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By A. Lee Barrett

SO commonplace that they are seldom noticed, mining-machinr, bits have a definite and important bearing on the cost of coal production. At the average mine many thousands of bits are used during the year. The actual cost represented by the purchase of the bits used, as well as that of sharpening and handling them, represents a considerable sum of money. From the point of view of indirect costs they are important, as the lack of good bits at a mining machine can seriously impair production. Good bits tend to ensure an adequate supply of coal. Classes OF Bits Mining-machine bits may be divided into three general classes, based on shape and method of use: (I) chisel, (2) pick-point and (3) one-use. The chisel and pick-point bits are shown in Fig. I. The so-called "chisel" bits were made of steel of various sizes and were sharpened to a wide chisel cutting edge. Few of this type of bit are used, except in places where coring is very bad. Sometimes chisel bits are used with standard bits to help cut out the core. The "pick-point" bit is widely used today. Normally it is made from ½ by I-in. steel, is about 4½ in. long when new, has a rake angle of about 25°, a front clearance of about 23O, a side clearance of approximsteji 8".' There are many variations in the shape of this bit, depending on the ideas of the individual that may be dressing the dies of the bit machine. This bit has been generally used for many years and at present, in one form or another, is by far the most popular bit used in coal mines. This bit usually is made from 0.85 carbon steel, although in recent years some alloy-steel bits have made their appearance. At present, carbon-steel bits are frequently tipped in. hard facing materials. A third class of bits might be called the L'one-use" bit; that is, a small bit that is used once and then thrown away. These bits have two or three points, are usually made from 0.85 carbon steel and sometimes from higher alloys. Recently some. of them have been tipped with hard facing material. Most of them were used at first with special

Jan 1, 1942

By A. Lee Barrett

SO commonplace that they are seldom noticed, mining-machinr, bits have a definite and important bearing on the cost of coal production. At the average mine many thousands of bits are used during the year. The actual cost represented by the purchase of the bits used, as well as that of sharpening and handling them, represents a considerable sum of money. From the point of view of indirect costs they are important, as the lack of good bits at a mining machine can seriously impair production. Good bits tend to ensure an adequate supply of coal. Classes OF Bits Mining-machine bits may be divided into three general classes, based on shape and method of use: (I) chisel, (2) pick-point and (3) one-use. The chisel and pick-point bits are shown in Fig. I. The so-called "chisel" bits were made of steel of various sizes and were sharpened to a wide chisel cutting edge. Few of this type of bit are used, except in places where coring is very bad. Sometimes chisel bits are used with standard bits to help cut out the core. The "pick-point" bit is widely used today. Normally it is made from ½ by I-in. steel, is about 4½ in. long when new, has a rake angle of about 25°, a front clearance of about 23O, a side clearance of approximsteji 8".' There are many variations in the shape of this bit, depending on the ideas of the individual that may be dressing the dies of the bit machine. This bit has been generally used for many years and at present, in one form or another, is by far the most popular bit used in coal mines. This bit usually is made from 0.85 carbon steel, although in recent years some alloy-steel bits have made their appearance. At present, carbon-steel bits are frequently tipped in. hard facing materials. A third class of bits might be called the L'one-use" bit; that is, a small bit that is used once and then thrown away. These bits have two or three points, are usually made from 0.85 carbon steel and sometimes from higher alloys. Recently some. of them have been tipped with hard facing material. Most of them were used at first with special

