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By R. Bakish, M. A. Badiali, N. W. Kirshenbaum

One pound of ultra pul-e molybdenum has been produced containing both metallic and nonmetallic impuvities close to or less than the limits of detection. various purification methods were investigated; althouglz the use of move than one purification step was consideved, it was found that a single, caefully-controlled sublimation of MoCl5 yielded a highly puvified product without prior treatment or recourse to repeated sublimation. Hydrogen reduction of MoC1, to metal was attempted at atmospheric pressure; however, reduced pressure was necessary to obtain substantial yields. The tubular deposits of metal were consolidated into bulk fovm by electron beam melting undev high vacuum yielding a very low gas content. Boblems involved in monitoring the puvity of these materials and analytical results obtained are also presented. THE pronounced effect of even trace amounts of impurities upon fundamental properties of materials is well known to metallurgists and solid-state physicists. Consequently, groups interested in basic studies of metals have in recent years immensely stimulated the preparation and production of numerous ultra-pure metals. Increased demand by scientists for these high purity materials has necessitated development of facilities to prepare them in significant quantities; the procedures reported here were devised to produce significant quantities of ultra-pure molybdenum. Previous work performed in the field of vapor phase purification and hydrogen reduction of several other refractory metal chlorides had demonstrated valuable techniques applicable to molybdenum.' Various purification and reduction steps were individually investigated. Those procedures which showed the most favorable results with respect both to attainment of high purity and to ease of operation were then incorporated in the process utilized to produce the metal.' STARTING MATERIALS It is well known that because of differences in volatility, chlorides may be separated by fractional distillation. It was presumed that distillation of molybdenum pentachloride offered a simple and straightforward method of purification due to its relatively low boiling point. Alternatively, sublimation of the solid chloride also appeared feasible since MoC15 has both a reasonably narrow temperature range in which it exists as a liquid (a property typical of refractory metal chlorides) and a low enthalpy of sublimation. Pertinent thermochemical data of MoC15 are given in Table I. It should be noted that this compound must be handled with care as it is extremely hygroscopic. Anhydrous MoC15 was obtained from the A Metal Climax Co. METHODS OF PURIFYING MOLYBDENUM PENTACHLORIDE Distillation. It was expected that distillation methods, while affording an efficient purification, would prove simple to control and would have a higher production rate than sublimation processes. Also considered was the possibility of effecting a high degree of purification by using both these volatilization methods in conjunction—possibly a distillation followed by sublimation of the solidified condensate. Distillation of MoC15 was investigated using a single stage distillation column packed with chemically resistant glass beads. Heating coils were wound around the column and collection tube (condenser). As-received MoCl5 was charged into a flask connected with the column using a side loading arm under an argon flow. After the column and condenser were brought to about 270" and 210°C, respectively, the apparatus was lowered until the flask was fully immersed in a constant temperature fused salt bath maintained at about 285 °C. Distillation was continued for about 10 or 15 min until 50 to 70 g of distillate had been collected. Analyses of these distillations indicated that several elements, e.g., Cu, Fe, Ni, Cr, and Mg, were lowered in quantity although not all were removed to the same extent. The occurrence of Na, B, Si, and A1 in the distillates appeared to be due to contamination, possibly from corrosion of the pyrex glass. An improved distillation system of larger capacity and longer distilling column was built. Improvements were effected in lowering the amounts of such impurities as B, Mn, Ni, Na, Mg, Cr, Cu, and Fe. These studies were pursued concomitantly with efforts to purify by sublimation; it was subsequently found that although improvements in purity were obtained by distillation, sublimation processes were simpler to control and effected a high degree of purity.

