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By Xin-liang Gao, Qing Li, Gui-qin Fu, Duo Jin, Miao-yong Zhu

"Optical microscope together with alternative wet-dry cyclic accelerated corrosion tests and XRD, SEM were employed on bridge weathering steel samples with different Mn and Ni contents which were vacuum induction melted and rolled to study their effects on the microstructure and rust layer evolution in er' containing condition. The results show that the microstructure is mainly ferrite and pearlite when Mn and Ni contents are 0.75 %, 0.42 %, respectively. Both the increase of Mn and Ni contents will make pearlite disappear while granular bainite appear, meanwhile the grain size decreases. With the increase of Mn content, the corrosion rate decreases in the initial stage, but the effect becomes little in the later stage. The increase of Ni not only improves the corrosion resistance of steel base at the initial stage but also hinders the tendency of further corrosion. As Mn content increases, a-FeOOH contents in rust layer decreases. With increase of Ni content, the content of a-FeOOH in the rust increases while that ofy-FeOOH decreases.IntroductionWeathering steels had been ~radually applied in manufacture of bridges owing to reducing the corrosion rate remarkably [I- l .Good weldability was needed for high performance bridge weathering steels. Since carbon was thought to be bad for weldability, low carbon content steel was adopted and Mn was added to amend the mechanical strength loss. Some scholars[6, 7l believed that Mn was beneficial for increasing corrosion resistance performance of the steel in marine atmospheric environment. Some scholars [S, 9l thought that Mn had little effect on corrosion resistance in marine atmospheric environment. Presently, the effect of Mn on bridge weathering steel in marine atmospheric environment still remained poorly understood. Ni was considered to be beneficial for increasing corrosion resistance performance in marine atmospheric environment [JO-l4l However, the high cost limited its application range. What would bring to the rust and corrosion by decreasing Ni content needed further research.Most researchers assumed that microstructures only affected the corrosion behavior of bare steel. But the study of Guo et al. P5l showed that the homogenous microstructures were beneficial for the corrosion resistance of steels. The effect of Mn, Ni content change on microstructure and microstructure on corrosion still remained poorly understood. In the present work, the effect of Mn and Ni on the microstructures of steel matrix, as well as the microstructures on the rust and corrosion was investigated."

Jan 1, 2014

By Colin G. ink

OUTSTANDI'NG in progress among the less familiar 'metals during 1936 is the electrolytic production of 99.9 per cent manganese meta1 readily and many quantity. Strictly speaking, manganese should not' be classed as 'a rare metal, since there is 800 times as much manganese in the earth's crust as there is zinc or lead. But manganese' as a metal is rare, just as titanium metal is rare though titanium is five times as abundant in the earth's crust as manganese.

Jan 1, 1937

By Gary Brierley, Lok Home

"The majority of tunnels for civil engineering applications are now being constructed using some form of mechanical excavation. Beginning in the 1960s with rock tunnel boring machines (TBM), the tunneling industry has introduced both earth pressure balance (EPB) and slurry pressure balance (SPB) soil machines; mixed soil and rock machines and a variety of different mechanical devices for the construction of small diameter tunnels. Over time, these machines have become more powerful and more adaptable to a wider variety of ground conditions; so much so that tunnels are now being constructed in ground conditions and in the vicinity of third-party impacts that would have been considered beyond the state of the art just 10 years ago. Figure 1 is an example of a mixed ground crossover TBM used successfully at Mexico City’s Túnel Emisor Poniente II.All of the above is highly advantageous for the tunneling industry, but it has also placed a much higher level of risk on the performance characteristics of the tunneling machines, on the contractors operating those TBMs and on the manufacturers of those machines. Most of the risks for a tunneling project are associated with creating the space inside of which the finished facility will be constructed. In order to create that space, the tunnel contractor must make many decisions about the best way to excavate the ground, the best way to control the ground at the face of excavation and the preferred method for supporting the ground around the tunnel in a manner that is safe for the workers and stable with respect to all of the overlying and adjacent existing structures. If it is proposed to use some form of TBM in order to build the tunnel, then the TBM becomes central to all three of these activities and becomes an integral part of managing the risks associated with these activities."

