Investigation of the influence of processing parameters on the properties of bioceramic materials based on calcium hydroxyapatite and calcium phosphate obtained by different sintering technique

Kalcijum-fosfatni biokeramički materiali na bazi kalcijum-hidroksiapatita (HAP) i trikalcijum-fosfata (TCP), zahvaljujući hemijskom sastavu, biokompatibilnosti, bioaktivnosti i osteokonduktivnosti imaju značajnu ulogu pri izradi koštanih implanta. Guste nanostrukturne i kontrolisano porozne forme biokeramičkih materijala na bazi hidroksiapatita i kalcijum-fosfata imaju veliku primenu u maksiofacialnoj, dentalnoj i ortopedskoj praksi. Pažljiva kontrola faznog sastava, veličine zrna, oblika i dimenzija pora, kao i mehaničkih svojstava sinterovanih biokeramičkih materijala jesu ključni faktori za dobijanje implanata optimalnih svojstava. Danas je ogroman broj istraživanja baziran upravo na definisanju optimalnih uslova procesiranja sa ciljem da se dobiju gusti i kontrolisano porozni biokeramički monofazni kalcijum-hidroksiapatitni i bifazni materijali na bazi HAP i TCP, pogodni za ugradnju u ljudski organizam. Cilj ove doktorske disertacije bio je proučavanje procesa formiranja gustih nanostrukturnih biokeramičkih materijala na bazi kalcijum-hidroksiapatita i kalcijum-fosfata mikrotalasnim sinterovanjem, spark plazma sinterovanjem i toplim presovanjem, polazeći od stehiometrijskih i kalcijum deficitarnih nanočestičnih prahova kalcijum-hidroksiapatita dobijenih modifikovanim precipitacionim sintezama. Ispitan je uticaj svojstava polaznih prahova HAP i parametara procesiranja na mikrostukturne i fazne karakteristike, kao i na mehanička svojstva dobijenih gustih sinterovanih biokeramičkih materijala. Definisan je uticaj mikrostrukturnih parametara na žilavost i tvrdoću dobijenih monofaznih i bifaznih biokeramičkih materijala. Nanoindentacijom je utvrđen uticaj veličine zrna i faznog sastava na nanomehaničke karakteristike gustih mikro i nanostrukturnih materijala na bazi HAP i HAP/β-TCP. Svojstva materijala dobijenih mikrotalasnim sinterovanjem, spark plazma sinterovanjem i toplim presovanjem upoređeni su sa svojstvima materijala dobijenih konvencionalnim sinterovanjem.Calcium phosphate bioceramics materials based on hydroxyapatite (HAP) and tricalcium phosphate (TCP), due to their chemical composition, excellent biocompatibility, bioactivity and osteoconduction have received considerable attention as suitable bioceramics for the manufacture of osseous implants. Dense nanostructured and controlled porous forms of hydroxyapatite and calcium phosphate are often used as reparation material in maxillofacial, dental and orthopedic surgery. Careful control of phase composition, grain size and shape and size of pores of sintered bioceramic materials in accordance with good mechanical properties can be key issue for a successful implant. A large number of studies were focused on determining the optimal conditions required to obtain dense or controlled porous HAP and HAP/TCP form suitable for incorporation in living bone. The aim of this PhD thesis was to investigate the processing of dense nanostructured pure hydroxyapatite and biphasic HAP/TCP bioceramics by microwave sintering, spark plasma sintering and hot pressing, starting from stoichiometric and calcium deficient nanosized HAP powders, obtained by two modified chemical precipitation syntheses. The effects of the processing conditions on the microstructure, phase composition and mechanical properties of the obtained materials based on HAP and TCP were investigated. The influence of microstructure and phase composition on the fracture toughness and hardness of sintered HAP and HAP/TCP bioceramics was also defined. The influence of the grain size and phase composition on the nanomechanical behaviour of dense nano and microstructured HAP and biphasic HAP/β-TCP bioceramic materials by nanoindentation was also investigated. The results obtained by microwave sintering, spark plasma sintering and hot pressing were compared with those obtained by conventional sintering methods..

