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By Donald W. Gentry, John F. Abel

This paper presents some of the results of a rock mechanics instrumentation program designed for, and implemented at, longwall panel 4N at the York Canyon Mine near Raton, New Mexico. The objective of this particular instrumentation program was to determine the response of the rock mass to longwall mining of a thick coal seam utilizing shield-type supports. Measurements were made in the rock along the ground surface, above the coal seam, in the coal seam, and immediately below the coal seam. Longwall test panel 4N had a total developed length of 762 m (2500 ft) and a face width of 168 m (550 ft), Fig. 1. The seam mining height in the panel area was approximately 3 m (10 ft). The average depth of overburden above the panel is 107 m (350 ft) although it ranges from 73-134 m (240-440 ft). Roof support at the face was provided by 116 Hemscheidt 320 HSL shields. These shield-type supports weigh 11.4 metric tons each.

Jan 3, 1978

George E. Collins, Nacoochee, Ga. (communication to the Secretary): The results tabulated below were obtained at the Reynolds mill, White county, Ga. They were noted, not with a view to investigating the point discussed by Mr. Clark, but in course of a test on a working scale to determine the com parative saving from a given free-milling ore on copper and silvered plates respectively. In every case the bullion assayed was the result of a separate clean-up on a considerable quantity of ore. The ore varied widely in grade and in other respects, but the runs bracketed in the table were made at the same time, in adjoining batteries, and on similar types of ore. In a * Result modified by the addition to the bullion-shipment of a little impure bullion left over from previous clean-ups.. On these occasions, the strips of copper were removed from the tables, and: their lower surfaces were cleaned. Hence the higher yield reported.

Jan 1, 1900

By E. A. Gulbransen, K. F. Andrew

In a recent communication14 we have reported on the kinetics of the reactions of zirconium with O2, N2 and H2 as a function of the time, temperature and pressure variables. A systematic study was made and the results correlated with fundamental theories of gas-metal reactions. This paper will present a similar study for titanium. Titanium and zirconium are members of the IV group of the periodic table and possess many similar physical and chemical properties as a result of their similar electronic configuration for the outer electrons. The two metals are relatively inert to both gas and liquid phase corrosion at room temperature. However, at moderate temperatures the metals become active and react readily with the common gases including O2, N2 and H2 which are of interest in this study. A study of the kinetics of these gas-metal reactions is of interest for three reasons: (1) to understand the rate of reaction of titanium and its role in the behavior of high temperature alloys; (2) to understand the practical difficulties of the reduction, refining and working of titanium; and (3) to correlate the data with fundamental theories of gas-metal reactions and crystal structure predictions. Literature Survey Several review papers8 and books4243 exist on the preparation and properties of titanium and its alloys. THE METAL Titanium has, at room temperature, a hexagonal lattice of the zinc type. Hagg19 gives a value of 2.953A for the (a) axis, a value of 4.729 for the (c) axis and a density of 4.427 at 20°C. Burgers and Jacobs6 have observed the transformation of the hexagonal to the body-centered cubic structure at 880°C and have established a value of 3.31 for the cube edge and a density of 4.31. TITANIUM-OXYGEN Carpenter and Reavell6 using a pressure change method have studied the reaction at temperatures of 742° and 1000°C and for a pressure of one-fifth of an atmosphere. The probabilities for reaction are calculated from kinetic theory and they report a value of 10-5 for O2 at 1000°C and 10-6 at 740°C. The titanium-oxygen system has been investigated by Ehrlich.10,11 Five phases are observed. Between (TiO2 and TiO1.90) an alpha-phase, consisting ofarutile lattice, is found. A beta-phase is observed between (TiO1.80 and TiO1.70). A gamma-phase is homogeneous between (TiO1.56 and TiO1.46) and has a structure of the corundum type. The delta-phase exists between TiO1.25 and TiO0.6 and has a sodium chloride structure. From TiO0.42 to Ti the metal structure is observed. The surface oxide films have been studied by Hickman and Gulbransen.20 The rutile structure is observed in the temperature range studied, 300 to 700°C. Three crystalline modifications of TiO2 exist: rutile and anatase which are tetragonal and brookite which has an orthorhombic structure. Anatase is reported36 to exist in two forms: I and II. Anatase II changes to anatase I at 642°C. Anatase I is stable up to 915°C where rutile becomes the stable modification. At 1300°C rutile transforms to brookite which melts at 1900°C. The monoxide, TiO, may be prepared from the dioxide by high temperature reduction with carbon or magnesium. Its melting point is 1750°C. TITANIUM-NITROGEN Carpenter and Reavell6 report that at 1000°C a linear rate law is observed. The probability of reaction is given as 10-8 at 1000°C. Fast12 has studied the solubility of nitrogen and its effect on the mechanical properties of the metal. The crystal structure of TiN has been shown by several workers2'21'44 to follow the sodium chloride structure. However, the calculated density is found to differ from the pycnometric value. This is studied by Brager3,4 in detail. He has suggested that the titanium sites in the lattice are only partially filled at low temperatures. As the temperature of preparation is raised the vacant sites become occupied which expands the lattice and increases the hardness and density. An (a) value of 4.22Å is given for room temperature. TITANIUM-HYDROGEN The solubility and the crystal structures observed in this system have been reviewed in a recent book by Smith.40

