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By D. L. Katz, M. J. Rzasa

The derivations of three methods of computing the static pressure gradients in natural gas wells have been presented to show the assumptions made. Charts were developed from which the pressure gradients may be read when the well-head pressure, the well fluid gravity, depth, and the average well temperature are given. A chart for estimating the well fluid gravity from the condensate content and separator gas gravity is included. The effect of the increased average well temperature after flow on the calculation of the static pressure gradient is discussed. Introduction Reservoir pressures have been calculated from well-head pressures for gas wells for many years. As the pressure measurements become more accurate, the need for a reliable calculation of the static pressure gradient often arises. This paper will develop the several methods for computing the pressure gradient in gas wells and make a comparison between them. The method of calculating static pressure gradients in common use is Eq. I (ref. I) or its counterpart which includes a factor for the deviation of the gas from the ideal gas law. P2 - P1 = P1(e0.0000347GX _ I) Eq. [I] in which P1 = pressure at well head, lb. per sq. in. abs. PP = pressure at bottom of well, Ib. per sq. in. abs. G = gas gravity X = depth of well, ft. An alternate method is to compute the average density of the gas in the well and multiply by the well depth in a manner similar to that used for liquid gradients. Derivation of Formulas A static pressure gradient is a special case of the general fluid-flow equation. Consider a pound of fluid flowing in a vertical column from point I to point 2, Fig. I. By an energy balance for fluid flowing from I to 2: U1 + P1V1 + u12/2g + X1 + q = U2 + P2V2+ u22/2g+X2 +W [2] in which U = internal energy, ft-lb. per lb. P = pressure, lb. per sq. ft. V = volume, cu. ft. per lb. u = average linear velocity, ft. per sec. X = height above datum, fl. q = heat absorbed by fluid, ft-Ib. pcr lb. W = work done by system, ft-lb. per lb. An energy balance on the fluid itself gives: U = ?TdS - ?PdV + etc. [3] in which T = temperature, deg- R- S = entropy, ft-lb. per deg. R. per lb.

Jan 1, 1945

By P. K. Kaiser, S. M. Maloney, S. P. Singh

"Corrosion of underground support measures constitutes a concern to industry in both safety and economic terms. It also represents a potential market for corrosion resistant materials such as stainless steel.In order to assess the market potential for a stainless steel friction rock bolt, a review of current corrosion processes and remedial or preventative measures in the underground environment was undertaken. This was supplemented by distribution to industry of a detailed questionnaire, concerning the magnitude and extent of support corrosion and the costs of current support measures, and by visits to selected sites. Following data synthesis, support costs were established and the economic benefit of stainless steel rock bolts evaluated.Stainless steel rock bolts can be an effective cost reducing measure in unscreened areas requiring frequent reconditioning. Their benefit is rapidly diminished, however, if only partial reconditioning is required, the reconditioning interval is long or if screening is required.While most industry personnel are receptive to the application of stainless steel support measures, the localization of corrosion problems and the potential high cost of this type of support are barriers to its widespread implementation. They have potential for use in extreme environments. However, this relatively small market may not be economically viable.IntroductionFriction rock bolts are the simplest of all interior rock fixtures. The friction resistance to sliding of the rock on the bolt is generated by a radial pressure against the borehole wall over the length of the bolt. Two types of friction rock bolts are currently marketed, the Split Set and the Swellex.Unlike conventional point anchor bolts, friction rock stabilizers may move relative to the rock strata and maintain their capacity even if rock shifts, a condition that sometimes loosens or breaks conventional bolts. Ease of installation, effectiveness in jointed as well as weaker rock, and the possibility of having relatively long bolts are a few of the many advantages which generate considerable interest in the application of friction rock bolts (Wijk and Skogberg, 1982). However, due to their thin-walled construction and large surface area, frictional rock stabilizers are more susceptible than conventional bolts to damage by corrosion. For this reason, they are normally not recommended for long-term use (Jolly and Neumeier, 1987).In light of the above discussion; the Nickel Development Institute commissioned a study by the Geomechanics Research Centre with the objective of generating a credible database for the assessment of the feasibility of a stainless steel friction bolt system in corrosive ground and mine environments."