Jan 9, 2018

By M. Baumann

Operating and maintaining the heavy equipment used in open-pit mining operations is an ongoing challenge for mines. Typical operations employ a combination of shovels, wheel loaders, and haul trucks to excavate and transport the material for further processing. As this is the first point of contact for the material after blasting, it is often a bottleneck of all downstream processes, thus, equipment uptime and efficiency is crucial. Automated systems for bucket tooth monitoring, payload measurement, proximity detection, and rock fragmentation analysis will be examined. The impact of these systems on operation safety, efficiency, and reliability, in real-world scenarios will be investigated. The process of managing all the above fleet of equipment in a mine can be streamlined by connecting the equipment monitoring systems to a central server. Using the central server, the distribution of this information can be automated to ensure that the right people see the data in a timely manner, improving both proactive and reactive responses to threats to safety and productivity.

Feb 23, 2014

By Herbert Hoover

YOUR committee asks that I speak today on the relations of the engineering profession to public affairs. That takes in a lot of ground. This being a cheerful occasion, I will assume that I should exclude the engineer's function as a taxpayer. This being a nonpartisan occasion, I will assume that I should not refer to his voting emotions in 1940. Perhaps what was in the minds of your committee was the application of engineering thought to the confusions of the times. That is also a lot of ground. I fear, however, its boundaries disappear in mirages and rainbows on all sides. Now any entry of the engineer into public affairs involves his breaking into the fields of the sociologists, the economists, and the politicians. However I don't know why, seeing the difficulties these professions are having, they should not welcome a little help.

Jan 1, 1939

By G L. Simmons, K M. LeVier, R Kappes

The low potential hydrophobic state of pyrite in amyl xanthate (PAX) flotation with nitrogen is of particular interest with regard to the N2TEC flotation technology currently being used for the recovery of auriferous pyrite at NewmontÆs Lone Tree Plant in Nevada. Initially, the N2TEC system had been found to operate satisfactorily, but cyanide in the flotation mill water appeared to be responsible for a loss in pyrite recovery. This supposition was confirmed with laboratory experiments, and a program was initiated to study flotation chemistry variables by electrochemically controlled contact angle measurements. Experimental results show that activation of pyrite in such cyanide solutions can be achieved more effectively with lead than with copper. Subsequently, based on these fundamental studies, significant improvement at the Lone Tree Plant was achieved by lead activation, in which case the recovery increased to expected levels. The effect of activator is particularly significant not only with respect to pyrite depression by residual cyanide, but also with respect to collector (PAX) consumption and the initial state of the pyrite surface. Experimental results show the importance of the pyrite surface state and the rather interesting features of the activation process.

Jan 1, 2005

By J. van der Merwe, C. Phetolo, V. Matjeke

The mechanical properties and microstructure of AlSi10Mg alloy samples that were printed by selective laser melting (SLM) were studied to determine the effect of processing parameters and building orientation. After printing, the alloy was stress relieved at 250°C for 2 hours. The microstructures were analysed by optical microscopy and scanning electron microscopy (SEM) to determine the alloy phases and distribution. Phase transformation characteristics of the material were evaluated using differential scanning calorimetry (DSC). Mechanical properties were determined by subjecting the XY- and Z-built samples to tensile and nano-indentation testing. The samples from the tensile tests were then used to perform fractographic analysis by SEM. The microstructural properties in each orientation revealed a non-homogeneous microstructure which was characterized by a semi-elliptical tract and fine silicon precipitates, which were found to be softer along the fusion zone. The DSC thermograms revealed that the material underwent two phase transformations during the first heating cycle. The mechanical properties revealed a higher UTS, higher yield strength, and a lower percentage elongation in the Z orientation than in the XY orientation. Fractographic analysis showed that crack initiation in both orientations started from the surface in a brittle manner due to surface flows, and then propagated via microvoid coalescence.