Jan 1, 1950

By C. E. Gregor

Current modern trends in mining show that hoisting shafts are being expected to fulfill an important ventilation function. However, where rigid guides and supporting structures are mandatory, ventilating power costs will be high, unless the transverse structures (shaft sets) are streamlined. In the complex configurations of hoisting shaft furniture patterns, either for original design purposes, or for the adjustment of an existing shaft, a useful degree of aerodynamic optimization, by reduction of overall resistance, can only be effectively evaluated by model studies in a special purpose wind tunnel, as described herein. The author has shown that, in one particular case, an annual power cost saving of more than $50,000 was indicated, mainly by the selection of buntons and dividers of improved aerodynamic profile. Mining companies are now realizing the advantages that can accrue through proper attention to the aerodynamic aspects of mine shaft design. With progressive demands of civilization for an ever greater supply of coal and metals, and with greater depths of working, higher rates of extraction, advanced degrees of mechanization, and improved standards of environmental health and work comfort, shaft design is becoming an extremely important aspect of mining operations. In addition, because the cost of sinking, equipping, maintaining, and operating a mine shaft is continually increasing, there is a greater incentive to use a shaft for the maximum duty, consistent with economy. The current natural tendency is therefore to sink multi-purpose shafts, to install as much equipment as is safely and effectively possible to operate; and then, over and above all these functions, to use the shaft to its maximum possible ventilating capacity, as a major, or auxiliary, airway. Clearly, this latter additional function can only be employed at a significant cost, since the most economic operating airways are smooth-lined and devoid of internal rigid furniture. It is true that hoisting functions can be carried out in such shafts if rope guides are used, but only under restricted conditions. Where a manway must be provided, fixed guides and supporting structures are mandatory, and ventilation costs become accentuated. It is generally recognized that the prime element of cost in ventilating a mine can be represented by the power required to drive the fan unit. It is also known that the largest component of total mine resistance is that of the downcast shaft, where this shaft is equipped with rigid guides for hoisting purposes. The pressure loss varies directly as the resistance of the shaft, in accordance with a modification of the Atkinson equation p = RQ2/3600. Furthermore, the air horsepower drawn is given by the equation AHP = (p x 0/33000. Therefore, the power required to drive the fan unit varies as the resistance of the shaft and the cube of the air quantity. Clearly, if Q is a specified minimum, then the only way to minimize the pressure loss (and the power costs) is to reduce the shaft resistance R. (See Table I for a list of symbols.) The resistance to airflow of a shaft equipped with rigid guides and supporting structural sets consists of two components which, for the sake of analytical simplicity, can be regarded as additive. 1) Frictional resistance, represented by the viscous frictional forces within the boundary layer, as air flows along the surfaces of the walls and the periphery of the vertical elements (guides, pipes, cables, ropes, etc.) of the furniture. The friction loss can be readily calculated by the Atkinson equation, after selection of a suitable value for the friction factor K from the McElroy compilation.' KxLxO xQ2 5.2 xA3 Friction loss can be minimized by lining the shaft walls (particularly if of circular or elliptical cross-section) with a smooth continuous lining of monolithic concrete.

Jan 1, 1968

By Robert H. Hafner, Irvin R. Kramer

IN recent years considerable interest has been shown in surface-alloyed metals, particularly those of chromium (chromized steels), which have excellent corrosion [ ] resistance under a variety of severe conditions, and may undergo bending and flanging operations without spalling. An early method1 employed to produce a high-chromium case on steel was developed by Kelley in 1921. It consisted of heating a low-carbon steel in intimate contact with powdered chromium in the presence of hydrogen at temperatures sufficiently high to permit diffusion of chromium into the steel. The usefulness of this process was limited because the extremely high temperatures of 1200° to 1400°C. (2200° to 2550°°F,) caused excessive grain growth and warpage, Louenstein and Ulmer2 packed iron castings in ferrochromium and com- [ ] mon salt, and heated for approximately three hours at 930° to 1040°C. (1700° to 1900°F,). A recent and more practical method of depositing chromium on steel surfaces has been developed in Germany by Daeves, Becker and Steinberg3-8 and in Russia by Izgaryshev and Sarkisov.9 This process consists of passing gaseous chromium chloride over the steel to be chromized at temperatures of 900° to 1000°C., or packing them in a porous, ceramic material that previously had been saturated with chromium chloride. They reported obtaining a chromized layer, 0.004 in, thick, on low-carbon steels. Later, Daeves4 established a relationship between the carbon content

