrated this region upon a hunting and fishing-trip. Their attention was drawn to numerous joints and crevices filled with black, glistening tourmaline, and con-

Oct 1, 1912

In traversing lately the Sierra Madre, west of Sail Pedro and Guanacevi, I estimated the topographic summit at several points, by aneroid barometer, at about 8,500 ft. Mr. Weed's measurements, 40 miles further north, are from 9,000 to 9,500 ft., and indicate the correctness of the impression I obtained at the time, namely, that the greatest movement in the elevation of the Sierra was between Guanacevi and Guadaloupe y Calvo. This is suggested also by the course of the headwaters of the Rio Conchas and of the Nazas, and by the relative corrasion of the branches of the two streams. Mr. Weed's statements as to the unevenness and great relief of the andesite floor underlying the later dacites and rhyolites are very interesting, and lead me to add that the floor of the andesite breccias and flows is uncovered for several square miles east of Guanacevi. This floor is of reddish, bluish and gray shales, lying horizontal or dipping slightly east. Their age is unknown; but from the interbedded occurrence of copper sulphides, I took it to be Triassic,

Jan 1, 1903

By T. A. Rickard

It has been stated, by Sir James M. Barrie, that "the man of science appears to be the only man who has something to say, just now-and the only man who does not know how to say it". The friendly jibe of the novelist contains enough exaggeration to make it humorous to the followers of Huxley and Spencer; but could any litterateur poke similar fun at the exponents of the avowedly utilitarian branches of science-the men of technology-without suggesting an unpleasant truth? Indeed the engineer does bungle language deplorably. He makes a fetish of efficiency, yet he shows no regard for the effective use of one of his most important tools-the pen; he believes devoutly in accuracy, yet he employs an instrument of precision as carelessly as a small boy handles a gun. This inconsistency may be due to causes such as were indicated by the Academic Senate when it undertook to explain the defective writing of the; students in this university.* The Senate suggested that the student is "constantly subjected by his environment to the unedifying influence of myriad examples of poor English", and that he is also affected by "a certain public prejudice against correctness of expression ". With these statements most of us will agree. Our local newspapers, for instance, tend to spoil the student's taste for good English; later in life, as an engineer, his daily contact with illiterate men inclines him to careless speech and slovenly writing. As

Jan 1, 1931

By J. L. Gregg, C. W. Kuttner

ReceNtly there has been considerable interest in the production and use of extra hard alloys composed primarily of tungsten and carbon. Dr. Hoyt's recent paper1 gives a good description of these alloys and describes their performance when used as tools. There are a number of these alloys on the market sold under various trade names, and it is the purpose of this paper to describe the results of an investigation of the structure of five of these alloys by means of microscopic and X-ray methods. The samples studied were in the form of small tools or wiredrawing dies, which were either purchased or supplied as samples. They were in some cases not supplied by the original makers but were furnished by the agents in this country, and we wish to call attention to the fact that they may not be truly representative of the materials supplied under the various trade names No performance data are given and no inference as to the inferiority of one alloy as against any other is made. K. Schröter2 recently described methods for polishing alloys of this type for microscopic examination and has presented photomicrographs of several alloys. However, he did not identify their constituents or describe methods for their identification. Constituents and Their Identification As far back as 1915 attempts were made to utilize tungsten carbides commercially, but the great brittleness of these carbides made these first attempts unsuccessful. Later, successful dies were made by sintering the powdered carbides with small amounts of iron, nickel, or cobalt. Due to the high melting points of the tungsten carbides (2600" to 2800" C.), it is difficult to melt the carbides without volatilizing almost quantitatively the added element of the iron group. Inasmuch as the added metal does not exceed 20 per cent. and is usually present in much smaller amounts, some understanding of the tungsten-carbon equilibrium dia-