Jul 1, 2021

Magnetite cenospheres 40-270 I/m in diameter have been found during the combustion of pyrite concentrate.Micrographs of the surface and internal structures are presented together with comment on the mechanism of forrnation.The similarity to cenospheres found during the combustion of pulverized fuel was noted and speculation raised to their contribution to the dust and fume load in flash smelters.

Jan 1, 1980

By T. Y. Yan

SUMMARY Laboratory high pressure column tests have shown that the presence of 1-20 ppm of aluminum ion effectively prevents permeability loss during uranium leaching with leachates containing sodium carbonate. If added after permeability loss has occurred, aluminum ion can restore the permeability to nearly its original value. No deleterious effect was observed on uranium leaching performance and the technique should be quite compatible with all field operations. INTRODUCTION The recovery of uranium values from underground deposits by in situ leaching or solution mining has become economically viable and competitive with conventional open pit or underground mining/milling systems (Merrit, 1971). In situ leaching processes are particularly suitable for small, low-grade deposits located in deep formations and dispersed in many thin layers. Many such ore bodies occur along a broad band of the Gulf Coastal Plain (Eargle et. al., 1971). The advantages of the in situ leaching processes have been reviewed (Anderson and Ritchi, 1968). In the in situ leaching process, a lixiviant containing the leaching chemicals is injected into the subterranean deposit and solubilizes uranium as it traverses the ore body. The pregnant lixiviant or leachate is produced from the production well and is then treated to recover the uranium. The resulting barren solution is made up with the leaching chemical to form lixiviant for re-injection. Upon completion of the leaching operation, the formation is contaminated with leaching chemicals and other species made soluble in the leaching operation and has to be treated to reduce the concentration of these contaminants in the ground water to levels acceptable to the regulatory agencies (Witlington and Taylor, 1978). Restoration is accomplished by injecting a restoration fluid, which could be the fresh water or water containing chemicals, into the formation. As it traverses the leached formation, the restoration fluid picks up the contaminants and is then produced at the production well. This produced water is either disposed or purified for recycle. In both phases of operation, formation permeability or well injectivity is one of the most important parameters which determines the viability of the in situ leaching process. Low formation permeability limits production rates, leading to uneconomical operations. The formation is said to be sensitive if there is a sharp loss of permeability on contact with water and other fluids. Many uranium bearing formations, for example, the Catahoula formation of the Texas Coastal Plain, contain significant amounts of clay minerals which are water sensitive. Serious permeability losses can occur when the pH and chemical composition of the lixiviant is significantly different from that of the formation water. Jones has investigated the influence of chemical composition of water on clay blocking of permeability (Jones, 1964) and Mungan studied permeability reduction through changes in pH and salinity of the water (Mungan, 1965). Various mechanisms of permeability damage have been proposed and reviewed (Jones, 1964; Mungan, 1965; Gray and Rex, 1966; and Veley, 1969). When large amounts of swelling clays are present, a significant fraction of the flow channels in the formation can be reduced due to swelling. However, in most cases, swelling need not be the main cause of permeability losses. Particle dispersion and migration or clay sliming can be more important causes for formation damage. Clay particles entrained in the moving fluids are carried downstream until they lodge in pore constrictions. As a result, microscopic filter cakes are formed by these obstructions, plugging the pores, effectively restricting fluid flow and reducing the formation permeability. Moore found that as little as 1-4 percent clays present in a fine grained sandstone could completely plug the formation if they are contacted by incompatible injected fluids (Moore, 1960). It has been found that injection of NaHC03/Na2CO3 lixiviant into formations with significant clay content often leads to loss of formation permeability and well injectivity. To alleviate this problem a change of the lixiviant composition to KHC03/K2CO3 has been proposed. At present, however, many in situ leaching operations employ NH4HC03/(NH4)2C03 mixtures as a source of carbonates. This approach has been successfully used in South Texas by Mobil, Intercontinental Energy, Wyoming Minerals and U.S. Steel, etc. The use of ammonium carbonates solutions, however, contaminates the formation and requires a time-consuming restoration operation. The other approach to reduce the permeability loss is to pretreat the sensitive formation with chemicals which prevent clay dispersion and migration. Such chemicals include hydroxy-aluminum (Reed, 1972 and Coppel et. al., 1973), hydrolyzable zirconium salts (Peters and Stout, 1977), hydrolyzable metal ions in general (Veley, 1969) and polyelectrolyte polymers (Anonymous). Still another approach, is to minimize the "shock" caused by sudden injection by gradually changing the chemical composition of the injected fluids from that of the formation water. THE APPROACH Since permeability loss can be an important factor limiting the efficiency and economic viability of the in situ leaching process, a study was initiated on