Jan 1, 1942

By A. E. Harnsberger

I is obvious that details such as the physical and chemical properties and methods of heat-treating of the materials mentioned must be omitted in a paper on the subject of materials used in oil-refinery pumps1. Only sufficient identification is given to enable the reader to find additional information from already published data. Also, the subject covers many operating conditions, but only the most important services can be discussed here. To the oil refiner, the pumping equipment is of vital interest. Practically every refinery operation, from the charging of crude oil to a distillation unit to the shipping of refined products, involves some form of pumping machinery. Intermediate refining stages involve a great variety of pumping machinery to carry out successfully the aims of the refinery technologist. Temperatures at which oils are handled vary from — 50" F. to 900" F. Pressure may vary from subatmospheric to 2000 1b. per sq. inch. The selection of the proper materials involves a careful consideration of the conditions under which the particular pump must operate. The four most important considerations are temperature, pressure, corrosion, and abrasion or wear. Consideration of temperature may be divided into three parts: (1) extremely low temperatures of the order of —50" F.; (2) temperatures at atmospheric or slightly above; (3) temperatures from 200" to 900" F. Pressures fall into two groups: (1) pressures reached by ordinary trade pumps of the order of 200 lb. per sq. in., (2) extreme pressure conditions involving pressures as high as 2000 lb. Noncorrosive and corrosive oils can be treated differently. Under the latter falls corrosion in the presence of water, which will occur up to 250" F. The second type of corrosion occurs in high-temperature pumping equipment, with temperatures from 450" to 900" F., largely caused by sulfur compounds. There are also other corrosive conditions met with in refinery operations, particularly in the handling of acids, acid sludges and other specialized processes. These problems, although difficult to

Jan 1, 1935

By A. E. Harnsberger

I is obvious that details such as the physical and chemical properties and methods of heat-treating of the materials mentioned must be omitted in a paper on the subject of materials used in oil-refinery pumps1. Only sufficient identification is given to enable the reader to find additional information from already published data. Also, the subject covers many operating conditions, but only the most important services can be discussed here. To the oil refiner, the pumping equipment is of vital interest. Practically every refinery operation, from the charging of crude oil to a distillation unit to the shipping of refined products, involves some form of pumping machinery. Intermediate refining stages involve a great variety of pumping machinery to carry out successfully the aims of the refinery technologist. Temperatures at which oils are handled vary from — 50" F. to 900" F. Pressure may vary from subatmospheric to 2000 1b. per sq. inch. The selection of the proper materials involves a careful consideration of the conditions under which the particular pump must operate. The four most important considerations are temperature, pressure, corrosion, and abrasion or wear. Consideration of temperature may be divided into three parts: (1) extremely low temperatures of the order of —50" F.; (2) temperatures at atmospheric or slightly above; (3) temperatures from 200" to 900" F. Pressures fall into two groups: (1) pressures reached by ordinary trade pumps of the order of 200 lb. per sq. in., (2) extreme pressure conditions involving pressures as high as 2000 lb. Noncorrosive and corrosive oils can be treated differently. Under the latter falls corrosion in the presence of water, which will occur up to 250" F. The second type of corrosion occurs in high-temperature pumping equipment, with temperatures from 450" to 900" F., largely caused by sulfur compounds. There are also other corrosive conditions met with in refinery operations, particularly in the handling of acids, acid sludges and other specialized processes. These problems, although difficult to

Jan 1, 1935

ZAY JEFFRIES (written discussion*).-I have read with much interest Mr. Ruder's discussion of Professor Howe's paper, "The Supposed Reversal of Inheritance of Ferrite Grain Size from that of Austenite." I am yet of the opinion that my first explanation' of Mr. Ruder's samples is substantially correct. In that explanation I did not intend, however, to convey the impression that "reversed inheritance" was the general rule nor even of common occurrence but rather that." Non-inheritance" was the general rule. Mr. Ruder suggests that a " perfectly formed" grain is an indication of inheritance. The grains in my Fig. 52 are perfectly formed and in fact more nearly equiaxed than those in Mr. Ruder's Fig: C,3 yet the grains in the former are known not to be inherited but to have been formed by the partitioning of larger austenite grains. On close examination of Mr. Ruder's Fig. C the very shapes of the grain suggest partitioning. Again, the grain size (25 to 30 grains per square millimeter) is at least 10 or- more likely 20 times smaller than might be expected of the austenite from which these grains were .formed under the given time and temperature conditions. Mr. Ruder's newer results on electrolytic and Armco iron are most interesting and instructive. His results fit in. nicely with my conclusions 5, 6 and 10.4 His photographs, however, indicate that the thickness of the pieces of sheet metal are such that abnormal grain growth is promoted. He indicates that equilibrium grain size after heating to 950° C., with furnace cooling, is about the same as his Fig. 1, above. I estimate this to be approximately one-half -grain per square millimeter, or 40 times as large as I have obtained with the same material (Armco iron) after heating Y4-in. bars to 1300° C. for 2 hr. and cooling in the furnace. The effect of thickness of sample on grain size is one which needs more attention.

