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By M. A. Neri

A lead-free solder alloy Sn-57.5Bi-0.5Ag has been developed by mechanical alloying and foundry processes, and has great potential as a lead-free solder system, to low temperature applications. The mechanical alloying powders show a microstructure different to the microstructure obtained by the foundry process for the same alloy. Its melting point of 142°C is slightly higher than that of eutectic tin- bismuth solder. Examination of the microstructure revealed that eutectic microstructure is refined by the mechanical alloying process Ag additions. The lamellar structure of tin-bismuth gradually disappeared with the process of mechanical alloying, while intermetallic compounds AgaSn phase was formed. The Cu-Sn intermetallic compound layer formed at solder-copper interface is the Cu6Sn5 phase. Keywords: Lead-free solder, Microstructure. Mechanical alloying

Jan 1, 2003

By C. H. Bucknam

Metallurgical processing of gold ores in positive water balance environments has been facing decreasing discharge concentrations in permits and additional requirements to pass acute toxicity testing before discharges will be allowed to native fisheries. In response to the challenge to meet 0.005 mg/L free cyanide guidance for discharges to fresh water fisheries, the American Society of Testing and Materials (ASTM) International Cyanide Task Group has undertaken an interlaboratory study for the free cyanide method in the metallurgical processing cyanide detoxified reverse osmosis effluent to determine if the quantitation limit for the method could be lowered from the current 0.009 mg/L free cyanide (1) to less than the 0.005 mg/L guidance concentration. Results of the testing are presented below.

Jan 1, 2012

By Catalin Florin Petre, Elahe Ghasemian Langeroudi, Abdelaaziz Azizi, Éric Proulx, Caroline Olsen, Paul Blatter, Faïçal Larachi, Claude Gagnon

"The recovery of gold from ores is often accompanied by the release of other species in the leach solution. This state of affairs leads to depleted free cyanide levels in the slurry. Therefore, separation and quantification of these cyanicides and free cyanide at different stages of the cyanidation process as well as in waste solutions is crucial to provide mitigation tools by preventing leaching of deleterious metals for environmental considerations.COREM and the research group of Prof. Larachi have been working together on the control of gold passivation and cyanicides during cyanidation for several years. Previously, a first capillary electrophoresis (CE) protocol for the speciation of sulfur and cyanicides (SCN-, Cu, Fe) during cyanidation of gold complex sulfide ores was developed and validated for assessing industrial process water.The separation of zinc cyanide complexes used to be confronted with a number of difficulties due to the weak and/or undetectable cyanocomplexes in formally available CE protocols. Moreover, according to our knowledge, no direct CE protocol exists to separate free cyanide. Therefore, a new study aimed at developing a second CE protocol for the detection and quantification of cyanide complexes of zinc and nickel as well as of free cyanide in the cyanidation process water.To achieve this goal, six common carrier electrolytes such as pyridine, trimellitic acid, 4-methylbenzylamine, sodium chromate, phthalic acid and tris base were studied, using an indirect UV detection method. The best results were obtained using sodium chromate for which all ions were successfully separated and quantified. In addition, the effect of electric field strength, injection volume, electro-osmotic flow (EOF) modifier and background electrolyte (BGE) concentration were examined, while peak height, peak area and noise were considered for optimization.As a result, the new protocol is expected to complete the initial CE protocol by detecting cyanide complexes of zinc and nickel as well as free cyanide. Moreover, analytical determination of free cyanide in the presence of weak cyanide complexes achieved by the new protocol was also compared to conventional titration using silver nitrate solution. This new CE protocol will contribute to applied research and help plants to better understand and eventually control the behaviour of cyanidation circuits."