Jan 1, 1929

By C. W. Kuttner, J. L. Gregg

ReceNtly there has been considerable interest in the production and use of extra hard alloys composed primarily of tungsten and carbon. Dr. Hoyt's recent paper1 gives a good description of these alloys and describes their performance when used as tools. There are a number of these alloys on the market sold under various trade names, and it is the purpose of this paper to describe the results of an investigation of the structure of five of these alloys by means of microscopic and X-ray methods. The samples studied were in the form of small tools or wiredrawing dies, which were either purchased or supplied as samples. They were in some cases not supplied by the original makers but were furnished by the agents in this country, and we wish to call attention to the fact that they may not be truly representative of the materials supplied under the various trade names No performance data are given and no inference as to the inferiority of one alloy as against any other is made. K. Schröter2 recently described methods for polishing alloys of this type for microscopic examination and has presented photomicrographs of several alloys. However, he did not identify their constituents or describe methods for their identification. Constituents and Their Identification As far back as 1915 attempts were made to utilize tungsten carbides commercially, but the great brittleness of these carbides made these first attempts unsuccessful. Later, successful dies were made by sintering the powdered carbides with small amounts of iron, nickel, or cobalt. Due to the high melting points of the tungsten carbides (2600" to 2800" C.), it is difficult to melt the carbides without volatilizing almost quantitatively the added element of the iron group. Inasmuch as the added metal does not exceed 20 per cent. and is usually present in much smaller amounts, some understanding of the tungsten-carbon equilibrium dia-

Jan 1, 1929

By WOOLSEY MCA JOHNSON

INDEPENDENTLY of the recognized chemical reactions involved in the production of metallic zinc, the process is affected by physical conditions in efficiency, and by commercial as well as technical economy. To offer some observations concerning these conditions is the purpose of the present paper. Among the important elements of this problem is the physical nature of the particles constituting the mass of zinc oxide to be reduced. This may be the result, either of the manner of the original deposition of the mineral, or of the treatment to which it has been subjected in the roasting-furnace. The physical character of the reducing-agent is another important factor, since the carbon of some coals is much more active in reduction than that of others. The degree of fineness, whether of ore or coal, or both, likewise plays a significant part. These factors, together with the physical admixture of foreign substances with the ore, may give rise also to chemical "side-reactions," sometimes hindering or retarding, and sometimes accelerating, the reduction. Finally, thermal conditions, including the relative conductivity of the materials, deserve to be taken into account. In firing a furnace with retorts charged with a mixture of roasted ore and coal, the first reaction is naturally the boiling-off of the contained water ; the next is the distillation of the light hydrocarbons from the coal; the next is the reduction of the iron oxide to protoxide and sub-oxide successively, and then to metallic sponge; and the final reaction is the reduction of the zinc oxide in the ore by the carbon to metallic zinc. This reaction commences at 1,022° to 1,060° C., according to the physical nature and condition of the coal and ore. Since the retort and the charge are far from being good con-

Sep 1, 1907

By T. V. Moore

DURING 1910, crude-oil production in the United States reached a record level averaging about 3.700,000 barrels daily. Export declined sharply while imports increased with the result that large quantities of crude oil were run to storage during the year. Imports consisted largely of residual fuel oil brought in from South America bit because of a shortage of that product in this country and of Mexican crude. The price of petroleum products followed the declining trend of the last three year resulting in serious disparity between crude and product prices. This condition was aggravated in some areas by the increasing production of distillate by recycling operations and by the high tanker rates prevalent in the last two months of the year. As a result two small purchasers found it necessary to reduce crude-oil price in the Corpus Christie area of Texas.

Jan 1, 1941

By A. M. Gaudin, C. S. Chang

Adsorption was measured for barium ion and laurate radical, using radioactively marked agents, over wide range of concentrations. Laurate adsorbed in absence of barium fails to float. With barium, flotation-effective laurate coating needs not exceed 5 pct of monolayer. Barium adsorption then is several fold larger. No barium laurate coating is obtained. IN general, fatty acids or their alkali salts do not cause clean quartz to float. However, the presence of multivalent ions, such as the alkaline-earth metal ions and heavy-metal ions, can activate quartz and thus make it respond to soap flotation. The mechanism of activation and soap flotation of quartz has been studied.'-' The problem was attacked by making flotation tests rather than by careful adsorption measurements on suspensions of ground quartz in solutions containing the activator and the collector. Attempts have been made to determine the adsorption of barium ion and calcium ion on quartz. The results have only qualitative value as the analytical methods were not adequately precise. Artificial radioactivity and progress in radioactivity detection have introduced a new analytical tool, which can have a sensitivity several orders of magnitude greater than that of other methods."-" In the experimental work described in this paper the radioactive tracers, barium 140 and carbon 14, were employed. Lauric acid was synthesized, having a radioactive carbon atom and was used with Ba" to study the adsorption of barium and laurate ions from aqueous solution on ground quartz. Flotation tests, using the vacuum flotation technique,' were run in conjunction with the adsorption experiments. The object of this investigation was to understand better the reaction mechanism of barium activation and soap flotation of quartz. Methods and Materials Quartz Sample Preparation: Lumps of hand-picked quartz, washed free of stains, were reduced in size to —20 mesh in laboratory crushers. The product was boiled in concentrated hydrochloric acid to remove the abraded iron. The cleaned product then was ground dry in a laboratory porcelain mill, using siliceous pebbles, to pass through a 200 mesh screen. The ground product was deslimed by sedimentation at 37 microns. This —200 mesh +400 mesh material was subjected again to boiling with concentrated hydrochloric acid, followed by washing with distilled water and further desliming. The cycle was repeated until no trace of iron could be detected in the wash liquor. During the final washing, the pH of the wash water was checked to insure the complete removal of the acid from the mineral. The quartz then was rinsed with conductivity water. The resulting product was dried in a drying oven and stored in mason jars. The impurities (spectrographic) were as follows: Al, 0.01 to 0.001 pct; Li, Mg, Mn, Na, each less than 0.001 pct; Fe and Cu not detected. The specific surface of the quartz sample was determined by the krypton gas adsorption method.' The average of two measurements was 881 sq cm per g. The calculated specific surface for 37/74-micron quartz particles, using a surface factor of 1.96; is 900 sq cm per g. This is in good agreement with the measured value of 881 sq cm per g. Beta-Counting Method: The radioactive isotope of barium used in the experimental work was barium 140. It has a sufficiently long half-life, 12.8 days, emits high-energy beta particles (up to 1.0