Jan 3, 1918

By Zay Jeffries

A. G. WORTHING, Nela Park, Cleveland, Ohio (communication to the Secretary*).-The paper by Mr. Jeffries is very interesting. He is to be commended for his pioneer work in the study of equilibrium systems at the very high temperatures which one obtains with tungsten and molybdenum. There is one statement, however, to which I must take exception. On page 1227, a statement is made which would seem to indicate that the Nela Research Laboratory joined Dr. Langmuir in the recommendation of 3,300°C. as the most probable melting point of tungsten. This is not the case. In. the paper referred to by Mr. Jeffries, I have given 3,630°K. or 3,357°C. as the melting-point temperature for tungsten. Confirming observations by other workers in our laboratory justify the belief that this latter value is correct to within a small part of the discrepancy between the two values quoted.

Jan 12, 1916

By Will Clark

HE who enters a mining claim within an Indian reservation of the United States of America acquires no rights thereby, because of the fact that the lands within such Indian reservation are not a part of the public domain, and cannot be located or acquired as mineral land. However, where such an entry is authorized as to a particular reservation by an Act of Congress, such claims as may be entered under such authorization are thereby segregated from the reservation, and the Indian title is extinguished. Under the Choctaw Constitution, any citizen of that nation, in other words any Choctaw Indian, who discovered a coal mine, acquired an exclusive right to all coal within a radius of 1 mile. The laws of the Chickasaw nation provided for the formation of corporations to develop coal and other mines, with authority to contract with others to develop and work the mines. Under these laws, leases were made; but Congress subsequently abrogated all existing leases, prohibited all persons from receiving royalties from such mines, and provided that all coal within the nation should remain the common property of the tribes. Such leases are now expressly prohibited by an Act of Congress (32 United States Statutes at Large, 655). All leases of mineral lands upon Indian reservations must now be made under regulations promulgated by the Secretary of the Interior, and the royalties must be paid into the United States Treasury for the benefit of the tribes. In Canada the Indians have no rights to the royal mines and minerals, and the government can make no stipulation with the Indians which would affect the rights of the Province in which the lands are situated. Therefore, while it is true that under our present law no rights can be acquired to a mining claim within an Indian reservation, it seems to be fully within the authority of Congress to make laws, giving such rights to mineral locators as it may deem necessary or expedient.

Jan 6, 1914

The Western World's gold reserves now exceed 23,000 mt (750 million oz), 65% of which exist in South Africa. Although several major mines are reducing production or closing because of depletion of reserves, new mines or expansions of existing mines are coming on-stream which will maintain an annual production of 684 mt (22 million oz) of gold well into the 1990s. These new operations by the South African mining industry represent the largest expansion since the opening of the Witwatersrand gold fields in 1886. Included in three new mines being opened is that of Anglo American Corporation's Elandsrand plant, their fir& new gold venture in South Africa in seventeen years. Current average grade of South African mines is 8.2 g Au per mt (0.24 oz per st); and while the cost of the Elandsrand 135,000 mt (149,000 st) operation, including mine development, was about $314 million, it is estimated that the cost of a comparable operation started today and completed in the mid-1980s would be of the order of $480 million. New mines to exploit low-grade ore bodies are, therefore, likely to be few in number, and further expansion will undoubtedly be in the form of extensions to existkg operations where cash flow can be used to finance development. The authors' first monograph, "Gold and Silver Cyanidation Plant Practice," devoted a section to South African cyanide plant operation; and it is believed that this new volume would not be complete without a description of Elandsrand, South Africa's newest gold plant. The Elandsrand mine is adjacent to Anglo American's Western Deep Levels on the Far West Rand. The decision to go ahead with the development was taken in mid-1974 from the results of exploration drilling carried out over a period of .lo years. Results of 17 bore holes and 68 intersections of the Ventersdorp Contact Reef had indicated a gold-.bearing reef less than one meter thick at a depth of 1,800 to 3,000 meters (5,900 to 9,840 ft). Preliminary studies indicated a mine of 900 km (560 miles) of underground workings would yield 725,000 kg (23. 3 million oz) of gold from 60 million mt (66 million st) of ore to be milled over a period of 34 years. Eventually, when the mine is in full production, the total hoisting capacity will be 300,000 mt per month (331,000 st) for a milling capacity of 225,000 mt per month (248,000 st). The Elandsrand surface facilities have been built on a low range of 0 hills to take maximum advantage of the 10 slope in transporting ore

