Experimental observations of the steel morphology as well as measurements of the solutes concentration in the macro-scale were made on the basis of the vertical cut at the mid-depth of the 15-tons steel forging ingot serially produced in one of the steel plant in Poland. Experimental observations of the morphology accompanied by the measurements of the Peclet Number were also made on the cross-section of the continuously cast brass ingots serially produced in the copper / brass industry in Poland. The performed measurements allowed to work out some maps of the alloying elements segregation for the longitudinal section of the steel static ingot and a Growth Law for the columnar grains formation in the brass ingots. The marginal stability criterion has been applied to the last mentioned development / description. Some suggestions for the micro-segregation measurement mode in the columnar structure are derived.
Coagulation and solidification of the copper droplets suspend in the liquid slag are usually accompanied by the appearance of the Cu-Cu2O eutectic. Locally, this eutectic is created in the stationary state. Therefore, frequently it has a directional morphology. Since the E = (Zn) + Zn16Ti – eutectic is similar in the asymmetry of the phase diagram to the Cu-Cu2O – eutectic, the (Zn) single crystal strengthened by the E = (Zn) + Zn16Ti precipitate is subjected to directional growth by the Bridgman’s system and current analysis. Experimentally, the strengthening layers (stripes) are generated periodically in the (Zn) – single crystal as a result of the cyclical course of precipitation which accompanies the directional solidification. These layers evince diversified eutectic morphologies like irregular rods, regular lamellae, and regular rods. The L – shape rods of the Zn16Ti – intermetallic compound appear within the first range of the growth rates when the irregular eutectic structure is formed. Next, the branched rods transform into regular rods and subsequently the regular rods into regular lamellae transitions can be recorded. The regular lamellae exist only within a certain range of growth rates. Finally, the regular rods re-appear at some elevated growth rates. The entropy production per unit time and unit volume is calculated for the regular eutectic growth. It will allow to formulate the entropy production per unit time for both eutectic structure: rod-like and lamellar one.
The suspension of copper droplets in the slag is considered. The copper/slug suspension is delivered as the product from the direct-toblister process which is applied in the KGHM – Polska Miedź (Polish Copper) S.A. factory. The droplets / slag suspension was treated by a special set of reagents (patented by the authors) to improve the coagulation process. On the other hand, the observations are made to estimate if the melting / reduction process in the furnace is sufficiently effective to avoid a remaining of carbon in the copper droplets. The coagulation process was carried out in the crucible (laboratory scale). However, conditions imposed to the coagulation / solidification process in the laboratory scale were to some extent similar to those applied usually in the industry when the suspension is subjected to the analogous treatment in the electric arc-furnace. Some suggestions are formulated how to improve the industrial direct-to-blister process.
The presented results of research on the effectiveness of enzymatic hydrolysis of lignocellulosic waste, depending on their initial depolymerisation in alkaline medium were considered in the context of the possibility of their further use in the fermentation media focused on the recovery of energy in the form of molecular hydrogen. The aim of this study was to determine the appropriate dose and concentration of a chemical reagent, whose efficiency would be high enough to cause decomposition of the complex, but without an excessive production of by-products which could adversely affect the progress and effectiveness of the enzymatic hydrolysis and fermentation. The effect of treatment on physical-chemical changes of homogenates’ properties such as pH, COD, the concentration of monosaccharide and total sugars and the concentration of total suspended solids and volatile suspended solids was determined. The enzymatic decomposition of lignocellulosic complex was repeatedly more efficient if the sample homogenates were subjected to an initial exposure to NaOH. The degree of conversion of complex sugars into simple sugars during enzymatic hydrolysis of homogenates pre-alkalized to pH 11.5 and 12.0 was 83.3 and 84.2% respectively, which should be sufficient for efficient hydrogen fermentation process.
This paper presents the idea of increasing the effectiveness of slag decopperisation in an electric furnace in the "Głogów II" Copper Smelter by replacing the currently added CaCO3with a less energy-intensive technological additive. As a result of this conversion, one may expect improved parameters of the process, including process time or power consumption per cycle. The incentives to optimize the process are the benefits of increasing copper production in the company and the growing global demand for this metal. The paper also describes other factors that may have a significant impact on the optimization of the copper production process. Based on the literature analysis, a solution has been developed that improves the copper production process. The benefits of using a new technology additive primarily include increased share of copper in the alloy, reduced production costs, reduced amount of power consumed per cycle and reduced time it takes to melt. At the conclusion of the paper, the issues raised are highlighted, stressing that mastering the slag slurry process in electric furnaces requires continuous improvement.
