The research focuses on assessing the metal content, mainly copper, lead, iron and also silver in metallurgical slag samples from the area where historical metallurgical industry functioned. In the smelter located in Mogiła, near Krakow (southern Poland), whose operation is confirmed in sources from 1469, copper was probably refined as well as silver was separated from copper. Based on the change of chemical and soil phase content and also taking cartographic and historical data into account, considering the restrictions resulting from the modern land use the area was determined whose geochemical mapping can point to the location of the 15th century Jan Thurzo’s smelter in Mogiła near Krakow. Moreover, using the same approach with the samples of this kind here as with hazardous waste, an attempt has been made to assess their impact on the environment. Thereby, taking the geoenvironmental conditions into account, potential impact of the industrial activity has been assessed, which probably left large scale changes in the substratum, manifested in the structure, chemical content and soil phase changes. Discovering areas which are contaminated above the standard value can help to identify historical human activities, and finding the context in artefacts allows to treat geochemical anomalies as a geochronological marker. For this purpose the best are bed sediments, at present buried in the ground, of historical ditches draining the area of the supposed smelter. Correlating their qualities with analogical research of archeologically identified slags and other waste material allows for reconstructing the anthropopressure stages and the evaluation of their effects. The operation of Jan Thurzo’s smelter is significant for the history of mining and metallurgy of Poland and Central and Eastern Europe.
The results of activity studies of four catalysts in methanol synthesis have been presented. A standard industrial catalyst TMC-3/1 was compared with two methanol catalysts promoted by the addition of magnesium and one promoted by zirconium. The kinetic analysis of the experimental results shows that the Cu/Zn/Al/Mg/1 catalyst was the least active. Although TMC-3/1 and Cu/Zn/Al/Mg/2 catalysts were characterised by a higher activity, the most active catalyst system was Cu/Zn/Al/Zr. The activity calculated for zirconium doped catalyst under operating conditions was approximately 30% higher that of TMC-3/1catalyst. The experimental data were used to identify the rate equations of two types - one purely empirical power rate equation and the other one - the Vanden Bussche & Froment kinetic model of methanol synthesis. The Cu/ZnO/Al2O3 catalyst modified with zirconium has the highest application potential in methanol synthesis.
The Bulletin of the Polish Academy of Sciences: Technical Sciences (Bull.Pol. Ac.: Tech.) is published bimonthly by the Division IV Engineering Sciences of the Polish Academy of Sciences, since the beginning of the existence of the PAS in 1952. The journal is peer‐reviewed and is published both in printed and electronic form. It is established for the publication of original high quality papers from multidisciplinary Engineering sciences with the following topics preferred: Artificial and Computational Intelligence, Biomedical Engineering and Biotechnology, Civil Engineering, Control, Informatics and Robotics, Electronics, Telecommunication and Optoelectronics, Mechanical and Aeronautical Engineering, Thermodynamics, Material Science and Nanotechnology, Power Systems and Power Electronics. Journal Metrics: JCR Impact Factor 2018: 1.361, 5 Year Impact Factor: 1.323, SCImago Journal Rank (SJR) 2017: 0.319, Source Normalized Impact per Paper (SNIP) 2017: 1.005, CiteScore 2017: 1.27, The Polish Ministry of Science and Higher Education 2017: 25 points. Abbreviations/Acronym: Journal citation: Bull. Pol. Ac.: Tech., ISO: Bull. Pol. Acad. Sci.-Tech. Sci., JCR Abbrev: B POL ACAD SCI-TECH Acronym in the Editorial System: BPASTS.
The article concerns investigations over benefits of application of HRC devices into sulphide copper ore processing plant. High pressure comminution appears to be very effective technology in hard ore processing circuits, especially in terms of energy consumption. This can be particularly observed in downstream grinding and beneficiation operations. A series of pilot-scale crushing tests in HRC roller press for various levels of operating pressure, were performed. HRC crushing effectiveness along with downstream grinding process course for each crushing product were also under analysis. The investigations were supplemented by analysis of flotation process effectiveness and impact of the process of high-pressure comminution on environment (dust emission). The results of investigation show that operating pressure level influences the obtained comminution results (comminution degree, yield of finest particle size fractions). The grinding effectiveness, measured through production of the finest particle size fractions was significantly influenced by the operating pressure. The results show that higher values of operating pressure (4.0 and 4.5 N/mm2) are not as efficient within this scope as the pressure 3.5 N/mm2. Dust emission is also correlated with the operating pressure value.
