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By R. H. Gautschi, F. C. Langenberg

Rare-earth additions were made to laboratory heats of Type 310 stainless to observe their effect on as-cast ingot structure, nitrogen and sulfur contents, and nonmetallic inclusions. Lanthanum had a grain-refining effect in 30-lb ingots, but results with 200-lb ingots were inconsistent. Cerium, lanthanum, and misch metal lowered the sulfur content when the sulfur exceeded 0.015 pct and the rare-earth addition was greater than 0.1 pct. The rare-eardh content in the metal dropped very rapidly within the first few minutes after the addition. The size, shape, and distribution of nonmetallic inclusions was not changed in 30-lb ingots, but changes were noticed in larger ingots. RARE-earth* additions have been made to austenitic Cr-Ni and Cr-Mn steels to improve their hot workability. The high alloy content of these steels often results in a considerable resistance to deformation and inherent hot shortness at rolling temperatures, particularly in larger ingots. Rare earths in the metallic, oxide, or halide form are usually added to the steel in the ladle after deoxidation although they can be added in the furnace prior to tap or in the molds during teeming. The literature- indicates that the effects of rare-earth treatments on these stainless steels are not consistent, and sometimes even contradictory. Since no mechanism has been presented which satisfactorily accounts for the claimed improvements, the effects of rare earths are a qualitative matter. The work described in this paper was initiated to expand the knowledge of the effects of rare-earth additions on melting variables such as ingot structure, chemical analysis, and nonmetallic inclusions. REVIEW OF LITERATURE Ingot Structure—Rare-earth additions to stainless steels have been reported to cause a change in primary ingot structure in that there are fewer coarse columnar grains. However, the results are inconsistent. While one investigation1 has shown a large reduction in coarse columnar crystals, another2 has been unable to observe this effect, particularly when small ingots were poured. Post and coworkers3 observed ingot structures for a number of years and found that the columnar type of structure is not definitely a cause of any particular trouble in rolling or hammering, provided the alloy is ductile. Knapp and Bolkcom4 found rare-earth additions to be quite effective in preventing grain coarsening in Type 310 stainless steel. Chemical Analysis—Many effects of rare-earth treatment on chemical analysis have been claimed in the literature. Russell5 observed that some sulfur is removed by rare-earth metals, and that a high initial sulfur content improved the efficiency of sulfur removal. Lillieqvist and Mickelson6 report that rare-earth treatment causes sulfur removal in basic open-hearth furnaces, but not in basic lined induction furnaces. Knapp and Bolkcom found no sulfur removal in acid open-hearth and acid electric furnaces, probably because the acid slag can not retain sul-fides. snellmann7 showed that sulfur could be lowered apprecfably with rare-earth additions; however, a sulfur reversion occurred with time. Langenberg and chipman8 studied the reaction CeS(s) = Ce(in Fe) + S(in Fe), and found the solubilit product [%Ce] [%S] equal to (1.5 + 0.5) X 10-3'at 1600°C. Results in 17 Cr-9 Ni stainless were about the same as those in iron. Beaver2 treated chromium-nickel steels with 0.3 pct misch metal and observed some reduction in the oxygen content. He also noted an inconsistent but beneficial effect of rare earths when tramp elements were present in amounts sufficient to cause difficulty in hot working. It is not known whether rare earths reduce the content of the tramp elements or change the form in which these elements appear in the final structure. No quantitative data are available concerning a possible effect of rare-earth treatment on hydrogen and nitrogen contents. However, Schwartzbart and sheehan9 stated that additions of rare earths had no effect on impact properties when the nitrogen content was low (0.006 pct), but served to counteract the adverse effects of high nitrogen content (0.030 pct) on these properties. Knapp and Bolkcom4 analyzed open-hearth heats in the treated and untreated conditions and found the nitrogen content (0.006 pct) to be unaffected. These two results lead to the speculation that rare-earth additions can reduce the nitrogen content to a certain level. Decker and coworkers10 have observed that small amounts of boron or zirconium, picked up from magnesia or zirconia crucibles, increased high-tem-