Jan 1, 1990

By C. P. Verschuren, P. W. Kingston, W. F. Caley

"In recent years, there has been rapid growth in the use of natural stone building and construct ion products. The largest growing markets are for pre-fabricated natural stone panels for interior and exterior wall facing and flooring. This increased demand is attributed to advanced quarrying and processing technologies, renewed appreciation for the aesthetic appeal of natural stone, and to the superior durability of natural stone when compared to glass, steel, and concrete. Geologically, plutonic rocks, and to a lesser extent marble and limestone/dolostone, are used extensively for these applications. This paper details the economic structure of the dimension stone industry, describes the necessary characteristics of a stone quarry, and outlines the geological criteria which favour an economic quarry.INTRODUCTIONThe world building stone industry has remained relatively stable over the last 5 to 6 years. In contrast, the North American stone industry has experienced substantial growth during that period. The increased use of commercial granite is primarily responsible for this growth, where use as exterior wall veneer for commercial, industrial, and institutional buildings represents the largest and fastest growing market.This increased usage in the construction industry has been sparked by the application of new technologies in quarrying, processing and installation , ma king natural stone more competitive with man-made materials which are energy intensive to produce, and have risen dramatically in price. The development of safer, time-saving stone installation techniques has also appealed to the liability-conscience construction industry. Finally, there is a trend by designers and architects toward utilizing long-la sting weather-resistant building materials, and a renewed appreciation of the aesthetic appeal of natural stone. The other large user of granite is the monument industry of North America which, although it has decreased slightly in recent years, still consumes approximately 40% of all commercial granite produced. The local use of commercial marble has remained relatively stable, and North America still relies heavily on European sources and suppliers. There has been some concern over the use of marble for exterior applications in areas subject to acid rain, and in colder climates where the marble ma y be vulnerable to freeze thaw cycles. Despite these concerns, the greatest problem is not with the structural breakdown of marble but the inability of some marbles to retain their polished finishes in the se environments. As a result, there has been an increase in the use of granite at the expense of marble for exterior applications. Finally, commercial marble is used extensively for interior flooring, wall s, counter tops, furniture, sculptures, and stairway components"

Jan 1, 1989

By T. J. McKeon

Partition curves are used to evaluate the separation performance of gravity-based concentrators. The partition curve is used to identify the nominal density cutpoint and relative sharpness of the separation. In addition, the graphical representation makes it possible to quickly identify the root cause of misplacement based on the characteristic shape of the partition curve. Partition curves have been traditionally constructed using data obtained from float-sink tests using heavy organic liquids. These toxic liquids are environmentally unfriendly and have been banned in several countries. Another method of establishing the partition curve is to introduce density tracers into the feed and plot the distribution to the lights and heavies. For heavy mineral separations, this approach is generally impractical due to the fine particle size. In addition, the partition data obtained using these existing techniques do not account for secondary factors such as particle shape that may influence the separation. In light of these problems, a methodology was developed for constructing partition curves using experimental data obtained from microscopic grain-counts. This technique, which essentially uses the different mineral species as density tracers, provides a powerful tool for evaluating heavy mineral separations. A case study is provided to demonstrate how this analytical approach can be used to assess and improve the separaton performance in an industrial upgrade plant.

Jan 1, 2005

By Alex C. Smith, Thomas A. Gray, Lynn M. Crayne, Michael A. Trevits, Phil Glogowski

Mine fires constitute one of the greatest threats to the health and safety of those working in the underground environment and each event has the potential for disastrous consequences. Of the major mine fires and thermal events that have occurred in the United States in the last 6 years, it is estimated that remotely installed seals could have been used in 63% of the events to control fire growth or to aid in fire suppression work. The National Institute for Occupational Safety and Health (NIOSH) is conducting full-scale tests at the NIOSH Lake Lynn Experimental Mine to evaluate and improve remote mine seal construction technology. The main focus of this work is to develop reliable technology that will completely close the mine opening from floor-to-roof and rib-to-rib. This paper presents the results of remote seal installations using grout-based materials.

