Institute of Fundamental Technological Research

The interest in the Spark Plasma Sintering (SPS) technique has continuously increased over the last few years. This article shows the possibility of the development of an SPS device used for material processing and synthesis in both scientific and industrial applications and aims to present manufacturing methods and the versatility of an SPS device, presenting examples of processing Arc-Melted- (half-Heusler, cobalt triantimonide) and Self-propagating High-temperature Synthesis (SHS)-synthesized semiconductor (bismuth telluride) materials. The SPS system functionality development is presented, the purpose of which was to broaden the knowledge of the nature of SPS processes. This approach enabled the precise design of material sintering processes and also contributed to increasing the repeatability and accuracy of sintering conditions.

spark plasma sintering, arc melting, semiconductor materials, half-Heusler, bismuth telluride, cobalt triantimonide, SHS, SPS

This work aims to revise and apply an original discrete element model (DEM) to evaluate effective thermal conductivity of sintered porous materials. The model, based on two-particle sintering geometry, calculates inter-particle neck using Constant Volume (CV) criterion. The model was validated using experimental measurements on sintered porous NiAl. For DEM simulations, heterogeneous samples with real particle size distribution and different densities were obtained by simulation of hot pressing. Neck size evaluated using Coble’s and CV models were compared to show that commonly used Coble’s model overestimates neck size and conductivity. The proposed model was improved by neck-size correction to compensate for non-physical overlaps at higher densities and by adding grain-boundary resistance to account for porosity within necks. Resistance contribution from grain boundaries was shown to decrease with increasing density. Thermal conductivity obtained from the improved model was close to experimental results, suggesting validity of the model.

Discrete element method,Effective thermal conductivity,Porous materials,Sintering,Heat conduction simulation

This paper aims to analyse electrical conduction in partially sintered porous materials using an original resistor network model within discrete element framework. The model is based on sintering geometry, where two particles are connected via neck. Particle-to-particle conductance depends on neck size in sintered materials. Therefore, accurate evaluation of neck size is essential to determine conductance. The neck size was determined using volume preservation criterion. Additionally, grain boundary correction factor was introduced to compensate for any non-physical overlaps between particles, particularly at higher densification. Furthermore, grain boundary resistance was added to account for the porosity within necks. For numerical analysis, the DEM sample was generated using real particle size distribution, ensuring a heterogeneous and realistic microstructure characterized by a maximum-to-minimum particle diameter ratio of 15. The DEM sample was subjected to hot press simulation to obtain geometries with different porosity levels. These representative geometries were used to simulate current flow and determine effective electrical conductivity as a function of porosity. The discrete element model (DEM) was validated using experimentally measured electrical conductivities of porous NiAl samples manufactured using spark plasma sintering (SPS). The numerical results were in close agreement with the experimental results, hence proving the accuracy of the model. The model can be used for microscopic analysis and can also be coupled with sintering models to evaluate effective properties during the sintering process.

Discrete element method, Effective electrical conductivity, Porous materials, Sintering, Resistor network model

This article discusses the morphology and thermomechanical properties of graphene oxide (GO) paper sheets and GO paper composites reinforced with carbon fibers. GO paper was fabricated using GO paste obtained by the condensation of GO aqueous solution synthesized using the Hummers' method. Carbon fibers were implemented to improve the mechanical properties of the pristine GO paper. All the investigated papers were subjected to thermal treatment to check thermo-related morphological and mechanical properties. The results presented in this study allowed for the deeper insight into morphological, structural, and mechanical volume and surface-related properties of pristine GO and GO-based composite materials reinforced with carbon fibers. We showed that there are two important factors that should be taken into consideration for the design and fabrication of GO-based papers. These factors were the concentration of the reinforcing agent and the thermal reduction of the papers. Both factors have influenced the final properties of the resulting GO-based papers. For the first time, it was revealed how the addition of the reinforcing material affects the GO paper thermal expansion coefficient.