Jan 1, 1981

[ ] TUNNELS TO BINS. Originally designed for tunnel work, the strong lightweight liner plates used to construct this 30-ft diameter, 31-ft high, aggregate storage bin have several advantages. Bins and conveyor to tunnels can be quickly erected in any season, for permanent service, or to be salvaged and reused. Armco Steel Corp. (16) ROLLER CHAIN: Engineering Data Book No. 2457 published by Link-Belt Co. is a comprehensive 148-page volume on roller chain and its application. Detailed engineering information covers installation, maintenance and lubrication of chains for drives, conveyors, and sprocket wheels. The book covers selection of drives to meet both standard and special installations. (17) LABORATORIES: The Fisher Scientific Co's. line of 21 basic units of standardized steel laboratory furniture is described in catalog no. 25. The Unitized line was designed to combine the advantages of custom installation with the convenience of selection, delivery and continued flexibility that goes with ready-made units. (18) PUMPS: Two similar, but functionally different types of vertical centrifugal wet-pit pumps; a heavy duty bilge pump for handling solids-free liquids and drainage; and a screenless sewage ejector, constructed to handle sewage and solids carrying liquid; are illustrated in a bulletin from Yeomans Bros. Co.

Jan 1, 1952

By Avnulf Muan, P. V. Riboud

The effect of Cr2O3 on melting relations of iron oxide at oxygen pressures slightly above those prevailing in contact with metallic iron has been determined. Liquidus and solidus temperatures of wüstite are raised by the addition of Cr2O3, from 1385°C for pure iron oxide to 1420°C at the peri-ledie point where wüstite, iron chromite, liquid, and gas coexist in equilibrium under the atmospheric conditions used in the present investigation (CO2/H2 = 1). It has been shown in a previous investigation1 that the liquidus and solidus temperatures of iron oxide are drastically increased by the addition of Cr2O3 under the relatively oxidizing conditions prevailing in air. This is to be expected in view of the easy substitution of cr3+ for Fe3+ in crystalline oxide structures which are stable at high oxygen pressures, as demonstrated for instance by the completeness of the solid solution series Fe2O3-Cr2O3 at high temperatures (>1000°C). The stable phase of iron oxide at oxygen pressures approximating those prevailing when metallic iron is present is wüstite. This phase, although commonly represented by the simplified formula FeO for sake of convenience, in reality has a defect structure in which a part of the iron ions are present as Fe3+. It is to be expected that at least a limited amount of cr3 ions will substitute for Fe in this structure when Cr2O3 is added to wüstite. Depending on the ease of this substitution in comparison with that of cr3 substitution for Fe in iron oxide-Cr2O3 liquids under the same atmos- pheric conditions, the liquidus and solidus temperatures of wüstite may increase or decrease upon addition of Cr2O3. The methods of establishing these melting relations and the results obtained are presented in the following. I) EXPERIMENTAL METHOD 1) General Procedure. The quenching technique was used in this study. Oxide mixtures were heated at chosen constant temperatures in an atmosphere consisting of equal parts of CO2 and H2 until equilibrium was established among gas and condensed phases. The samples were then quenched in mercury to room temperature, and the phases present were determined by microscopic and X-ray investigation. 2) Preparation of the Mixtures. Starting mixtures were prepared by weighing and thoroughly mixing Fe2O3 and Cr2O3, or wüstite and Cr2O3. The Fe2O3 and Cr2O3 used were "Baker Analyzed" reagent grades, whereas wüstite of composition was synthesized by reducing Fe203 at 1325°C in an atmosphere consisting of equal parts of CG andHz. In order to avoid contact with crucibles, the equilibration runs were made with small pellets suspended from thin (-0.004-in.) platinum wires. Mixtures made from FOs and Cr203 were readily pelletized at a pressure of 500 atm in a 9.5-mm die, whereas mixtures made from wüstite and Cr203 when treated identically were too weak for handling. In order to obtain a stronger product, these pellets were sintered by heating for 2 min at -1200°C in the same atmosphere as was subsequently used for the equilibration runs (CG/H2 = 1:1). During the sintering, these pellets were wrapped in thin (0.0004-in.) platinum foil, which was stripped off before the equilibration runs. In order to reduce the time needed for equilibrium to be attained, preliminary equilibration of relatively large pellets of each mixture was carried out at -1200°C for 4 to 12 hr. Smaller pellets