Jan 1, 1953

By R. C. Edwards, T. G. Kirkland, Will Mitchell

A scrubber of new design has been invented for the beneficiation of glass and chemical sands. The machine is described and its capacity and metallurgical efficiency compared with the performance of other sand cleaning devices. THREE years ago, when the Process Research Laboratory at Allis-Chalmers Manufacturing Co. sought a remedy for the increasing cost of disposing of great quantities of spent sands from foundries, R. C. Edwards developed a continuous inclined paddle scrubber which removed a substantial amount of the charred coatings from the grains with a surprisingly small amount of degradation of the sand itself.' The satisfactory results obtained on foundry sand, using this piece of equipment in conjunction with classification, suggested that a similar procedure could probably be applied to the cleaning of other sands, such as those required by the glass and chemical industries. This paper describes the flowsheet and the results of tests performed on impure natural sands. The four materials tested were silica sands obtained from widely separated geographical areas. Three of the sands tested contained various amounts of iron oxide and the fourth an excessive amount of calcareous bonding material. The iron oxide was present predominantly in the form of grain coatings, which were scuffed by the paddle scrubber, and in all cases a product was manufactured which would meet one of the sets of specifications imposed by the glass industry.' The Edwards paddle scrubber used in these tests consists of a rubber-lined steel cylinder 18 in. in diam and 48 in. long, mounted on a frame so that its slope can be varied 5" to 35" from horizontal. This variable slope permits controlled flow of material through the machine. Rubber paddles rotate inside the cylinder and are secured to a center shaft 2 in. square, which extends through the entire length and is turned at both ends so that it can be supported by sleeve bearings centrally fixed in the end plates of the shell. At the upper or feed end it extends through the bearing on the end plate into a sheave, to which the motor drive is connected by means of Texrope transmission. The four sets of paddles mounted on the shaft, two in each set, are made of rubber belting, 1/4 in. thick, 9 in. wide, and 16 in. long. The two paddles in each set are secured on opposite sides of the square shaft, but in the same longitudinal position along the shaft axis. In other words, the two paddles in the set operate 180" apart. Each successive set is mounted 90" from the preceding one. One end of each paddle is bolted to the square shaft and the other weighted by a steel bar, lx1 1hx9 in. long, which is attached about Yz in. from the outer tip of the paddle. By centrifugal force at proper shaft speed, these weights force the paddle surface to rub smoothly against the rubber lining of the cylinder. During operation, the sand forces its way between the paddle face and the surface of the cylinder, providing the necessary abrading action as the pulp flows by gravity down the length of the cylinder. The capacity of the machine is limited by the amount and the hardness of the coating material and by the quality of product desired. The degree of scrubbing is governed by the retention time in the scrubber, which in turn may be changed by varying the feed rate, water content of the feed, and