The scope of this work is to investigate the precipitation of two Al-Mg-Si alloys with and without Cu and excess Si by using the differential scanning calorimetry (DSC), transmission electron microscopic (TEM), Vickers hardness measurement and X-ray diffraction. The analysis of the DSC curves found that the excess Si accelerate the precipitation and the alloy contain the excess Si and small addition of copper has higher aging-hardness than that of free alloy (without excess Si and Cu) at the same heat treatment condition. The sufficient holding time for the precipitation of the β'' phase was estimated to be 6 hours for the alloy aged at 100°C and 10 hours for the alloy aged at 180°C. The low Copper containing Al-Mg-Si alloy gives rise to the forming a finer distribution of β (Mg2Si) precipitates which increases the hardness of the alloy. In order to know more about the precipitation reactions, concern the peaks on the DSC curve transmission electron microscopy observation were made on samples annealed at temperatures (250°C, 290°C and 400°C) just above the corresponding peaks of the three phases β'', β' and β respectively.
The paper presents the results of the research on the effect of copper on the crystallization process, microstructure and selected properties of the compacted graphite iron. Compacted graphite in cast iron was obtained using Inmold process. The study involved the cast iron containing copper at a concentration up to approximately 4%. The effect of copper on the temperature of the eutectic crystallization as well as the temperature of start and finish of the austenite transformation was given. It has been shown that copper increases the maximum temperature of the eutectic transformation approximately by 5C per 1% Cu, and the temperature of the this transformation finish approximately by 8C per 1% Cu. This element decreases the temperature of the austenite transformation start approximately by 5C per 1% Cu, and the finish of this transformation approximately by 6C per 1% Cu. It was found that in the microstructure of the compacted graphite iron containing about 3.8% Cu, there are still ferrite precipitations near the compacted graphite. The effect of copper on the hardness of cast iron and the pearlite microhardness was given. This stems from the high propensity to direct ferritization of this type of cast iron. It has been shown copper increases the hardness of compacted graphite iron both due to its pearlite forming action as well as because of the increase in the pearlite microhardness (up to approx. 3% Cu). The conducted studies have shown copper increases the hardness of the compacted graphite iron approximately by 35 HB per 1% Cu.
The criteria, with which one should be guided at the assessment of the binding properties of bentonites used for moulding sands, are proposed in the paper. Apart from the standard parameter which is the active bentonite content, the unrestrained growth indicator should be taken into account since it seems to be more adequate in the estimation of the sand compression strength. The investigations performed for three kinds of bentonites, applied in the Polish foundry plants, subjected to a high temperature influences indicate, that the pathway of changes of the unrestrained growth indicator is very similar to the pathway of changes of the sand compression strength. Instead, the character of changes of the montmorillonite content in the sand in dependence of the temperature is quite different. The sand exhibits the significant active bentonite content, and the sand compression strength decreases rapidly. The montmorillonite content in bentonite samples was determined by the modern copper complex method of triethylenetetraamine (Cu(II)-TET). Tests were performed for bentonites and for sands with those bentonites subjected to high temperatures influences in a range: 100-700ºC.
Archaeometallurgical investigations presented in this work focus on analysing the microstructure as well as mechanical properties of artefacts from the17th in form of findings performed from cast iron as well as copper casts. The presented research results extend the up-to-date knowledge and present the analysis of structural compounds found in the microstructure of the artefacts from the time dating back to the late Middle Ages in the region around Czestochowa, Poland. The tested samples were found in earth in the city centre under the present marketplace. The excavation works were carried out in summer in the year 2009, and have resulted in the excavation of artefacts in form of copper block of the weight of several kg. The excavation action was led by a group of Polish archaeologists collaborating with the local authorities. The performed pre-dating of this element determines the age of the artefacts as the 17th century AD. The excavations that have been taking place since 2007 have widened the knowledge of the former Czestochowa. Historians of this town have suggested, that the found weight and traces of metallurgical activity suggest that the exposed walls were an urban weight. The weight is visible on the 18th century iconography. What was find on the Old Market indicates that there was a lush economic life before the Swedish invasion in this part of Poland. Some buildings lost their functions or were changed, others died in fires, but new places developed. To describe the microstructure, with its structural components, research was done using microscopy techniques, both of the light as well as electron microscopy (SEM), also chemical composition analysis was carried out using the EDS technique, as well as tool for phase analysis were applied in form of X-Ray Diffraction (qualitative analysis), especially for the reason to describe the phases present in the excavated material. This research will help to obtain new information in order to investigate further archaeometallurgical artefacts, extending the knowledge about middle age metallic materials its usage and manufacturing.