Flake graphene, Graphene oxide, Graphene oxide paper, Carbon fibers, Mechanical properties

The paper presents the experimental, numerical, and theoretical investigation of the microstructure of nickel aluminide samples manufactured by spark plasma sintering using electron backscatter diffraction and computer assisted software. The aim of the work was to reveal the evolution of the microscopic and macroscopic parameters related to the microstructure of the material and its dependence on the applied sintering parameters—temperature and pressure. The studied porous samples with different relative density were extracted from various planes and then tested by electron backscatter diffraction to evaluate the crystallographic orientation in every spot of the investigated area. On this foundation, the grain structure of the samples was determined and carefully described in terms of the grain size, shape and boundary contact features. Several parameters reflecting the grain morphology were introduced. The application of the electric current resulting in high temperature and the additional external loading leads to the significant changes in the structure of the porous sample, such as the occurrence of lattice reorientation resulting in grain growth, increase in the grain neighbours, or the evolution of grain ellipticity, circularity, grain boundary length, and fraction. Furthermore, the numerical simulation of heat conduction via a finite element framework was performed in order to analyse the connectivity of the structures. The numerical results related to the thermal properties at the micro- and macroscopic scale—local heat fluxes, deviation angles, and effective thermal conductivity—were evaluated and studied in the context of the microstructural porosity. Finally, the effective thermal conductivity of two-dimensional EBSD maps was compared with those obtained from finite element simulations of three-dimensional micro-CT structures. The relationship between the 2D and 3D results was derived by using the analytical Landauer model.

This work presents a comprehensive analysis of heat transfer and thermal conductivity of porous materials manufactured by spark plasma sintering. Intermetallic nickel aluminide (NiAl) has been selected as the representative material. Due to the complexity of the studied material, the following investigation consists of experimental, theoretical and numerical sections. The samples were manufactured in different combinations of process parameters, namely sintering temperature, time and external pressure, and next tested using the laser flash method to determine the effective thermal conductivity. Microstructural characterisation was extensively examined by use of scanning electron microscopy and micro-computed tomography (micro-CT) with a special focus on the structure of cohesive bonds (necks) formed during the sintering process. The experimental results of thermal conductivity were compared with theoretical and numerical ones. Here, a finite element framework based on micro-CT imaging was employed to analyse the macroscopic (effective thermal conductivity, geometrical and thermal tortuosity) and microscopic parameters (magnitude and deviation angle of heat fluxes, local tortuosity). The comparison of different approaches toward effective thermal conductivity evaluation revealed the necessity of consideration of additional thermal resistance related to sintered necks. As micro-CT analysis cannot determine the particle contact boundaries, a special algorithm was implemented to identify the corresponding spots in the volume of finite element samples; these are treated as the resistance phase, marked by lower thermal conductivity. Multiple simulations with varying content of the resistance phase and different values of thermal conductivity of the resistance phase have been performed, to achieve consistency with experimental data. Finally, the Landauer relation has been modified to take into account the thermal resistance of necks and their thermal conductivity, depending on sample densification. Modified theoretical and finite element models have provided updated results covering a wide range of effective thermal conductivities; thus, it was possible to reconstruct experimental results with satisfactory accuracy.

thermal conductivity, porous materials, spark plasma sintering, micro-computed tomography, nickel aluminide, finite element modelling, tortuosity

Additive manufacturing (AM) has seen remarkable development in recent years due to relatively high efficiency of the process. Cold spraying (CS) is a particular method of AM, in which titanium and titanium alloy powders are used. CS is a very competitive technology enabling the deposition of coatings, repairing machine parts, and manufacturing new components. For specific applications, the surface of cold-sprayed materials may require further processing. This paper reports an attempt to employ laser surface treatment (LST) of cold-sprayed coatings on an aluminium alloy substrate. The influence of laser beam interaction time on the coatings’ properties was analysed. The microstructure was investigated and observed employing scanning electron microscopy (SEM). To evaluate residual stress after CS and LST, the sin2ψ technique was used. Investigations were also performed on Vickers hardness, contact angle, and surface roughness. Significant changes in the surface morphology of the coatings and elevated residual stress levels dependent on the laser beam interaction time were observed. Increased Vickers hardness was recorded for titanium alloy Ti6Al4V. LST also led to increased surface hydrophilicity of the modified materials Ti and Ti6Al4V.

cold spray, laser surface treatment, titanium coating, Ti6Al4V, residual stresses

Doping is one of the possible ways to significantly increase the thermoelectric properties of many different materials. It has been confirmed that by introducing bismuth atoms into Mg sites in the Mg2Si compound, it is possible to increase career concentration and intensify the effect of phonon scattering, which results in remarkable enhancement in the figure of merit (ZT) value. Magnesium silicide has gained scientists’ attention due to its nontoxicity, low density, and inexpensiveness. This paper reports on our latest attempt to employ ultrafast selfpropagating high-temperature synthesis (SHS) followed by the spark plasma sintering (SPS) as a synthesis process of doped Mg2Si. Materials with varied bismuth doping were fabricated and then thoroughly analyzed with the laser flash method (LFA), X-ray diffraction (XRD), scanning electron microscopy (SEM) with an integrated energy-dispersive spectrometer (EDS). For density measurement, the Archimedes method was used. The electrical conductivity was measured using a standard four-probe method. The Seebeck coefficient was calculated from measured Seebeck voltage in the sample subjected to a temperature gradient. The structural analyses showed the Mg2Si phase as dominant and Bi2Mg3 located at grain boundaries. Bismuth doping enhanced ZT for every dopant concentration. ZT = 0:44 and ZT=0.38 were obtained for 3wt% and 2wt% at 770 K, respectively.