By Oliver Bowles

This paper is the third of a series of reports on asbestos prepared by the Bureau of Mines. The reports already issued contain general information, including descriptions of deposits throughout the world.3/ The present paper deals chiefly with milling and marketing. Many grades of asbestos are marketed, and an important phase of milling is the grading of fiber; these subjects therefore are related so intimately that contiguity in their treatment is fully justified. Although the Bureau of Mines is interested primarily in the mining and preparation of raw materials, the fabrication of asbestos products has attained such importance in the United States that brief reference to processes of manufacture is included. CLASSIFICATION OF FIBER Canadian asbestos fibers are divided into three main groups - crudes, mill fibers, and shorts. The term "crude" is applied to fiber of spinning grade measuring three eighths inch or longer, that is. hand-cobbed and not passed through a mill. Mill fibers are obtained by crushing and beating the fiber-bearing" rock, until the, asbestos is freed and, then removing the fiber from the rock by screening or air separation. Shorts are the lowest grades of mill products.

Jan 1, 1935

By D. S. Pye, J. P. Gallus

Successful hydraulic pressure treatment of oil and gas wells that have long producing intervals, multiple pay zones, fluid thief zones, or natural or induced fractures has long been a serious problem plaguing the petroleum industry. High fluid-injection rates, straddle packers, ball sealers, and either liquid or solid additives to the treating fluids are being used to cope with this difficult and costly problem.l-6 The use of ball sealers and straddle packers is limited, in practice, to wells that have been completed with perforated cemented casings or liners. Well stimulation with ball sealers and straddle packers is usually successful as long as the cement remains competent. The other techniques of diverting are used with all types of completions. However, there are two significant disadvantages of the high rate method: excessive horsepower requirements, and the need of large treating-fluid volume. Consequently, most well stimulation techniques that involve diverting depend upon ball sealers or granular materials. Liquid diverting agents, and some of the solid ones in use today, frequently will cause formation damage. On the other hand, the most popular particulate diverting agents often are so soluble in the treating fluid that they become largely ineffective; their particle size is severely reduced as they dissolve while being transported through thousands of feet of pipe to the formation face down hole. In our attempts to deal with the shortcomings of these diverting agents, we experimented with a large variety of potentially suitable deformable materials the solubility of which could be controlled. Following are the criteria for the diverting agent sought: 1. The material must be effective in reducing fluid loss to thief zones, including existing fractures and very high permeability layers in the formation to be pressure treated. 2. The material must have enough strength to bridge under the treating pressure. 3. The material must be insoluble or slowly soluble in the treating fluids so that the particles retain sufficient size to be effective after they reach the formation face. 4. The material must be completely soluble in the produced oil or condensate liquid so that it can be removed readily; it must not cause formation damage. A number of products consisting of various polymers blended with waxes and other solid hydrocarbons were examined. All these materials satisfied the criteria for a diverting agent and also exhibited some degree of plastic deformability. On the basis of initial tests of strength and hardness, several blends of wax and polymer were selected for extensive testing in the laboratory and the field. These compounds have congealing temperatures ranging from 140 to 190F; they are insoluble in water and soluble in oil. They conformed, therefore, to the criteria specified for a theoretically superior diverting agent. Laboratory and field tests were conducted using these wax-polymer materials to demonstrate that the use of a deformable diverting agent can significantly improve fluid diverting performance. Data in this