Jan 1, 1961

By F. R. Jones

AT Tahawus, N. Y., National Lead Co. operates the MacIntyre development. Here the world's largest titanium mine produces 5200 long tons of ore per day and pours 8000 long tons of waste rock over its dumps. Concentrated ilmenite is sent by rail to National Lead Co. pigment plants, and a second product, magnetite, is sold to steel producers in raw form or is agglomerated and shipped as sinter. Several earlier attempts had been made to produce iron from the deposits, which have been known since 1826. These attempts failed, chiefly because of titanium impurity. In 1941 the present owners reestablished the operation for production of war-scarce ilmenite, and the impurity became the main product. The Ore: The MacIntyre ore zone is about 2400 ft long and 800 ft wide in horizontal measurements. Ore outcrops were found on the northwest side of Sanford Hill, 450 ft above Sanford Lake and 2500 ft southeast. The zone dips at about 45" toward the lake and plunges to the southwest. The ore minerals, ilmenite and magnetite, are unevenly distributed in bands roughly parallel to the long axis of the ore zone and are interspersed with bands and horses of waste. Hanging wall ores are fine grained and grade from rich ore to waste rock or gabbro. Footwall ores are coarse grained and are almost entirely ilmenite and magnetite. The foot-wall waste rock, anorthosite, is the common country rock. Several faults cut the ore zone. These faults have no great displacement but do contribute to the great physical variations in ore rock and surrounding waste. The Mine: The MacIntyre mine is an open pit operation, with benches at 35-ft intervals. The lowest bench is now 54 ft below lake level. Loading equipment consists of three electric-powered shovels (a P & H model 1400 with 4-yd dipper and two Bucyrus-Erie models 85-B with 2%-yd dippers) and one diesel-powered shovel (a Northwest model 80D with 2%-yd dipper). Ore and waste are transported to a 48x60-in. jaw crusher in ten 22-ton Euclid trucks with 300-hp diesel engines. Ordinarily the two Bucyrus-Erie 2 % -yd shovels load ore into a fleet of three or four trucks. This combination works two 8-hr shifts per day, moving 5200 long tons of ore to the crusher and removing a small portion of the waste rock. The P & H model 1400 shovel, with a fleet of four trucks, loads waste on three shifts per day. The mine operates on a 5-day week, with a small maintenance crew working Saturday. Oversize rock is broken by a dropball handled by an Osgood model 825 rubber-mounted crane.' Ore and waste are broken by drilling and blasting 9-in. diam vertical holes behind the benches. Bucyrus-Erie 42-T churn drills are used to drill the holes, which are extended 4 ft below the bench level on which the broken rock will fall. Drilling and Blasting History: In its early years the mine was equipped with Bucyrus-Erie 29-T churn drills, which drilled 6-in. holes. To keep up with production requirements the hole diameter was soon increased to 9 in., and by 1950 the three 42-T drills now in use had been acquired. Early blasting experiments with different kinds and grades of explosive led to adoption of 90 pct straight gelatin dynamite as standard. It was recognized that this explosive was expensive, and from the start of operations until 1950 extensive experiments were made using blasting agents of the ammonium nitrate family. Results were recorded as uniformly poor, with great build-up of oversize rock. The expense of these experiments, and the discouraging results, caused the abandonment of any expectation of breaking MacIntyre rock with anything but 90 pct straight gelatin dynamite. Further standardization led to 9-in. well drillhole spacings set at 16 ft in ore and 18 ft in waste, exceptions being permitted only for unusual conditions. The hole burdens were theoretically about 22 ft. Due to the extreme back-slope of bench faces, caused by blasting with heavy charges of dynamite, actual burdens were commonly well over 30 ft. Lack of precise control resulted in many holes having a burden as light as 15 ft. General practice was to stem 6 or 7 ft of hole with magnetite concentrate, the amount of stemming being left to the discretion of the pit foreman. Usually all holes in a row were fired instantaneously with Primacord detonating fuse. Millisecond delays were

Jan 1, 1957

By Clarence Woods

ONCE a millionaire's plaything, the Santo Domingo mine, in Peru, is now, because of its metallurgical problem, an engineer's nightmare. It is deep in the montaña jungles of the Amazon basin, 140 mi. northeast of Tirapata, which is a rail- way station between Puno and Cuzco, and about 250 mi. east of Mollendo on the Pacific. The discovery was 111ade by Marian(-) Quispe, an Indian, who, while searching for quinine bark, was attracted by a slab of gold quartz 1x1 the rock wall of a narrow canyon. He broke off a piece, weighing 47 Spanish ounces and, that time, worth approximately $900. This he took to Francisco Velasco and Manuel Estrada, merchants of Coaza, who persuaded Quispe to lead them to the place, five days' journey on foot through a tangled wilderness. Velasco ' and Estrada denounced the claim