Jan 1, 1982

By O. D. Gonzalez, R. A. Oriani

The migration of hydrogen and of deuterium dissolved in a iron and in nickel induced by an applied electrical potential has been measured over a range of temperature. In all cases the intevstitial solute migrates to the cathode. The deduced charges of transport are positive, independent of or slightly dependent on temperature, and markedly larger for the beavier mass. These results are interpreted as showing predominating momenlum transfer between electron holes and the acticated complex of the elementary diffusion act. THE migration of components of a metallic system under the action of an applied electrical potential is called electromigration or electratransport. This phenomenon has been known since 1861 and is becoming of increasing interest to metal scientists because of the opportunity it offers to explore the connections between mass transport and electron transport. Until recently, reliable data have been very scarce because of the difficulties inherent in the measurements. In addition, theoretical understanding has been either nonexistent or rudimentary and at present this situation is only moderately improved. Whereas the prevalent notion had been (and is still widely held) that electromigration directly reflects the state of ionization of a component in its equilibrium state in the metal, it is now becoming clear that the major, if not the sole, factor is the momentum transfer between the charge carriers, themselves in motion because of the applied field, and the metallic components in their activated state. It becomes important therefore to obtain reliable data over a range of temperature on electrornigration in systems where only one component moves, that is, either in pure metals (vacancy motion) or in interstitial solid solutions. Our choice of systems was dictated by our measurements' of the Soret effect in solid solutions of hydrogen and deuterium in iron and nickel. Indeed, the main reason for making measurements on electromigration at all is that we suspected a mechanistic connection between thermal diffusion and electromigration. In our former paper' we proposed that what is common to both phenomena is the momentum transfer between the charge carriers in the metal and the atom as it jumps from one equilibrium position to another. In Soret diffusion, however, there is in addition the dissipation of the energy of the jumping atom via pho-nons. We have since found that similar ideas for this interconnection have been developed by Fiks.2 In the present paper we will discuss in more detail our understanding of the mechanism of electromigration itself, but we turn first to a presentation of the experiments and results. EXPERIMENTS AND RESULTS Let us consider a metallic system in which only one component, m , can diffuse at the temperature in question, and to which are applied simultaneously an electrical potential gradient, grad cp, and a chemical potential gradient, grad p,. One may write3 for the material flux Jm and the electronic charge flux Je by applying the condition, grad = 0, to Eq. [I] and evaluating grad(um/T) for the isothermal case and for activity coefficient independent of composition over the relevant composition range. ere, c is the concentration and D the diffusivity of the mobile component. The experimental technique that we have used to measure Z* for the isotopes of hydrogen individually dissolved in each of two transition metals has been developed from a method used by Wagner and Heller.4 (A somewhat similar method was also used by Herold.5) A wire or thin rod of the metal under study connects two volumes of gaseous hydrogen at identical pressures; hence grad um = 0. A direct current is made to pass through the specimen, serving to maintain the specimen at the desired temperature and also to produce the electromigration of the hydrogen dissolved in the metal in equilibrium with the gaseous hydrogen. Under these conditions, the flux of hydrogen from one volume to the other is given, from Eq. [I] for grad( um/T) =0by