Arsenic removal from water using low-cost adsorbents: A comparative study

Inorganic arsenic removal from water using low-cost adsorbents is presented in this paper. Selective removal of As(III) and As(V) from water was performed with natural materials (zeolite, bentonite, sepiolite, pyrolusite and limonite) and industrial by-products (waste filter sand as a water treatment residual and blast furnace slag from steel production); all inexpensive and locally available. Kinetic and equilibrium studies were realized using batch system techniques under conditions that are likely to occur in real water treatment systems. The natural zeolite and the industrial by-products were found to be good and inexpensive sorbents for arsenic while bentonite and sepiolite clays showed little affinity towards arsenic. The highest maximum sorption capacities were obtained for natural zeolite, 4.07 mg As(V) g-1, and waste iron slag, 4.04 mg As(V) g-1

Investigation of the influence of processing parameters on the properties of bioceramic materials based on calcium hydroxyapatite and calcium phosphate obtained by different sintering technique

Kalcijum-fosfatni biokeramički materiali na bazi kalcijum-hidroksiapatita (HAP) i trikalcijum-fosfata (TCP), zahvaljujući hemijskom sastavu, biokompatibilnosti, bioaktivnosti i osteokonduktivnosti imaju značajnu ulogu pri izradi koštanih implanta. Guste nanostrukturne i kontrolisano porozne forme biokeramičkih materijala na bazi hidroksiapatita i kalcijum-fosfata imaju veliku primenu u maksiofacialnoj, dentalnoj i ortopedskoj praksi. Pažljiva kontrola faznog sastava, veličine zrna, oblika i dimenzija pora, kao i mehaničkih svojstava sinterovanih biokeramičkih materijala jesu ključni faktori za dobijanje implanata optimalnih svojstava. Danas je ogroman broj istraživanja baziran upravo na definisanju optimalnih uslova procesiranja sa ciljem da se dobiju gusti i kontrolisano porozni biokeramički monofazni kalcijum-hidroksiapatitni i bifazni materijali na bazi HAP i TCP, pogodni za ugradnju u ljudski organizam. Cilj ove doktorske disertacije bio je proučavanje procesa formiranja gustih nanostrukturnih biokeramičkih materijala na bazi kalcijum-hidroksiapatita i kalcijum-fosfata mikrotalasnim sinterovanjem, spark plazma sinterovanjem i toplim presovanjem, polazeći od stehiometrijskih i kalcijum deficitarnih nanočestičnih prahova kalcijum-hidroksiapatita dobijenih modifikovanim precipitacionim sintezama. Ispitan je uticaj svojstava polaznih prahova HAP i parametara procesiranja na mikrostukturne i fazne karakteristike, kao i na mehanička svojstva dobijenih gustih sinterovanih biokeramičkih materijala. Definisan je uticaj mikrostrukturnih parametara na žilavost i tvrdoću dobijenih monofaznih i bifaznih biokeramičkih materijala. Nanoindentacijom je utvrđen uticaj veličine zrna i faznog sastava na nanomehaničke karakteristike gustih mikro i nanostrukturnih materijala na bazi HAP i HAP/β-TCP. Svojstva materijala dobijenih mikrotalasnim sinterovanjem, spark plazma sinterovanjem i toplim presovanjem upoređeni su sa svojstvima materijala dobijenih konvencionalnim sinterovanjem.Calcium phosphate bioceramics materials based on hydroxyapatite (HAP) and tricalcium phosphate (TCP), due to their chemical composition, excellent biocompatibility, bioactivity and osteoconduction have received considerable attention as suitable bioceramics for the manufacture of osseous implants. Dense nanostructured and controlled porous forms of hydroxyapatite and calcium phosphate are often used as reparation material in maxillofacial, dental and orthopedic surgery. Careful control of phase composition, grain size and shape and size of pores of sintered bioceramic materials in accordance with good mechanical properties can be key issue for a successful implant. A large number of studies were focused on determining the optimal conditions required to obtain dense or controlled porous HAP and HAP/TCP form suitable for incorporation in living bone. The aim of this PhD thesis was to investigate the processing of dense nanostructured pure hydroxyapatite and biphasic HAP/TCP bioceramics by microwave sintering, spark plasma sintering and hot pressing, starting from stoichiometric and calcium deficient nanosized HAP powders, obtained by two modified chemical precipitation syntheses. The effects of the processing conditions on the microstructure, phase composition and mechanical properties of the obtained materials based on HAP and TCP were investigated. The influence of microstructure and phase composition on the fracture toughness and hardness of sintered HAP and HAP/TCP bioceramics was also defined. The influence of the grain size and phase composition on the nanomechanical behaviour of dense nano and microstructured HAP and biphasic HAP/β-TCP bioceramic materials by nanoindentation was also investigated. The results obtained by microwave sintering, spark plasma sintering and hot pressing were compared with those obtained by conventional sintering methods..