Jan 1, 1938

By AIME AIME

MANY producers have held that the only workable quicksilver ore is easily recognized by its .cinnabar content. In most cases this is true. A noticeable exception is a. particular opalite deposit where part of the ore now being mined in considerable quantity shows only the yellow mineral, calomel, or its alteration products. This mineral, on exposure to the sunlight, quickly becomes coated with gray or black layers that may be removed by scraping to reveal the yellow mineral beneath. The blackening of this mercuric chloride on exposure to sunlight shows reaction to form metallic mercury, which is usually plainly present in this class of ore.

Jan 1, 1929

By J. George Gregr

INTRODUCTION This part contains field case studies of typical mishaps, accidents, equipment damage or post installation failures resulting from mistakes in design, manufacturing and construction, as well as improper storage, handling and installation procedures of the equipment covered in Part 1. GENERAL Certain mistakes are repeated and common rules violated on almost all industrial equipment installations, with the inevitable consequences of additional cost, construction delays and aggravation of all parties involved. The most common failures are in the following areas: Cleanliness of all components during installation and later in operation. Adherance to manufacturer' s recommendations and tolerances for equipment installation. Comprehensive, properly identified installation and maintenance records. Handling of the components. Adequate tooling and auxiliary equipment in working order. An inoperable hydraulic power unit for torque wrench or for jacking of the mill, or faulty crane can be a very costly proposition. A special area in comminution circuits are wear components. Apart from the mill liners, the wear components such as, feed chutes, rock boxes, mill trunnion liners, discharge sumps, etc. are designed to the best theoretical configuration, based on experiences in similar installations. However, each process is different to a various degree, mainly because of various types of ores and grinding requirements. Consequently the first generation of wear components is very seldom the ideal one. Based on operational experience, the shape and material of wear components should be modified, until the optimum, most economical design is achieved. SHIPPING AND STORAGE Considerable damage to the equipment can be done by careless packing, shipping or storage.

Jan 1, 1982

By J. Wes Blakely

In the mid-1950s the importation of foreign oil began to encroach on traditional coal markets such as railroad steam engine fuel, home heating, electrical generating plants, and others. Many of the smaller coal companies with substantial coal reserves subsequently found that they could no longer continue to mine economically and merged in various ways with larger established coal mining concerns. As the seats of top management and authority were removed from the mines to large metro centers such as New York, Pittsburgh, and Chicago, the more personal relationship between mine workers and management that had existed prior to these mergers began to be eroded and replaced by 'remote control mine management. The disappearance of this face-to-face contact of upper management with mine employees tended to create barriers blocking simple effective communications between coal mine management and labor. In examining the human relations aspects of the coal mining industry, many elements, some concerned with work and others not, have depicted the industry as almost devoid of good applied human relations and communications practices, and, in truth, little has been done to alleviate this situation . In past years many coal producing companies, with the exception of one of the largest, failed to adequately define the term “communications” as it applied to their companies, whether internally or externally. Internally many still place heavy reliance on written communications such as company-wide newspapers to do the job of communicating with their employees which they feel ought to be done. One company puts an inordinate belief in its company "newspaper" as the primary instrument to stimulate its work force into increasing productivity. Primarily aimed at the workers, who greatly outnumber the salaried administrative people, this publication mainly documents the fortunes of individual mine workers who are felt to have achieved something with their lives, e.g., a mine worker who had managed to put four children through universities, the

Jan 1, 1981

Jan 1, 1932

By AIME AIME

A STUDY of subsidence and ground movement in the copper and iron mines of the upper peninsula of Michigan has been made by W. R. Crane of the United States Bureau of Mines and published as Bulletin 295 of 66 pages and 49 illustrations. As a result of subsidence, the country adjacent to the mines and over- lying the mine workings in this district is often broken to such an extent as to affect its value; mine shafts and development openings are occasionally so damaged as to be rendered useless, and water can enter the workings through fractures and cave-ins. The problem is more serious in the iron-mining districts, where villages and towns not owned by the operating companies have grown up around mining operations.