Jan 1, 1953

By R. C. Edwards, T. G. Kirkland, Will Mitchell

A scrubber of new design has been invented for the beneficiation of glass and chemical sands. The machine is described and its capacity and metallurgical efficiency compared with the performance of other sand cleaning devices. THREE years ago, when the Process Research Laboratory at Allis-Chalmers Manufacturing Co. sought a remedy for the increasing cost of disposing of great quantities of spent sands from foundries, R. C. Edwards developed a continuous inclined paddle scrubber which removed a substantial amount of the charred coatings from the grains with a surprisingly small amount of degradation of the sand itself.' The satisfactory results obtained on foundry sand, using this piece of equipment in conjunction with classification, suggested that a similar procedure could probably be applied to the cleaning of other sands, such as those required by the glass and chemical industries. This paper describes the flowsheet and the results of tests performed on impure natural sands. The four materials tested were silica sands obtained from widely separated geographical areas. Three of the sands tested contained various amounts of iron oxide and the fourth an excessive amount of calcareous bonding material. The iron oxide was present predominantly in the form of grain coatings, which were scuffed by the paddle scrubber, and in all cases a product was manufactured which would meet one of the sets of specifications imposed by the glass industry.' The Edwards paddle scrubber used in these tests consists of a rubber-lined steel cylinder 18 in. in diam and 48 in. long, mounted on a frame so that its slope can be varied 5" to 35" from horizontal. This variable slope permits controlled flow of material through the machine. Rubber paddles rotate inside the cylinder and are secured to a center shaft 2 in. square, which extends through the entire length and is turned at both ends so that it can be supported by sleeve bearings centrally fixed in the end plates of the shell. At the upper or feed end it extends through the bearing on the end plate into a sheave, to which the motor drive is connected by means of Texrope transmission. The four sets of paddles mounted on the shaft, two in each set, are made of rubber belting, 1/4 in. thick, 9 in. wide, and 16 in. long. The two paddles in each set are secured on opposite sides of the square shaft, but in the same longitudinal position along the shaft axis. In other words, the two paddles in the set operate 180" apart. Each successive set is mounted 90" from the preceding one. One end of each paddle is bolted to the square shaft and the other weighted by a steel bar, lx1 1hx9 in. long, which is attached about Yz in. from the outer tip of the paddle. By centrifugal force at proper shaft speed, these weights force the paddle surface to rub smoothly against the rubber lining of the cylinder. During operation, the sand forces its way between the paddle face and the surface of the cylinder, providing the necessary abrading action as the pulp flows by gravity down the length of the cylinder. The capacity of the machine is limited by the amount and the hardness of the coating material and by the quality of product desired. The degree of scrubbing is governed by the retention time in the scrubber, which in turn may be changed by varying the feed rate, water content of the feed, and

Jan 1, 1953

By A. J. Opinsky

ThE superior performance of nonsag tungsten wire in lamps has been ascribed to the large-grained micro-structure that can be developed in it. The orientations of these large grains have been studied several times; most published data1-' appear to be similar to those plotted in Fig. 1. These new data were obtained by X-ray back-reflection Laue technique from all of the large grains occurring in thirteen different wires that had been heated at the lowest possible temperature for the formation of large grains. Here the wire axis is plotted in terms of the principal directions of the cube. Rosi decided that the preferred orientation of the large crystals could be described by a single ideal orientation, (531), being parallel to the wire axis.' Rieck2,3 and Mannerkoski' have essentially confirmed this finding. Opinsky, Orehotsky, and Seigle argued that the data suggest that (211) is parallel to the wire axis instead of a single ideal orientation.5 This {211} contains the (531) ideal orientation and would appear to be a more general case. Ahlborn and Wassermann report that their orientation data stretch from ( 110) through (531) to (311) 8 This is part of the locus of (211). All these investigators have determined the orientations of the large grains by back-reflection Laue techniques. They have all obtained essentially similar results. On the other hand, Swalin and Geisler, who obtained their data by neutron diffraction, indicated that the preferred orientation of the large grains in doped wire is (110) .7 These findings cannot presently be reconciled with the pole density data described in the previous paragraph. Rosi1 and Rieck2 have advanced arguments about how their orientations could occur. Nevertheless, the crystallographic link between the (110) (cold-worked) fiber texture and the preferred orientation of the large grains has remained missing. This link can be provided through the concept of coincidence-type boundaries. Such boundaries separate two grains that have a certain number of common lattice sites. Coincidence relationships that result from rotations about low index directions are given by Brandon et a1 .' What is desired is a calculation of those orientations that bear a coincidence relationship with the (110) fibers of the cold-worked matrix. This situation arises in the following fashion. Heating the tungsten wire for a combination of time and temperature falling short of the formation of the nonsag structure yields a structure that is still fibrous in nature and the preferred orientation remains (110). During grain growth, the growing grain is in contact with these fibers. It is hence possible that the entire process may begin by the passage of a coincidence boundary into a (110) fiber. The calculations were carried out analytically and checked graphically. Following Brandon et a1.,8 coincidence relationships from 1 in 5 to 1 in 19 have been considered. The results of the calculations are given in Fig. 2. Of the coincidences examined, some of those occurring upon rotation about ( 110) come closest to the experimental points in Fig. 1. Nineteen of the twenty-three data points in Fig. 1 can be attributed to the ideal orientations A, B, C, and D in Fig. 2. As determined analytically, three crystals lie within 4 deg of point A, four lie within 21/2 deg of point B, eleven lie within 5 deg of point C, and one lies within 1 deg of point D-a total of nineteen. The off-lying points are near the |110| point of the triangle.