Processing of dense nanostructured HAP ceramics by sintering and hot pressing

A nanosized HAP powder was sintered and hot pressed, in order to obtain dense HAP ceramics. In a first series of experiments, the powder was isostatically pressed into uniform green compacts and sintered at temperatures ranging from 1000 degrees C to 1200 degrees C in air atmosphere for different times. In a second series, the isostatically pressed green compacts were hot pressed in argon atmosphere at 900 degrees C, 950 degrees C and 1000 degrees C. The SEM micrograph of the sample sintered at 1200 degrees C for 2 h showed a uniform 3 mu m mean grain size dense microstructure. In the case of hot pressed HAP compacts, full dense, translucent nanostructures were obtained having mean grain size below 100 nm and improved mechanical properties. With the grain size decreasing from 3 mu m to 50 nm, the fracture toughness of pure HAP ceramics increased from 0.28 MPa m(1/2) to 1.52 MPa m(1/2)

Processing and properties of scaffolds based on calcium phosphate doped with magnesium, copper and zinc-ions coated with gelatin

The main goal of this study was to examine the possibility for obtaining macroporous scaffolds with defined properties based on calcium phosphate doped with magnesium, copper and zinc ions, coated with gelatin, which would potentially provide controlled conditions for the formation of new bone tissue after implantation. As a first, multi-doped nanoparticles of hydroxyapatite (HAp), which represents the main component of the inorganic part of bone tissue, was synthesized by autoclaving the precursor solution obtained at a Ca/P molar ratio of 1.52. Calcium in the initial solution was partially replaced by ions of magnesium (5 mol.%), copper (0.4 mol.%) and zinc (0.4 mol.%). Obtained powder was further calcinated, the changes in the morphology of the powders during calcination at 1000 ̊ C were reflected in the transition of spherically agglomerated needle-like nanoparticles of the multi-doped hydroxy-apatite powder to a spherical grained morphology. Macroporous bioceramic structures were obtained using the sponge replica method, green macroporous samples made of calcinated multi-doped powder, polyvinyl alcohol and water were sintered at 1.370°Ϲ and 1.430°Ϲ. X-ray diffraction analysis deter-mined that the presence of magnesium in the structure of hydroxyapatite favors the phase transformation of HAp into b-tricalcium-phosphate (b-TCP), which contributed to the formation of the biphasic HAp/b-TCP system during the calcination of the powders, but also during the sintering of macroporous beads. Examination of the antimicrobial activity of the obtained macroporous supports against E. coli showed a more effective degree of inhibition compared to S. aureus. A significant increase in the compressive strength of sintered macroporous scaffolds was obtained after the formation of coating based on 7.5% gelatin solution

Characterization of sepiolite by inverse gas chromatography at infinite and finite surface coverage

The adsorption properties of sepiolite from Andrici, Serbia, were studied by inverse gas chromatography at zero and finite surface coverage between 483 and 513 K. The thermodynamic parameters (free energy, enthalpy, entropy) of adsorption, as well as the dispersive and specific components of the free energy of adsorption and the acid/base of the solid were calculated from the IGC data at zero coverage. The K(D)/K(A) ratio indicated basis character. The adsorption isotherms were used to estimate the specific surface area, isosteric heat of adsorption and the adsorption energy distribution for the adsorption of organic molecules. (C) 2008 Elsevier B.V. All rights reserved

Microwave sintering of fine grained HAP and HAP/TCP bioceramics

The effect of microwave sintering conditions on the microstructure, phase composition and mechanical properties of materials based on hydroxyapatite (HAP) and tricalcium phosphate (TCP) was investigated. Fine grained monophase HAP and biphasic HAP/TCP biomaterials were processed starting from stoichiometric and calcium deficient nanosized HAP powders. The HAP samples microwave (MAT) sintered for 15 min at 900 degrees C, with average grain size of 130 nm, showed better densification, higher density and certainly higher hardness and fracture toughness than samples conventionally sintered for 2 h at the same temperature. By comparing MW sintered HAP and HAP/TCP samples, it was concluded that pure HAP ceramics have superior mechanical properties. For monophase MW sintered HAP samples, the decrease in the grain size from 1.59 mu m to 130 nm led to an increase in the fracture toughness from 0.85 MPa m(1/2) to 1.3 MPa m(1/2). (C) 2009 Elsevier Ltd and Techna Group S.r.l. All rights reserved