Jan 1, 1929

Jan 1, 1933

By D. H. Forbes, H. M. Manasevit, F. L. Morritz

Single-crystal thin films of molybdenum have been grown. by the pyrolytic decomposition of molybdenum hexafluoride in a hydrogen ambient on various insulating substrates at temperatures front 650° to 900° C. Single-crystal discs of various orientations of magnesium aluminate spinel, a aluminum oxide, magnesium oxide, and the natural facets of beryllium oxide were all observed to exert epitaxial control on the depositing film. Determinations of the crystallographic relationships existing between film and substrates have been made, using X-ray diffraction three-circle goniometry and Laue back-reflection techniques. Using these data, crystallographic overlays have been constructed which suggest a possible interfacial geometry on the basis of a match between metal deposit atoms and metal ion sites in the substrate. A continuing program has been in effect in the Auto-netics Laboratories over the past several years aimed at the development of electronic materials in new and useful forms using chemical vapor deposition techniques. During the course of these investigations, the epitaxy of silicon1"5 and tungstenep7 on single-crystal metal oxide insulators was studied extensively. The deposition of molybdenum is a logical extension of the tungsten work since the crystal structure is identical and the lattice dimensions differ by less than 1 pct. The pyrolytic decomposition of molybdenum hexafluoride in hydrogen was used to grow molybdenum films on the oxide substrates AlzOs, MgA1~04, MgO, and Be0 at from 650" to 900°C, depending on the substrate material. Under the experimental conditions to be described, monocrystalline films of controlled orientation were obtained. The materials investigated and their crystal structure are listed in Table I. EXPERIMENTAL The molybdenum depositions were effected by the hydrogen reduction of molybdenum hexafluoride (MoFe) in a flowing system of hydrogen at atmospheric pressure. The schematic of the apparatus is shown in Fig. 1. The hydrogen, purified by passage through a heated palladium thimble, was mixed with the vapor of the liquid MoFe maintained in a steel bottle at room temperature (25°C). The mixture was passed over the substrate, which was heated by rf induction of a sup-

Jan 1, 1969

HONORARY Membership in the Institute is limited to twenty and the roster is now only fifteen, so Dr. Reynders becomes a member of a select circle. All of his life, following graduation from Rensselaer Polytechnic Institute in 1886 at the age of twenty, lie has been connected with the steel industry. For about thirty years he stayed with the same company, the Pennsylvania Steel Co., until it was acquired by the Bethlehem Steel Corp., in 1916. For many years he had been vice-president and general manager. Before he attained that position, Dr. Reynders organized and remained in charge of the bridge-building department of the company, and during his professional life he has directed the construction of many