Jan 1, 1968

By Frank D. Lamb

"INTRODUCTION The use of beryllium and its alloys has come into prominence in the last 15 years and increased considerably during the war. In contrast to other light metals, such as aluminum and magnesium, beryllium is relatively hard, has a high melting point (1,285° C.), and other properties that make it resemble steel in many respects. It has a specific gravity of 1.85, is only slightly heavier than magnesium (specific gravity 1.74), and is appreciably lighter than aluminum (specific gravity 2.7). Its lack of ductility prevents its use as a structural material, but this difficulty may be overcome in the future by the use of various alloy forms. The only important commercial alloy in which beryllium is used today is with copper. The addition of small percentages (1/2 to 2 percent) of beryllium to copper imparts properties to the alloy that make it desirable for use in springs carrying electrical current, particularly at high temperature. Many other uses of berylliam are known, and new uses are being found constantly that make the metal of increasing interest.Possibly the main factor preventing the use of more beryllium is the lack of a large source of beryllium ore. Many beryllium minerals are found as minor constituents of natural deposits, some of the more common ones being beryl (Be3Al2(Si03)6), chrysoheryl (Be A1204), helvite (3(Mn, Fe) Be Si04. MnS), and phenacite (Be2Si04). Of the known beryllium minerals, beryl is by far the most common and has been found distributed rather widely throughout the world. It usually occurs associated with granitic rocks and is commonly found as a constituent of granitic pegmatite."

Mar 1, 1947

By X. Bai

A new heuristic sublevel mining stope optimizer is presented. The optimizer seeks the best locations and lengths of a series of vertical raises that, together with the blocks linked to each raise, define a mining stope. Five design constraints ? the footwall angle, the hangingwall angle, the number of raises, the maximum distance of a block from a raise, and the minimum width required to move the farthest block towards the raise ? allow the shape of the sub-stopes associated with each raise to be controlled. The optimization is done on the locations and lengths of raises using a genetic algorithm to efficiently sample the parameters? space. For each raise, a local network is defined in cylindrical coordinates around the raise such as to impose the design constraints. A maxflow algorithm on the local network is used to determine the optimal sub-stope for each raise. All substopes are combined to define the global stope for the entire deposit. The best global stope is obtained using a genetic algorithm to find the raise parameters providing the best profit over the entire deposit. Two synthetic cases and one real deposit are used to evaluate the new algorithm and compare the results with the single-raise optimizer. The multiple raises approach leads to significantly improved economics compared with the single-raise stope optimizer, and the dilution is also substantially reduced compared to the single-raise case.

Jan 1, 2014

By Nicholas C. Lias

Quartz crystals are the raw material from which are made the crystal units utilized in filters and oscillators so vital to the performance of all long distance communications systems. These devices act as the heart of equipment that permits a single telephone cable to carry hundreds of conversations simultaneously. Quartz crystals are of value in communications because of this piezoelectric nature, that is when an electric signal is applied to the quartz, there is a resulting mechanical motion and conversely, a mechanical stress results in an electrical output signal. A plate cut from a quartz crystal will oscillate at some specific frequency, which is determined by the physical dimension of the plate. During the early stages of telephony, all quartz plates were cut from natural quartz, which was imported mainly from Brazil. Since the source of this important raw material was based upon a foreign supply which is located at a great distance from the user and could be vulnerable in time of a national emergent, it became necessary to maintain a large inventory of this strategic material. Also due to the considerable cost of natural crystals of a size and quality suitable for Bell System use, an investigation was made by Bell Laboratories into the possibility of developing a substitute material. The effort was successful and led to a joint development program between Bell Laboratories and Western Electric. This program brought about the design of manufacturing facilities capable of producing large quantities of cultured quartz at Western's Merrimack Valley Works, No. Andover, Massachusetts.