Jan 1, 1963

By B. J. Nelson, F. N. Rhinos

Studies upon the rates of oxidation of copper alloys containing small quantities of the alloying elementsl,2 have shown that steady growth of the scales at predictable rates is limited to a small concentration range and to oxidation at temperatures above 600°C., whereas unpredictable and erratic oxidation behavior is found with alloys containing larger additions and at low temperatures. The latter effect appears to be associated with modifications in the geometric disposition of the oxides. At low concentrations of the baser elements in copper, simple oxidation behavior is typified by the formation of two distinguishable zones of oxidation: (I) a subscale composed of discrete particles of the oxide of the alloying element embedded in substantially pure copper and (2) an external scale composed of cuprous oxide (with a very thin layer of cupric oxide on the outside) containing particles of the alloying element distributed throughout, but most profusely near the metal surface (see Fig. 2, top). Where this type of structure obtains, the process of oxidation is believed to be implemented, and its rate controlled, by the diffusion of the reacting elements through a' continuous matrix phase; i.e., through the alpha (metallic) phase of the subscale and alloy and through the cuprous oxide of the external scale. Copper is presumed to diffuse outward through the cuprous oxide layer to the external surface, where it reacts to form more cuprous oxide.3 Oxygen is delivered at the oxide-metal interface in the form of cuprous oxide, which may either react with the alloying element to deposit its oxide at the inner limit of the external scale or dissolve in the pure copper that remains at the surface of the metal after it has become depleted in its oxidiza-ble alloying elements. Both oxygen and the alloying element are pictured as diffusing through the metal, the oxygen inward and the alloying element outward. Where the two diffusion streams meet in sufficient concentration the oxide of the subscale is precipitated. If the oxygen pressure in the surrounding atmosphere is just below the pressure necessary to maintain cuprous oxide undecomposed, no cuprous oxide can be formed; some of the oxide of the alloying element may form upon the external surface, if its decomposition pressure is below that of cuprous oxide, and a normal sub-scale appears. This condition is achieved experimentally by enclosing the alloy with cuprous oxide together with an excess of copper. At temperatures from 600°C. downward, the precipitated oxides tend to accumulate at the grain boundaries of the alpha phase where a relatively small volume establishes a partial barrier to the diffusion of the reactants- Similarly, large volumes of Precipitated oxides tend to deposit in various patterns that may be expected to

Jan 1, 1944

By F. N. Rhinos, B. J. Nelson

Studies upon the rates of oxidation of copper alloys containing small quantities of the alloying elementsl,2 have shown that steady growth of the scales at predictable rates is limited to a small concentration range and to oxidation at temperatures above 600°C., whereas unpredictable and erratic oxidation behavior is found with alloys containing larger additions and at low temperatures. The latter effect appears to be associated with modifications in the geometric disposition of the oxides. At low concentrations of the baser elements in copper, simple oxidation behavior is typified by the formation of two distinguishable zones of oxidation: (I) a subscale composed of discrete particles of the oxide of the alloying element embedded in substantially pure copper and (2) an external scale composed of cuprous oxide (with a very thin layer of cupric oxide on the outside) containing particles of the alloying element distributed throughout, but most profusely near the metal surface (see Fig. 2, top). Where this type of structure obtains, the process of oxidation is believed to be implemented, and its rate controlled, by the diffusion of the reacting elements through a' continuous matrix phase; i.e., through the alpha (metallic) phase of the subscale and alloy and through the cuprous oxide of the external scale. Copper is presumed to diffuse outward through the cuprous oxide layer to the external surface, where it reacts to form more cuprous oxide.3 Oxygen is delivered at the oxide-metal interface in the form of cuprous oxide, which may either react with the alloying element to deposit its oxide at the inner limit of the external scale or dissolve in the pure copper that remains at the surface of the metal after it has become depleted in its oxidiza-ble alloying elements. Both oxygen and the alloying element are pictured as diffusing through the metal, the oxygen inward and the alloying element outward. Where the two diffusion streams meet in sufficient concentration the oxide of the subscale is precipitated. If the oxygen pressure in the surrounding atmosphere is just below the pressure necessary to maintain cuprous oxide undecomposed, no cuprous oxide can be formed; some of the oxide of the alloying element may form upon the external surface, if its decomposition pressure is below that of cuprous oxide, and a normal sub-scale appears. This condition is achieved experimentally by enclosing the alloy with cuprous oxide together with an excess of copper. At temperatures from 600°C. downward, the precipitated oxides tend to accumulate at the grain boundaries of the alpha phase where a relatively small volume establishes a partial barrier to the diffusion of the reactants- Similarly, large volumes of Precipitated oxides tend to deposit in various patterns that may be expected to