Jan 1, 1970

By Christopher J. Bise

INTRODUCTION The control of nuisance water in a mine is extremely important; left uncontrolled, nuisance water can have a severe effect on haulage, ventilation, production, and the health and safety of miners. To control water in mines, a four-step process is followed: (1) prevention, (2) collection, (3) transportation, and (4) treatment. This chapter will be devoted to the collection and transportation of mine water because prevention is usually dictated by pre-mining conditions and initial planning, while treatment is variable and highly site specific. A mine drainage system is nothing more than a collection of gathering points (sumps), machines that impart energy to the fluid (pumps), transportation ducts (pipes), and control devices (fittings, valves, etc.). A pump does not pull the fluid up the suction pipe; atmospheric or external pressure pushes the liquid up the suction pipe to the pump. All references in this chapter will be to centrifugal pumps, due to their popularity for mine drainage. PUMP CHARACTERISTIC CURVES The performance of a pump is plotted on a graph as an indication of its characteristic. To develop the data points, a test facility similar to that shown in Fig. 1 is established. The calibrated Venturi meter is used to measure quantity, the Bourdon gage measures pressure, and the wattmeter measures power input. Various discharge pressures are obtained by throttling with a gate valve in the discharge pipe. Quantity and power are measured at each of these pressure levels, giving the necessary data for plotting the characteristic curves. Fig. 2 shows a typical characteristic curve for a centrifugal pump. Notice that pressure is measured as so many feet of vertical water column above the outlet level, or head. Knowing the quantity (in gallons per minute), head (in feet), and power input (brake horsepower), the pump's efficiency can be plotted based upon the following relationship:

Jan 1, 1986

By French D

In presenting this paper may I preface my remarks by recognizing the presence here to-day of the many delegates from the overseas mining communities throughout the world. That is to say - those delegates not representative of Companies resident in Australia. This does not mean that my comments following are directed solely to the Australian exporter - far from it. The Company which I represent is internationally based. The experiences we have had in dealing and negotiating with our good friends the mineral cargo shippers vary very little in any operational area. However for the purposes of this exercise this address is based on some of our experiences within the Australian trade scene with the emphasis on the fact that we believe it has application to all trading areas.

Jan 1, 1989

By R. O. Burt

"Gravity Concentration, the oldest form of Mineral Processing, remains of major importance to the Industry. Current applications of Gravity Concentration are briefly examined.The Paper details one approach to the development of a Gravity Concentration Plant, from laboratory and mineralogical techniques, through Pilot Plant testing, where applicable, to the actual design of the plant.INTRODUCTIONGravity Concentration, once the major method of concentrating minerals has, for much of the twentieth century been regarded, like the dodo bird, as obsolete. However, in more recent years it is enjoying something of a renaissance, and is once again being treated as a useful, economic alternative in the Mineral Processing Engineers' arsenal.An indication of the broad application of gravity concentration is the variety of minerals presently recovered. A list is given in Table 1; this list is not exhaustive."

Jan 1, 1984

The Bureau has published much data on sulfur (4, 15, 23)3, most of it dealing with national or international aspects of the sulfur industry. Little information, however, is available on sulfur marketing in specific States or areas, Therefore, the Bureau has conducted a survey of the resources, production, consumption, and economic future of the sulfur and sulfuric acid industry in States of the Central and Southern Rocky Mountain area - Wyoming, Colorado, Utah, Arizona, and New Mexico - and in the Northern Plains States - North Dakota, South Dakota, and Nebraska, even though these States do not represent an economic or marketing unit. The purpose of this survey is to review the demand for sulfur and primary sulfur compounds that draws upon the natural resources of the region, to discover opportunities for better use of these resources, and also to analyze and evaluate the patterns of consumption, sources of supply, and other factors that affect the demand for these mineral products. While this survey stresses the economic and marketing phases of the industry, a complementary report (32) emphasizes the resources of sulfur in Wyoming, Colorado, Utah, New Mexico, and Arizona.