Jan 1, 1938

By U. K. Custred, E. W. Long, V. R. Degner

In 1973, the United States production of marketable phosphate rock set a record in excess of 42 million tons. This production rate is expected to continue to increase, due to the growing international requirement for fertilizer, at a rate exceeding 5% per year well into 1977. One approach towards increasing plant production capacity to meet the growing demand is through large-capacity flotation cells, provided they achieve metallurgical performance comparable to existing smaller cells. A 9-month evaluation test program recently completed at the Haynsworth mine at Bradley, Fla., demonstrated the feasibility of achieving economically acceptable concentrate grade and recovery levels using large, high-capacity flotation cells. The composition of the feed to the Haynsworth beneficiation plant is a typical Florida pebble phosphate matrix composed of phosphorite pebbles ranging in size from approximately 1-1/2 in. down to 150 mesh and intimately associated with a mixture of clay and sand (essentially silica). The feed contains approximately 22 to 28% phosphate reporting as tricalcium phosphate, Ca3 (PO,) 2, or "bone phosphate of lime" (BPL). The flotation section utilizes the double-float procedure typical of Florida plants. The phosphate is first floated away from the silica in the rougher circuit, using crude fatty acid, ammonia, and fuel oil or kerosene. Rougher conditioning is accomplished at 60 to 70% pulp solids with sufficient ammonia added to raise the pH to 9 to 9.5. Following coarse and fine rougher flotation, the concentrate (overflow) streams are joined and conditioned (sulfuric acid cleaned and washed) prior to entering the cleaner circuit where an amine float (cationic reagent and kerosene added in the feed box; pH 7.3 to 7.8) is employed to float the silica. The feed to the coarse rougher circuit averages 29% +35 mesh while the fine rougher feed averages 10%+35 mesh. Primary attention was directed toward the large rougher cell performance (recovery and grade) on coarse feed during the Haynsworth evaluation program. Flotation Cell Test Program A row of three No. 120 size (300 cu ft) WEMCO flotation cells was installed in parallel with an existing air-cell row. The total installed volume of the large cell circuit was 900 cu ft and required a floor space of 306 sq ft. This compared to the air-cell total volume of 200 cu ft and 152 sq ft floor space. (Both floor areas include feed and tails hoppers but exclude walkways.) Fig. 1 is a schematic cross section of the large flotation cell showing the relative location of key mechanism elements. In operation, the rotor generates a fluid vortex extending up along the walls of the standpipe and creating a sufficient vacuum within its core to ingest air into the standpipe/rotor cavity through the air inlet duct. The ingested air mixes with the pulp, which has been recirculated through the false bottom and draft tube, in the rotor. Further mixing occurs as the air and pulp move radially outward from the rotor, finally passing through the disperser into the flotation cell. Flotation is accomplished outside the disperser, where phosphorite laden air bubbles rise and the remaining pulp recirculates down along the cell wall to the false bottom and draft tube. Large-flotation-cell performance is influenced by the ability of the mechanism to (1) circulate, or suspend, the solids in the pulp; (2) ingest air into the rotor cavity; and (3) mix the air and pulp effectively. The proper balance between pulp circulation and air ingestion is a key consideration in achieving good recovery in a course feed application. Large-flotation-cell pulp circulation and air transfer characteristics are significantly influenced by rotor speed and rotor submergence; therefore, these two operational parameters can be used to "optimize" a particular mill application. Fig. 2 maps the hydraulic performance of the WEMCO No. 120 size flotation cell. This map can be used to relate the cell operational parameters which influence metallurgical performance. At a given rotor speed, power intensity (i.e., pulp circulation) is seen to increase, and airflow decrease, as rotor submergence is increased. The inverse relation between power and airflow is due to the two-phase air-liquid mixture density reduction accompanying the increased airflow rate. For any fixed rotor submergence, the power intensity (i.e., fluid circulation) and airflow both increase as rotor speed is increased. The selection of these two mutually related operating conditions (i.e., rotor speed and submergence) was a key consideration in the Haynsworth evaluation program.

Jan 1, 1976

By Maxwell Adams

OLIVER C. RALSTON, Salt Lake City, Utah.-We are indebted to these two gentlemen for the work which they have done with the oils derived from sage brush. Their work should not be confused, however, as the work of Mr. Adams deals with steam-distilled oils and that of Mr. Clevenger with destructively distilled oil, largely. In other words, Mr. Adams' oil is probably the original essential oil that existed' in the brush before distillation while Mr. Clevenger's oil not only contained this essential oil but also some products of destructive distillation of the wood constituents. I had noticed the work of Mr. Adams on attempting to separate the various constituents in the oils of some of the Western conifers and had sent to him to ask if he could send me small samples of some of. these pure products. This he very kindly did, and with them included some samples of oil from the common sage brush, whose characteristics he has here described, as well as a sample of oil from the common "rabbit brush." Only the sage brush oil proved of much value for flotation, but it, was very powerful, and I so informed Mr. Adams. Even in amounts as small or smaller than 1/10 lb. per ton of ore, it gave very quick and positive flotation of many ores, with high-grade concentrates and good extractions. It proved to be especially desirable for the flotation of carbonates of lead and of copper which had received an artificial coating of sulphide by treatment with a solution of a soluble sulphide. I also received a sample of crude pyroligneous acid from sage brush prepared by Dr. W. C. Ebaugh, of Salt Lake City. It did not do very good work in flotation, but it is possible that by concentration of this product to obtain the residual tar a good flotation oil might result. This has not been done as yet and I am sorry to see that Mr. Clevenger has not done this. It might be that the dissolved tar, added to the settled tar, would make a total yield of flotation oil higher than the 4 per cent. which Mr. Clevenger feels is a safe estimate. The importance of this point will be seen in the following discussion of the possible costs of sage brush oils for flotation.