An innovative method for determining the structural zones in the large static steel ingots has been described. It is based on the mathematical interpretation of some functions obtained due to simulation of temperature field and thermal gradient field for solidifying massive ingot. The method is associated with the extrema of an analyzed function and with its points of inflection. Particularly, the CET transformation is predicted as a time-consuming transition from the columnar- into equiaxed structure. The equations dealing with heat transfer balance for the continuous casting are presented and used for the simulation of temperature field in the solidifying virtual static brass ingot. The developed method for the prediction of structural zones formation is applied to determine these zones in the solidifying brass static ingot. Some differences / similarities between structure formation during solidification of the steel static ingot and virtual brass static ingot are studied. The developed method allows to predict the following structural zones: fine columnar grains zone, (FC), columnar grains zone, (C), equiaxed grains zone, (E). The FCCT-transformation and CET-transformation are forecast as sharp transitions of the analyzed structures. Similarities between steel static ingot morphology and that predicted for the virtual brass static ingot are described.
There are two methods to produce primary copper: hydrometallurgical and pyrometallurgical. Copper concentrates, from which copper matte is melted, constitute the charge at melting primary copper in the pyrometallurgical process. This process consists of a few stages, of which the basic ones are roasting and smelting. Smelting process may be bath and flash. Slag from copper production, on the end of process contain less 0,8%. It is treat as a waste or used other field, but only in a few friction. The slag amount for waste management or storage equaled 11 741 – 16 011 million tons in 2011. This is a serious ecological problem. The following slags were investigated: slag originated from the primary copper production process in the flash furnace of the Outtokumpuja Company in HM Głogów 2 (Sample S2): the same slag after the copper removal performed according the up to now technology (Sample S1): slag originated from the primary copper production process in the flash furnace of the Outtokumpuja Company in HM Głogów 2, after the copper removal performed according the new technology (Sample S3). In practice, all tested slags satisfy the allowance criteria of storing on the dumping grounds of wastes other than hazardous and neutral.
The Structural Peclet Number has been estimated experimentally by analyzing the morphology of the continuously cast brass ingots. It allowed to adapt a proper development of the Ivantsov’s series in order to formulate the Growth Law for the columnar structure formation in the brass ingots solidified in stationary condition. Simultaneously, the Thermal Peclet Number together with the Biot, Stefan, and Fourier Numbers is used in the model describing the heat transfer connected with the so-called contact layer (air gap between an ingot and crystallizer). It lead to define the shape and position of the s/l interface in the brass ingot subjected to the vertical continuous displacement within the crystallizer (in gravity). Particularly, a comparison of the shape of the simulated s/l interface at the axis of the continuously cast brass ingot with the real shape revealed at the ingot axis is delivered. Structural zones in the continuously cast brass ingot are revealed: FC – fine columnar grains, C – columnar grains, E – equiaxed grains, SC – single crystal situated axially.
A special Slag-Prop Cu database has been developed to archive data from laboratory and industrial tests related to post-reduction slags. In order to enrich the data areas, it was decided to design a system for measuring the temperature of the liquid slag and its viscosity. Objectives of research work are to gather information on the properties of post-slags such as the temperature of liquid slag and its viscosity. The discussed issues are especially important in the foundry practice. Designed research stand and using of database applications can greatly facilitate the work of metallurgists, foundrymen, technologists and scientists. The viscosity measurement was developed and presented earlier. The author's analytical methodology was supplemented by a thyristor measuring system (described in the article). The system temperature measurement can be performed simultaneously in 3 ways to reduce the measurement error. Measurement of the voltage mV - using the Seebeck effect can be measured throughout the entire range of thermocouple resistance, up to 1300 °C. Direct temperature measurement ⁰C - measurement only below 1000 ⁰C. Additional measurement - the measurement can also be read from the pyrometer set above the bath. The temperature and the reading frequency depend on the device itself. The principle of measurement is that in a molten metal / slag crucible, we put a N-type thermocouple. The thermocouples are hung by means of a tripod above the crucible and placed in a crucible. The thermocouple is connected to a compensating line dedicated to this type of thermocouple. The cable is in turn connected to a special multimeter that has the ability to connect to a computer and upload results. Temperature measurement can be performed simultaneously in 3 ways to reduce the measurement error. The Sn-Pb alloy has been subjected to testing for proper operation of the device. In this foot should be observed the supercooling of the liquid, which initiates the crystallization process and in which latent heat begins to exude raising the temperature until the coagulation temperature is reached.