Jan 1, 1962

By J. A. Finch

"Gas dispersion in flotation defines the efficiency of the process once the chemistry has been established. There are three measurements, superficial gas velocity, gas holdup, and bubble size, which along with the derived quantity bubble surface area flux, are used to define “gas dispersion.” Sensors for measuring gas dispersion in industrial machines have been developed. This communication describes the working principle of the techniques and illustrates their potential to detect problems and to improve the operation of individual cells, banks and circuits. IntroductionFlotation is the most widely used process to separate minerals and is finding increasing application in other chemical and environmental fields. The process exploits natural and induced hydrophobicity to collect selected particles on the surface of a bubble. Once the process chemistry to control hydrophobicity has been established, the efficiency depends on dispersion of air to generate the necessary bubble surface area. Bubble surface area flux, Sb, the interfacial area generated per unit time and unit area of the machine, is emerging as one of the most useful variables to quantify gas dispersion (Gorain et al., 1997, 1998) although not without its critics (Heiskenan et al., 2001).For a bubble population of mean size db at a superficial gas velocity (or rate) Jg, the bubble surface area flux can be derived from geometric considerations (Finch et al., 1999):"

Jan 1, 2002

By Robin J. Hickson

El Abra has mining concessions granting the right to exploit minerals in more than 130 km2 (32,122 acres). SCM El Abra owns “rights to occupy” the surface of these claims. The company also owns the surface rights over the process plant area and over land conveyor route. The project has procured all material easements relating to the mine area, processing facilities and access rights of way. Engineering, procurement and construction Figure 1 sets out the development and construction schedule for the project. Development is already well under way. As of early January 1996, about 70% of the project was complete and more than 80% of the capital expenditures were committed.

Jan 1, 1996

By Patiño E

Bioleaching is an established technology for the pre-treatment of refractory gold ores and concentrates and the leaching of whole ore copper heaps. In many cases, it offers economic, environmental and technical advantages over pressure oxidation and roasting. However for bioleaching to compete successfully with others pre-treatment processes it needs to be optimized with regard to the parameters that affect the bioleaching reactions and the growth of the microorganism involved. In this sense, this paper focus on the thermodynamic approach applied in bioleaching through of the definition of the growth system and it is thermodynamics analysis, the effect of heat production and energy dissipation on growth and thermodynamic analysis of growth kinetics and the effect of nonstandard conditions.

Sep 12, 2005

An experimental study of the soil mechanics of brown coal showed that brown coal consolidates in the same manner as does a clay and that the theory of consolidation for soils may be applied to brown coals. Moisture content is a function of the coal type, the existing effective stress, and the stress history of the coal.The effective stress in a brown coal seam is a function of the overburden pressure, the pore stress and tectonic stresses. Stress history may be deduced from geological evidence and determined by consolidation tests. Application of these principles to the brown coal seams of the Latrobe Valley shows that the distributions of natural moisture contents are consistent with consolidation.INTRODUCTIONThe nature and geology of the brown coals of Victoria, particularly of the Latrobe Valley, were discussed in some detail by Edwards (1945, 1948), Thomas and Baragwanath (1949) and Gloe (1960). A salient feature of these studies was the distribution of moisture contents in the brown coal seams. Recent experimental work, part of a soil mechanics study of the structure and strength of brown coal, showed that moisture content variation is a reflection of consolidation phenomena in brown coal and application of the results to .field condItions verified and modified the conclusions of Edwards in his pioneer work. Further detail of this experimental work is recorded elsewhere (Rosengren, 1961).EFFECTIVE STRESS AND CONSOLIDATIONEffective stresses in soilsA saturated soil is a two-phase system, consisting of a compressible skeleton of rigid soil particles and pores filled with water, an incompressible fluid. (In this context, the terms compressible, incompressible, and rigid are relative only and refer to orders of magnitude). If this system is subjected to stress we define...