Jan 1, 2011

By N. J. Olson, G. W. Toop

A series of equations previously derived for calculating ternary thermodynamic properties using binary data has been applied to the problem of predicting ternary phase diagrams and quaternary excess free energy. The methods are considered to be rigorous for regular ternary and quaternary systerns and empirical for nonregular systems. The equations have been used to predict ternary phase boundaries in the Pb-Sn-Zn system at 926°K and the Ag-Pd-Cu system at 1000ºK. Calculated quaternary excess free-energy values are presented for the Pb-Sn-Cd-Bi system at 773°K. A method for predicting the location of ternary phase boundaries would be a useful supplement to experimental measurements in ternary systems. This has been recognized with the considerable work that has been done to find models to predict or extend thermodynamic properties and phase diagrams in binary and ternary systems1-18 for which direct experimental measurements are limited. With the access to highspeed digital computers and mechanical plotting devices, it is currently rather easy to compare mathematical models with experimental data. The regular-solution model is consistent with systems which exhibit negative heats of mixing, positive heats of mixing, and miscibility gaps, and therefore it is applicable to simple phase diagrams. The purpose of this paper is to illustrate the use of regular-solution equations to predict, empirically, phase equilibria in some types of nonregular ternary systems. Corresponding equations for regular quaternary systems are given and used to calculate empirical quaternary excess free-energy data. METHOD FOR PREDICTING THE LOCATION OF TERNARY PHASE BOUNDARIES USING BINARY DATA Meijerin1,6 has used the regular-solution model to calculate common tangent points to ternary free energy of mixing surfaces and hence to determine phase boundaries in ternary systems involving miscibility gaps. He used the following equation to calculate ternary excess free energy of mixing values: stants characteristic of the binary solutions, and Ni is the mole fraction of component i. An alternate expression which gives for regular solutions as a function of binary values of along composition paths with constant N1/N2, N2lN3, and N1/N3 may also be derived:15 ternary r xs 1 ?c-*n.Ti*.U*. This expression for is more useful for the empirical calculation of ternary excess free-energy values for nonregular systems because actual binary AFXS data may be used in the expression rather than attempting to find suitable constants for Eq. [I]. The results of this feature of Eq. [2] are illustrated in Table I where calculated excess free-energy values for the Ni-Mn-Fe system at 1232°K are compared with experimental data of Smith, Paxton, and McCabe.19 Although regular-solution equations have been shown to give calculated thermodynamic quantities which agree quite well with experiment for single-phase nonregular ternary systems,14,15 care should be exercised in the use of the equations to predict thermo-dynamic properties of multiphase ternary systems in which strong compound formation is suspected. This precaution is consistent with the simple regular-solution model which for negative values of ai_j will indicate a tendency toward compound formation but even for very large negative values of ai-jwill not give multiphase binary or ternary systems involving a distinct stable compound. Hence, calculated ternary free-energy data using Eq. [2] might be expected to vary between being rigorous and poor, in the following order, for ternary systems which are: a) regular solutions, b) nonregular single-phase liquids in which random mixing is nearly realized, c) nonregular single-phase solids, d) nonregular multiphase systems exhibiting miscibility gaps, e) nonregular multiphase systems with binary compounds but no ternary compounds, f) nonregular multiphase systems with highly stable binary and ternary compounds. The calculated data will be expected to be least accurate for the last two cases. The general method adopted in this paper involves two-dimensional plots of ternary activity curves. The principle used is that tie lines indicating two-phase equilibria join conjugate phases a and B for example, for which a1(a) = a1(B), a2(a) = a2(B), and a3(a) = a3(B). Tie lines may be determined by plotting the ternary activities of two components along an isoactivity line for the third component and the unique points where the above equalities hold may be found graphically.

Jan 1, 1970

By Vernon F. Swanson

An equation has been developed which will permit the direct determination of free settling velocity of any sized particle encountered in mineral benefici-ation. The equation is based on Newton's Law with the friction factor defined as a function of the laminar boundary layer. Development of the equation is described first from an empirical trial-and-error approach. Examples are given of actual settling data from the literature versus calculated data to prove the validity of the new equation. Newton's law of resistance of a fluid to flow around a sphere is expressed in Eq. 1. Free settling velocities can be determined by setting Eq. 1 equal to the gravitational force on a particle and solving for V. Experience has shown that when the solids are greater than 1 mm in diam, or when Reynold's number for the system is greater than 800-1000, the friction factor term, fD, essentially becomes a constant, and Eq. 2-b becomes Newton's equation for free-settling and is applicable under the conditions stated. Another special condition exists for particles smaller than 0.05 mm or when Reynold's number for the system is less than three. In this case fD=24/NRor24µ/pL,dV,. Eq. 2-b can then be rewritten as