Jan 1, 1942

By J. J. Hauser, H. C. Theuerer

A cathode sputtering technique is described which elin7inates the need for ultrahigh vacuum in preparing thin films of materials sensitive to gaseous impurities. This technique uses a fraction of the atoms sputtering within an anode container to getter actice gases, such as HzO, Oz, and Nz. The gases alzd gettering metal are deposited on the container walls, thus shielding the coating zone of the system from contamination. The use of the method for preparing superconducting-normal metal couples such as Ph-Cu and Ph-Pt is described, and the properties of the individual and composite films are given and discussed. GETTER sputtering is a method which greatly simplifies the preparation of thin films in cases where composition control is critical. A major difficulty with conventional sputtering and other vacuum-deposition techniques is the contamination of the forming film caused by residual gases, such as H20, CO, Oz, and Nz, in the coating equipment. The difficulty arises from the fact that even when the residual pressure in the system is as low as 1 x 10"6 Torr, with a deposition rate of 10A per sec, there are as many contaminating gas collisions with the substrate as there are with film-forming metallic atoms. It is not surprising, therefore, that with reactive metals, such as tantalum and niobium or with semiconductors, such as silicon and germanium, films with properties far different from the starting materials are obtained. In the case of niobium and tantalum, deposited either by sputtering or vacuum evaporation in systems with reactive gases at pressures of the order of 1 x l0-' Torr, the loss of superconductivity is traceable to interstial oxygen or nitrogen. On the other hand, working in vacuum of the order of 1 x l0-" Torr, Marchand and enema' have shown that superconducting films of tantalum with properties approaching those of bulk material are possible. At this level of gaseous impurities -lo6 metallic atoms arrive at the substrate before a contaminating collision occurs again assuming a deposition rate of 10A per sec. It is evident from the above that any successful vacuum technique requires the elimination of reactive gases from the region of the system where coating is occurring. Getter sputtering accomplishes this using conventional vacuum equipment with residual pressures in the 106 Torr range. In fact? vacuum systems with residual pressures of lo-" Torr are adequate for most purposes. With this method, sputtering is confined within an anode can and, by geometric design, sputtering itself is used to purify the argon at the lower and upper parts of the system by the gettering action of the reactive metal. In consequence, the central region of the system where coating occurs is shielded from gaseous contamination. Getter sputtering is particularly useful for the preparation of alloy and compound films. With this method, if a cathode of homogeneous composition is bombarded with high-energy argon ions, transfer of material to the substrate having the same composition as the cathode will occur. This is true after an initial equilibration time, even though the constituents of the cathode may have different sputtering rates. During equilibration, the surface of the cathode changes composition due to differences in sputtering rate, but mass conservation demands a steady-state condition such that the atoms sputtered from the surface have the same composition as the cathode material from which the surface is generated. GETTER-SPUTTERING APPARATUS The original form2 of the getter-sputtering apparatus is shown in Fig. 1. It consists of a closed nickel or stainless-steel can 4 in. tall and 2-3/8 in. in diameter. Mounted symmetrically from each end

Jan 1, 1965

By K. U. Snowden, J. N. Greenwood

EARLY studies by Gough and sopwith' have shown that the fatigue resistance of certain metals increased when the test was carried out in a partial vacuum; lead showed this effect to a marked degree. This communication describes surface deformation differences between high-purity lead fatigued in air and in a vacuum of approximately 5 X l0-3 mm Hg. Both air and vacuum tests were carried out by the same alternating flexure machine at a frequency of 500 cpm. Flat cantilever-bend specimens with tapered sides were cut from strip, annealed at 100°C, and chemically polished.

Jan 1, 1959

By J. S. Marsh

TUESDAY, Feb. 16, was no day for strolling along the cold sidewalks of New York, and a large number of metallurgists sat down with pleasure to the warming task of wiping a few soldered joints. Presented by a joint-wiper of the modern school, G. M. Bouton, of the well-known team of Schumacher, Bouton, and Phipps, the initial paper brought into focus the theme of conservation of strategic metals and described the technique of making the fillet-type joint now employed by the Bell System. Using an over-all average of only 40 per cent of the solder formerly used by the conventional method. this important development bids fair to stick when the war is over. D. L. Martin and E. R. Parker then described the embrittling effect of hydrogen on silver previously heated in oxygen and the less serious but troublesome result obtained under the converse conditions. An interesting example of grain growth restriction created additional material for the lively discussion that ensued among those who have encountered one or another of these phenomena in silver and copper.

Jan 1, 1943

G. D. Kneip, Jr., and J. 0. Betterton, Jr. (Union Carbide & Carbon Corp., Oak Ridge, Tenn.)—The authors have contributed to the theory of zone melting by considering the effects of the solidification of the final zone on the distribution curves for the finite length bar. However, they do not consider in sufficient detail the restrictions imposed by the particular metals involved. Eq. 4 has the analytical solution which is equivalent to Pfann's' equation for normal solidification of the final zone. For distribution coefficients less than one, it is apparent from this form of the equation that, as the solidification approaches completion, the concentration attains extremely large values which are inconsistent with the density of physical materials. The necessary restrictions then are that the solute concentration cannot exceed the density of the alloy, or more frequently, the solubility limit in the solid phase. Secondly, the distribution coefficient cannot be constant from 0 to 100 pet solute unless the liquidus and solidus coincide over this whole region. It would thus be more correct to impose limits on the solubility such as would be indicated by a typical eutectic diagram. Furthermore, in this case the assumption that the distribution coefficient remains constant is more likely to be realized. Eq. 4 should then be replaced by the following C,,(x) =k/L-x [ ?11 3 C11 (x)Ddx - ?11 4 Cn(x)dx= k[Cn (L-l)/k] [ L-x/l]x-1 L-l = x = L-l [kCenterlie/Cn (L-l)]1/k-1 The typical shape for the distribution curve in the final zone is indicated schematically in Fig. 12 for the simple eutectic case. The solidification proceeds according to Pfann's' expression until the concentration reaches the maximum solubility in the solid phasc. At this point, the concentration changes abruptly to the eutectic composition and remains at this value for the duration of the solidification. The width of the flat region, and the back reflection of this effect into the concentration curve on subsequent passes, depends upon the ratio of the eutectic concentration to the original concentration, upon the distribution coefficient, and upon the number of passes. Similar effects on the concentration curves in the first zone length would be expected in many systems for which the distribution coefficient is greater than one, and where the maximum solubility is not too much larger than the original concentration. The discussers agree with the authors that the assumption that the liquid is uniform in concentration should be considered with caution. Kneip and Better-ton' have shown, however, that in floating zone refining of zirconium, using induction heating, the distribution of iron agrees with theory which assumes a uniform liquid composition. Hence, in this case, the experimentally realized distribution coefficient agrees with the present phase diagram within the experimental uncertainty. L. Burris, Jr., C. H. Stockman, and I. G. Dillon (authors' reply)—The authors are happy to have received the comments of G. D. Kneip, Jr., and J. 0. Betterton, Jr., which provide additional insight into the zone refining process. It is true that the equations developed are inapplicable if the solute solubility in the solid phase is exceeded. However, this restriction on the use of the equations was clearly stated in the paper. A closer approach to