Jan 1, 1944

By FREDERICK J. ALCOCK

THE high prices which lead and zinc have commanded during recent months have given a great impetus to search for workable deposits of these metals, and there has accordingly risen a demand for information about deposits which have been worked in the past and which might possibly be opened up anew under these more favorable conditions. Production of zinc and lead in Canada has been on the increase during the last few years. In 1924, 175,- 485,499 lb. of lead with a computed value of $14,221,- 345 were mined. Of this, 96 per cent. was produced in British Columbia, 3 per cent. in Ontario, while Quebec and the Mayo district of the Yukon accounted for the remaining one per cent. During the same year the production of zinc amounted to 98,909,077 lb.. valued at $6,274,791. Of this 96,000,069 lb. were produced in British Columbia and the remaining 2,909,008 in Quebec. The large producer of zinc and also of lead is the Sullivan Mine at Kimberley, B. C. In comparison with the Sullivan, the deposits which are known to occur in eastern Canada are relatively small. Two, however, the Kingdoll lead mine at Galetta, Ontario, and the Tetreault zinc property at Notre Dame des Anges, Quebec, are steady producers. The object of this paper is to describe briefly these and other deposits of eastern Canada, to show their relation to geological events and to point out what are the chances of any of those which are idle at present developing into active producers or what are the possibilities of new deposits being discovered.

Jan 1, 1926

By J. J. Rutledge

I. DESCRIPTION OF THE CLINTON ORES AND ASSOCIATED POCKS. THE Clinton rocks in Stone Valley comprise (1) thick layers of deep-red shale, (2) layers of reddish-gray shale interspersed with beds of sandstone and thin beds of extremely fossiliferous limestone, and (3) yellowish-gray shales alternating with thin layers of olive-colored shales. These layers of shale are all very thin and are at no point massive.1 A bed of gray-white sandstone varying in thickness from 12 to 30 ft. occurs in the tipper portions of the Clinton shales. This is called the ore sandstone, a name given to it by Rogers and adopted also by the Second Pennsylvania Geological Survey. It is the surest guide to the presence of the iron-ore bed, which lies below its lower edges at distances varying from 10 to 20 ft. This ore sandstone, in the valley, lies generally at very low inclinations, but often is locally subjected to considerable changes in dip. At its outcrop this ore sandstone weathers very easily and yields a rather sparse crop of stone, Composed of dirty, iron-stained boulders. Upon the roads these boulders are quite well rounded, and bear fragments of crinoid stems and other fossil forms. The ore sandstone exhibits at many points evidences of former movements in this very great thickness of the shales, and as it is the only stratum in this series competent to transmit and record stresses due to structural movements, its evidence is of considerable importance in determining the occurrence of movements in times past.

Nov 1, 1908

By B. D. Saklatwalla

FOR the proper understanding of the inclusion of certain elements in this review it seems necessary to state the meaning of "rare metals." Certain elements occur in deposits limited in extent or concentration, so that the extraction of the element in relation to market conditions becomes uneconomical. Others may occur in extensive and rich deposits but the reduction of the metal may be difficult and costly. Both these conditions effect the same result, namely, make the metal rare and costly. As an example of the first kind may be mentioned radium and of the second, calcium.

Jan 1, 1939

By Norman D. Fitzgerald

IN 1943 the petroleum industry completed a series of practical adjustments to the acute problems which dominated the scene a year earlier. The crisis in petroleum transportation from the Gulf Coast to the East Coast was met by the completion of overland pipe lines supplementing emergency haulage by tank car so pressure on consumers along the Atlantic Seaboard was appreciably relieved. Later in the year when the western Atlantic was largely cleared of submarines, the sharp reduction in the hazards of marine transportation permitted the resumption of coastwise traffic and imports from South America. Nationwide restrictions in the use of gasoline and fuel oils became necessary as military demands for all petroleum products mounted to high levels.

Jan 1, 1944

By Samuel B. Christy

As is well known, the ore at New Almaden is cinnabar. Native quicksilver occurs also; but, as a rule, in small quantities only. Pyrite occasionally accompanies the ore. Bitumen is quite common,

Jan 1, 1885

By A. Perry Thompson

I. GENERAL DISTRIBUTIONS APPEARANCE, AND RELATIONS MINING in Butte has seldom encountered covellite in commercial quantities. The notable occurrences, extending vertically and laterally perhaps several hundred feet, presented scattered, bladed lenses of this mineral in a matrix of quartz, pyrite, enargite, bornite, and chalcocite. But under the microscope covellite is seen to be widespread in the Butte ores, though in such small quantity that megascopic examination will not discover it. In early mining operations covellite was found in the Gray Rock vein, a member of the Blue vein system. As described by Sales,1 it persisted as an occasional ore mineral, associated with quartz, pyrite, tetrahedrite, bornite, chalcocite, and minor amounts of sphalerite, from the 700-ft. to the 1,200-ft. level of the East Gray Rock and Diamond mines. Crushed quartz-monzonite and later quartz completed the vein filling between