Double-layer bioactive glass coatings obtained by pulsed laser deposition

Pulsed laser deposition was used to obtain functionally graded bioactive glass coatings on titanium substrates. An UV KrF* (lambda=248 nm, tau gt 7 ns) excimer laser was used for the multi-pulse irradiation of the targets. The depositions were performed in oxygen while keeping substrate temperature at 400 degrees C. We used sintered glass targets in the system SiO2-Na2O-K2O-CaO-MgO-P2O5 that differed in SiO2 content, which was either 57 wt.% (6P57) or 61 wt.% (6P61). A glass 6P61 was used as the first layer in direct contact with the metallic substrate, while the outer bioactive layer was made of glass 6P57. Both the bioactive coatings and the bulk glasses were analyzed by Fourier transform infrared spectrometry (FTIR), grazing incidence X-ray diffraction (GIXRD), and scanning electron microscopy (SEM). The FTIR spectra of the glass powders and glass coatings showed the main vibration modes of the Si-O-Si groups. GIXRD analysis confirmed that the glass coatings had an amorphous structure. The SEM micrographs of the glass coatings showed the films to consist of droplets with diameters ranging from 0.2 to 5 Pm. SEM was used to determine the rate of apatite formation on the coating when exposed to simulated body fluid (SBF) solution for 7 days. We demonstrated that pulsed laser deposition leads to good glass-metal adhesion on the substrate and well attached bioactive particles on the surface. We consider therefore this method appropriate for forming implants that can develop an apatite layer after immersion in SBF

Double-layer bioactive glass coatings obtained by pulsed laser deposition

Pulsed laser deposition was used to obtain functionally graded bioactive glass coatings on titanium substrates. An UV KrF* (lambda=248 nm, tau GT 7 ns) excimer laser was used for the multi-pulse irradiation of the targets. The depositions were performed in oxygen while keeping substrate temperature at 400 degrees C. We used sintered glass targets in the system SiO2-Na2O-K2O-CaO-MgO-P2O5 that differed in SiO2 content, which was either 57 wt.% (6P57) or 61 wt.% (6P61). A glass 6P61 was used as the first layer in direct contact with the metallic substrate, while the outer bioactive layer was made of glass 6P57. Both the bioactive coatings and the bulk glasses were analyzed by Fourier transform infrared spectrometry (FTIR), grazing incidence X-ray diffraction (GIXRD), and scanning electron microscopy (SEM). The FTIR spectra of the glass powders and glass coatings showed the main vibration modes of the Si-O-Si groups. GIXRD analysis confirmed that the glass coatings had an amorphous structure. The SEM micrographs of the glass coatings showed the films to consist of droplets with diameters ranging from 0.2 to 5 Pm. SEM was used to determine the rate of apatite formation on the coating when exposed to simulated body fluid (SBF) solution for 7 days. We demonstrated that pulsed laser deposition leads to good glass-metal adhesion on the substrate and well attached bioactive particles on the surface. We consider therefore this method appropriate for forming implants that can develop an apatite layer after immersion in SBF.20th International Symposium on Ceramics in Medicine, Oct 24-26, 2007, Nantes, Franc

Synthesis and properties of nano-hydroxyapatite/poly (methacrylic acid) composite hydrogels

Goals. The goal of this study was a development of biocompatible composite hydrogels, structurally similar to native bone tissue, by incorporation of ~60 wt % of calcium hydroxyapatite (HA) into a matrix of hydrogels. Also, a possibility to control swelling kinetic and equilibrium swelling degree (SDeq) of hydrogels, by altering the degree of neutralization of the precursor (DN) was examined. Methods. Composite hydrogels, based on HA and poly(methacrylic acid) (PMAA), were synthesized by free-radical polymerization with different DN. Theoretical content of HA in synthesized composites was 60 wt %. Composites were synthesized by methods of dynamic mechanical analysis and scanning electron microscopy. SDeq and swelling kinetic were examined in distilled water and simulated body fluid. Results. Morphological observations revealed uniform distribution and strong bond of spherical HA particles within the polymer matrix. Swelling analyses demonstrated that SDeq is directly proportional to DN, while rheological examinations indicated inverse proportion between DN and storage modulus, but due to the HA particles inclusion, mechanical properties of composites were significantly better compared to monophasic PMAA hydrogels. Significance. Simple method of synthesis of composite hydrogels with high content of filler nanoparticles is presented. Incorporation of HA nanoparticles significantly improved mechanical properties of hydrogels, while at the same time was demonstrated a possibility to control swelling kinetic by influencing the DN