thermoelectric materials, magnesium silicide, bismuth doping, SHS, spark plasma sintering

Tomography allows embedding of one space in another, especially ℛ2→ℛ3, and observation of the nature of the volumetric internal composite structure. Now, not only a simple interpretation is expected of geometry defined via single thresholds of structures. The binary segmentation used for numerical struc-ture analysis requires more detailed presentation. This paper shows an example of image analysis tech-niques applied to study the homogeneity of two-phase material. Using tomography analysis, the results of the homogeneity of the SiC particles with 10vol.%, 20vol.%, 30vol.%, 40vol.% volumetric bulk density of Cu/SiC composites are presented. Finally, for two independent coordinate systems, the distribution of SiC particle masses and their total moments of inertia were determined. The results confirmed that for well-mixed composite powders the homogeneity of the reinforcing phase is expected in samples with a SiC volume near 30vol.%. In this case, segregation by translation and rotation of SiC particles in the matrix, during the sintering process is restricted.

Cu/SiC composite materials, image analysis, isotropy, uniformity

This paper presents the results of studies concerning the production and characterization of Al-SiC/W and Cu-SiC/W composite materials with a 30% volume fraction of reinforcing phase particles as well as the influence of corrosion and thermal shocks on the properties of selected metal matrix composites. Spark plasma sintering method (SPS) was applied for the purpose of producing these materials. In order to avoid the decomposition of SiC surface, SiC powder was coated with a thin tungsten layer using plasma vapour deposition (PVD) method. The obtained results were analysed by the effect of the corrosion and thermal shocks on materials density, hardness, bending strength, tribological and thermal properties. Qualitative X-ray analysis and observation of microstructure of sample surfaces after corrosion tests and thermal shocks were also conducted. The use of PVD technique allows us to obtain an evenly distributed layer of titanium with a constant thickness of 1.5 μm. It was found that adverse environmental conditions and increased temperature result in a change in the material behaviour in wear tests.

metal-matrix composites, silicon carbide, wear resistance, corrosion, thermal shocks

The thermal and oxidation resistance of elements found in the combustion boilers of power generation plants are some of the most important factors deciding their effectiveness. This paper shows the experimental results of the influence of NiCr-based material composition on the microstructure and phase changes occurring during the oxidation and corrosion process. NiCr alloy was modified by the addition of rhenium and aluminum oxide. Materials were densified using the spark plasma sintering method at a sintering temperature of 1050 °C. Oxidation tests conducted up to 1100 °C under synthetic airflow revealed the formation of a thin Cr2O3 layer protecting the material against in-depth oxidation. Results of electrochemical corrosion in a 0.5 M NaCl solution indicated a positive role of Re and Al2O3 addition, confirmed by low corrosion current density values in comparison to the other reference materials. According to the provided positive preliminary test results, we can conclude that a NiCr-Re-Al2O3 system in coating form was successfully obtained by the plasma spraying method.

NiCr, rhenium, aluminium oxide, metal matrix composites, oxidation, corrosion

The presented research investigation comprises the study of the mechanical properties of modified copper–silicon carbide composites at the micro- and macroscopic scale. The improvement of a copper–silicon carbide composite refers to the addition of a protective layer at the ceramic reinforcement in order to prevent the dissolution of silicon in the copper matrix. The macromechanical behaviour has been evaluated by the performance in a small punch test. The investigation has been carried out with samples with varying volume content of ceramic reinforcement and different protective layers of the silicon carbide particles. Moreover, the influence of temperature during the strength test has been studied. Next, the results have been referred to the interfacial bonding strength of Cu and SiC particles. SEM characterization of samples has been performed to link the composites' microstructure with the mechanical behaviour. Finally, the experimental results of the small punch test have been predicted via a numerical approach. Finite element analysis has been employed to reproduce the response of the composite specimen during the test. Satisfactory agreement with the experimental curve has been obtained.

metal matrix composites, silicon carbide, metallic layers deposition, small punch, interface strength, finite element method