Jan 4, 1915

By Max Hebgen

I. Natural Features of State Affecting Power Development .. 792 II. Early Developments. 1. Big Hole Plant................. 792 2. Canyon Feny Plant............... 793 3. Madison Plant No. 1............... 593 4. Black Eagle Plant................ 795 III. Later Developments. 1. Madison River System .............. 795 2. Missouri River System.............. 797 3. Great Falls System............... 797 4. Missoula River Development............ 797 5. Big Fork Development.............. 802 $ IV. Present Capacity of Power Developments....... 802 V. Transmission System...............: . 802 VI. Character of Load. 1. Lighting and Small Power Uses........... 804 2. Street Railways ................ 804 3. Mining................... 804 4. Railroads.................... 808 5. Irrigation................... 810 VII. Operation of System................. 812 VIII. Increase in Use of Power............... 811 IX. New Power Developments............... 814 X. Undeveloped Powers................. 815 It is estimated that the total stationary power now used in the United States. steam. water and gas. is probably over 30.000.000 h. p. The total developed water power is about 6.000.000 h. p. The water power in the United States now economically capable of development probably exceeds 25.000.000 h. p. The total developed and undeveloped power is

Jan 1, 1914

By Henry Wurtz

HERACLITUS, a sage of antiquity, called the dark philosopher, who refused a throne, preferring a hermit's cell, propounded, twenty-four centuries since, the maxim : [ ] War (or strife) engenders all things. This, though probably intended by Heraclitus to apply especially to the internal forces of nature, is often said, with equal reason, of the affairs of men. Controversial strife, whether fortunately or unfortunately, is a crucible through which all new discoveries in science, and all technical applications of science must pass-a test which they must all endure before they can become so vitalized as to germinate, so to speak, take root in the human mind, grow tip, and overspread the earth. The greater the number and the power of the elements arrayed against such a growth, and of the influences hostile thereto, the greater should be the inherent vitality of the germ, the more strenuous, skilful, and persistent its cultivators and upholders. During the decade last past we have had, in spite of the severe stringency of the times, an active growth of this kind in progress, whose prospective importance it would now be difficult to overrate. This is the movement which has for its motive the idea that, generally speaking, fuel should be gaseous in form, and which has for its goal the introduction into general public use of gaseous products, made by cheap and rapid processes and on a gigantic scale, distributed throughout our cities and towns in distribution-systems which shall be proportionately gigantic, and sold at prices which will bring such fuel within the means of the poorest householders. Personally, for ten years past, the writer has never failed, on occasions public or private, to urge his belief that the realization of this idea, deemed by him a certainty of the future, will bring about

Jan 1, 1880

By Bruno Nordberg

THE high cost of coal in Butte and the development of large amounts of cheap electric power from the Missouri river caused the Anaconda Copper Mining Co. in 1908 to make an investigation as to the possibility of adapting this cheap electric power for the operation of their many large hoisting plants. At this time electric power had already been adopted for practically all other power purposes around the mines, such as pumping, compressing air, etc. The map (Fig. 1) shows the location of the mines of the Butte mining district. These mines are located within a circle of approximately a 1-mile