Jan 1, 1964

By K. G. Black, B. P. Faulkner

Laboratory batch flotation rests are used for comparison of the floatability of ores and for comparison of the effect of various treatments on ore floatability. Although it is difficult to predict exact recoveries for continuous flotation on the basis of batch tests, considerable quantitative information can be obtained through their use. A simple method is presented which provides a convenient means of quantitatively evaluating results from laboratory batch tests. The information obtained is in the form of a discrete flotation rate distribution, which, if desired, can be used directly in a simulation of continuous flotation. Equation of Batch Flotation The validity for batch flotation of the first-order kinetic equation is accepted: [ ] where k is flotation rate of a class of articles and W (t) is weight of particles of the class in cell at time t. Thus, at time t, the fraction of the original amount of the class of particles still remaining in the cell is [ ] where W (0) is weight of class of particles in cell at time zero. If there are several classes of particles in the cell, each with its own flotation rate, k4, the fraction of the particles remaining is [ ] where W (t) is now the total weight of n classes, a, being the original fraction of W (0) belonging to the ith class. Accordingly, [ ] [Fig. 1] shows the result of a typical batch test. Such result can be characterized by a set of particle classes, each set described by a flotation rate, [ki,] and a corresponding fractional magnitude, [ai.] [ ] Multiple Regression Equation Eqs. 3 and 4 may be combined to give

Jan 1, 1973

By Ralph W. M. Lai, D. W. Fuerstenau

This paper presents the results of a study of the principles which control the distribution of ultrafine particles between an oil phase and an aqueous phase. Alkyl sulfonates were used to control the wettability of fine alumina particles and to stabilize the water-isooctane emulsion system in the extraction process. The effects of sulfonate chain length, sulfonate adsorption, pH, and oil-water ratio on the recovery of solids in the oil phase were investigated. Higher extraction was found under conditions which yield higher hydrophobicity and large interfacial area of the oil-water emulsion. Today there is considerable interest in developing methods for the recovery of fine particles from disseminated ores. One such method might be the extraction of fine particulate solids from aqueous suspensions into an oil phase, and one example of a successful industrial process based on oil-water distribution phenomena is the emulsion flotation process used in concentrating manganese ore.' The oil agglomeration process of Farnand, Smith, and Puddington has been suggested for concentrating tin ore. Patents 3-4 for oil flotation processes extend back to that of William Haynes in 1860. The basis of all these processes is directly related to the stabilization of emulsions with solid particles. The first extensive study of oil-water emulsions stabilized by finely divided solids was made by Pickering. Later, Briggs,6 weston, 7 Chessman and King,8 and Leja and Schulman9 experimentally demonstrated how solid particles control water-oil and oil-water systems. Hildebrand10 suggested that fine particles can stabilize an emulsion because the fine particles are partially wettable by both oil and water, that is, that the contact angle must be finite. Takakuwa and Takamori 11 recently applied emulsion inversion to the study of collector adsorption in flotation systems. At the Royal School of Mines, Shergold and Mellgren12 are currently carrying out a comprehensive study of the extraction of fine particles into an organic liquid phase. In the present study of the liquid extraction or oil flotation of ultrafine particles, the recovery of hydro-philic alumina particles of 0.1-µ average diameter was determined after separating an isooctane-water mixture (emulsion) into its two phases. Alkyl sulfonates of different chain lengths were used to change the wettability of the alumina and to effect emulsifi-cation of the oil-water mixture. The effects of the oil-water volume ratio, sulfonate adsorption, and pH on the recovery of the fine particles were investigated. Since the surface charge on an oxide such as alumina is determined by the adsorption or interaction of H+ and OH- with the surface, pH control is extremely important. Furthermore, since the zero point of charge (zpc) of alumina13-14 occurs at pH 9 to 9.4, major adsorption effects with anionic collectors in these systems will occur below pH 9. The results of the foregoing investigation are discussed in terms of the recovery of the fine particles, the oil-water ratio, contact angles, surface tension, the adsorption of sulfonate onto the solid surface, and the emulsifica-tion of oil. MATERIALS AND EXPERIMENTAL METHODS Materials: The particulate solid used in all the experiments was Linde "A" alumina, a high-purity, readily available form of a-alumina. The surface area of the alumina, as evaluated from measurements of stearic acid adsorption from benzene, was 14.5 sq m per gm, based on a value of 20.5 sq Å for the cross-sectional area of stearic acid.13 All aqueous solutions were prepared from triply distilled conductivity water. Other materials included high-purity crystals of sodium alkyl sulfonates, isooctane, and, for pH adjustments, reagent grade hydrochloric acid and sodium hydroxide-Because sulfonic acids are strong acids, they are

