Papers by Author: Konstantinos M. Paraskevopoulos

Abstract: This paper presents the effect of adding nanoparticles SiO₂ and Al₂O₃ in the cement with respect to mechanical, physical and structural properties. Nanoparticles were chosen for the development of nanocomposite building materials with high mechanical strength, durability and low permeability. Correspondingly, the cement used is Portland Cement CEMI42.5N. Five compositions have been prepared, a reference sample (OPC) and pastes with different nanoparticles. Nanoparticles of SiO₂ and Al₂O₃ were added in 1.5% and 3% by weight of cement and the produced samples were tested after 7, 28, 90 and 120 days of curing. All the samples, in every hydration period, were tested for compressive strength, while their open porosity was measured and their microstructure was examined by means of infrared spectroscopy. Furthermore, for certain hydration periods, the chemical and elemental composition of the samples was evaluated by means of X-ray diffraction and scanning electron microscopy. The samples were also evaluated for capillary water absorption and shrinkage, while thermal analysis was performed for specific samples. The comprehensive analysis revealed a positive effect, in terms of structural properties, of nanoparticle admixture in cementitious systems. The addition of nanoparticles influence the workability of the composites and contributes to the formation of crystallization nuclei, which in turn enhance the durability of the material. Interestingly, it was found that high concentration of nanoAl₂O₃ in the admixure, results in high mechanical properties. Highlights: Different analytical techniques were combined in order to holistically test nanomodified cement pastes. nanoalumina is systematically tested as additive in cement pastes.

Abstract: We Report on the Structural and Vibrational Properties of the X = 0.11 and X = 0.33 Compositions of a New Class of Nanostructured Thermoelectric System (PbTe)1-X(PbSnS2)x by Means of X-Ray Diffraction, Scanning and Transmission Electron Microscopy and Infrared Reflectivity. both Compositions Are Phase Separated, where Pbsns2 Self-Segregates from Pbte to Form Features with Dimensions Ranging from Tens of Micrometers to Tens of Nanometers. Effective Medium Approximation Was Used in Order to Determine the Volume Fraction and the Dielectric Function of the Nanoscale Pbsns2 Embedded in Pbte. by Comparing the Phonon Parameters of the Nanoscale Pbsns2 and Bulk Pbsns2 Single Crystals, we Concluded that Phonon Confinement Effects and Bilayer Thickness Anisotropy within the Pbsns2 Nanostructures Embedded within Pbte Are Responsible for the Observed Variations in the Frequencies of the Shear and the Compression Modes Not Observed in Pure Crystals of Pbsns2.

Abstract: In most biphasic composite systems consisting of sol-gel derived bioactive glass and a second system that is usually used as a reinforcing agent, thorough stirring is necessary to prevent the precipitation of the grains of the second system. Consequently, the aim of this work is to investigate the impact of various stirring rates on the crystallinity and bioactivity of a bioactive glass in the system 58S. Sol-gel-derived bioactive glass (58S) was produced as described in literature. During the gelation, stirring rates of 0, 200, 400, 600 and 800 rpms were applied producing, respectively, the corresponding glass powders. The in vitro bioactivity of the powders was tested in Simulated Body Fluid (SBF) for various immersion times, while the solution was renewed after 6h, 24h and then every 2 days. Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM) and X-ray Diffractometry (XRD) were used to characterize all materials before and after immersion in SBF solution. FTIR and XRD measurements of all powders revealed mainly the formation of an amorphous glass, while the main crystalline phase was identified to be Ca2SiO4. After immersion in SBF solution for 12h, SEM microphotographs revealed apatite formation on the surface of all samples, while FTIR and XRD confirmed the aforementioned findings. Furthermore, since EDS analysis proved a mean molar Ca/P ratio of about1.7 after 6 days of immersion of all samples- besides those stirred at 400 and 600rpm- it can be assumed that a thick apatite layer was formed covering the whole surface.

Abstract: The clinical use of plasma-sprayed hydroxyapatite (HA) coatings on metal implants has been widely investigated as the HA coating can achieve the firm and direct biological fixation with the surrounding bone tissue. It is shown in previous studies that the mechanical properties of HA coatings are improved by the addition of ZrO2 particles during the deposition of the coating on the substrate. Subsequently, the cohesive and adhesive strengths of plasma-sprayed hydroxyapatite (HA) coatings were strengthened by the ZrO2 particles addition as a reinforcing agent in the HA coating (HA+ZrO2 composite coating). The aim of the present work is to investigate and evaluate the in vitro bioactivity assessment of HA and HA/ZrO2 coatings, on stainless steel substrate, soaked in c-SBF, in order to study and compare their biological responses. The coatings were produced using vapor plasma spraying (VPS). The characterization of the surface of the coatings before and after soaking in SBF solution was performed using Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM) and X-ray Diffraction analysis (XRD). All samples were smoothed before insertion in the medium and the in vitro bioactivity of all coating samples was tested in conventional Simulated Body Fluid (c-SBF) solution for various immersion times.