The casting workshop was discovered with numerous artifacts, confirming the existence of the manufacturing process of metal ornaments using ceramic molds and investment casting technology in Lower Silesia (Poland) in 7-6 BC. The research has yielded significant technological information about the bronze casting field, especially the alloys that were used and the artifacts that were made from them. Based on the analyses, the model alloys were experimentally reconstructed. Taking advantage of the computer-modeling method, a geometric visualization of the bronze bracelets was performed; subsequently, we simulated pouring liquid metal in the ceramic molds and observed the alloy solidification. These steps made it possible to better understand the casting processes from the perspective of the mold technology as well as the melting and casting of alloys.
Comparison of the electromagnetic performance of a flux-switching permanent magnet (PM) machine having two separate stators as well as different winding topologies is investigated in this paper. Different stator and rotor pole combinations of these machines are also considered. The analysis includes the open-circuit and on-load characteristics of the analyzed machines. It is observed that, the largest fundamental values of electromagnetic torque, for each winding topology, is seen in the 11-rotor-pole and 10-rotor-pole machines having alternate- and all-pole-wound configurations, respectively. Moreover, significant ripple is observed in the waveforms of the even-number rotor pole machines compared to their corresponding odd-number rotor pole counterparts. Overall, the alternate-pole-wound machines essentially have larger torque-density than their equivalent all-pole-wound ones. The investigated machine is also tested for validation.
The article discusses the process of copper production in a slurry furnace and in a converter, with the indication of corrosion effects of the extractor. The furnace shaft and settling furnace of the flash furnace were analyzed. The basic factors determining the choice of singlestage technology of copper smelting in relation to the exploitation of refractory materials were indicated. The effects of dissolving the furnace lining material through slag have been presented. Structural analysis results using a scanning microscope are also included. The kinetics of destruction of ceramic materials under the influence of copper slag were evaluated. It has been shown that detailed analyzes are necessary in order to extend the time of furnace extensibility of furnaces in copper processes. The surface layer of the crucible softens due to saturation with slag reagents and is then washed out and moves in the solid form to the slag. The research in the article indicate not only the possibility of dissolution of the ceramic material in the molten slag, but also possibility of erosive activity of the slag on that material.
The aim of our research was to investigate the genotoxic effects of cobalt chloride and copper chloride in mouse bone marrow cells using the micronucleus (MN) assay. The three different concentrations of cobalt chloride (11.2, 22.5 and 45 mg kg-1) and copper chloride (1.17, 2.35 and 4.70 mg kg-1) were injected intraperitoneally to mice for 24 and 48 hours. It was observed that both of these heavy metals induced a significant increase in frequency of micronucleated polychromatic erythrocytes (MNPCE) at different concentrations in mice for 24 and 48 hours when compared with the control. Furthermore, the significant reduction for the polychromatic erythrocyte/normochromatic erythrocyte (PCE/NCE) ratio which is indicative of bone marrow cytotoxicity was observed in bone marrow cells which were treated with copper chloride at all concentrations for 24 and 48 hours. No reduction of the PCE/NCE ratio was observed both 24 and 48 hours after all the doses of cobalt chloride tested as compared to the negative control. These results lead us to the conclusion that copper chloride may have genotoxic and cytotoxic properties due to induction in the frequency of MN and a reduction in PCE/NCE ratio in bone marrow cells of mice, whereas cobalt chloride induced only genotoxic effect in mice bone marrow
Internal casting defects that are detected by radiography may also be detected by ultrasonic method. Ultrasonic testing allows investigation of the cross-sectional area of a casting, it is considered to be a volumetric inspection method. The high frequency acoustic energy travels through the casting until it hits the opposite surface or an interface or defect. The interface or defect reflects portions of the energy, which are collected in a receiving unit and displayed for the analyst to view. The pattern of the energy deflection can indicate internal defect. Ultrasonic casting testing is very complicated in practice. The complications are mainly due to the coarse-grain structure of the casting that causes a high ultrasound attenuation. High attenuation then makes it impossible to test the entire volume of material. This article is focused on measurement of attenuation, the effect of probe frequency on attenuation and testing results.