Jan 10, 1916

By Theodore Hatch

The pneumatic rock drill operates essentially as a crusher. The rock is shattered into a powder that is removed from the drill hole by the air stream introduced through the hollow drill steel. Particles thus produced vary in size from 1/4 in. or larger down to diameters too small to be revealed by the ordinary microscope. The power consumed by the drill is proportional to the new surface area of the powdered material, therefore the greater the proportion of "dost" produced, the higher the power consumption and the lower the drilling speed. A considerable amount of material ejected from the hole settles on the rock and much of this falls back as the mound builds up to be crushed further before it is removed again. The cushion of dust at the bottom of the hole reduces the effectiveness of the blow of the bit and thus lowers the rate of drilling. The unfavorable working conditions created by the dust also reduce the drilling speed by lowering the efficiency of the operator. Thus, the dust produced by rock drills constitutes a serious drawback to economical performance on all drilling operations. To the economic objections, one must add the more important objection to the health hazard created when the dust contains free silica (quartz). The silicosis problem is a familiar one in many mines, tunnels, and other underground operations as well as in quarries and other types of open rock excavation. Dust is a necessary end product of all pneumatic drilling operations. Its production cannot be eliminated although the proportion of microscopic particles can be reduced by using improved drill steel, proper methods of sharpening, more efficient drills, etc.—improvements that increase the drilling speed largely by increasing the size of the cuttings. The absolute improvement secured in this way is not great, however, and the pneumatic drill must always remain a dust-producing machine. Definite benefits do result, on the other hand, from the use of dust-control equipment that captures the dust as it emerges from the hole and conveys it to a remote point of discharge. Dust production continues, but dust dispersion into the atmosphere is prevented. The dust is removed as rapidly as it is formed, with the following results: (I) The silicosis

Jan 1, 1937

By C. A. WARNER

IN all the meetings of the Petroleum Division, emphasis was placed on the essential importance, in the successful furtherance of our war effort, of efficiently producing, transporting, refining, and utilizing maximum quantities of crude oil and natural gas with the minimum expenditure of critical material. With representatives present from all branches of the petroleum industry, from all parts of the United States, the sessions were opened Tuesday morning with Commander Harry P. Stolz. U.S.N.R., Chairman of the Division, and A L. Haider as associate chairmen. From that time until the symposium on petroleum economics was closed Thursday afternoon papers of exceptional interest and importance were presented and discussed in a most frank and open manner.

Jan 1, 1943

By C. L. Berrier, Wm. B. Daly

Jan 1, 1923

By Wm. B. Daly, C. L. Berrier

Jan 1, 1923

By H. M. FRENCH

ARC welding can be defined as a process whereby two A pieces of metal are brought together, heated to a molten state by the heat of an electric arc, and fused into one piece. There are several kinds of arc welding: the metallic arc, the carbon arc, the atomic hydrogen arc and the shielded arc methods. A short description of each, together with its major applications, will serve to distinguish between them. Metallic arc welding involves an arc drawn between a metal electrode and the material to be welded, called the work or the "parent metal." It may be further subdivided into hand and automatic welding, depending on whether the electrode is fed to the arc by hand or by motor drive. This form of arc welding can be applied to most welding operations. Exceptions to its use consist of applications where very thin metals are to be welded; where it is desired to join the work with- out adding metal; or where extreme ductility may be required:

Jan 1, 1930

By J. V. Gluck, Ping-Wang Chiang

The tellurium-rich region of the Sb-TI-Te ternary system was investigated by means of DTA, metallo-graphic, X-ray, and electron beam microprobe techniques on the sections Sb2Te3-T12Te3, SbTlTe2-Te, SbT1Te2-Sb2Te3, and SbTlTe2-T12Te3. The phase behavior of this region is summarized in terms of four ternary invariant reactions and a schematic reaction diagram is suggested. Isopleths for the sections SbT1Te2-Sb2Te3, Sb2Te,-T12Te3, and SbTlTe2-Te were constructed, and a schematic diagram of the projections of the liquidus lines and invariant planes is presented. No evidence was found to support the existence of the ternary compound "SbTlTe3", or pseudo-binary behavior of the section T12Te3-Sb2Te3, as reported by Borisova and Efremova. Electrical conductivity, Seebeck coefficient, and thermal conductivity measurements were made at room temperature on fully annealed samples. 1 HE phase relationships in chalcogenides are often complex and difficult to resolve, particularly since the approach to equilibrium is a rather slow process. For example, the phase diagram of the T1-Te binary system was in doubt until clarified by Rabenau et al.,1 the phase fields at compositions near Bi2Te3 in the Bi-Te binary system have only recently been satisfactorily elucidated by Glatz,2 and there may still be some question as to the extent of the Sb2Te3 field in the Sb-Te system.3-5 In ternary systems, the existence of the compound "AgFeTe2" was the subject of a number of conflicting reports6-8 and the stoichiometry of the composition "AgSbTe2" was in doubt for a period of time.9 Recently, questions have arisen regarding the existence of certain compounds in the ternary systems Bi-Tl-Te10-14 and Sb-Tl-Te.15 The impetus for studies of these latter systems stemmed from the report of Borisova et a1.10 of a congruently melting ternary compound, "BiTlTe3", which apparently had extremely favorable thermoelectric properties for room-temperature cooling applications. Attempts by other investigators to produce the compound or confirm the transport properties proved to be unsuccessful.12-14 Recently, Chiang and Gluck14 reported studies of the phase relations in the tellurium-rich region of the Bi-T1-Te system which indicated that the section T12Te3-Bi2Te3 was not pseudobinary as suggested by Borisova et a1.10 The contention of Spitzer and sykes12 was supported that the composition "BiT1Te3" was multiphase, with the primary constituent actually being BiTlTe2, a compound whose existence has been well demonstrated.16,17 The investigation reported in the present paper was prompted by a later report of Borisova and Efremova15 on a similar study of the section T12Te3-Sb2Te3 from the Sb-T1-Te system. They also claimed this section to be pseudobinary, and that a ternary compound "SbTlTe," was formed peritectically. Some "preliminary" crystallographic data were given for the compound and thermoelectric transport properties were presented. In view of the questions concerning the behavior of the Bi-T1-Te system and the existence of the compound "BiT1Te3" it was suspected that the Sb-T1-Te system might behave in a similar fashion, particularly in light of the known existence of a compound SbT1Te2, iso-structural with BiT1Te2.17 Consequently, an investigation was undertaken to clarify the phase relationships in the tellurium-rich region of the Sb-T1-Te system. It is the purpose of this paper to present the results of this study, including a representation of the phase relations, isopleths for various composition sections, and the determination of some phase compositions and transport properties. EXPERIMENTAL PROCEDURES Commercially available high-purity (99.999+ pct) elements, purchased from the American Smelting and Refining Co., were used for the sample preparation. All samples were made from thoroughly mixed powders of previously prepared master alloys: SbTlTe2, Te, Sb2Te3, and T12Te3. Stoichiometric quantities of the constituents for each 10-g sample were weighed into a specially cleaned fused silica tube and sealed under a vacuum of better than 5 x 10-5 torr. The sealed constituents were fused and reacted at 650° to 750°C for at least 4 hr under continuous agitation in a "rocking" furnace, and the resulting product was air-cooled. The tube was opened and the sample was ground to a powder. A portion of the powder was rebottled in a DTA tube under vacuum, and the rest of the material was similarly resealed in a separate tube, re-fused in the rocking furnace, and again cooled to make the ingots for electrical and microstructural studies. All samples were subjected to further heat treatments as discussed in the section on experimental results. Each DTA tube was made of 7-mm-OD fused silica tubing with a concentric 2-mm-ID depression about 4 mm long formed in the bottom to accommodate a thermocouple. The size of a DTA sample was 0.5 to 1.0 g. An Aminco Thermoanalyzer whose accuracy was within 2°C18 was used for the DTA measurements. The metallographic samples were prepared by conventional techniques. A solution of FeCL dissolved in a methanol-HC1 mixture was found to be the most satisfactory etchant. Electron beam microprobe scanning and point-count examinations were made on polished and unetched samples using an ARL Electron Microprobe at an electron beam voltage of 20 kv. The detectors were set to receive characteristic La1 radiation. Calibration standards of the pure elements were incorporated in each sample mount; quantitative point counts were calibrated by a method similar to Ziebold