Abstract: Scaffold-based tooth engineering is currently the most popular approach towards replacing dental tissues or even engineering a bio-tooth. Although, various scaffold materials have been employed in tooth regeneration, the scaffold-based tooth design has, until now, achieved only limited success. Recently, bioactive Mg-based ceramics have attracted interest as Mg plays an important role on skeletal metabolism and affects the quality and structure of hard dental tissues. Mg has been reported to improve the mechanical properties of calcium phosphate ceramics, control biodegradation rate and stabilize the cell-material interface improving cell attachment and growth. The aim of this study was the development of an experimental Mg-based ceramic material, with enhanced bioactivity and adequate mechanical properties, in order to be potentially used in dental tissue regeneration. The Mg-based ceramic was prepared by the sol-gel method, while the stabilization was performed at 1300, 1400 and 1450oC in order a fully crystalline material to be obtained. The characterization of the materials -before and after immersion is Simulated Body Fluid (SBF)- was performed by Fourier Tranform Infrared Spectroscopy (FTIR), X-Ray Diffractometry (XRD) and Scanning Electron Microscopy associated with an EDS analyzer (SEM-EDS), while the flexural strength of uniaxially pressed pellets was measured using a universal testing machine for 3- point bending tests (Instron 3344). FTIR spectra and XRD patterns of all powder samples before immersion in SBF solution confirmed the presence of three crystalline phases; akermanite, merwinite and diopside. The onset of apatite formation on the surface of all powders was observed even after three days of immersion, while the apatite formation on the surface of the sintered pellets was slightly delayed. Flexural strength values were in the range of 30Mpa. In conclusion, Mg-based glass-ceramics attain adequate mechanical integrity and high rate of bioactivity and could be potentially used in the construction of ceramic scaffolds for dental tissue regeneration.

Abstract: Chitin is a polysaccharide abundant in nature. Its’ deacetylation product-chitosan- in combination with gelatin (collagen product) is commonly used as biopolymer scaffold for tissue engineering. The aim of this study was to investigate diffrerences in surface characteristics of chitin (CHN CCS) and chitosan –gelatin (CHS-G CCS) composite ceramic scaffolds (CCS), during their incubation in culture medium (DMEM) with or without human periodontal ligament fibroblasts (HPDLF). CHN CCS and CHS- G CCS, with pore size 70-200μm, were fabricated on the surface of ceramic disks, being coated with a mixture of bioactive glass – ceramic (1:1 wt). Three CCSs of each type were constructed. Each CCS was incubated at 37 °C up to 10 days, either only in DMEM supplemented with 10% FCS or in DMEM with the presence of 10⁵ HPDLF. SEM microphotographs and EDS analysis, before and after incubation, were used to investigate CCSs’ surface alterations. Before incubation, all type of CCSs appeared to be macro porous with high interconnectivity. Exposed to incubation, CHN CCSs’ surface porosity seemed to be rapidly reduced and a rough surface without pores was observed with or without HPDLF. Attached HPDLF were rarely detected. CHS-G CCSs appeared to retain surface porosity in DMEM without cells. In HPDLF culture an almost uniform surface with organic aggregates and attached cells was observed. Until day 10, HPDLF could only be detected at CHS-G CCS’s surface. Conclusion: SEM microphotographs observations indicate that CHN CCSs’ incubation in DMEM led in early and rapid coalescence of surface pores, thus inhibiting HPDLF attachment. HPDLF attachment on CHS-G CCSs confirm the beneficial role of gelatin, while differences in CHS-G CCSs’ surface with and without HPDLF culture indicate that not only sedimentation of medium's ingredients, but cell attachment and function could decrease surface’s porosity, affecting consequently HPDLF proliferation.