Hydrogen is the fuel of the future, therefore many hydrogen production methods are developed. At present, fuel cells are of great interest due to their energy efficiency and environmental benefits. A brief review of effective formation methods of hydrogen was conducted. It seems that hydrogen from steam reforming of methanol process is the best fuel source to be applied in fuel cells. In this process Cu-based complex catalysts proved to be the best. In presented work kinetic equations from available literature and catalysts are reported. However, hydrogen produced even in the presence of the most selective catalysts in this process is not pure enough for fuel cells and should be purified from CO. Currently, catalysts for hydrogen production are not sufficiently active in oxidation of carbon monoxide. A simple and effective method to lower CO level and obtain clean H2 is the preferential oxidation of monoxide carbon (CO-PROX). Over new CO-PROX catalysts the level of carbon monoxide can be lowered to a sufficient level of 10 ppm.
In this research, the high arsenic content dust of copper smelting, as a raw material, the extraction of copper and arsenic from the high arsenic content dust in the leaching system containing acidic and alkaline compounds was investigated. Meanwhile, the effects of acid/alkaline initial concentration, liquid to solid ratio, leaching temperature, leaching time on the leaching rate of copper and arsenic were studied. The optimum conditions for the leaching of high arsenic content dust and preparation of copper arsenate were determined. The results showed that acidic/alkaline leaching of high arsenic content dust was particularly effective. 93.2% of the copper, and 91.6% of the arsenic were leached in an acidic leaching process and 95% of the arsenic, while less than 3% of the copper, less than 5% of the antimony, less than 2% of the bismuth was also leached in an alkaline leaching process. A new method (the parallel flow drop precipitate method) was developed in the synthesis of copper arsenate process. The parallel flow drop method was employed to adjust the molar ratio (copper to arsenic) of the mixed solution of the acid-leaching solution and the alkali-leaching solution by taking the drop acceleration of an acidic leaching solution and an alkaline leaching solution at 10 mL/min and 12 mL/min, at a temperature of 60°C and a reaction time of 1 h. Copper arsenate was prepared by mixing an acidic leaching solution and an alkaline leaching solution. The main phases of copper arsenate were CuHAsO4·1.5H2O and Cu5As4O15·9H2O. Copper arsenate contained 30.13% copper and 31.10% arsenic.
The article presents chosen aspects of foundry engineering of the settlement dwellers, including the archaeometric characteristics and metal science analysis of the artefacts, as well as an attempted reconstruction of the production organization. Discovered in Szczepidło (Greater Poland), the foundry workshop is unique in Central European Bronze Age. This workshop foundry operated roughly XIV-XII Century BC. Its production is evidenced by the presence of markers of the whole production cycle: semi-finished and finished products, production waste, fragments of crucibles and casting ladles with traces of usage, and tools. On this basis, the alloys and foundry technologies used have been described. The analysis of foundry technology of copper alloys in the settlement area was carried out by observing the surface and structure of the products, semi-finished artefacts and fragments of crucibles by applying optical microscopy (OM), confocal microscopy (CLSM) and Xray radiography (RT). The investigations of compositions were made by means of the energy dispersive X-ray fluorescence spectroscopy (ED-XRF) and scanning electron microscopy (SEM) coupled with an energy dispersive X-ray analysis system (EDS).
Bending strength, thermal and electric conductivity and microstructure examinations of Cu based composite materials reinforced with Saffil alumina fibres are presented. Materials were produced by squeeze casting method applying the designed device and specially elaborated production parameters. Applying infiltration pressure of 90MPa and suitable temperature parameters provided manufacturing of copper based composite materials strengthened with Saffil alumina fibres characterized by the low rest porosity and good fibre-matrix interface. Three point bending tests at temperatures of 25, 100 and 300ºC were performed on specimens reinforced with 10, 15 and 20% of Saffil fibres. Introduced reinforcement effected on the relatively high bending strengths at elevated temperatures. In relation to unreinforced Cu casting strength of composite material Cu – 15vol.% Saffil fibres increase by about 25%, whereas at the highest applied test temperature of 300o C the improvement was almost 100%. Fibres by strengthening of the copper matrix and by transferring loads from the matrix reduce its plastic deformation and hinder the micro-crack developed during bending tests. Decreasing of thermal and electrical conductivity of Cu after incorporating fibres in the matrix are relatively small and these properties can be acceptable for electric and thermal applications.
