<p>In view of the important applications of carbides and carbo-nitrides of transition metals in the heat-resistant and hard materials industries, the thermodynamic activities of Cr and Mn in the Cr-C, Fe-Cr-C, Mn-Ni-C and Mn-Ni-C-N systems have been studied in the present work by the use of the galvanic cell technique. CaF₂single crystals were used as the solid electrolyte. The phase relationships in selected regions of the systems in question were investigated by the use of the equilibration technique. The phase compositions and microstructures of the alloys were analysed by X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM).</p><p>In the Cr-C system, the Gibbs energy of formation of Cr3C2 were obtained from ElectroMotive Force (EMF) measurements conducted in the temperature range 950-1150 K. The values of the enthalpy of formation of Cr₃C₂ were evaluated by the third-law method. The ground-state energy of the hypothetic end-member compound CrC3, in the bcc structure at 0 K, was calculated by use of the Ab-initio method. Based on the obtained results the Cr-C system was reassessed by use of the CALPHAD approach.</p><p>In the Fe-Cr-C system, 16 different alloys were quenched at 1223 K and their equilibrium phases identified by XRD. The experimental results show that the substitution of Cr by Fe in the (Cr,Fe)₇C₃ carbide changes the lattice parameters of the phase. A slight decrease of the lattice parameters with an increase in the Fe content was established. The lattice parameters of the γ-phase in the Fe-Cr solid solution did also show a decrease with an increase of the Fe content. The activities of chromium in Fe-Cr-C alloys were investigated in the temperature range 940-1155 K. The activity of chromium decreases with an increase in the Fe content when the ratio of C/(Cr+C) was constant. It was also established that the activity of chromium decreases with an increase of the carbon content when the iron content was constant. The experimental results obtained were compared with the data calculated by use of the Thermo-Calc software. </p><p>In the Mn-Ni-C system the phase relationships were investigated at 1073 K as well as at 1223 K. The experimental results obtained showed that the site fraction of Ni in the metallic sublattice of the carbides M₂₃C₆, M₇C₃ and M₅C₂ (M=Mn and Ni) was quite low (approximately 2~3 percent). The activities of manganese in Mn-Ni-C alloys were investigated in the temperature range 940-1165 K. The three-phase region γ/M₇C₃/graphite was partly constructed at 1073 K. </p><p>In the Mn-Ni-C-N system, nitrogen was introduced into Mn-Ni-C alloys by equilibrating with N2 gas. It was established that the solubility of nitrogen in the investigated alloys was effected by the carbon content, and that a (Mn,Ni)₄(N,C) compound was formed in the nitrided alloys. EMF measurements were performed on Mn-Ni-C-N alloys in the temperature interval 940-1127 K. The addition of nitrogen to Mn-Ni-C alloys was found to decrease the activity of manganese. The negative effect of nitrogen on the activity of manganese was found to decrease as the carbon content increased.</p><p><b>Keywords:</b> Thermodynamic activity; Galvanic cell technique; Transition metal carbides; Transition metal nitrides; Phase equilibrium; Thermodynamics; Differential thermal analysis; Scanning electron microscopy; Transmission electron microscopy; Ab-initio calculations; CALPHAD approach;</p>

In view of the important applications of carbides and carbo-nitrides of transition metals in the heat-resistant and hard materials industries, the thermodynamic activities of Cr and Mn in the Cr-C, Fe-Cr-C, Mn-Ni-C and Mn-Ni-C-N systems have been studied in the present work by the use of the galvanic cell technique. CaF2single crystals were used as the solid electrolyte. The phase relationships in selected regions of the systems in question were investigated by the use of the equilibration technique. The phase compositions and microstructures of the alloys were analysed by X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). In the Cr-C system, the Gibbs energy of formation of Cr3C2 were obtained from ElectroMotive Force (EMF) measurements conducted in the temperature range 950-1150 K. The values of the enthalpy of formation of Cr3C2 were evaluated by the third-law method. The ground-state energy of the hypothetic end-member compound CrC3, in the bcc structure at 0 K, was calculated by use of the Ab-initio method. Based on the obtained results the Cr-C system was reassessed by use of the CALPHAD approach. In the Fe-Cr-C system, 16 different alloys were quenched at 1223 K and their equilibrium phases identified by XRD. The experimental results show that the substitution of Cr by Fe