Jan 1, 1969

The Lead-Line Update held in conjunction with the 1977 SME-AIME Fall Meeting in St. Louis provided sessions on mining, mineral processing, extractive metallurgy, and economies to brief the record on the industry's activities and developments since the 1970 World Symposium on Lead and Line convened, also in St. Louis. Changes in the industry since 1970 have not been profound, notes the program committee, consisting of D. O. Rausch, F. M. Stephens, and B.C. Mariacher, cochairmen; and H. L. Clifford, S. C. Fall), and M. Snedeker. However, various environmental and conservation factors have had a direct impact on process consideration and operating practice; the result has been new mines, improved technology, and changing market opportunities. The general consensus of the participants is that the future for the Lead-zinc industry looks promising as new applications are found and new products resulting from intensive research reach the marketplace. The highlights of the HS technical papers presented at the 1977 session follows.

Jan 11, 1977

By J. F. Stiehr, R. L. Sanford, T. L. Myers

This paper summarizes the development of a Directory of Computer Programs Applicable to US Mining Practices and Problems. The directory is funded by the US Bureau of Mines and includes a sampling of computer usage in operating and manufacturing companies, consulting firms, computer companies, research organizations, universities, and various US government agencies. General references to computer applications throughout the mining industry are discussed as well as the availability of programs to interested organizations or individuals.

Jan 9, 1979

Polluted air and water, despoiled land and excessive noise are the unwelcome results of the population growth and a rising standard of living. The consumption of goods and services, including metal products and minerals, by all people is increasing so rapidly that civilization is in danger of destroying the environment in which it lives. This is true because every human activity affects the environment, whether it is air, water or land. While E. F. Osborn, director, U.S. Bureau of Mines, says . . . "some members of the mineral industry are reluctant to recognize environmental demands" . . . William T. Pecora Under Secretary of the U.S. Department of the Interior.. . says that, "to maintain levels of resource development and environmental quality needed to satisfy our affluence, we must trade off values rather than turn off troublesome operations." What it seems to boil down to is how much control of its operations is the mineral industry willing to accept-internal policing or strict government control? The answer lies in how well the mineral industry maintains a balance between mineral development and environmental quality.

Jan 1, 1971

By L. D. Frink

Those actively interested in mining are fully aware of the ever-increasing difficulty of making conditions such that efficient work can be done in underground openings, especially as higher rock temperatures are encountered in depth. This is also true where an effort is being made to cut down the burden of overhead expense by working headings 24 hr. in a day if blasting is done as often as is possible in that time. That the conditions resulting from both these causes have driven the native-born Americans from the mines and that their places have been taken by less efficient foreigners is a fact that we must all admit. The great war now being fought in Europe and the educational qualification clause written into our immigration law by the last Congress will probably limit very materially the supply of labor, such as we are now using in our mines, and will force upon mine operators the necessity of making this work appeal again to Americans. Metal tubing, with blower or exhaust fans, has long been used in supplying air to dead ends where natural ventilation is impossible, or in driving the smoke from such places, or in doing both, as the need might be. Here in Butte we have now come to use canvas tubing very extensively and find that it has many advantages not possessed by the metal. The use of flexible tubing is not new, but it has not been generally used in mining operations. Recent improvements, however, in the canvas itself and in the jointing of sections and manner of suspension have so increased its usefulness that it promises to add much to the efficiency of mining. There is now on the market a product that is impervious to air, is fireproof, and has a system of jointing which permits it to be put up or taken down in a few seconds. In this article an effort will be made to explain the manner in which canvas tubing is being used in the North Butte company's operations at Butte, Mont. The accompanying photographs will, I hope, help make clear what may be done with this material.