Jan 1, 1957

By Garth M. Crosby

Hugh E. McKinstry (Professor of Geology, Laboratory of Mining Geology, Harvard University, Cambridge, Mass.) Pre-Cambrian age for the Coeur d'Alene mineralization, as indicated by isotope studies and recently discussed by Silverman, Long, and Kulp' would explain some features of the mineralogy of the district that have long been a puzzle. In the Silver Belt, especially in the Sunshine mine, lead-zinc min erali zation passes downward into tetrahedrite ore. Although commercially speaking this is a rich silver zone, the silver is, quantitatively, a mere impurity amounting to a small fraction of 1 pct. In effect the zonal change is from lead-zinc down into copper mineralization—-the usual zonal change that occurs in many districts. In the Burke-Mullan portion of the district, on the other hand, lead-zinc ore does not pass downward into copper mineralization of the Sunshine type. Instead, pyrrhotite appears in depth while the tenor in lead and zinc declines. The change occurs at increasingly greater depth away from the Gem stocks, deepening irregularly by some 3000 ft within two to four miles. As noted by Crosby, biotite, grunerite, and garnet appear in the deep zone. The marked difference between this apparent zonal change and the more nomal change to a copper zone is quite explainable if already existing pre-Cambrian veins have been locally metamorphosed by a Tertiary intrusive. The chief obstacle to this explanation is the evidence that mineralization cuts Laramide intrusives, but evidence on this point is conflicting as indicated by Crosby's observations and summary. This is not the first instance of a problem in determining the time-relationship of mineralization to a spatially associated intrusive. At the Noranda mine veins of chalcopyrite extend into a diabase dike which apparently cuts the ore, although Price2 concludes that the ore is later. However, at the Normetal mine diabase of a similar dike is thought3 to intrude the orebody but is cut by stringers of chalcopyrite. In the Sullivan Mine, B. C.,4 galena follows a fracture in a larnprophyre dike which, itself, cuts the main orebody. In the Sudbury district dikes of olivine diabase are clearly younger than the nickel ore, yet where they cut the Creighton orebody they contain stringers of chalcopyrite. In the laboratory, Hawley5 has developed veinlets of sulfide (chalcopyrite) it] silicate gangue by heating specimens of ore in a stream of H2S at 410 °C. From this and other evidernce. it seems clear that sulfides can be transferred from one site to another — at least through short distances — at temperatures well below their melting points. It would seem then that even if sulfide Mineralization in the Gem stocks can be shown unequ ivocably to be later than the intrusive the possibility of "remobiliza tion" need not be more than local. Thus the zonal relationships are quite in accord with a pre-Cambrian age for original deposition of the lead, zinc, copper, silver, and uranium in the Coeur d'Alene district. REFERENCES 1. A. Silverman, A. Long, and J. L. Kulp: Discussion of: The Gem Stocks and Adjacent Orebodies, Coeur d'Alene District, Idaho. Mining Engineering, May 1960, pp. 470-471; AME Trans., 1960, vol. 217, p. 117. 2. Peter Price: Geol. & O. D. at the Home Mine, Noranda, Quebec. Can. Inst. M & M Bull 263, 1934, p. 108; also,Trans. CIMM 1939, pp. 108-140. 3. w. L. Brown Nometal Mine in structural Geology of Canadian Ore Deposits, Montreal, 1948, p. 690. 4. C. O. Swanson and H. C. Gunning: Geology of the Sullivan Mine. Can. Inst. Mining & Met. Trans. vol. 48, 1945, p. 653. 5. J. E. Hawley: Heat Effects on Sulphides and Possible Applications. Univ. Toronto Studies, Geol. Ser. No. 46, 1941, p. 34.

Jan 1, 1961

By C. F. Jackson

THE work of, the Mining Methods Committee is now well under way. Following discussions previous to and during the February meeting, an Outline for Papers on Mining Methods was prepared, and over a thousand copies have now been distributed to committee men, to section secretaries and to members who have indicated any interest in the subject. The objective of the committee is to prepare a symposium on mining methods which will be of real practical value to the operator and engineer in the solution of every-day mining problems. It is planned to cover the entire field of mining in such a way that the different branches of mining, such as coal and ore (iron, copper, lead, zinc and precious metal) can benefit from the experience of the others at points where they have problems in common.. It is realized fully that each of these branches of mining possesses its own peculiar problems, but at the same time, there are prob-lems in connection with each, where the experience in others should be of value. The committee proposes to proceed along the following lines: 1. To present a general classification of mining methods, showing their inter-relationship, and at the same time .provide a common language for the discussion of mining methods and a nomenclature that will have the same meaning wherever used. A com-plete set of illustrations will accompany the classi-fication to make clear the terminology adopted and to show graphically the inter-relationship of methods. 2. To show the relationship between the physical characteristic of the deposit, the economic consider-ations and the. mining method., It is not proposed to treat this subject as a mere academic problem, but to secure reports from every mining company of impor-tance in this country, which will show what methods or modifications and combinations of methods have actually been applied and the physical conditions and economic considerations which have led to the adoption of these methods in each case. The Mining Methods Committee has drawn up an Outline for Papers on Mining Methods to be distributed among mining engineers and operators, giving in detail the information desired. This outline is the result of several months of careful thought and is a composite of the suggestions of many engineers and mining company officials from all parts of the United States.