Jan 1, 1968

By Pedro Bolsaitis, Paul M. Sullivan

The activities of zinc in liquid Zn-A1 alloys in the temperature range of 1000' to 1160°K were determined by means of the isopiestic technique. The results are in reasonable agreement with the previous values determined by the radioactive tracer dew point method. Slightly negative excess entropies of mixing were found. The measured activities suggest that the a function for these alloys is not a constant, as has frequently been assumed, but is better represented by two straight line segments of different slopes. THE thermodynamic data of Al-Z alloys have been the subject of investigation by many authors. However, in the recent compilation of such data by Hult-gren et al.,5 the conclusion is reached that none of the previous measurements are reliable or consistent with each other. Since then two new sets of measurements have been reported,2, 8 both laying claim to good accuracies, yet showing very significant disagreement in the measured activity coefficients of zinc in Zn-A1 alloys and in the magnitude and sign of the excess entropies of mixing. Information on the thermodynamics of the system is of particular interest for interpreting results of the Bureau of Mines research on refining of zinc by distillation of die cast scrap. The present study was undertaken as an independent check on the recent values obtained from dew point measurements 8 and electromotive force measurements.' The isopiestic method, first introduced by Herasy-menko,' was chosen because it is one of the few thermodynamic techniques which, in principle at least, is carried out under perfect equilibrium conditions. The disadvantage of the method is that data are obtained at various random compositions and temperatures, which makes the interpretation somewhat cumbersome. The random errors arising from temperature gradients and fluctuations appear to be comparable to those of other techniques, as evidenced by the magnitude of the estimated uncertainties in the calculated integral thermodynamic quantities. An advantage of the method is that each run provides a relatively large amount of data; thus, it is less time consuming than those methods where samples of each composition must be measured individually. EXPERIMENTAL PROCEDURE The activities of zinc in liquid Zn-A1 alloys were measured by the isopiestic method which uses the principle of the tendency toward equilibrium of a series of samples at various temperatures under an imposed vapor pressure of the more volatile component (i.e., zinc, in this case). The basic apparatus is shown in Fig. 1. The small graphite crucibles that contained the metal samples were 15 mm ID and 13 mm deep with approximately 3 mm wall thickness. Each crucible was notched at the top and bottom to allow easy passage of vapor from one to another. At the beginning of an experiment each crucible was weighed on an analytical balance. Zinc and aluminum of spectrographic purity (99.999 pct) were then weighed into the crucibles. The amounts of each metal added were such that initial compositions varied above and below equilibrium values. One crucible contained only pure zinc. After weighing, the crucibles were stacked with the pure zinc on the bottom (corresponding to the lowest temperature in the furnace) and richest aluminum alloys at the top. The entire stack of crucibles was then placed in the silica glass container "E" which was then sealed under vacuum. Sixteen to twenty calibrated Chromel-Alumel thermocouples were attached by wire along the length of the silica tube, one or more adjacent to each sample.

