Papers by Author: Miroslav Hnatko

Abstract: The study deals with the development of highly porous undegradable ceramics based on silicon nitride as potential replacement of trabecular bone. These materials were produced using replication method with polyurethane foams as pore-forming agents to achieve similar porous structure to trabecular bone. Prepared porous ceramics had a bimodal pore structure with macro-pores larger than 200 μm and micro-pores smaller than 1 μm in diameter, which are necessary for tissue ingrowths, cell adhesion, adsorption of biological metabolites and nutrition delivery in organism. The microstructure and local mechanical properties (Young’s modulus and Yield strength) were evaluated and compared with human trabecular bone. Results showed that studied porous materials have satisfactory porosity and pore sizes for trabecular bone replacement. Young’s modulus of bone was 12.6 ± 2.23 GPa and porous silicon nitride samples ranged from 10.9 ± 3.38 GPa to 12.9 ± 1.13 GPa. The values of Yield strength of trabecular bone was determined as 493 ± 30.7 MPa and the values of porous samples varied from 250 ± 19.3 MPa to 558 ± 36.5 MPa. Young’s modulus and Yield strength increase with increasing of the pre-sintering temperature and multiple infiltrations.

Abstract: Local mechanical properties, particularly the hardness and Youngs modulus of highly porous silicon nitride based foams were studied in this work. Silicon nitride foams were prepared using polyurethane foam replication method to obtain appropriate cellular structure suitable for bio-application. Two types of the polyurethane foams were used (with average pore size 0.48 mm and 0.62 mm). Some of these samples were prepared by single or multiple infiltrations. The effects of structures, temperature of calcination, volume fraction of Si₃N₄ powder and number of the infiltrations on the local mechanical properties were investigated. The Youngs modulus of studied samples range from 12 to 46 GPa at the macroscopic scale measured by resonant frequency technique and from 10 to 28 GPa at the microscopic scale measured by instrumented indentation. Results showed increase of the hardness and Youngs modulus with increasing of the calcination temperature, with increasing of the number of infiltrations and also with increasing of volume fraction of Si₃N₄ powder in suspension. The results obtained from nanoindentation carry out lower values in comparison with the values measured by resonant frequency technique.

Abstract: Mechanical properties of porous silicon nitride prepared by two different processing routes have been studied. Depth sensing methods was used to measure the hardness and elastic modulus of experimental materials. The results were compared with the hardness and elastic modulus of trabecular bone in order to find out porous ceramics with properties close to that of trabecular bone. Material prepared by infiltration of polyurethane sponge exhibited properties close to the properties of bone and it is the potential material for further investigation in the bioapplication field.

Abstract: The corrosion resistance of liquid phase sintered (LPS) alumina ceramics in aqueous environments strongly depends on composition and chemistry of grain boundary glass formed during sintering. The chemical durability of model alumino-silicate glasses with various contents of CaO in aqueous solutions was therefore evaluated. Prepared glasses were corroded under hydrothermal conditions in deionized water under static conditions. The examination of surface morphology of corroded specimens after the contact with deionized water, together with the analysis of corrosion solution provided information on mechanism of dissolution of grain boundary glasses in LPS aluminas and confirmed that dissolution process is hindered due to saturation of solution with respect to leached elements. The initial dissolution rates for studied glasses were determined. The results are applicable for optimization and enhancement of corrosion resistance of LPS alumina under hydrothermal conditions.

Abstract: Corrosion resistance of solid state (SSS) and liquid phase sintered (LPS) alumina under hydrothermal conditions (subcritical water and sodium chloride solution at temperatures up to 290 °C, and pressures up to 7 MPa) was evaluated. The influence of sintering additives as well as the conditions of the test (temperature, corrosion medium) on dissolution of ceramics was studied. For evaluation of the corrosion mechanisms special attention was paid to determination of the eluate chemistry combined with the chemical and phase analysis of corroded surfaces. Corrosion of LPS alumina in both media was controlled by dissolution of calcium aluminosilicate grain boundary glass. Corrosion rates of SSS ceramics were several times lower and were largely controlled by dissolution of highly resistant alumina matrix. Corrosion of the ceramics was moderately faster in sodium chloride solution. The data are supplemented by calculations of phase equilibria in the corrosion solutions.