Jan 7, 1922

Agnico-Eagle Mines Ltd. comprises a Gold Division at Joutel, Quebec, and a Silver Division at Cobalt, Ontario. In 1979 the Silver Division milled 41,700 mt (46,000 st) of ore at a recovered grade of 139 g per mt (4.06 oz per st) for a production of 5,816 kg (187,000 oz) of silver. The 100 -year -old mining, camp of Cobalt has long been noted for its high-grade silver ores, and now seems to be on the threshold of being revived with several companies operating in the area. In 1979, the Gold Division milled at the rate of 27,200 mt per month (30,000 st) and processed 333,000 mt (367,000 st) at a grade of 6.58 g per mt (0.192 oz per st) with a mill recovery of 91.670 to produce 2,013 kg (64,700 oz) of gold. The average total cost per ton milled was $22.10 per mt ($20.05 per st) which was $3.66 per g ($1 13.90 per 0s). These figures make Agnico-Eagle one of the lowest cost producers in North America. Gold occurrence in the Joutel ore is fine-grained and contained within sulfide facies composed mainly of pyrite with minor pyrrhotite. Two underground mining methods are employed with long hole stoping accounting for about 75% of the ore mined and shrinkage stoping the remainder. Ore from underground is hoisted into a 545 mt (600 st) coarse ore bin from where it is conveyed to a 45 mt (50 st) surge bin ahead of the 10-51 Hydrocone crusher. Crushed ore is then screened to make a 13 mm (112 in.) product with the oversize being recrushed in a 7-60 Hydrocone. Mill feed is conveyed to two 900 mt (1,000 st) fine ore bins. The Hydrocones were installed as part of a new crushing plant in March of 1980 and have contributed substantially to an increase in mill capacity. Space has been left to install a third crusher in the future. The fine ore bins discharge to a 2.75 m by 3.66 m (9 ft by 12 ft) rod mill, followed by a 3. 7 m by 5.5 m (12 ft by 18 ft) ball mill in closed circuit with a Krebs 380 mm (15 in.) cyclone to produce a 7070 minus 37 micron (400 mesh) .flotation feed. This pulp is first treated in a 34 cu m (1, 200 cu ft) Maxwell flotation cell and then in an additional twelve 2.8 cu m (100 cu ft) cells. Combined flotation concentrates are reground to 9070 minus 37 microns (400 mesh) in a 1.8 m by 4.9 m (6 ft by 16 ft) ball mill in closed circuit with a single Krebs 254 mrn (10 in.) cyclone. Flotation tailings are sent to the tailings dam. Reground concentrates are then aerated with lime to a single Pachuca and thickened in a 16.75 m (55 ft) diameter thickener with the addition of diesel fuel to render any activated graphite inert to adsorption of

Jan 1, 1981

By J. H. Smith, H. W. Paxton

ALTHOUGH many structural and kinetic investigations have been made for alloys of iron and nickel, only meager data exist from thermodynamic investigations. The purpose of this note is to estimate the free energy of the Fe-Ni solid solutions from thermodynamic data available for ternary alloys containing iron and nickel. The lack of a description of the thermodynamic behavior for the Fe-Ni system has required the structural and kinetic analyses of the system to assume some form of solution behavior, usually regular, e.g., the mar-tensite transformation analysis of Kaufman and Cohen, 1 consistent with the limited thermodynamic data. Indications that this system could exhibit ideal solution departures might have been suggested by the large deviations from additivity rules observed in the density and lattice-parameter measurements of Jette and Foote2 who interpreted this in terms of possible solute-solvent interactions. Later Turkdogan et al. 3 and more recently Ward and wright 4 found a minimum in the graphite solubility in liquid Fe-Ni solutions near the concentration of FeNi3 with deviations from linearity persisting at all concentrations. This was interpreted by Ward and wright4 to indicate negative heats of solution and was suggestive of short-range ordering. The infinitely dilute activity coefficient of carbon (?oC) was also observed by smith5 to pass through a maximum near the FeNi3 concentration in Fe-Ni solid solutions. Recent investigations of the liquid solutions over the entire concentration range by Zellars et a1.' and Speiser et a1.," using vapor-pressure determinations, revealed both negative departures from Raoult's law and a nonregular solution behavior. The solid alloys have been studied by Oriani 8 and Kubaschew-ski and von Goldbeck6 employing gaseous H2/H2O equilibria with Fe and FeO. Both investigations were in substantial agreement, indicating very small departures from ideality. However, Oriani observed the formation of Fe3O4 (instead of FeO) at XFe= 0.441 which severed the equilibrium and precluded experimental investigation of the nickel-rich alloys. Heat-capacity and heat-content measurements have been evaluated by Montgomery10 and found generally unsatisfactory for gleaning thermodynamic information. This is due to the unknown final states of the alloys caused by the interference of the martensite transformation on cooling iron-rich concentrations and superlattice formation, magnetic transformation, and the varied heat treatments used by investigators of nickel-rich concentrations. As an alternative to the experimental difficulties, indirect estimates of the solid-solution behavior have been made by Fleischer and Elliott11 and Smith et a1.12 From their measurements of the solubility of Fe-Ni alloys in liquid lead, Fleischer and Elliott calculated the nickel activity (aNi) (and integrated for aFe) by assuming: 1) liquid lead has no solubility in solid Fe-Ni alloys, 2) Henry's law is obeyed throughout the liquid lead-rich phase (0— 12 at. pct Nil, and 3) Henry's law constant is independent of relative iron and nickel concentrations. The estimate of Smith et a1.12 was obtained