Jan 1, 1970

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

Phases present at 2200° and 1500°F (1204° and 816°C) were identified in sixty wrought developmental austenitic alloys possessing wide compositional variations. The bases were iron-, cobalt-, and nickel-rich as well as a base with equal parts of each. There are only two structure types previously not found in similar alloys, viz .-the Co3 W and the Fe3Al types. A molybdenum-rich monocarbide decorates dislocations with unusual clarity. Other results provide correlations between alloy composition and phas e precipitation. Grouping intermetal -lic phases into three general classes : I) geometrically close-packed, 2) topologically close-packed, and 3) bcc derivatives, the nickel base prefers the first, the iron base the second, and the cobalt base the third—each base tending to shun the other two classes. Thus, a crystal-chemistry effect previously noted by Laves and Wallbaum can he expanded for these Group VIII elemental bases. There appear to he no quaternary or higher -order structure types requiring more than three atomic species. AFTER studying aging reactions in many diverse commercial austenitic alloys1-4 as a function of detailed time-temperature variations in heat treatment, it became apparent that matrix composition influenced structure types and morphologies to a large extent. These tendencies were related4 to a crystal-chemistry effect uncovered by Laves and Wallbaum.5,6 We have now directed our efforts to exploration of the whole ternary field, covering the standard base elements—iron, cobalt. and nickel— with 10 to 20 pct Cr and moderate amounts, up to 10 pct, of the usual alloy additions. Solutioning and aging treatments were held constant with major emphasis on X-ray identification of microconstituents. The possible existence of exceptions to the Laves-Wallbaum effect, or any new phases, was sought. Phases appearing in austenitic alloys can be classified as geometrically close-packed (gcp), octahedral or nonoctahedral interstitial compounds, topologically close-packed (tcp), semicarbides, and bcc derivatives. Crystal structures of the first four classifications can be visualized as a dense packing of semirigid spheres of different sizes, while the bcc derivatives represent a less efficient packing of spheres. The Laves-Wallbaum effect involves the gcp and tcp phases. Gcp phases possess both tetrahedral and large octahedral interstices; examples are Ni3Ti(n), NiSAl(y'), Co3W(E), and other ordered AB3 compounds where B atoms are smaller than A. Their precipitation is primarily intragranular, presumably coherent with an austenitic matrix, and a chief source of strengthening. Most octahedral interstitial compounds (e.g., CbC, Tic, TiN, Mo2C) have a gcp lattice of large metal atoms which accommodate small carbon or nitrogen atoms in the octahedral interstices. The compound Ti2SC, previously designated Y phase or T phase, can, with some reservation due to its partial co-valency, be placed in this category.7 The nonoctahedral interstitials (e.g., M7C3, Fe3C) represent close-packings of spheres in structures that provide larger triangular-prism interstices for carbon, since the octahedral interstices formed by chromium and iron atoms are too small. Tcp phases possess only tetrahedral interstices; examples are Laves (Fe2Ti, Fe2Cb, Fe2W...AB2), p(Fe7MO6, Co7W8.... A8B7), and (FeCr, Co2Cr3)

Jan 1, 1965

By R. C. Edwards, Will Mitchell, T. G. Kirkland

A scrubber of new design has been invented for the beneficiation of glass and chemical sands. The machine is described and its capacity and metallurgical efficiency compared with the performance of other sand cleaning devices. THREE years ago, when the Process Research Laboratory at Allis-Chalmers Manufacturing Co. sought a remedy for the increasing cost of disposing of great quantities of spent sands from foundries, R. C. Edwards developed a continuous inclined paddle scrubber which removed a substantial amount of the charred coatings from the grains with a surprisingly small amount of degradation of the sand itself.' The satisfactory results obtained on foundry sand, using this piece of equipment in conjunction with classification, suggested that a similar procedure could probably be applied to the cleaning of other sands, such as those required by the glass and chemical industries. This paper describes the flowsheet and the results of tests performed on impure natural sands. The four materials tested were silica sands obtained from widely separated geographical areas. Three of the sands tested contained various amounts of iron oxide and the fourth an excessive amount of calcareous bonding material. The iron oxide was present predominantly in the form of grain coatings, which were scuffed by the paddle scrubber, and in all cases a product was manufactured which would meet one of the sets of specifications imposed by the glass industry.' The Edwards paddle scrubber used in these tests consists of a rubber-lined steel cylinder 18 in. in diam and 48 in. long, mounted on a frame so that its slope can be varied 5" to 35" from horizontal. This variable slope permits controlled flow of material through the machine. Rubber paddles rotate inside the cylinder and are secured to a center shaft 2 in. square, which extends through the entire length and is turned at both ends so that it can be supported by sleeve bearings centrally fixed in the end plates of the shell. At the upper or feed end it extends through the bearing on the end plate into a sheave, to which the motor drive is connected by means of Texrope transmission. The four sets of paddles mounted on the shaft, two in each set, are made of rubber belting, 1/4 in. thick, 9 in. wide, and 16 in. long. The two paddles in each set are secured on opposite sides of the square shaft, but in the same longitudinal position along the shaft axis. In other words, the two paddles in the set operate 180" apart. Each successive set is mounted 90" from the preceding one. One end of each paddle is bolted to the square shaft and the other weighted by a steel bar, lx1 1hx9 in. long, which is attached about Yz in. from the outer tip of the paddle. By centrifugal force at proper shaft speed, these weights force the paddle surface to rub smoothly against the rubber lining of the cylinder. During operation, the sand forces its way between the paddle face and the surface of the cylinder, providing the necessary abrading action as the pulp flows by gravity down the length of the cylinder. The capacity of the machine is limited by the amount and the hardness of the coating material and by the quality of product desired. The degree of scrubbing is governed by the retention time in the scrubber, which in turn may be changed by varying the feed rate, water content of the feed, and