Jan 1, 1963

The preeipitation of dissolved lead from a strong brine by metallic iron is a chemically controlled, first order reaction. The precipitation rate is sensitive to changes in chloride concentration and temperature. The precipitation of dissolved silver is a diffusion controlled, first order reaction. The precipitation rate is insensitive to changes in chloride concentration and temperature.INTRODUCTIONLead and silver sulphates can be extracted from electrolytic zinc plant tailings, or residues, by leaching with strong brine solutions, the lead and silver going into solution as complex chlorides. One of the methods which can then be used to recover the dissolved lead and silver is to precipitate them with metallic iron. The deposition reactions which take place are of the type Pb++ Fe - Fe++ Pb............ (a)To fit such a method of precipitation successfully into a practical flowsheet it is necessary to have some knowledge of the kinetics of the various reactions, Le. to know how the precipitation rates vary with temperature, brine and metal concentrations, and so on. Reaction rates are also needed to design suitable precipitation vessels. However, when examining the possibility of using a brine leaching process to extract the lead and silver from the residue produced at the Risdon plant of the Electrolytic Zinc Co. of Australasia, it was found that, although the use of metallic iron to recover lead and silver from the pregnant brine had been reported by Ralston (1924) and by TrumbulI, Hardiek and Lawford (1948), very little was known about the precipitation reactions. Consequently a laboratory investigation was undertaken, and this paper covers those aspects considered to be...

Jan 1, 1961

By G. V. Krishnan, L. Adler

A rock classification for drilling and boring is presented covering most equipment types and providing an estimation of the key parameters for operation, such as thrust and speed, and of performance such as penetration rate and bit life. Drilling and boring are significant and integral aspects of both the mining and heavy construction industries. Together these constitute over 20% of the G.N.P. Drilling and boring represent the most arduous mechanical processes performed in industry. Their misapplication quickly leads to equipment destruction, hazards, and to major delays. The classification is unified in two ways: 1) for a particular rock class several parameters can be estimated, 2) the classification integrates most excavating activities (i.e. digging, ripping and even blasting), and is derived from ground control. The rock classification provides a job property, based on fundamental and index properties, which yields quick and rough estimates of vital information. However it does not obviate the need for a more thorough analysis, and maintaining field records. BACKGROUND In order to adequately describe a drilling operation the conditions, activity, and equipment must be characterized. Of these the major independent variables are the conditions. Conditions focus on the geologic mass and also consider whether the site is surface or underground. The primary component of the geologic mass is the rock type, detailed below in Rock Characteristics. The other components

Jan 1, 1983

By F. W. Glaser, Benjamin Post

A LTHOUGH most transition metals form a wide variety of boride compounds, the existence of only one zirconium boride, ZrB2, had been established prior to this investigation.' The crystal structure and some properties of a hitherto unreported zirconium boride, ZrB12, are described in this paper. Only one other dodecaboride of a transition metal, UB12, has been reported up to the present.' Chemical analysis of the new compound showed 44 pct Zr and 56 pct B, compared with 41 pct Zr and 59 pct B computed for ZrB12. The difference is within the range of error of the analytical method employed. ZrB12 shows marked metallic properties. It is obtained as a fine black powder. Measurements of electrical resistivity were made at —79°C, + 22°C and +64°C. At 22°C the electrical resistivity is approximately 60 microhm-cm. Over this range the temperature coefficient of resistivity is +0.00162. The thermal conductivity at room temperature is 0.122 watts per cm per "C. The product of the electrical resistivity and thermal conductivity is therefore 8.05, which is not far from the normal Wiedemann-Franz ratio (approximately 7.5 at room temperature). These measurements were made on hot pressed samples which were not always high density specimens. The hardness of ZrB12 on the Rockwell A scale varies between 92 and 92.5. Crystal Structure Determination Single crystals of ZrB12 of a size suitable for X-ray diffraction analysis could not be obtained and powder samples had to be used. Filtered Cu radiation was used throughout. Powder diagrams were indexed on the basis of a face-centered cubic unit cell. After correction for film shrinkage, a Bradley and Jay extrapolation³ to ? = 90" indicated that a, = 7.408 ±0.002A. The volume of the unit cell is 406.5A.V he assumption that there are four "molecules" of ZrB12 per unit cell leads to an X-ray density of 3.63 g per cc. The measured density is 3.7 g per cc (as measured by the immersion method). Relative intensities of reflections were determined by integrating the intensities of diffraction peaks using the count register of a North American Philips wide range spectrometer. Intensities measured in this way showed good agreement with photographic intensities estimated visually using multiple film techniques. The usual Lorentz, polarization, and multiplicity corrections were applied to the observed intensity measurements. There are striking similarities between ZrB12, and UB12. The unit cell of the latter is also face-centered cubic and contains four molecules. a, = 7.473, compared with 7.408 for ZrB12. The radius ratio rB/rU is 0.57; rB/rZr is 0.54. In both ZrB12, and UB12 the four metal atoms in each unit cell are in special positions; only the boron positions need be determined. The latter may be inferred from the extent to which diffraction of X-rays by the 48 boron atoms reinforces or weakens the diffraction by the metal atoms. This effect is relatively much greater in the case of the zirconium compound. In their determination of the crystal structure of UB12, Berthaut and Blum' assumed holohedral symmetry (space group Oh5 , Fm3m) and reported that the U atoms are in positions 4(a): 000; 01/2 1/2; ½ 0 ½ ; ½ ½; the boron atoms were reported to be in positions 48(i) with x = 1/6: ½xx; ½xx; x½x; x½x; xx½; xx½; ½xx; ½xx; x½x; x½x; xx½; xx½