Jan 1, 1964

By Edgar Bain

OF THE important phenomenon of the hardening of steel, Professor Sauveur1 says: "It would seem as if the methods used to date for the elucidation of this complex problem have yielded all they are capable of yielding and that further straining of these methods will only serve to confuse the issue, the point having been reached when this juggling, no matter how skilfully done, with allotropy, solid solutions, and strains is causing weariness without advancing the solution of the problem.. The tendency of late has been to abandon the safer road of experimental facts and to enter the maze of excessive speculations, in which there is great danger of some becoming hopelessly lost. The conclusion seems warranted that new avenues of approach must be found if we are to obtain a correct answer to this apparent enigma. With some degree of fitness we may say, this of other problems. It seems likely that one of the new avenues of approach to many metallographic problems is the study-of crystal structure, or more accurately, the atomic arrangement by means of the X-ray spectrometer. The crystal structure of some materials has been carefully worked out by the mineralogist, but his methods are, in general, unsuited to commercial metals and a method that yields even better information is at hand as the result of work on the diffraction of X-rays by Laue and the Braggs2 and later by Hull,3 St. John, and others. It should be understood that the contour of free crystals, which is the subject of measurements by the crystallographer, is the result of the atomic structure and, in general, bears a simple and obvious relation to it. The use of the X-ray spectrometer4 has been described frequently, so the procedure will not be given here.

Jan 2, 1922

By Edgar C. Bain

Of the important phenomenon of the hardening of steel, Professor Sauveurl says: It would seem as if the methods used to date for the elucidation of this complex problem have yielded all they are capable of yielding and that further straining of these methods will only serve to confuse the issue, the point having been reached when this juggling, no matter how skilfully done, with allotropy, solid solutions, and strains is causing weariness without advancing the solution of the problem. The tendency of late has been to abandon the safer road of experimental facts and to enter the maze of excessive speculations, in which there is great danger of some becoming hopelessly lost. The conclusion seems warranted that new avenues of approach must be found if we are to obtain a correct answer to this apparent enigma. With some degree of fitness we may say this of other problems. It seems likely that one of the new avenues of approach to many metallo-graphic problems is the study of crystal structure, or more accurately, the atomic arrangement, by means of the x-ray spectrometer. The crystal structure of some materials has been carefully worked out by the mineralogist, but his methods are, in general, unsuited to commercial metals and a method that yields even better information is at hand as the result of work on the diffraction of x-rays by Laue and the Braggs2 and later by HullI3 St. John, and others. It should be understood that the contour of free crystals, which is the subject of measurements by the crystallographer, is the result of the atomic structure and, in general, bears a simple and obvious relation to it. The use of the x-ray spectrometer4 has been described frequently, so the procedure will not be given here.

Jan 1, 1923

By Edgar C. Bain

Of the important phenomenon of the hardening of steel, Professor Sauveurl says: It would seem as if the methods used to date for the elucidation of this complex problem have yielded all they are capable of yielding and that further straining of these methods will only serve to confuse the issue, the point having been reached when this juggling, no matter how skilfully done, with allotropy, solid solutions, and strains is causing weariness without advancing the solution of the problem. The tendency of late has been to abandon the safer road of experimental facts and to enter the maze of excessive speculations, in which there is great danger of some becoming hopelessly lost. The conclusion seems warranted that new avenues of approach must be found if we are to obtain a correct answer to this apparent enigma. With some degree of fitness we may say this of other problems. It seems likely that one of the new avenues of approach to many metallo-graphic problems is the study of crystal structure, or more accurately, the atomic arrangement, by means of the x-ray spectrometer. The crystal structure of some materials has been carefully worked out by the mineralogist, but his methods are, in general, unsuited to commercial metals and a method that yields even better information is at hand as the result of work on the diffraction of x-rays by Laue and the Braggs2 and later by HullI3 St. John, and others. It should be understood that the contour of free crystals, which is the subject of measurements by the crystallographer, is the result of the atomic structure and, in general, bears a simple and obvious relation to it. The use of the x-ray spectrometer4 has been described frequently, so the procedure will not be given here.

Jan 1, 1923

By Francis Foley

FROM the point of view of the metallographist, the adaptation of x-rays to the study of the crystal structure of metals is of the greatest importance. While one may hardly consider the findings resulting from x-ray study as revolutionary, their positive nature, compared with the deductions we have been forced to accept from the work that had gone before, gives firmer ground on which to build and furnishes new fields for speculation. Prior to the advent of the crystallogram, the best work on the crystal structure of steel was that of Osmond and Cartaud.1 They concluded, from their investigation with percussion figures formed at various temperatures, that alpha, beta, and gamma irons belonged to the cubic system and that they showed well-marked specific characteristics and could not have the same internal structure. What the internal structures were, they had no direct method of determining; but from a consideration. of the fact that the 001 plane (that parallel to the cube face) is a plane of perfect cleavage and minimum hardness in alpha iron and that the 111 (octahedral) plane is by far the most important in the crystallography of gamma iron, they were led to suggest the simple cubic arrangement as that of alpha and the face-centered cubic arrangement as that of gamma iron. They suggested the body-centered cubic arrangement as that of beta iron. The atomic arrangement of the various crystal forms of iron has been quite definitely determined in recent years by means of x-rays and the work of Westgren2 and Westgren and Phragmèn3 has been rather conclusive. They not only determined the atomic arrangement of alpha, beta, and gamma iron but also that of the high-temperature modification delta.