Jan 1, 1973

By Ozgul Keles, Dila Sivlin

Lithium ion batteries are potential energy source of next generation electric vehicles (EVs). However, some problems such as safety, durability, low capacity, cycle life etc. restrict their use in EVs. These problems mostly related with cathode materials, an improvement in cathode materials may cause significant changes in battery performance. In this work, to overcome cycle life problem Al2O3 coating on LiNi0.5Mn0.3Co0.2O2 cathode material produced by sol-gel method. The surface modification of LiNi0.5Mn0.3Co0,2O2 was started by adding LiNi0.5Mn0.3Co0.2O2 powders into alumina sol. Then, sonication was started and two different sonication powers were tested (45, 100%). After the second gel is obtained, last heat treatment for Al2O3 crystallization was done at 600 °C for 4 h. X-ray diffraction (XRD) measurements showed that the material had a well-ordered layered structure and Al was not in the LiNi0.5Mn0.3Co0.2O2. Al2O3 coated materials show better cycling performance compared to the pristine material. It is believed that, this improvement is caused by the fact that Al2O3 layer prevents direct contact between active material and electrolyte and reducing decomposition reactions.

Mar 1, 2018

By W. F. Whittaker

Systematic control of process parameters during electrorefined copper cathode production and final product inspection ensures high quality of produced "ORC brand copper. Since 1986, substantial increases in tankhouse productivity have been achieved by a number of technological and process control changes. This paper reviews the changes implemented to achieve higher productivity and cathode quality.

Jan 1, 1992

By Aaron L. Sacks, David R. Good, Srinivas Yennamanda, Joseph K. Carey

Construction of Parcels 6 and 7, the second phase of The Wharf, began in 2019 and geotechnical construction was completed by December 2020. The overall project consisted of horizontal site, parks, and office buildings. The Wharf’s Phase 2 development includes approximately 1.2 million ft2 (110,000 m2) of above-grade construction including five multi-story, mixed-use buildings constructed over up to three levels of underground parking. The site is located between the WMATA Green Line Tunnels to the north and the Washington Channel to the south; it is bisected by a 108-in. (2740-mm) diameter DC Water outfall pipe. This arrangement, along with very difficult ground conditions, created challenges in the geotechnical design and construction. The support of excavation for this complex project required several different methodologies, including sheet piles, soldier piles, displacement piles, tiebacks, deep foundation anchors, jet grouting, and internal bracing with multi-tier rakers. Ground improvement was also required for support of spread footings in soft soils over the garage footprint. Underpinning of the active 108-in. (2740-mm) diameter DC Water outfall pipe running on a north/south alignment through the center of the site between the two garage structures was also performed. Since portions of the support of excavation are below the groundwater table, an extensive pre-excavation dewatering program was necessary and was separate from the foundation package. On the north side of the project, support of excavation (SOE) was required on a curved alignment, offset approximately 10 ft (3 m) from the outbound Green Line tunnel. Due to the proximity of the tunnel, a stiff, near-zero displacement wall was required. A portion of the buildings extend over the tunnels, imparting load to the tunnels to approximately restore original overburden loads excavated for the basement space. The building foundation is a 3 to 4-ft (0.9 to 1.2-m) thick mat slab anchored into the Potomac clay formation. Continuous movement monitoring of the tunnels was performed by an automated system. This paper describes the design and construction of the SOE and foundations for this high-profile project, which required collaboration between the Owner, Engineer, Construction Manager, and Specialty Geotechnical Contractor to solve many challenges.