Abstract: Two alumina based ceramics with 99.99 % and 95 % of Al2O3 were evaluated after dissolution in an aqueous solution containing 0.5 mol/l NaCl at temperatures of 150 and 200 °C. The weight loss of liquid phase sintered alumina was mainly attributed to congruent dissolution of SiO2 and CaO from grain-boundary amorphous film, which is accelerated at higher temperature, accompanied by precipitation of silicaceous phases from oversaturated solution at 200 °C. Pure polycrystalline alumina corroded by loss of alumina grains, which do not dissolve in the corrosion media.

Abstract: The present work studies the corrosion of three most widely used types of structural ceramics – silicon nitride, solid state sintered alumina and liquid phase sintered alumina – in 3 % aqueous solutions of sodium chloride at temperatures up to 290 °C and pressures up to 7 MPa. The corrosion of silicon nitride was controlled by attack of Si3N4 matrix grains, while yttrium oxynitride amorphous grain boundary phase was corrosion resistant. Corrosion of Si3N4 in reference media -distilled water - at 290 °C was characteristic by formation of passivation layer, which hindered further dissolution of silicon nitride matrix. The presence of sodium chloride resulted in formation of discontinuous layer of corrosion products, resulting in more severe corrosion than in distilled water. The corrosion of liquid phase sintered alumina was mainly attributed to congruent dissolution of SiO2 and CaO from grain-boundary amorphous film, which was accelerated at higher temperature, and accompanied by precipitation of siliceous phases from oversaturated solution at 200 °C. Pure polycrystalline alumina corroded by loss of alumina grains, which did not dissolve in the corrosion media. The corrosion impaired significantly the fracture strength of silicon nitride, creating new, corrosion related defects at the surface, while the influence of corrosion on fracture strength of polycrystalline aluminas was negligible.

Abstract: Bending and contact strength of a carbon derived in-situ reinforced Si3N4-SiC micro/nanocomposite have been investigated. Four-point bending strength was measured using specimens with different effective volume and Weibull statistical analysis has been used for characterization of the strength values in the form of characteristic strength and Weibull modulus. The characteristic strength values of the investigated composite were σ0 = 675 MPa and σ0 = 832 MPa with the Weibull modulus of 6,4 and 8,6 for the specimens with effective volume 15,9 mm3 and 1,28 mm3 respectively. Contact strength of the investigated material was carried out using sphere on sphere and roller on roller methods and the obtained results are σ0S = 1997 MPa, σ0R = 1242 MPa, and mS = 17,1 mR = 6. Fracture origins in the specimens with effective volume of 15.9 mm3 tested in four-point bending were surface and volume located technological defects with dimensions from 10 μm to 180 μm, mainly in the form of clusters of pores and large SiC grains. Fracture mirror sizes were measured and the mirror constant was calculated. Fracture origins in the specimens with effective volume of 1.28 mm3 tested in four-point bending were surface (subsurface) defects with the same type as for the specimens with a higher effective volume. The fracture during the contact strength test „roller/roller“ has been initiated under the surface of the specimens and during the contact strength test „sphere/sphere“ by creation and growth of the cone cracks to critical size.

Abstract: Si3N4/SiC nanocomposite material with yttria as sintering additive was prepared by hot pressing method. SiC nanoinclusions were produced by in situ reaction between SiO2 and C during the sintering process. The homogenous microstructure of hot pressed samples contained fine Si3N4 grains with average diameter of 200 nm. The post-sintering treatment at 1750°C for 26 and 70 hours significantly changed the microstructure of Si3N4/SiC composites. The difference between the average grain size of hot pressed sample and sample treated for 70 hours is approx. 300 %. In sake of this fact the mechanical properties (KIC, HV1) were not changed significantly. The largest differences between the mechanical properties of hot pressed and annealed samples were only 8 %.

Abstract: Silicon nitride - silicon carbide nanocomposite has been prepared by an in-situ method that utilizes formation of SiC nanograins by C+ SiO2 carbothermal reduction during the sintering process. The developed C/SiO2 derived nanocomposite consists of a silicon nitride matrix with an average Si3N4 matrix grain diameter of approximately 200 nm with inter- and intra- granular SiC inclusions with sizes of approximately 150 nm and 40 nm, respectively. The mean value of room temperature 4-point bending strength is 670 MPa with the Weibull modulus of 7.5 and indentation fracture toughness of 7.4 MPa.m1/2. The creep behaviour was investigated in bending at temperatures from 1200°C to 1450°C, under stresses ranking from 50 to 150 MPa in air. A significantly enhanced creep resistance was achieved by the incorporation of SiC nanoparticles into the matrix. The inserts machined from this composite have three times longer life time compared to those available on the market.