Jan 10, 1925

By Jacques Steininger, Robert E. England

Single crystals of ZnTe and ZnTe1-,Sex with x up to 0.13 have been grown from the elements by temperature gradient solution zoning using excess tellurium as a solvent. Best results have been obtained with charges with the compositions 45/55 at. pct Zn, Te, for ZnTe and increasing amounts of selenium for ZnTe1-xSex. The temperature in the molten zone was maintained at about 1070°C with a gradient of about 10°C per cm. Chemical analyses of quenched ZnTe ingots show tellurium concentrations in the molten zone as high as 70 pct with concentration differences across the zone of 1 to 2 at. pct Dark dots which are observed by transmitted light microscopy in as-grown crystals can be removed by annealing in zinc vapor at 900 C. INTEREST in wide band gap semiconductors has led to a new study of ZnTe and ZnTel-xSex crystal growth. ZnTe is the only II-VI compound with a wide band gap (2.3 ev) that can be made p type with low resistivity. Attempts to make it n type with low enough resistivity to be useful for p-n junctions have so far been unsuccessful.1 ZnSe has a band gap of 2.65 ev but can be made n type only. However, ZnTel-xSex solid solutions with x as low as 0.36 have been made both highly n and p type2 with a minimum band gap around 2.12 ev3 at room temperature and appear to hold the best promise for efficient injection electroluminescence in the visible. ZnTe has the lowest melting point of the zinc chal-cogenides (1295°C) and consequently attempts have been made to grow crystals from both the liquid and the vapor phase.4 Complicated apparatus is required for growth from stoichiometric melts because of the high vapor pressures of the elements at the melting point of ZnTe and because of the problem of quartz devitrification. Small crystals have thus been grown in high-pressure equipment by Fischer5 and by Narita et a1.6 with pressures of the order of 50 atm of argon to prevent excessive evaporation from the melt. Large crystals of ZnTe can be obtained by growth from the vapor phase4 but they often present numerous dislocations and inclusions. An improvement in the quality of vapor- grown ZnTe crystals was reported by Albers and Aten7 by equilibration of mixtures of small crystals with compositions lying on either side of the solid single-phase field at fixed temperature. The same technique was later applied by Aten8 to the growth of ZnTe1-xSex crystals with less than 1 pct inhomo-geneity. Because of the higher liquidus temperatures of the solid solutions and the high vapor pressure of selenium, previous attempts to grow ZnTel-xSex from the melt have been limited and unsuccessful.9 The phase diagram of the Zn- Te system is reproduced in Fig. 1, based on data from Kobayashi10 and Kulwicki.11 Carides and Fishher12 have reported lower liquidus temperatures on the tellurium-rich side, but their data would require confirmation. The liquidus temperature on the tellurium-rich side decreases rapidly with increasing tellurium concentration and the Te2 vapor pressure over the liquidus also decreases accordingly.'3 The decrease in liquidus temperature and vapor pressure therefore makes it possible to use conventional apparatus if there is a sufficient excess of tellurium in the melt. Single crystals of ZnTe have thus been grown by Kucza,14 in a modified Bridgman technique, from solutions containing up to 60 at. pct of Te by lowering unsupported quartz ampoules through a temperature gradient at about 1200°C. Under these conditions, the phase diagram indicates that the entire charge is initially molten. Crystal growth can therefore proceed by normal freezing and rejection of excess tellurium into the melt. The modified Bridgman technique has several major limitations. Because of the rejection of excess tellurium into the melt during freezing, the melt composition and the temperature at the growth interface vary continuously. They tend to follow the liquidus until the eutectic which is very close to pure tellurium (447°C, >99 pct Te). Since the solidus composition also varies with temperature,15 crystals grown by this method are inhomogeneous. They present small variations from stoichiometry which may affect their structure and physical properties. The simultaneous increase in tellurium content and decrease in melt temperature also combine to reduce the rate of diffusion of tellurium away from the growth interface, thereby causing constitutional supercooling and possibly dendritic growth. To minimize these effects, the initial melt composition is in practice kept relatively close to stoichiometry (less than 60 pct Te). This however limits the possibilities of operating at low temperatures and pressures. This paper describes a modified method of crystal growth by temperature gradient solution zoning (TGSZ) which is an adaptation of the temperature gradient zone-melting technique developed by pfann16 and of the traveling solvent method of Mlavsky and weinstein.I7 The TGSZ method now applied to the growth of ZnTe and ZnTel-xSex crystals is characterized by its very simple experimental arrangement and sample preparation technique. Unlike the modified Bridgman technique, there is no increase in the tellurium concentration in the melt and therefore it is possible to operate at lower temperatures and pressures. This method is also suitable for maintaining a constant temperature at the growth interface.