Jan 9, 1913

Jan 1, 1961

By N. H. Emmons

An interesting development of copper blast-furnace construction has been brought about in adapting the blast-furnace to be a "burner" for sulphuric acid making. When the Tennessee Copper Co. first decided to construct an acid-plant, the standard type of brick-top furnace, supported by structural steel, was the only one in use at its plant. All the tests for temperature and strength of gas had been made on these furnaces, and had been satisfactory. When, however, the acid-plant was put on the flue, and the flue had to have a damper put in it to force the gas into that plant, troubles began. The furnaces were fairly tight, and for a few months the work was quite satisfactory. Fig. 1 shows the old type of furnace-top used at the start. It was soon found that this top would not stand the temperatures, particularly when dampered back, as was necessary to force the gas into the Glover towers. The structural steel, of which the furnace skeleton was constructed, warped and twisted so badly that it was not safe to use the furnaccs. This effect is shown by Fig. 2, which is a photograph of old No. 4 furnace, after the brick-work had been removed. It became apparent that a new type of top mas necessary and the engineering force was started on the design of a new furnace-top, with the result that a low top, with brick-lined flues at each end below the feed-floor, leading to the main concrete dust-chamber, was constructed. This furnace, No. 7, is shown in Fig. 3. The charging-doors are made of cast-iron sections, three sections to a door, and three doors to a side. A door to the furnace was made of east copper, but the heat was great that the copper bent readily, due to the jarring of its

Jan 1, 1911

By N. LILIENBERGS

DURING the past few years, the requirements for steel have been raised so high that soundness is more important than ever before. The old practice was to mike steel ingots of sufficiently large sections to permit a considerable reduction of area in rolling and hammering to a given size, relying on the fact that by such rolling and hammering all cavities will be squeezed together and practically eliminated. The finished sizes, if found by inspection of the surface to be faultless, were therefore pronounced to be sound. But when such steel is ?worked up,? the manufacturer is surprised and disappointed to find that it splits, or that streaks and seams make the product unmarketable. Large sections, such as rails, beams or heavy forgings, may, within certain limits, be sufficiently strong, even if the sides of the cavities are only squeezed, and not welded together. But it is well known that, in the interior of heavy articles, under certain conditions, forging may develop small streaks into large cavities. Small sections, steel for ordnance and tubes, and numberless articles in the tool-trade, always show up the defects. It may be doubted whether cavities in steel ingots can ever be completely welded. The old theory, is, that the silver-clear blow-holes, without the blue oxide, can be welded by sufficient working. They are, however, not empty, but are filled with carbonic oxide. It is admitted that the "blue" cavities, resulting from air mechanically drawn down into the mold during the casting, can never be welded, because the oxide does not melt, and there would be no escape for it if it did. The only way in which steel can be made satisfactory for the above-named particular purposes is by having it ?dead molten." But then the trouble of piping is encountered. As is well known, a pipe is the result of the contraction of

May 1, 1906

By R. G. Treuting

Germanium single crystals strained in tension at 600°C slip on the {Ill} plane and, macroscopically at least, in the <110> direction. Deformation is in homogeneous: various localized rotations are observed, as is a banding consistent with secondary slip banding. The structure after deformation is polygonized with a domain size of about 2x1O-3 cm. In relaxation tests, an incubation period prior to flow is observed, of duration inversely related to temperature and applied stress. Under continuous loading, there is a sharp first yield point. A critical resolved shear stress therefore must be cited with respect both to temperature and to rate of loading. At 600°C, when loading proceeds at 2900 psi per min, it is 1310 psi. The yield point phenomenon is suggestive of Cottrell&apos;s solute atom atmosphere theory and five points of qualitative agreement with this theory are found. PLASTICITY of germanium at elevated temperatures has been reported by Gallagher,&apos; who ascribed it to slip on {Ill) planes and described some associated effects. Preliminary experiments with single crystals of silicon and germanium loaded as simple beams confirmed {ill) as the slip plane of both materials.V his was demonstrated by the standard technique employing traces on two surfaces of known angle on a deformed crystal of known orientation.3 These experiments did not fix the slip direction, since more than one glide system operated. Uniaxial tensile straining is preferred for this purpose in order to restrict slip to one predominant system and to provide an unequivocal determination of the orientation change with respect to the stress axis. Experimental Method Specimens were diamond-sawed from germanium crystals containing about 5x10-5 wt pct Sb prepared by the zone-leveling process described by Pfann and Olsen;4 these specimens measured about 81/2 in. long, 0.20 in. wide, and were of various thicknesses from 0.035 to 0.060 in. Prior to testing, a specimen was coated over 1 in. or more of length at each end with Apiezon wax, chemically polished (in a solution of 15 ml HF, 25 ml HNO,, 15 ml CH3COOH, and 3 to 4 drops Br2), and dewaxed in warm xylene. A brief re-etching after scribing through a complete wax coating with vernier dividers provided gage marks at 0.200 in. intervals on the polished surface. A specimen with grips soft soldered to the ends was passed through the furnace tube and the grips pinned to the tensile machine in series with a stress gage. The Schopper testing machine is best described by reference to the illustration on p. 107 of Schmid and Boas5 and is operated with the pendulum arm locked, fixing the upper head. Load is applied through the screw-driven lower head, manually or by reduced speed motor. The furnace is 21/2 in. long surrounding a 4x7/16 in. ID quartz tube and was positioned about the specimen to permit free motion. The inert or reducing atmosphere required was sufficiently provided by a flow of helium introduced at the center of the furnace tube, with the tube ends loosely plugged with asbestos paper. Surface corrosion was slight. The stress gage employs a Be-Cu strip with SR-4 units incorporated in a simple bridge network with provision for balancing and calibrating. The bridge output on loading is fed through a Leeds and North-rup dc amplifier to a Speedomax 10 mv recorder, and calibration is obtained by dead loading. Experiments of two types have been conducted. Most have been in relaxation at constant elongation. One stress-strain curve has been taken with the machine continuously driven. Following extension of a specimen, Laue X-ray photographs were taken to obtain the orientation change between deformed and undeformed regions, recorded on a single film by translating the specimen in a plane normal to the beam between exposures. Sequences of such multiple exposures were made on some specimens to include the entire orientation range on one film. Slip Direction To obtain a maximum orientation change with a single slip system, crystals of very closely <110> axial orientation were used. The classic determination of slip direction rests on establishing that direc-