Jan 1, 1968

By R. Barany

Thermodynamic calculations pertaining to the minerals gibbsite, kaolinite, halloysite, and dickite have been hampered by the lack of adequate heat and free energy of formation data. Previous data for gibbsite were highly uncertain, and there were no data for the other three substances. By use of hydrofluoric acid solution calorimetry, the Bureau of Mines derived heat of formation values from the elements and from the oxides for the four substances, and the data were combined with known entropy values to obtain the corresponding free energies of formation. The results show that gibbsite and halloysite are thermodynamically unstable with respect to the oxides (a- alumina, a- quartz, and liquid water) at 298.15° K,, while kaolinite and dickite are only moderately stable (to about the same degree), The instability of halloysite, in comparison with kaolinite and dickite, results in a 60°-lower equilibrium decomposition temperature.

Jan 1, 1961

By W. H. Ode, W. A. Selvig

In 1938 , the Bureau of Mines cooperated with Subcommittee XV on Plasticity and Swelling of Coal ( C. C. Russell , chairman ) , of Committee D-5 on Coal and Coke , A.S.T.M. , by testing various methods for determining expansion and plastic properties of a series of coals of widely different coking properties . One of the tests made by the Bureau was the British Standard Method for the Crucible Swelling Test for Coal.5/ Briefly , this swelling test consists in heating 1 gram of pulverized coal in a silica crucible over a gas flame under prescribed conditions to form a coke button which is compared in size and shape with a series of standard profiles numbered 1 to 9. These profiles are intended to cover the size and shape of buttons obtained from coals covering a wide range in plastic properties .. The number of the standard profile with which the maximum cross -sectional area of the button most nearly corresponds is recorded as the swelling index . Although the swelling test showed poor relationships with the various tests that were used for measuring expansion or contraction of coal during carbonization , it gave indications of having value in measuring free - swelling and caking properties of coals when burned on fuel beds . An opportunity to investigate this occurred when an engineer of an eastern public utility 'company reported pronounced differences in burning characteristics on grates of various shipments of Pocahontas coal . Some of these coals gave trouble by swelling 'excessively and clogging the grates . Samples were ob- · tained , and it was found that the troublesome coals gave decidedly higher free -swelling numbers than did the coals that performed satisfactorily . Also , it was found that the free - swelling index test gave better differentiation between coals than could be obtained from the coke buttons from the · ´`standard volatile -matter test or from agglutinating - value results . The results of the free - swelling tests were considered by the Subcommittee on Plasticity and Swelling , and a special group of the subcommittee , under the chairmanship of R. A. Sherman , was delegated to study the test method . Ostborg , Limbacher , and Sherman , ofthe Battelle Memorial Institute , ' investigated the various factors affecting the test and found that the swelling index was a good indication of the suitability of coal for performance on residential -type stokers from the standpoint of the coking characteristics of the coal . Data were presented also showing that the indexes wer helpful in the selection of coal for industrial underfeed stokers .

Oct 1, 1946

By F. A. Penning

A number of highly instrumented free fall tests were performed on an arrestment system for a man cage in a vertical shaft. Tests were conducted in the U.S. Bureau of Mines free fall test tower at the Colorado School of Mines. A single tooth safety dog was used to stop on 4x6-in. Keruing (Phillipine mahogany) wet and dry wood guides. The safety dog had a penetration depth of 1 in., an adjustable width from 1-1/2 to 2-1/4 in., and a tooth angle of 80 deg. Twenty-seven free fall tests were performed covering a range in weights from 3-1/2 to 10-1/2 tons, hoisting velocities from 850 to 1350 feet per minute. Average g loads were measured from a low of 0.6 to a high of 3.4. The electronic instrumentation included piezoelectric and seismic mass accelerometers, strain gages on structural and mechanical elements, load cells in the guides, and distance measuring. Computer analysis was used to correlate with experimental measurements used to calculate stress. A statistical analysis gave no indication that the velocity or area affected the wood crushing stress. The instrumentation revealed a chatter occurring during the stop as shown by the accelerometers, strain gages, and load cells. Additional work is required to analyze this newly discovered phenomenon. The chatter imposes loads much higher than the average g load.