Jan 1, 1953

By V. Kondic, W. M. Rumball

HUNT and Jackson' have recently suggested that binary eutectics might be classified according to the entropy of fusion of the component phases. Such a classification was in fact proposed2 some time ago by the authors and the purpose of this communication is to present some supporting evidence. As pointed out by Hunt and Jackson' typical metals of low entropy of fusion, ?S, tend to form normal eutectics (using Scheil's terminology3). Where one phase is metallic (low ?S) and the other nonmetallic (high AS) then anomalous structures are formed. These anomalous structures may either be regular (e.g., Bi-Sn)or irregular (e.g., A1-Si). Finally Hunt and Jackson suggest that where both phases are of high ?S regular faceted structures are formed. In the proposed classification2 the ratio of the entropies of fusion is taken as the quantitative parameter, i.e., ?Sa/?SB = E, where e > 1.0. An extensive literature survey has been carried out2,4 for reliable photomicrographs of eutectic structures. The structures, numbering 151, have been classified into two classes, viz., normal (i.e., lamellar and rodlike) and anomalous. The latter group has been arbitrarily subdivided into regular and irregular anomalous eutectics. Details and sources of the structures are given elsewhere.2,4 In the absence of better thermodynamic data the value of E has been determined for each of the systems making the following assumptions and approximations: l) The entropy of fusion of solid solutions may be calculated additively;5 ii) Inter metallic compounds are treated similarly but with the addition of the following term for fully ordered structures.5 -4.573(Ni lOg10 Nl + N2 log10 N2) where Nl and N2 are the atomic fractions. It might be argued that the entropies of fusion are meaningless as the eutectic phases form at some temperature (T,°K) below their true melting point (Ta or Tb). As AS, = Lo/To if La the latent heat of fusion of a, is assumed independent of temperature, the actual entropy change AS& is given by La/Te. The ratio of entropies of fusion then becomes Fig. 1 shows E' plotted against cumulative totals for normal and anomalous systems from which it is seen that normal eutectics predominate at low values of E'; e.g., some 90 pct of normal systems lie below E' = 1.5 with 65 pct of anomalous systems above this value. Fig. 1 also shows that the regular anomalous structures occur mostly at low values of c' possibly suggesting growth more akin to normal than anomalous growth. The choice of c as a classification parameter was based on nucleation concepts, it being observed that metals widely separated in Sundquist and Mondolfo's8 nucleation series were anomalous and those close together normal. The basis of these classification views is really outside the intended scope of this communication but it is hoped to explain them fully in the near future.7 Having arrived at this entropy of fusion classification by nucleation considerations it is interesting to note that Hunt and Jackson's ideas are based on growth considerations. Elsewhere one of the authors4 has shown that an even better classification of the metallographic structures reviewed is obtained from purely conventional heterogeneous nucleation concepts. It has been found that systems having a value of the parameter +b less than 0.28 are almost certainly normal and above this anomalous: V, is the gram atomic volume. This parameter is nevertheless closely related to c and c', these being an approximation of p. The parameter is also related to the other classification3,8,9 which have met with any success in the past. All these classifications are to be reviewed shortly by the authorsU7 A significant thing about the classifications based on