The copper droplets contained in the post-processing liquid slag are subjected to the treatment by the complex reagent. The complex reagent has been recently elaborated and patented in frame of the Grant No. PBS3/A5/45/2015. In particular, the complex reagent is dedicated to the post-processing slags coming from the Smelter and Refinery Plant, Głogów, as a product of the direct-to-blister technology performed in the flash furnace. The recently patented complex reagent effectively assists not only in agglomeration, and coagulation but also in the deposition of the copper droplets at the bottom of crucible / furnace as well. The treatment of the postprocessing slags by the complex reagent was performed in the BOLMET S.A. Company as in the industrial conditions which were similar to those usually applied in the KGHM – Polish Copper (Smelter and Refinery Plant, Głogów). The competition between buoyancy force and gravity is studied from the viewpoint of the required deposition of coagulated copper droplets. The applied complex reagent improves sufficiently the surface free energy of the copper droplets. In the result, the mechanical equilibrium between coagulated copper droplets and surrounding liquid slag is properly modified. Finally, sufficiently large copper droplets are subjected to a settlement on the crucible / furnace bottom according to the requirements.
The aim of this work is the development of Cu-Al2O3 composites of copper Cu-ETP matrix composite materials reinforced by 20 and 30 vol.% Al2O3 particles and study of some chosen physical properties. Squeeze casting technique of porous compacts with liquid copper was applied at the pressure of 110 MPa. Introduction of alumina particles into copper matrix affected on the significant increase of hardness and in the case of Cu-30 vol. % of alumina particles to 128 HBW. Electrical resistivity was strongly affected by the ceramic alumina particles and addition of 20 vol. % of particles caused diminishing of electrical conductivity to 20 S/m (34.5% IACS). Thermal conductivity tests were performed applying two methods and it was ascertained that this parameter strongly depends on the ceramic particles content, diminishing it to 100 Wm-1K-1 for the composite material containing 30 vol.% of ceramic particles comparing to 400 Wm-1K-1 for the unreinforced copper. Microstructural analysis was carried out using SEM microscopy and indicates that Al2O3 particles are homogeneously distributed in the copper matrix. EDS analysis shows remains of silicon on the surface of ceramic particles after binding agent used during preparation of ceramic preforms.
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 post-processing slags containing about 0.8 wt.% of copper were subjected to the treatment of a complex reagent. The chemical composition of the complex reagent has been elaborated and patented in frame of the Grant No. PBS3/A5/45/2015. The slags had an industrial origin and were delivered by the Smelter and Refinery Plant, Głogów, as a product of the direct-to-blister technology performed in the flash furnace assisted by the arc furnace. An agglomeration of copper droplets suspended in the liquid slag, their coagulation, and deposition on the bottom of furnace were observed after the treatment this post-processing slag by the mentioned reagent. The treatment of the post-processing slags by the complex reagent was performed in the arc furnace equipped with some additional electrodes situated at the furnace bottom (additional, in comparison with the arc furnace usually applied in the Smelter and Refinery Plant, Głogów). The behaviour of the copper droplets in the liquid slag within the competition between buoyancy force and gravity was studied from the viewpoint of the required deposition of coagulated copper droplets. The applied complex reagent improves sufficiently the surface free energy of the copper droplets. In the result, the mechanical equilibrium between coagulated copper droplets and surrounding liquid slag is properly modified. Eventually, sufficiently large copper droplets are subjected to a settlement on the furnace bottom according to the requirements. The agglomeration and coagulation of the copper droplets were significantly improved by an optimized tilting of the upper electrodes and even by their rotation. Moreover, the settlement was substantially facilitated and improved by the employment of both upper and lower system of electrodes with the simultaneous substitution of the variable current by the direct current.
In the present study, butt joints of aluminum (Al) 8011-H18 and pure copper (Cu) were produced by friction stir welding (FSW) and the effect of plunge depth on surface morphology, microstructure and mechanical properties were investigated. The welds were produced by varying the plunge depth in a range from 0.1 mm to 0.25 mm. The defect-free joints were obtained when the Cu plate was fixed at the advancing side. It was found that less plunging depth gives better tensile properties compare to higher plunging depth because at higher plunging depth local thinning occurs at the welded region. Good tensile properties were achieved at plunge depth of 0.2 mm and the tensile strength was found to be higher than the strength of the Al (weaker of the two base metals). Microstructure study revealed that the metal close to copper side in the Nugget Zone (NZ) possessed lamellar alternating structure. However, mixed structure of Cu and Al existed in the aluminum side of NZ. Higher microhardness values were witnessed at the joint interfaces resulting from plastic deformation and the presence of intermetallics.