Abstract: End temperature of the firing cycle, during processing of dental ceramics, directs the interaction of both sintering and crystallization pathways, tailoring physicochemical properties and bioactivity. Thus, the purpose of the present study was to investigate the influence of end temperature over the structural properties and composition, along with the bioactive behavior of dental porcelain, modified by bioactive glass. Sol-gel derived specimens of bioactive glass (58S)- commercial dental porcelain composites synthesized (BP) and underwent firing cycles at the crystallization temperature (Tc=1040oC) and the temperature just below the melting range (Tm=1080oC), as the composite material. The recommended temperature for the commercial porcelain (Ta=930oC) was examined, too. All specimens were characterized using X-ray diffraction (XRD), Fourier Transform Infrared spectroscopy (FTIR), Scanning Electron Microscopy (SEM). The assessment of bioactivity was performed in vitro, via the detection of apatite layer development. The well-defined particles, observed by SEM, at 930oC, developed contact formation during the stage of neck growth at 1040oC and 1080oC, indicating the initiation of sintering process. Increasing temperature, the complex porei network became smoother, while spherical and closed porei were evident. FTIR revealed the predominance of wollastonite at the increased temperatures, along with the appearance of cristobalite, while XRD confirmed the results. Finally, the in vitro tests evidenced the bioactivity of the specimens independently of the final temperature, though the increased temperature caused delayed apatite layer formation on their surface. The, microstructural and chemical evolution of the studied composite is temperature-dependent. Increased temperature favored the sintering process initiation, along with the surface crystallization, which delays bioactivity.

Abstract: The aim of this work was to improve a newly developed family of glass-ceramic composite materials by incorporating silver ions in the ceramic structure, thus developing new Ag-doped materials with the ability of showing antibacterial activity for dental applications. Two different sol-gel methodologies were applied for the fabrication of colorless, homogenous and chemically durable materials which can slowly release silver ion for relatively long periods. Both methods led to the successful development of Ag-doped glass-ceramics with silver ions incorporated in the structure that can slowly release in buffer solution, during a period of 45 days. The potential, application of these materials involve the development of bioactive surfaces on dental substrates which can seal the marginal gap creating a bacterial free environment finally supporting the success of dental restorations.

Abstract: High strength of Yttria stabilized tetragonal zirconia polycrystal (Y-TZP) zirconia ceramics are sensitive to low temperature degradation (LTD) that leads to exaggerated tetragonal to monoclinic transformation and a surface to depth propagating degradation that diminishes their mechanical properties. In vitro tests for accelerating ageing have been proposed for the prediction of zirconia ceramics clinical performance. The aim of the present work was to investigate the in vitro ageing of a cold isostatic-pressed zirconia ceramic for all ceramic restorations. Bar-shaped specimens milled from a zirconia block (Ivoclar IPS e.max ZirCAD) were sintered to full density, mirror-polished and cut into two equal pieces. One piece was used as control while the other was subsequently aged (steam 134°C / 2 bars / 10 hours). Atomic Force Microscopy (AFM) was used to evaluate the surface profile and the micro-structural features before and after ageing. Fourier Transform Infrared Spectroscopy (FTIR) and X-Ray Diffraction Analysis (XRD) were used to determine the degree of the m-ZrO₂ transformation. Ageing resulted in an increase of the surface roughness, while the formation of monoclinic spots on the surface of the specimens was verified by surface uplifts in the AFM images. The peaks of the m-phase were clearly observed in the FTIR spectra while an average increase of 16% w.t. of the m-ZrO₂ phase was recorded by XRD. Although, no sound lifetime predictions can be made from accelerated tests, based on the ISO standard that imposes that the m-phase should not exceed 25% wt after 5h at 134 °C and 2 bar pressure , it can be concluded that the tested ceramic resisted an extreme transformation that could negatively affect its clinical performance.

Abstract: Results of the present study provide strong indications towards the effective application of the 110oC Thermoluminescence (TL) peak in discriminating between different bioactive responses for the case of the 58S bioactive glass. The in vitro bioactivity of this glass in the form of powder in SBF solution was tested for various immersion times, ranging between 0 and 6 days. This TL peak is ubiquitously present in all 58S samples, for all immersion times. The intensity of the110oC TL peak was proven to be very sensitive to the different bioactive responses, indicating a strongly decreasing pattern with increasing immersion time in SBF, easily identifying thus the loss of silica. This loss is reflected to the decrease of the 110oC TL peak intensity, which appears to be fast even for the shorter immersion times. The 110oC TL glow peak intensity and sensitization could also be yielding a time scale regarding the beginning of some among the several stages included in the bioactivity sequence.