in the (Cr,Fe)7C3 carbide changes the lattice parameters of the phase. A slight decrease of the lattice parameters with an increase in the Fe content was established. The lattice parameters of the γ-phase in the Fe-Cr solid solution did also show a decrease with an increase of the Fe content. The activities of chromium in Fe-Cr-C alloys were investigated in the temperature range 940-1155 K. The activity of chromium decreases with an increase in the Fe content when the ratio of C/(Cr+C) was constant. It was also established that the activity of chromium decreases with an increase of the carbon content when the iron content was constant. The experimental results obtained were compared with the data calculated by use of the Thermo-Calc software. In the Mn-Ni-C system the phase relationships were investigated at 1073 K as well as at 1223 K. The experimental results obtained showed that the site fraction of Ni in the metallic sublattice of the carbides M23C6, M7C3 and M5C2 (M=Mn and Ni) was quite low (approximately 2~3 percent). The activities of manganese in Mn-Ni-C alloys were investigated in the temperature range 940-1165 K. The three-phase region γ/M7C3/graphite was partly constructed at 1073 K. In the Mn-Ni-C-N system, nitrogen was introduced into Mn-Ni-C alloys by equilibrating with N2 gas. It was established that the solubility of nitrogen in the investigated alloys was effected by the carbon content, and that a (Mn,Ni)4(N,C) compound was formed in the nitrided alloys. EMF measurements were performed on Mn-Ni-C-N alloys in the temperature interval 940-1127 K. The addition of nitrogen to Mn-Ni-C alloys was found to decrease the activity of manganese. The negative effect of nitrogen on the activity of manganese was found to decrease as the carbon content increased. Keywords: Thermodynamic activity; Galvanic cell technique; Transition metal carbides; Transition metal nitrides; Phase equilibrium; Thermodynamics; Differential thermal analysis; Scanning electron microscopy; Transmission electron microscopy; Ab-initio calculations; CALPHAD approach;

An experimental investigation of the binary system Co-Cr and the ternary system C-Co-Cr has been carried out in the present thesis. The experimental strategy adopted for the binary system was to measure the thermodynamic activities of Cr, the molar heat capacity as function of time, the phase transformation temperatures with corresponding enthalpies, the Curie transition temperature as well as melting temperatures with corresponding enthalpies. In the ternary system the strategy was to determine the solubility of Co in the Cr7C3 phase as well as the C and Cr contents in the Co rich (fcc) binder phase. The experimental results were compared with atomistic simulations of the solubility of Co in the Cr7C3 phase. Solid state galvanic cell measurements were conducted with both ZrO2-7.5 mol % CaO and CaF2 as the solid electrolyte. In view of possible errors in the measurements with ZrO2-7.5 mol % CaO, as a result of electronic contributions to the conduction of the solid electrolyte, new measurements were conducted with CaF2 as the solid electrolyte. The results indicated that the measured EMF values showed trends which were contrary to the thermodynamic behaviour expected from phase diagram considerations. It was concluded that further detailed experimentation was necessary in order to throw more light on the thermodynamic behaviour of the Co-Cr system. Two different series of DSC measurements were conducted, i.e. one in an atmosphere of pure hydrogen and another in pure argon. In the first investigation, conducted in an atmosphere of pure hydrogen in the temperature interval 318-1660 K, evidence was obtained for the existence of a phase transformation around 900 K in the compositional range 20.7-67.1 wt.% Cr. No indications of such a phase transformation had earlier been seen. In the second investigation, conducted in an atmosphere of pure argon in the temperature interval 298-1823 K, special attention was given to alloys in the Co rich corner of the phase diagram, i.e. 0-10 wt.% Cr. This investigation verified earlier findings of a phase transformations around 900 K in the compositional range 20.7-67.4 wt.% Cr. The magnetic transition temperatures for alloys low in Cr content were also obtained. With the use of the DTA technique the melting temperatures with corresponding enthalpy values for alloys in the compositional range 0.9-7.7 wt.% Cr were obtained. The three-phase triangle fcc+Cr7C3+graphite was investigated at 1373 K, 1423 K and 1473 K. The obtained results showed that the solubility of cobalt in the Cr7C3 phase was significantly higher than previously predicted by thermodynamic calculations. / QC 20100930