Jan 1, 1953

By R. C. Edwards, Will Mitchell, T. G. Kirkland

A scrubber of new design has been invented for the beneficiation of glass and chemical sands. The machine is described and its capacity and metallurgical efficiency compared with the performance of other sand cleaning devices. THREE years ago, when the Process Research Laboratory at Allis-Chalmers Manufacturing Co. sought a remedy for the increasing cost of disposing of great quantities of spent sands from foundries, R. C. Edwards developed a continuous inclined paddle scrubber which removed a substantial amount of the charred coatings from the grains with a surprisingly small amount of degradation of the sand itself.' The satisfactory results obtained on foundry sand, using this piece of equipment in conjunction with classification, suggested that a similar procedure could probably be applied to the cleaning of other sands, such as those required by the glass and chemical industries. This paper describes the flowsheet and the results of tests performed on impure natural sands. The four materials tested were silica sands obtained from widely separated geographical areas. Three of the sands tested contained various amounts of iron oxide and the fourth an excessive amount of calcareous bonding material. The iron oxide was present predominantly in the form of grain coatings, which were scuffed by the paddle scrubber, and in all cases a product was manufactured which would meet one of the sets of specifications imposed by the glass industry.' The Edwards paddle scrubber used in these tests consists of a rubber-lined steel cylinder 18 in. in diam and 48 in. long, mounted on a frame so that its slope can be varied 5" to 35" from horizontal. This variable slope permits controlled flow of material through the machine. Rubber paddles rotate inside the cylinder and are secured to a center shaft 2 in. square, which extends through the entire length and is turned at both ends so that it can be supported by sleeve bearings centrally fixed in the end plates of the shell. At the upper or feed end it extends through the bearing on the end plate into a sheave, to which the motor drive is connected by means of Texrope transmission. The four sets of paddles mounted on the shaft, two in each set, are made of rubber belting, 1/4 in. thick, 9 in. wide, and 16 in. long. The two paddles in each set are secured on opposite sides of the square shaft, but in the same longitudinal position along the shaft axis. In other words, the two paddles in the set operate 180" apart. Each successive set is mounted 90" from the preceding one. One end of each paddle is bolted to the square shaft and the other weighted by a steel bar, lx1 1hx9 in. long, which is attached about Yz in. from the outer tip of the paddle. By centrifugal force at proper shaft speed, these weights force the paddle surface to rub smoothly against the rubber lining of the cylinder. During operation, the sand forces its way between the paddle face and the surface of the cylinder, providing the necessary abrading action as the pulp flows by gravity down the length of the cylinder. The capacity of the machine is limited by the amount and the hardness of the coating material and by the quality of product desired. The degree of scrubbing is governed by the retention time in the scrubber, which in turn may be changed by varying the feed rate, water content of the feed, and