Jan 1, 1918

By A. U. Seybolt

In part 111' of this series it was shown that during the selective oxidation of a 3 1/4 pct Si-Fe alloy in damp hydrogen, only silica, (observed at room temperature) as low cristobalite or low tridy-mite or both, was formed as an oxidation product. In some in- „ stances where the film was fairly thin (probably well under 100A) there was some suggestion of an amorphous form of SiO2. The present investigation of oxidation rate showed that the selective oxidation of silicon-iron can be rather complicated, and apparently impossible to rationalize in an unequivocal manner. In some temperature regions, notably near 800" and 1000°C, the data seem to obey the familiar parabolic rate law. However, at intermediate temperatures complications were noted, some of which are possibly due to the order-disorder reaction in the silicon-iron solid solution. IN an earlier report' it was shown that during the oxidation of 3 1/4 pct Si-Fe alloys in H2O-H2 atmospheres only silica films were formed in the temperature range from 400° to 1000°C in hydrogen nearly saturated with water at room temperatures, or at dew points as low as -45°C. In the work to be reported here, some observations are made on the rate of oxide film formation. As in the earlier investigation, electron diffraction patterns generally showed either low tridymite or low cristobalite or both, except for some very thin films. These sometimes showed diffuse rings, presumably due to a very small crystallite size, or in a few cases, diffuse bands probably caused by an amorphous film. EXPERIMENTAL PROCEDURE Vacuum-melted silicon iron made of high-purity materials was rolled into strips 0.014 in. thick, and cut into samples 1/2 in. wide by 1 in. long. Chemical analysis showed 3.2 pct Si and 0.002 pct C. All samples were surface abraded with 600-grit paper, were solvent cleaned, and then placed in an paper,apparatus containing a "Gulbransen type"2 micro-balance. Here the gain in weight of the samples of about 5 sq cm area could be followed as a function of time during the oxidation caused by the water in atmospheres of various controlled water-hydrogen ratios. The water-hydrogen ratios can most easily be described as varying from a dew point of 0°C (PH2O-p^2 = 6.2 x 10-3 , to K (P j -40°C (PH2O/PH^= 1.3 X 10-* Most of the experiments were conducted at the 0°C dew-point atmosphere because drier atmospheres caused so little gain in weight that the accuracy of measurement was poor. Because of this, only the data obtained at PH2O,/P,,,= 6.2 x X3 will be reported. The temperature range extended from 800" to 1000°C; and most of the oxidation runs lasted for about 24 hr. The reproducibility of any reading was about ± 1 ?, but the sensitivity of the balance was about 0.2 ?. The atmosphere, flowing at 200 cm per-min, was preheated to the furnace temperature before contacting the specimen. While the gas flow caused a measurable lift on the sample, it was ordinarily sufficiently constant so that it was not an appreciable source of error. X-ray and electron diffraction checks of the samples before and after oxidation showed no evidence of preferred orientation, either on the metal samples or on the silica films formed. EXPERIMENTAL RESULTS The data obtained are summarized in Table I, and some are given in detail in Figs. 1 to 4. In the fourth column of Table I, kp refers to the parabolic rate constant in the expression (?/cm2)2 = kpt + c [1] where ? = micrograms gain in weight kp = parabolic rate constant in units r2 /cm4 t = time in minutes c = constant It will be noted that in many cases no value for kp is given; this is because in these instances the data did not obey the parabolic rate law. The silica film thicknesses given in the last columns are values calculated from the weight gain, an average tridy-mite-crystobalite density, and by assuming a perfectly plane surface. Fig. 1 shows the data plotted in the form of Eq. [I], hence a linear plot indicates parabolic behavior. It has been frequently observed in the literature that