Jan 1, 1980

By P. G. Shewmon, F. R. Winslow

An experimental method is describedfor Ihe determination of the derivative of the surface free energy (y,) with surface orientation using symmetric bicrystals. The method measures the equilibrium root-angle of grain boundary grooves for the same grain boundary on two different surfaces. In contrast to previous methods, the presence of annealing twins is not necessary. Results on silver at 900°C indicate that ??s/?3 is 0.014y, on the (loo), 0.075y, on the (111), and < 0.004?s on the (110). DURING an investigation of the kinetics of grain-boundary grooving on silver&apos; values of the derivative of the surface free energy ?s with respect to orientation were needed. Previous investigations of these so-called torque terms show that, for low-index planes in copper2 and nickel,&apos; a finite derivative exists even near the melting point. These two studies give the only previously published values of the torque on low-index metal surfaces. These investigators measured the equilibrium root angles, both greater than and less than 180 deg, along the lines where a twin boundary intersects a free surface. The technique described here is suitable for materials which do not have annealing twins, and enables the surface for study to be chosen instead of having to work in a direction normal to the twin trace on the surface. The purpose of this paper is to describe this new technique and to report the values found for the (111): (100), and (110) surfaces of silver. To check the technique proposed above, a series of 99.99 pct Ag bicrystals were used. These bicrystals were grown from the melt by a modified Bridge-man technique so that a low-index direction was parallel to the growth direction. Two orthogonal faces were studied on each bicrystal. One of these contained the low index or simple plane normal to

Jan 1, 1963

By MKS Vel, S. Mukhopadhyay, R. Mishra

Off late, the criteria of selecting the refractory have acquired a trend line aiming to a cleaner environment and the utmost importance is given to the eco-friendly approach. The stainless steel making furnaces normally use mag-chrome refractories for the obvious reasons of changing slag basicity from acidic to basic. Such refractories generate toxic fumes and compounds with hexavalent chrome, which is unhygienic if inhaled. The present paper describes the development of a chrome free alumina magnesia carbon refractory, it&apos;s different test properties, simulative testing and microstructures. The optimum quantity and distribution of carbon in the brick restricts the carbon pick-up by the steel. Bricks with the same composition were manufactured in the commercial scale and used in a stainless steel making furnaces in USA. The performance of same refractory in this furnace was quite encouraging and at present the same quality brick has become a normal practice in this furnace. Since no chromite is used in making this brick, so no toxic compounds are generated environment remains pollution free.

Jan 1, 2004

By M. Huang

A conductivity-based sensor for on-line measurement of free acid was recently built. This sensor is suitable for high ionic strength solutions and its corrosion-free operation is based on induction currents. It has been tested against literature data and measurements made using a previous developed contact-type conductivity cell, with an average difference within 1%. The electrical conductivities of H2SO4?H2O, H2SO4?MgSO4?H2O and NaCl?Laterite-H2Osolutions at temperatures up to 250 °C were discussed. It was found that the solution conductivity depends on various factors, such as the electrolyte concentrations, the type of electrolytes, temperature and the amount of dispersions. A semi-empirical model was developed to account for all the factors discussed. This model was further tested on actual process solutions from the hydrometallurgy of nickel where sulphuric acid solutions containing a variety of metal sulphates and solids. The average difference between the estimated acid concentration from this model and the one from titration was generally less than 5%, which is excellent for industrial applications.