Oct 1, 2022

By J. L. Mehaffey

A variety of chemicals offered by Armak were evaluated as dewatering aids for aqueous slurries of silica sand, sparsand and feldspar; an established commercial dewatering aid was used as a control. A number of Armak's potential dewatering aids yielded lower moisture retention values than did the commercial product on all of the mineral samples. In addition to the chemical dewatering evaluations, some of the mechanisms involved in the removal of water from these mineral samples were examined.

Jan 1, 1983

By Matthew Goff, Russell Lutch

The Great Lakes Water Authority (GLWA) operates the largest regional water authority in the State of Michigan. Two of the tunnels supplying raw water to the system from the Detroit River are the Springwells and Northeast Tunnels. The existing 70- to 90-year old concrete lined tunnels have experienced distress and cracking over their life requiring non-structural repairs to sections of the tunnels. For the repair, an interior stainless-steel segmental liner plate system has been designed to restore the watertight capacity of the tunnel liner and resist the exterior hydrostatic groundwater pressure in a dewatered condition. The team is utilizing a “wet repair” approach to perform the necessary repairs while the tunnel remains fully flooded and operational. To test and validate the tunnel repair approach, a full-scale mock-up of the proposed repair has been performed using underwater equipment and divers.

Dec 1, 2022

By C. W. Sherman, John Chipman

IN the mathematical statement of the law of mass action, the activity of each substance consumed or produced in a reaction is used to obtain a numerical constant which is characteristic of the equilibrium of that reaction at the given temperature. The activity in many cases is equal to, or proportional to, the concentration. If this is the case, any units denoting concentrations, such as weight percentage or mol fraction, may be substituted in the equilibrium expression. It is even permissible to use mixed units provided only that each unit is that used in defining the activity of the corresponding substance. The indiscriminate use of concentration units in writing equilibrium constants sometimes leads to very erroneous results. On the other hand, what appear to be contradictory results from similar investigations often might be resolved if the activity is the quantity that is used to determine the equilibrium constant for the reaction in question. De-sulphurization serves as an important illustration. Sulphur in lron and Steel The control of the sulphur content of the finished product is one of the oldest and broadest problems in the metallurgy of iron and steel. In general, this control must be exercised through the action of a slag, and for this reason experimental studies of the distribution of sulphur between slag and metal have assumed considerable importance. Under slags of the type found in the basic open-hearth furnace the ratio (% S)/[% S] does not in general exceed about 8. Under blast-furnace conditions, however, de-sulphurization ratios of 50 to 100 are readily obtained, and under laboratory conditions using similar slags, the ratio may be as high as 400. The fact that blast-furnace metal is much more readily desulphurized than is molten steel rests upon two distinct phenomena. The first of these is connected with the slag reaction. In the open-hearth furnace, the equilibrium in the following reaction places a definite limit on the sulphur content of the slag: S + 0-- = 0 + S- - where the symbols underlined indicate elements dissolved in the liquid metal, while slag constituents are represented as ions. The high oxygen content of the open-hearth bath prevents this reaction from proceeding far enough to effect good desul-phurization. In the blast-furnace process, however, the oxygen activity is limited by the presence of carbon in the metal and in the coke bed and the controlling reaction becomes: S_+O- + C_=S- + CO(gas) [2] The second phenomenon which contributes to the easier desulphurization of blast-furnace metal is the effect of high concentrations of other elements. These elements, notably carbon, silicon, and phosphorus, increase the thermodynamic activity of sulphur several fold. As a result of this increase, the escaping tendency of sulphur from the metal phase is increased and its removal facilitated. Previous Studies It becomes, therefore, a matter of importance to determine the effects of various elements upon the activity of sulphur in the melt. The experimental approach to this problem has been made through the equilibrium between sulphur in the melt and gaseous atmospheres containing hydrogen and hydrogen sulphide. The reaction and its equilibrium constant are written as follows: S + H2(gas) =H2S(gas);K1 = -- [3] Pn2 • as where the symbol a, represents the activity of the sulphur in solution in the metal. The understanding of the chemical behavior of sulphur in steel and pig iron rests on a firm knowledge of the binary system Fe-S. A number of studies of the equilibrium have given closely agreeing results from which the activity and free energy of the dissolved sulphur may be found. The recent paper by Sherman, Elvander, and Chipman1 includes a discussion and quantitative comparison of the results of several of the significant researchesr-" on dilute solutions of sulphur in iron. The results of this study indicate that the relationship between the ratio Ph,s/p+ and the percentage of sulphur in solution is not a linear one. This