Jan 1, 1960

By Charles F. Brush

THE compression of gases to a very high degree, for purposes of scientific research, has long presented serious difficulties to the physicist. Great advances have been made of late years in the construction of ordinary air or exhaust pumps, while very little has been done towards the improvement of compression pumps. The principal difficulties encountered in the construction of such apparatus are the existence of the so-called "dead space" in the pump barrels, leakage of the piston packings under high pressure, and the trouble arising from the unequal expansion of parts caused by the development of the latent heat of the gas during compression. Of these obstacles to success, the "dead space" is far the most serious, as it fixes a limit to the performance of the pump beyond which it is impossible to carry the compression. The writer having occasion, some time since, to make a series of investigations on gases very highly compressed, and finding no apparatus, or description of apparatus, adequate to produce the required

Jan 1, 1876

By Charles F. Brush

The compression of gases to a very high degree, for purposes of scientific research, has long presented serious difficulties to the physicist. Great advances have been made of late years in the construction of ordinary air or exhaust pumps, while very little has been done towards the improvement of compression pumps. The principal difficulties encountered in the construction of such apparatus are the existence of the so-called "dead space" in the pump barrels, leakage of the piston packings under high pressure, and the trouble arising from the unequal expansion of parts caused by the development of the latent heat of the gas during compression. Of these obstacles to success, the "dead space" is far the most serious, as it fixes a limit to the performance of the pump beyond which it is impossible to carry the compression. The writer having occasion, some time since, to make a series of investigations on gases very highly compressed, and finding no apparatus, or description of apparatus, adequate to produce the required

By D. Turnbull, J. H. Hollomon, J. C. Fisher

UNDERSTANDING of the diffusion problem has recently been furthered by the analysis of Birchenall and Mehl.1 They pursued the problem of the variation of the diffusion coefficient with composition for non-ideal solid solutions. Their analysis follows the tradition of Wagner,2 Jost,3 Dehlinger,4 and Darken,' who assumed the net flux of dif¬fusing material to be proportional to the gradient of a quantity related to free energy. The basic assumption in Birchenall and Mehl's formulation of the problem is that the net flux of diffusing material is proportional to a thermodynamic activity gradient. To estimate the applicability of the derived relations, they corrected the diffusion coefficients of carbon in austenite by utilizing Smith's' activity data for carbon, and the diffusion coefficients for zinc in copper with activity data computed from the vapor pressure measurements of Hargreaves.7 The corrected coefficients for carbon were virtually independent of carbon concentration. For the diffusion of zinc in copper a moderate variation of diffusion coefficient with concentration remained after the correction. The problem of diffusion can be formulated in another way than that used by Birchenall and Mehl. The method is that of chemical rate theory and has been used by Eyring and his coworkers8,9 as well as by Eyring and Zwolinski10 in a discussion to Birchenall and Mehl's paper. As yet the method has not been applied to substitutional solid solutions. On the basis of their assumptions, Eyring and Zwolinski derived a relation between the diffusion coefficient and activity that is identical with that of Dehlinger and Darken but which does not correct for the variation of the diffusion coefficient with concentration as well as does the relation derived by Birchenall and Mehl. It was thought that the theory of diffusion would be more complete if the inconsistency between the two analyses could be rationalized and if diffusion in substitutional alloys were analyzed on the basis of the concepts of the chemical rate theory. CHEMICAL RATE THEORY According to the theory of absolute reaction rates8 the reaction [A,+A2+ ... +.A;->X,+X2 +...+X; EqI] is viewed as taking place in two steps. First the reactants A1, A2, . . . A[i] combine to form an activated complex M with which they are in equilibrium; [A, + A2 + .. . + Ai = M. Eq 2] Second the activated complex decomposes to give the products X1, X2. . .. X[j]; [M->X1+X2+ ... +.X;. Eq3] It has been shown8 that the number of activated complexes decomposing per unit volume per unit time is given by the expression† [kT]

Jan 1, 1948