Jan 1, 2006

By M Davies, G Theletsane, A H. Gray

Recovery of gold from gold ores has been driven by the available technology and its configuration in the process plant flow sheet.Conventional practice in test work programs has the ore being ground fine (to 106 or 75 microns) to ensure liberation ahead of leaching or flotation. This paper identifies that, in many cases, gold and gold sulfide carriers will liberate and be recovered to a concentrate at much coarser sizes.There is an exponential increase in energy consumption relative to particle size reduction. This impact becomes extreme when comparing crushing a product to 1 mm against grinding to 75?microns.The resultant reduction in energy consumption when liberating and separating at 1 mm or coarser compared to grinding to 75 microns can be in the order of 15 kWh/t or 60 per cent of energy in the comminution circuit.Recovery of free gold and gold sulfide carriers by preconcentration (using continuous gravity devices such as the InLine Pressure Jig), combined with flotation of the fine gold and gold carriers, can result in significant power savings.There are multiple locations within the flow sheet that can be targeted using this process, including recovery in the cyclone underflow of existing plants, preconcentration ahead of the plant or complete greenfield, low-energy process plants designed from first principles based on data from a Gekko developed test work regime.We will describe the process of defining mineralogy in the laboratory and the decision-making process through to actual applications in the field.Several examples will be provided, including a South African Witwatersrand gold ore, several Australian gold ores and others, indicating the benefits of this process and where it has been brought to commercial reality.CITATION:Gray, A H, Davies, M and Theletsane, G, 2014. Coarse liberation and recovery of free gold and gold sulfide carriers for energy reduction in process plants, in Proceedings 12th AusIMM Mill Operators’ Conference 2014 , pp 117–128 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Sep 1, 2014

By S. Zador, C. B. Alcock, K. Sudo

Measurements have been made of the standard free enevgies of formation of the sulfates of cobalt, Cupric copper, nickel, and ferric iron in the temperature range of 750° to 950°C. Dynamic gas-solid techniques have been employed in which oxide-sulfate and basic sulfate mixtures were placed in a stream of gas of controlled SO3 potentials. Thermal analysis and thermogvavimetry were used as detection methods, and it was found THE formation of sulfates during the roasting of sulfide ores is now considered to arise in many cases from the interaction of sulfur trioxide in the gas and the metal oxide which is formed on the sulfide as a first step.&apos; As a preliminary to the investigation of the kinetics of sulfate formation during roasting, measurements have been made of equilibria from which the free energies of formation of cobalt, copper, nickel, and iron sulfates can be that the range of temperatures which could be investigated and the choice of method was largely controlled by the kinetics of these gas-solid reactions. The results are compared with previous results obtained from static measurements with which they agree quite well, and calculations have been made employing themal data to interrelate the present results with those for other sulfates. calculated. The method used has been to expose the solid sulfate (or basic sulfate) to a controlled flowing gas mixture of SO,, 02, and SOs and to observe the temperature of decomposition. The onset of decomposition was detected by thermal analysis or thermogravimetry. EXPERIMENTAL METHODS The thermal-analysis method was similar to that employed by Dewing and Richardson.&apos; The sulfate was dehydrated at 250°C in air, and placed in a small alumina crucible which was held by a quartz ring in the hot zone of a horizontal furnace. The reaction tube of this furnace was made of mullite.

Jan 1, 1965

By Rina Kim

There are many factors which affect the gold cyanidation mechanism— mineral composition, free cyanide and dissolved oxygen (DO) concentrations, heavy metal additions, etc. This study combines electrochemistry and surface analysis methods to examine the effectiveness of the above factors on gold cyanidation process. Three gold ore samples were used in this study. Sample 1 was a pyrite concentrate, contained mercury and silver. Sample 2 also contained sulfide minerals, including galena. Sample 3 contained pyrite with sphalerite and galena. In the case of samples 1 and 2, the presence of heavy metals enhanced gold cyanidation kinetics, though the addition of higher DO was not effective on improving the kinetics. Sample 3 showed an opposite behavior: the kinetics was not enhanced by galena, because of its relatively small amount, however, the use of higher DO made improvement in the gold leaching kinetics, likely caused by iron species generated by pyrite oxidation.

By Alla D. Mah

The heat of formation of scandium sesquioxide (Sc203) has not been measured previously, and existing values for gallium sesquioxide (Ga203) are subject to large uncertainties. As a consequence, thermodynamic calculations involving these oxides hare lacked scientific exactness. This paper reports newly determined values of the heats of formation of gallium and scandium sesquioxides at 298.15° K., by combustion calorimetry. The corresponding free energies of formation are derived from heat and entropy data.