Jan 1, 1969

By R. G. Davies, R. H. Richman

Several techniques, X-ray diffraction, transmission electron microscopy, conventional, metallography, and mechanical property measurements are combined to investigate decomposition in the suPersaturated solid solution Fe-27 at. pct Be. The following sequence of structures for aging temperatures below 400°C is established: massive short-range order, pseudo-FeBe (L2o) order, Fe3Be (DU3) order, sinusoidal modulation of composition, general or continuous precipitation, and discontinuous or cellular precipitation. In addition to this sequence itself, several features of the individual stages are noteworthy; for example, when coherent modulations occur, their development is parallel to (100) everywhere in the specimen apparently without incubation, and both the wavelength and the composition amplitude of the modulations increase with aging time. Two types of discontinuous reaction are observed, depending upon the aging temperature. At low temperatures (<550°C) the boundary-nucleated variety of discontinuous precipitate predominates; but at higher temperatures (>600°C) the crystallographic variety occurs instead. Hardness and flow-stress measurements clearly reflect the quoted structure sequence. Some qualitative aspects of the structure changes and of the relationship between mechanical properties and structure are discussed. BERYLLIUM in solid solution markedly strengthens iron.&apos;" A recent study demonstrated that not only were supersaturated single crystals of Fe-27 at. pct Be very strong, but they deformed primarily by mechanical twinning.3 Such behavior, coupled with the decrease in solid solubility of beryllium in a Fe from about 33 at. pct at 1165°C to about 10 at. pct at 500°C4 as shown in Fig. 1, leads naturally to questions about property changes with aging in this system. In 1929 roll,1 and later Seljesater and Rogers,5 reported that useful increases in strength could be obtained by aging quenched Fe-Be alloys, but it was not until quite recently that any of the details of precipitation in these alloys were studied. Richman6 observed that both an Fe3Be superlattice (with a DO3 crystal structure the same as Fe3A1, illustrated in Fig. 2) and a modulated structure preceded the appearance of a discrete second phase in the 20 at. pct Be composition. Here, a modulated structure refers to a periodic composition fluctuation within one crystal, while its lattice remains coherent. Subsequent work on a Fe-Be alloys by Heubner7 and von Heimendahl and Heubner8 confirmed the existence of the modulated structure, although only an FeBe (L20) ordered structure was detected (also shown in Fig. 2). Both Rich-man and Heubner corroborated the large increases in hardness during aging reported earlier, but other mechanical properties were not examined. Since modulated systems are encountered relatively infrequently, the influence of coherent modulation upon mechanical properties is not well-known. With the accumulation of information about age-hardening systems, it has become clear that many precipitation reactions cannot always be described by the concept of heterogeneous nucleation at some lattice discontinuity followed by diffusional growth. Rather, complex sequences involving prior "preparation" of the matrix are quite common; that is, a transition structure occurs in the parent phase, instead of in some "nucleus" form. Delineation of such subtle sequences appears to be a worthwhile step toward the understanding of solid-state precipitation. Since not many structural progressions of comparable nature have been reported, the objectives of the present survey are to identify and elucidate the various

Jan 1, 1967

By R. W. Fountain, W. D. Forgeng

A new constitutional diagram is presented for the cobalt-rich end of the cobalt-titaniurn system. The modifications result from the presence of a new, intermediate, fcc phase, ?, the existence and homogeneity limits of which were established by metallo-graphic and X-ray studies of alloys containing from about 3 to 30 pct Ti. The precipitation of the ? phase from supersaturated solid solution was studied by hardness and electrical resistivity measzsrements, and two distinct stages in the process were observed. COBALT forms the base for a number of precipitation -hardenable alloy systems which may be divided into two distinct categories of practical interest, a) those hardened by intermetallic compounds and b) those hardened by carbide formation. The precipitation of intermetallic compounds from solid solution in cobalt-rich alloys has, however, received very little attention. Although the phase diagrams for some binary systems capable of precipitation have been determined,&apos; there is an almost complete lack of data on the property changes associated with the precipitation, and even less information on the kinetics of the reactions or morphology of the products. More information is available on the precipitation of carbides because of the practical significance in superalloys. A survey of cobalt binary phase diagrams suggested that the cobalt-titanium alloys might provide interesting and useful precipitation-hardenable alloys. The equilibrium diagram as proposed by Wallbaum2 is shown in Fig. 1. Köster and wagner3 have indicated that the maximum solubility of titanium in cobalt is about 10 pct at the eutectic temperature (1135oC), and this decreases to about 7.2 pct at room temperature. The temperature of the allotropic transformation in cobalt is lowered by the addition of titanium, about 5 pct being sufficient to retain the high-temperature fcc modification to room temperature. Wallbaum and Witte 4,5 have indicated that the precipitating phase in alloys containing up to about 29 pct Ti is Co2Ti, a hexagonal Laves phase of the MgNi, type. With slightly higher titanium contents, they also report a cubic modification of Co2Ti of the MgCu2-type Laves phase. Duwez and Taylor6 confirmed the existence of the hexagonal (MgNi2) modification but not the cubic (MgCuz) modification of Co2Ti and suggested that existence of the cubic form may have resulted from impurities in Wallbaum&apos;s alloys. In their work on Laves-type phases, Elliott and Rostoker 7 reported the cubic modification of Co,Ti, but did not confirm the existence of the hexagonal modification. However, Dwight8 in a discussion of the work of Eliott and Rostoker again showed the existence of both modifications of Co2Ti, a result which was confirmed at that time by Elliott and Rostoker. As a result of a study on the iron-cobalt-titanium system, Köster and Gellers suggested the existence of a Co3Ti phase isomorphous with Fe3Ti. Witte and Wallbaum,&apos; however, established the fact that no compound, Fe3Ti, exists in the iron-titanium system, and in a later publication, wallbaum2 stated that Kitster and Geller&apos;s reasoning was not valid, and no compound, Co3Ti, exists. This conclusion was later acknowledged by Köster.10 Preliminary experiments by the present authors to determine the precipitation-hardening characteristics of the cobalt-rich, cobalt-titanium alloys re-

Jan 1, 1960