Jan 1, 1968

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The room-temperature Knoop hardness of single -crystal titanium diboride has been determined. Variations in microhardness have been correlated with orientation and structural imperfections in the crystals. Maximum differences in hardness values of 750 kg per sq mm with respect to orientation and 450 kg per sq mm with respect to substructure were found. The effects of etchants, load on indenter, and degvee of cracking of indentation were studied. The average hardness was determined as 2800 kg per sq mm on the as-grown crystals. Annealing increased the average hardness to 3375 kg per sq mm. ThE microhardness of polycrystalline titanium diboride approximating the stoichiometric composition TiB, has been studied by several investigators. The values for the Knoop hardness number range from 2710 kg per sq mm (Khn = 2710 kg per sq mm) to 3400 kg per sq mm.'-4 Samsonov et al.' reported a Vickers hardness number of 3400 kg per sq mm (Vhn = 3400 kg per sq mm) at 120-g loads for a 98 pct Ti + B material of 96 pct theoretical density. Recently Dunegan measured the Vickers hardness and obtained 2060 kg per sq mm with a 10-g load (Vhnlo = 2060 kg per sq mm), 1425 kg per sq mm for Vhnloo, and 1320 kg per sq mm for Vhnlooo. We have obtained a Khnloo = 3000 * 350 kg per sq mm for hot-pressed polycrystalline TiB2 that was 99.1 pct Ti + B and 96.6 pct of theoretical density. The present investigation has been made on single-crystal titanium diboride boules, and is believed to be the first such study on TiB, crystals of known orientation. EXPERIMENTAL The single crystals were prepared by a Verneuil-type process using an electric arc by the Linde Division of Union Carbide Corp. The largest specimens were 6 mm in diameter by 12 mm long. The crystals were of theoretical density (4.50 g per cm3) with a Ti + B content of 99.8 pct. The major impurities present were: 0.03 pct (by weight) 0, 0.06 pct C, 0.01 pct Si, 0.05 pct Fe, 0.01 pct Cr, and 0.01 pct Ni. The crystals were boron-rich, the average boron content being 31.S7 wt pct (stoichiometric value is 31.12 wt pct), and titanium-poor, the average titanium content being 68.2 wt pct (stoichiometric value is 68.88 wt pct). Titanium was determined gravimetrically by cupferron precipitation and boron by titration of H3B03 from a NaOH-fused specimen after removal of titanium with BaC03. The outer edge of the boule accounted for some of the excess boron. An electron-microprobe analysis showed that the titanium content increased from 60.0 wt pct at the edge to 68.5 wt pct at D, ~ 1000 p, where D, = distance from outer edge (see Fig. 5). X-ray measurements indicate that the boules are single crystals with considerable substructure. Upon etching this structure is seen in the form of a Widmanstatten-type rhombohedral line pattern in the basal (c) plane and a parallel "lines" pattern in the prism (a) planes. A typical WidmanstHtten-type pattern is seen in in Fig. 1. Electron microscopy reveals that the lines are less than 1 p across, which does not allow direct electron probe or microfocus X-ray determination of their composition. The identity of the second phase has not been established. It might be a higher boride or a nonstoichiometric TiB2. On annealing above 2200°C the precipitate is dispersed and dissolves in the matrix. The best etchants found were HF/HNO/HO, KF(CN)$NOH/HO (Murakami's Etch), and A large number of other etchants were previously Studied. The acidic etchant produced an acicular or "needles" pattern in the (a) planes which is an etchant effect on the "lines" pattern.

Jan 1, 1965