Jan 1, 1962

By James Ransford Dankwah

High sulphur carbonaceous materials like petroleum coke and rubber tyre are unsuitable as reductants in ironmaking because part of the sulphur is transferred to the reduced metal. Globally, while large amounts of petroleum coke are produced annually from the industrial processing of crude oil, billions of end-of-life rubber tyres are held in landfills and stockpiles. This work therefore investigates the potential feasibility of utilising these high sulphur carbonaceous materials as reductants in ironmaking without transferring the sulphur into the reduced metal. Composite pellets of iron oxide containing end-of-life rubber tyre (RT), petroleum coke and blends of RT/petroleum coke and petroleum coke/high density polyethylene (HDPE) were heated under argon atmosphere in a horizontal tube furnace. Reduced pellets were analysed after 10 minutes of reduction for their sulphur content. The results showed that sulphur-free metallic iron can be successfully synthesized using RT and petroleum coke as reductants. The level of desulphurisation depends on the nature of blending of the carbonaceous materials.

Jan 1, 2014

By G. Swan, E. Nordlund, P. Zhang

"SynopsisThe most widely used support design damage criterion for rockburst-prone mines is based upon kinetic energy, which is proportional to the square of the ejection velocity and is commonly expressed in terms of peak particle velocity (PPV). Field monitoring and back-analyses have shown that ejection velocities of the order of 10 m/s and higher can result from seismic events of moderate magnitude. Such velocities are much higher than those predicted using PPV obtained from scaling laws. It has also been found that the peak ground motion (i.e. PPV) on the surface of an excavation is preferentially amplified (by four- to tenfold) compared to the motion in solid rock at a similar distance from the source. However, the wave propagation and interaction processes involved within the fractured rock in generating high ground motion are very complex and are not well understood at this time.In this paper, velocity amplification was investigated by modelling the dynamic interaction between fractured rock and a free surface using a 2D discontinuum-based numerical program, UDEC (Universal Distinct Element Code). A 1D model with a fractured zone was used to represent the fractured rock. Velocity amplification, quantified by PPV, predicted at the free end of the model was 2.0–3.6 times higher than the input velocity. It was found that the wave frequency, fracture stiffness, fracture spacing, and thickness of fractured zone are the main factors that affect the velocity amplification. The results have proved that the interaction of the seismic wave and multiple fractures near the free surface strongly influences the ground motion.IntroductionSince mining-induced seismicity is almost inevitable in deep mines, ground support is generally employed to mitigate the risk of seismically-induced damage. The most widely used support design criterion for seismicallyprone mines is one that seeks to maximize the absorption of the kinetic energy (plus potential energy if a gravity component is considered) of key rock blocks. Based on this criterion, design methods for rock support were first proposed by Wagner (1984) in South Africa and later improved, among others, by Roberts and Brummer (1988) and Kaiser et al. (1996)."

Jan 1, 2015

By A. C. Fieldner

[The Sectional Committee on Classification of Coals, functioning under the sponsorship of the American Society for Testing Materials and the rules of the American Standards Association, in its 1934 report recommended to the American Society for Testing-Materials that Specifications for Classification of Coals by Rank be adopted as tentative. These specifications, slightly modified as recommended by the Sectional Committee, in its 1935 report,6 wore approved as tentative standards by the society in 1935. The specifications rover the classification of coals according; to their degree of metamorphism, or progressive alteration, in the natural eerie s from lignite to anthracite. The basic scheme of classification is according to fired carbon and calorific value (expressed in B.t.u.) calculated to the mineral-matter-free basis. The higher-rank coals are classified according to fixed carbon on the dry basis, and the lower-rank coals according to B.t.u. on the moist basis, that is, containing its natural bed moisture but free of visible surface moisture. Agglutinating and weathering indices arc used to differentiate between certain adjacent groups.]