Jan 1, 1969

By Kun Li, Alex Simkovich

The rate of dissolution of alumina in carbon-saturated liquid iron has been studied experimentally in a system where alumina was in the form of a cylindrical rod immersed in an iron bath contained in a graphite crucible. Data obtained consisted of the concentrations of aluminum in the melt as a function of time. In the case of static experiments, the data are shown to agree with theoretical prdictions based on the diffusion of aluminum.. The rate of dissolution was greatly increased by the rotation of the alumina rod. It is concluded that the diffusion of aluminum from the alumina/metal interface is the rate-controlling step. In the past, thermodynamic investigations of systems encountered in ferrous process metallurgy have received widespread attention. More recently, considerable work has been devoted to the study of kinetics associated with these systems in an effort to determine their rate controlling mechanisms. The alumina-iron system is of great importance in ferrous metallurgy. Yet information concerning kinetics of reaction in this system is seriously limited. The present study was made in order to establish the rate-controlling step for dissolution of solid alumina in liquid iron. LITERATURE REVIEW A number of papers concerning dissolution of solid metals in liquid metals have been reported in the literat~re. Generally, for these simple systems, dissolution is controlled by mass transfer of the dissolving species. Complex systems involving dissolution of solid metal carbides and oxides in liquid metals and slags have been studied to a much lesser extent. Skolnick5,6 reported on the reaction between liquid cobalt and poly-crystalline cylinders of tungsten carbide, in which the cylinders were dissolved while being rotated about their longitudinal axes at various speeds and temperatures. As a result of unexpected preferential grain boundary attack by the liquid cobalt, large errors in the measured dissolution rates occurred because of loss of tungsten carbide grains to the liquid cobalt. Nevertheless, it was possible to establish that the liquid Co-W carbide reaction was not controlled by mass transfer. In a similar approach, cooper7 was able to show that artificial sapphire rods, (alumina single crystals) dissolving in lime-alumina-silica slags obeyed a mechanism of mass transfer control. Here, again, the rods were rotated at various speeds and temperatures, and the process was followed as a function of these variables. Forster and Knacke8 took a practical approach to reaction between slags and refractories. By blowing argon through refractory cylinders of silica, silli-manite, or dolomite and directing the gas to rise along the slag-refractory interface, it was possible to increase the rate of mass transfer. Although the method was admittedly crude, it nevertheless permitted an evaluation of the relative stabilities of refractories with respect to slag attack. Data were interpreted on the basis of mass transfer control. EXPERIMENTAL TECHNIQUE Apparatus. An illustration of the apparatus used in this study is shown in Fig. 1. The furnace consisted of a Morganite recrystallized alumina tube wound with a molybdenum coil. A secondary molybdenum heater was mounted around the upper half of the primary coil to aid in controlling the thermal gradient within the furnace. The primary heater tube was 3 in. in ID and 30 in. long. A reducing mixture of 95 pct N and 5 pct H was maintained around the heating elements. Thermal insulation was provided by alumina powder. The chamber within the primary combustion tube contained a boron nitride block near the top to assist in controlling the thermal gradient to the furnace and also to provide a bearing surface for the rotating graphite shaft. The outside diameter of the graphite shaft was $ in. A separate threaded graphite specimen holder was screwed into the end of the shaft. The holder contained a tapered hole drilled into the end to guide the oxide specimens as they were pressed into it for mounting. Additional guidance for the rotating graphite shaft was furnished by a water-cooled bronze bushing attached to the top of the furnace. A steel clamp was fastened to the upper end of the graphite shaft and rested on a thrust bearing; the shaft and clamp were driven by a dc motor through a set of gears. Two O-rings located immediately above the bronze bushing maintained a gas-tight seal about the graphite shaft. The lower half of the alumina tube housed the crucible and charge, which were placed on a 3/4-in. diam movable alumina support tube. With this arrangement, charges could be inserted into or removed from the furnace while the hot zone was maintained at or above 1000°C. To control the temperature of the furnace, the thermocouple was mounted inside the support tube and in contact with the crucible bottom. Stray electric fields in the furnace were of sufficient intensity to cause erratic indications by the thermocouple. By enclosing the thermocouple protection tube in a molybdenum sheath and grounding this shield, the problem was eliminated. Output of the thermocouple went to an automatic continuous balance controller. Procedure. A typical run was as follows. First, electrolytic iron was premelted in graphite crucibles and cast into graphite molds with the same configura-

Jan 1, 1970