Particles of the Fe-Al type (less than 50 µm in diameter) were sprayed onto the 045 steel substrate by means of the detonation method. The TEM, SAED and EDX analyses revealed that the Fe-Al particles have been partially melted in the experiment of coating formation. Particle undergone melting even within about 80% of its volume. Therefore, solidification of the melted part of particles was expected. Solidification differed significantly due to a large range of chemical composition of applied particles (from 15 at.% Al up to 63 at.% Al). A single particle containing 63 at.% Al was subjected to the detailed analysis, only. The TEM / SAED techniques revealed in the solidified part of particle three sub-layers: an amorphous phase, A ε , periodically situated FeAl + Fe2Al5 phases, and a non-equilibrium phase, Nε . A hypothesis dealing with the inter-metallic phases formation in such a single particle of the nominal composition 0 N = 0.63 is presented. At first, the solid / liquid system is treated as an interconnection: substrate liquid nonmelted particle part / / . Therefore, it is suggested that the solidification occurs simultaneously in two directions: towards a substrate and towards a non-melted part of particle. The solidification mechanism is referred to the Fe-Al meta-stable phase diagram. It is shown that the melted part of particle solidifies rapidly according to the phase diagram of meta-stable equilibrium and at a significant deviation from the thermodynamic equilibrium.
Discusses an attempt to optimize the operation of an electric furnace slag to be decopperisation suspension of the internal recycling process for the production of copper. The paper presents a new method to recover copper from metallurgical slags in arc-resistance electric furnace. It involves the use of alternating current for a first period reduction, constant or pulsed DC in the final stage of processing. Even distribution of the electric field density in the final phase of melting caused to achieve an extremely low content of metallic copper in the slag phase. They achieved by including the economic effects by reducing the time reduction.
The suspension of the copper droplets in the post-processing slag taken directly from the KGHM-Polska Miedź S.A. Factory (from the direct-to-blister technology as performed in the flash furnace) was subjected to the special treatment with the use of the one of the typical industrial reagent and with the complex reagent newly patented by the authors. This treatment was performed in the BOLMET S.A. Company in the semi-industrial conditions. The result of the CaCO3, and Na2CO3 chemicals influence on the coagulation and subsequent sedimentation of copper droplets on the crucible bottom were subjected to comparison with the sedimentation forced by the mentioned complex reagent. The industrial chemicals promoted the agglomeration of copper droplets but the coagulation was arrested / blocked by the formation of the lead envelope. Therefore, buoyancy force forced the motion of the partially coagulated copper droplets towards the liquid slag surface rather than sedimentation on the crucible bottom. On the other hand, the complex reagent was able to influence the mechanical equilibrium between copper droplets and some particles of the liquid slag as well as improve the slag viscosity. Finally, the copper droplets coagulated successfully and generally, were subjected to a settlement on the crucible bottom as desired / requested.
Some metallographic studies performed on the basis of the massive forging steel static ingot, on its cross-section, allowed to reveal the following morphological zones: a/ columnar grains (treated as the austenite single crystals), b/ columnar into equiaxed grains transformation, c/ equiaxed grains at the ingot axis. These zones are reproduced theoretically by the numerical simulation. The simulation was based on the calculation of both temperature field in the solidifying large steel ingot and thermal gradient field obtained for the same boundary conditions. The detailed analysis of the velocity of the liquidus isotherm movement shows that the zone of columnar grains begins to disappear at the first point of inflection and the equiaxed grains are formed exclusively at the second point of inflection of the analyzed curve. In the case of the continuously cast brass ingots three different morphologies are revealed: a/ columnar structure, b/ columnar and equiaxed structure with the CET, and c/ columnar structure with the single crystal formation at the ingot axis. Some forecasts of the temperature field are proposed for these three revealed morphologies. An analysis / forecast of the behavior of the operating point in the mold is delivered for the continuously cast ingot. A characteristic delay between some points of breakage of the temperature profile recorded at the operating point and analogous phenomena in the solidifying alloy is postulated.
Some eutectic stripes have been generated in a hexagonal (Zn) - single crystal. The stripes are situated periodically with the constant interstripes spacing. The eutectic structure in the stripes consists of strengthening inter-metallic compound, Zn16Ti, and (Zn) – solid solution. The rod-like irregular eutectic structure (with branches) appears at low growth rates. The regular lamellar eutectic structure is observed at middle growth rates. The regular rod-like eutectic structure exists exclusively in the stripes at some elevated growth rates. A new thermodynamic criterion is recommended. It suggests that this eutectic regular structure is the winner in a morphological competition for which the minimum entropy production is lower. A competition between the regular rod-like and the regular lamellar eutectic growth is described by means of the proposed criterion. The formation of branches within irregular eutectic structure is referred to the state of marginal stability. A continuous transitions from the marginal stability to the stationary state are confirmed by the continuous transformations of the irregular eutectic structure into the regular one.