Antimony telluride (Sb2Te3) is an intermetallic compound crystallizing in a hexagonal lattice with R-3m space group. It creates a c lose packed structure of an ABCABC type. As intrinsic semiconductor characterized by excellent electrical properties, Sb2Te3 is widely used as a low-temperature thermoelectric material. At the same time, due to unusual properties (strictly connected with the structure), antimony telluride exhibits nonlinear optical properties, including saturable absorption. Nanostructurization, elemental doping and possibilities of synthesis Sb2Te3 in various forms (polycrystalline, single crystal or thin film) are the most promising methods for improving thermoelectric properties of Sb2Te3.Applications of Sb2Te3 in optical devices (e.g. nonlinear modulator, in particular saturable absorbers for ultrafast lasers) are also interesting. The antimony telluride in form of bulk polycrystals and layers for thermoelectric and optoelectronic applications respectively were used. For optical applications thin layers of the material were formed and studied. Synthesis and structural characterization of Sb2Te3 were also presented here. The anisotropy (packed structure) and its influence on thermoelectric properties have been performed. Furthermore, preparation and characterization of Sb2Te3 thin films for optical uses have been also made

antimony telluride, thermoelectric materials, thin films, PVD magnetron sputtering, topological insulator

The presented paper investigates the relationship between the microstructure and thermal properties of copper–silicon carbide composites obtained through hot pressing (HP) and spark plasma sintering (SPS) techniques. The microstructural analysis showed a better densification in the case of composites sintered in the SPS process. TEM investigations revealed the presence of silicon in the area of metallic matrix in the region close to metal ceramic boundary. It is the product of silicon dissolving process in copper occurring at an elevated temperature. The Cu-SiC interface is significantly defected in composites obtained through the hot pressing method, which has a major influence on the thermal conductivity of materials.

metal matrix composites, silicon carbide, interface, spark plasma sintering, thermal conductivity

The main aim of this work was to construct and test an apparatus for characterization of high temperature thermoelectric modules to be used in thermoelectric generator (TEGs) applications. The idea of this apparatus is based on very precise measurements of heat fluxes passing through the thermoelectric (TE) module, at both its hot and cold sides. The electrical properties of the module, under different temperature and load conditions, were used to estimate efficiency of energy conversion based on electrical and thermal energy conservation analysis. The temperature of the cold side, Tc, was stabilized by a precise circulating thermostat (≤0.1°C) in a temperature range from 5°C to 90°C. The amount of heat absorbed by a coolant flowing through the heat sink was measured by the calibrated and certified heat flow meter with an accuracy better than 1%. The temperature of the hot side, Th, was forced to assumed temperature (Tmax = 450°C) by an electric heater with known power (Ph = 0–600 W) with ample thermal insulation. The electrical power was used in calculations. The TE module, heaters and cooling plate were placed in an adiabatic vacuum chamber. The load characteristics of the module were evaluated using an electronically controlled current source as a load. The apparatus may be used to determine the essential parameters of TE modules (open circuit voltage, Uoc, short circuit current, Isc, internal electrical resistance, Rint, thermal resistance, Rth, power density, and efficiency, η, as a function of Tc and Th). Several commercially available TE modules based on Bi2Te3 and Sb2Te3 alloys were tested. The measurements confirmed that the constructed apparatus was highly accurate, stable and yielded reproducible results; therefore, it is a reliable tool for the development of thermoelectric generators.

energy conversion efficiency, power generation, thermoelectric modules, performance characterization, heat recovery, renewable energy

In the case of the sintering of composite materials exhibiting mutual solubility, intermediate phases with varying concentrations of elements may appear during the densification process. Microstructural and structural changes, especially in the area of the interface, strongly influence mechanical or thermal properties [1]. A good example of such materials is nickel – silicon carbide composites. At elevated temperatures nickel reacts with silicon carbide, which causes total SiC decomposition, and as a result, new Ni-Si phases are formed and free carbon is precipitated within the reaction zone. In this work, nickel-silicon carbide composites were obtained via the Spark Plasma Sintering method. The detailed microstructural analyses using X-ray diffraction, Raman spectroscopy, scanning electron microscopy and transmission electron microscopy revealed the material’s evolution during sintering. To investigate the correlation between microstructure and properties of obtained materials, the mechanical test at three different length scales (in macro-, micro- and nanoscale) was conducted. To evaluate the strength of Ni-SiC composites at a macroscopic scale the uniaxial tensile and compression tests were employed. The sample deformation and failure mechanism for different stages of sintering were analyzed. The strength of the nickel-silicon carbide interface was determined by bending tests of micro-cantilever beams. Nanoindentation was used to evaluate the hardness of each composite component. The conducted research revealed a strong relation between mechanical strength and sintering conditions.