Jan 1, 1935

By R. W. Gurry, L. S. Darken

The solubility of cementite in austenite is computed by thermodynamic methods from the observed solubility of graphite. It is found that the solubility of cementite is greater than that of graphite in the entire austenite temperature range. Thus the prior discrepancy between this portion of the phase diagram and the observed metastability of cementite is partially resolved. FOR several years it has been apparent that a serious discrepancy exists in certain observations pertaining to the Fe-C system. Direct experimental data indicate: 1-That the curve representing the solubility of graphite in austenite&apos;" crosses that for cementite4 at about 945°C as shown in Fig. 1. 2— That graphite and austenite saturated therewith are stable1 relative to cementite at all temperatures between the eutectoid, about 723°C, and the eutectic, about 1153°C. These observations are mutually incompatible in view of a well-known consequence of the second law of thermodynamics, namely, that the stable phase (presumably graphite at all temperatures) has a lower solubility than the metastable phase (presumably cementite). Hence either 1 or 2 above must be in error; either the measured solubility of graphite or of cementite, or the observation as to the stability of graphite, is in error. Our present purposes are: 1—To collate the available data on cementite and prepare a table of HO — HO° and of (Fa— HO°)/T. This tabular method seems the best and most convenient way to represent the heat and free energy of formation. 2—To determine whether the measured solubilities of cementite and graphite in austenite are in accord with the above table and the measured thermodynamic properties of austenite, in order to resolve, if possible, the existing paradox of these two solubilities. Enthalpy of Cementite The enthalpy of cementite at 273 °K, H279 — HOcem, was computed by integration of the low temperature heat capacity as measured by Seltz, McDonald, and Wells" 68" to 298 °K) and as given by the Debye functions recommended by them (0" to 68°K); the result is included in Table I. At higher temperature HCem — H,,"" is given by Kelley who used the data of Naeser7 (298" to 1037°K) and of Umino8,9 (273° to 1923°K). We have recalculated Hcem — H273 cem from the data of UminoO in the following way. In the equilibrated alloy at temperature the weight fraction of cementite Pct c -Pct cr is PctC -PctCr designated f(C), and the

Jan 1, 1952

By N. S. Dalal, V. Castranova, X. Shi, W. Wrr, V. Vallyathan

"SUMMARY Data presented here indicate that freshly fractured silica exhibits surface characteristics and biologic reactivity distinct from aged silica, and on this basis we propose that these surface features may lead to enhanced manifestations of lung Injury. Grinding of silica produces ~10"" Si and SI-O (silicon-based) radicals per gram of dust on the particulate surface which are characterized by an electron spin resonance (ESR) spectrum centered around g = 2.0015. These silicon-based radicals react with aqueous media to produce OH radicals, which are demonstrable using a DMPO spin trap. The concentration of silicon-based radicals in silica decreases with aging in air and exhibits a half-life of ~30 h, whereas its ability to generate OH radicals in aqueous solution decreases with a half-life of ~20 h. However, on storage in aqueous media, the concentration of silicon-based radicals end the dust's ability to generate OH radicals decrease significantly within a few minutes. Freshly ground silica is also more biologically reactive than aged silica, because freshly crushed silica activates a greater respiratory burst In alveolar macrophages than aged silica, i.e., storage of ground dust in air decreases silica-Induced superoxide anion secretion, hydrogen peroxide release, and NBT reduction by 25%, 68%, and 43%, respectively. Furthermore, compared to aged silica, freshly ground silica exhibits a greater cytotoxic effect on cellular membrane Integrity, i.e., a 1.5-fold increase in LDH release from macrophages, a 36-fold increase in hemolytic activity, and a three-fold increase in the ability to induce lipid peroxidation. Because acute silicosis is frequently associated with occupations in which freshly fractured crystalline silica of respirable size is generated, the present study suggests that fracture-generated silicon-based radicals may play a significant role in the pathogenesis of this disease. AM REV RESPIR DIS 1955; 133:1213-1218IntroductionOccupational exposure to crystalline silica can be associated with either chronic or acute pulmonary disease. Chronic silicosis becomes manifest 20 to 40 years after first exposure and is characterized by development of concentric hyalinized nodular lesions in the lung with the de-velopment of dyspnea over a period of several decades. Acute silicosis, on the other hand, is manifested by a rapid on-set after exposure and is characterized by the accumulation of an amorphous granular lipoprotein exudate in the airspaces and rapid development of respiratory disability within a few years (1-3).Information is growing concerning the etiology of chronic silicosis. Studies sug-gest that several mechanisms may be in-volved in the development of fibrosis. Lung injury may result from silica-induced release of lysosomal enzymes from alveolar macrophages (4, 5). In ad-dition, silica-induced activation of su-peroxide anion and hydrogen peroxide release from alveolar macrophages may result in oxidant-induced damage to lung parenchyma (6). Silica exposure can also result in the release of mediators from alveolar macrophages which enhance the proliferation of fibroblasts and the syn-thesis of collagen by these pneumocytes (7, 8)."

Jan 1, 1988