Jan 1, 1956

By AIME AIME

ONE hundred and eighty-three A.I.M.E. members, W. S. Morris with an excellent technical program, John Suman, "oil" President of the Institute, and a Texas norther blew into Dallas for the fall meeting of the Petroleum Division at the Adolphus Hotel, Oct. 16-18. and the most successful result will give future meeting committees a high mark to equal. People were still talking of the terrific heat the week before and it was quite noticeable that with the lowered temperatures, the members were in fine fettle for the technical sessions. The total attendance on Friday noon was

Jan 1, 1941

By Benjamin F. Merembeck

A mutispectral scanner (MSS) obtains remotely sensed data of the earth&apos;s surface in vector form, one vector element for each spectral sensing band of the MSS. Data generated by either airborne or orbiting MSS systems are organized in a lattice of scan lines and elements within scan lines. Each element, called a pixel, is represented by an observational vector and corresponds to a relatively small specific area on the ground. The total observations for a sensed scene frequently are in the millions and are composed of a number of populations, each representing a different land form category. Based on samples from the populations, the mean vectors, or spectral signatures, and the covariance matrices for the categories may be estimated. From these, an among category covariance matrix and a combined within category covariance matrix can be found. The total among category variance is the trace of the among category covariance matrix. Canonical analysis finds a linear transformation matrix such that the first transform variable accounts for the maximum possible part of the total among category variance. Similarly, the second transform variable, orthogonal to the first, accounts for the maximum possible part of the remainder of the total variance, and so on. Such transformation often results in over 95 percent of the total variance accounted for in the first three canonical variables, even though the initial number of spectral bands exceeded twenty. Transformation of bulk data into three canonical variates allows color map products to be developed by assigning each variable to a different basic color. Such color products are believed to be more useful for photo-interpretation than color products resulting from any combinations of three of the initial spectral bands.

Jan 1, 1977

By M. A. Schimmelpfennig, A. D. S. Gillies

Loss of visibility due to the occurrence of atmospheric fogging in underground mine airways can lead to longer travel times and loss of production efficiency, an increase in the frequency of vehicular and foot traffic accidents and difficulty in checking rock surfaces for instability and loose material. Where hot and humid surface air meets colder underground air, conditions for fog formation may be present. Further, suspended particulate matter from diesel exhausts or stoping operations together with slow movement of air along passageways may contribute to formation. This study describes an investigation being undertaken with the cooperation of Kennecott&apos;s Ozark Lead Co. to identify causes of the problem.

Jan 1, 1984

By C. M. Marquardt

Tramp iron and steel moving on a conveyor belt cause small currents to be generated in a coil situated in a strong magnetic field, which are converted to an alternating current and are amplified. The output voltage from the amplifier fires a thyratron with a relay in its anode circuit, which actuates a howler and simultaneously drops a spot of marker material on the belt.

Jan 1, 1950