Jan 1, 1953

By Eric R. Morgan, J. C. Shyne

STRAIN aging is the name given to time-dependent changes which occur in the properties of cold-worked metals and alloys during storage. These changes are best observed through a study of mechanical properties, as illustrated in Fig. I for low-carbon steel. The effects of strain aging are usually regarded as being detrimental, particularly in deep-drawing steels. For example, an increase in yield strength and loss in ductility lead to buckling and tearing during drawing. At the same time the return of the yield point results in the formation of Luders bands or stretcher strains during the pressing operation. As a result of these effects many attempts have been made to eliminate strain aging from low-carbon steel. The problem still remains, however, because all known methods of preventing strain aging result in a more costly steel. The present work is an assessment of the situation in terms of theoretical, practical, and economic factors and suggests a new solution to the problem. Previous Work According to the Cottrell theory,' strain aging in a-iron may be regarded as the migration of interstitial atoms to free dislocations and the anchoring of dislocations by the resulting atmospheres. It may be concluded that the important factors which will govern the degree of strain aging are the diffusivity, the effective amount of interstitial element in solution, and the time of aging. The diffusivities and effective amounts of carbon and nitrogen in solution in low-carbon rimming steel are such that significant aging occurs in a few hours' storage at room temperature. Strain aging in deep-drawing steels cannot be controlled by controlling the time of aging because in commercial practice this is determined by economic factors concerned with inventories and may be several weeks. The diffusivity of nitrogen is twice that of carbon at room temperature but the diffusivities can be controlled by controlling the storage temperature. The retardation produced by only a 25 °C drop in temperature is significant but the cold storage of large steel inventories is an impractical solution to Table I. Analysis of Base Materials Alloy Pet C Yet 0 Pet N Vac 0.0037 0.052 0.0003 H 0.0044 0.013 0.0008 C 0.06 0.0014 0.0001 the problem. By far the most simple and effective ways to control strain aging are through control of the amount of carbon and nitrogen in solution. This may be effected through alloying, controlled precipitation, or by eliminating the carbon and nitrogen. Consider first the control of the amount of carbon in solution. The simplest approach would be alloy -ing in which strong carbide-forming elements are added. Examples of this approach are the additions of titanium' and niobium9 0 steel. These elements also combine with nitrogen and oxygen and when added in sufficient quantity result in a completely killed and non-aging steel. They are, however, impractical additions because they result in a costly steel. Carbon and nitrogen are often removed from iron on a laboratory scale by annealing in wet hydrogen, but because of cost this process has never been adopted on a commercial scale. In practice the amount of carbon in solution is controlled by the rate of cooling from the annealing temperature (710°C or 1310°F). In commercial box

Jan 1, 1958

By A. M. Gaudin, C. S. Chang

Adsorption was measured for barium ion and laurate radical, using radioactively marked agents, over wide range of concentrations. Laurate adsorbed in absence of barium fails to float. With barium, flotation-effective laurate coating needs not exceed 5 pct of monolayer. Barium adsorption then is several fold larger. No barium laurate coating is obtained. IN general, fatty acids or their alkali salts do not cause clean quartz to float. However, the presence of multivalent ions, such as the alkaline-earth metal ions and heavy-metal ions, can activate quartz and thus make it respond to soap flotation. The mechanism of activation and soap flotation of quartz has been studied.'-' The problem was attacked by making flotation tests rather than by careful adsorption measurements on suspensions of ground quartz in solutions containing the activator and the collector. Attempts have been made to determine the adsorption of barium ion and calcium ion on quartz. The results have only qualitative value as the analytical methods were not adequately precise. Artificial radioactivity and progress in radioactivity detection have introduced a new analytical tool, which can have a sensitivity several orders of magnitude greater than that of other methods."-" In the experimental work described in this paper the radioactive tracers, barium 140 and carbon 14, were employed. Lauric acid was synthesized, having a radioactive carbon atom and was used with Ba" to study the adsorption of barium and laurate ions from aqueous solution on ground quartz. Flotation tests, using the vacuum flotation technique,' were run in conjunction with the adsorption experiments. The object of this investigation was to understand better the reaction mechanism of barium activation and soap flotation of quartz. Methods and Materials Quartz Sample Preparation: Lumps of hand-picked quartz, washed free of stains, were reduced in size to —20 mesh in laboratory crushers. The product was boiled in concentrated hydrochloric acid to remove the abraded iron. The cleaned product then was ground dry in a laboratory porcelain mill, using siliceous pebbles, to pass through a 200 mesh screen. The ground product was deslimed by sedimentation at 37 microns. This —200 mesh +400 mesh material was subjected again to boiling with concentrated hydrochloric acid, followed by washing with distilled water and further desliming. The cycle was repeated until no trace of iron could be detected in the wash liquor. During the final washing, the pH of the wash water was checked to insure the complete removal of the acid from the mineral. The quartz then was rinsed with conductivity water. The resulting product was dried in a drying oven and stored in mason jars. The impurities (spectrographic) were as follows: Al, 0.01 to 0.001 pct; Li, Mg, Mn, Na, each less than 0.001 pct; Fe and Cu not detected. The specific surface of the quartz sample was determined by the krypton gas adsorption method.' The average of two measurements was 881 sq cm per g. The calculated specific surface for 37/74-micron quartz particles, using a surface factor of 1.96; is 900 sq cm per g. This is in good agreement with the measured value of 881 sq cm per g. Beta-Counting Method: The radioactive isotope of barium used in the experimental work was barium 140. It has a sufficiently long half-life, 12.8 days, emits high-energy beta particles (up to 1.0

Jan 1, 1953