Jan 1, 1953

By John Chipman

THE equilibrium between titanium in liquid iron and titanium oxides has been studied by Hadley and Derge.' They have shown that a minimum occurs in the oxygen content of the metal between 0.1 and 1.0 pct Ti, but its exact level was not fixed. The oxide phase in this minimum range was principally TiO, containing some iron oxide. On the other hand, for concentrations above 5 pct Ti the oxide phase was TiO and the oxygen content of the metal increased rapidly with increasing titanium content. From their observations and the free energy of Ti0 and TiOz reported by Kelley and ah,' it is possible to derive approximate values for the activity coefficients of titanium and oxygen in liquid iron-titanium alloys and the conditions for equilibrium in steel deoxidation. Neglecting possible departures from the stoichio-metric composition, the condition of equilibrium with Ti0 may be expressed as follows: TiO= Ti_ + C) log K = log NTl + log [% O] + log yTi + log fQ Here as a matter of convenience the titanium concentration is expressed in mol fraction while that of oxygen is in weight percent. The activity coefficients are yTi and fo. The value of log fo approaches zero as the concentration of titanium approaches zero, while that of log yTi approaches a limiting value of In Fig. 1 the sum of log NTi + log [% 0] is plotted for mol fractions of titanium between 0.05 and 0.50. The smooth extrapolation gives a value of —4.15 which corresponds to log K — log y:i . We therefore have the equation: According to the data of Kelley and Mah,' the free energy of formation of Ti0 at 1900°K is -82,400 cal. The free energy of solution of half a mol of oxygen in iron, taking 1 pct 0 as the standard state, is -29,300 cal. From these we write: From these equations the activity coefficient of titanium at infinite dilution in iron is found to have a value of 0.011 or log y°. = -1.96. This is only an approximate value but is certainly better than the estimated 0.05 in Basic Open Hearth Steelmaking To obtain approximate values for the activity coefficient at intermediate concentrations, it is as- sumed that log yTi(l is constant and equal to -1.96. This corresponds to a value of E;: = 3 In yTi/aNTi = 9.0 which is not unreasonable We now have the value for the activity of titanium and the percentage of oxygen in equilibrium with TiO. It is therefore a simple matter to calculate the activity coefficient of oxygen which is shown in Fig. 2. The effect of titanium is rather large, being comparable to that of vanadium, but not so large as has been reported for aluminum. The slope of the line at low concentrations corresponds to E: = aln yo/ aNTi=-0.37. At concentrations below 1 pct Ti the deoxidation constant and oxygen content for equilibrium with TiO, can be calculated from the foregoing data and the free energy of formation of TiO,, which according to Kelley and Mah is -144,600 cal at 1900°K. The free energy of solution of oxygen has been given; that of Ti to form a dilute solution with 1 pct Ti as the standard state is RT ln (0.5585 y:i/47.9) = -34,800 cal. From these data we find (for concentrations in wt pct): TiO, = Ti + 2 -0; hFTgO0= + 51,200 cal log if =-5.89 The interaction coefficients, concentrations being expressed as wt pct, are e;: = alogfTi/a[% Ti] = +0.048 and e:' = a logfo,/a[ojTi] = -0.187. The calculation gives the following results which, in view of the impurity of the oxide phase, must be regarded as approximate:

Jan 1, 1961