Eric Champion

Calcium phosphate apatites with variable Ca/P atomic ratio I. Synthesis, characterisation and thermal stability of powders.

Single phased apatitic calcium phosphate powders Ca(10-x)(PO4)(6-x)(HPO4)x(OH)(2-x) with Ca/P molar ratio ranging from 1.5 to 1.667 (0 < or = x < or = 1) were synthesised using wet method. Outside this compositional range the powders were biphasic mixtures composed of a calcium phosphate apatite and CaHPO4 (Ca/P < 1.5) or Ca(OH)2 (Ca/P > 1.667). Temperature and pH of synthesis were the preponderant parameters for the control of the precipitate composition. The precise determination of the chemical composition requires the use of several complementary techniques and thermal treatments of powders. These techniques include high resolution and high temperature X-ray diffractometry and FTIR spectroscopy and show that very small variations of the Ca/P molar ratio of the powder lead to great changes in powder composition and characteristics after thermal treatment.

Calcium phosphate apatites with variable Ca/P atomic ratio II. Calcination and sintering

The calcination and natural sintering of calcium deficient hydroxyapatite powders Ca(10-x)(PO4)(6-x)(HPO4)x(OH)(2-x) (with 0 < or = x < or = 1) were studied. For temperature below 700 degrees C, particle coalescence occurs without densification. The particle coalescence is associated with a reduction of the specific surface area. This surface decreases all the more as the Ca/P molar ratio of the powder is small. The mechanism agrees with a transfer of matter occurring by superficial diffusion, which is enhanced by the augmentation of vacancies in the apatitic structure (i.e. by a decrease of the Ca/P ratio). The sintering of compacted powders begins at 700 degrees C. At the same temperature, the calcium deficient hydroxyapatites dissociate into biphasic mixtures of hydroxyapatite and tricalcium phosphate. The sintering is slowed down when the content of TCP in the biphasic mixture increases. In parallel, the grain size increases. This result relates to the augmentation of the coalescence of particles at low temperature.

Calcium phosphate apatites with variable Ca/P atomic ratio III. Mechanical properties and degradation in solution of hot pressed ceramics.

Calcium deficient hydroxyapatite powders Ca(10-x)(PO4)(6-x)(HPO4)x(OH)(2-x) (0 < or = x < or = 1) were hot pressed to produce dense hydroxyapatite-tricalcium phosphate (HAP/TCP) biphasic materials. Ceramics hot pressed at 1000 degrees C were composed of an homogeneous distribution of the HAP and beta-TCP grains with an average size of 0.2 microm. Grain growth was observed for TCP loading > 70 wt%. The strength exhibited a maximum of sigma(f) = 150 MPa for 90/10 (w/w) HAP/TCP and it dropped for smaller and greater amounts of TCP. This value was twice that of pure HAP. When placed in Ringers solution, only the surface of biphasic compounds was degraded after 60 days of immersion with a preferential etching of the TCP phase. After hot pressing at 1200 degrees C, grain growth was observed and the mechanical properties were decreased. This was explained by the allotropic transformation alpha/beta of TCP.

Sintering of calcium phosphate bioceramics

Calcium phosphate ceramics have become of prime importance for biological applications in the field of bone tissue engineering. This paper reviews the sintering behaviour of these bioceramics. Conventional pressureless sintering of hydroxyapatite, Ca10(PO4)6(OH)2, a reference compound, has been extensively studied. Its physico-chemistry is detailed. It can be seen as a competition between two thermally activated phenomena that proceed by solid-state diffusion of matter: densification and grain growth. Usually, the objective is to promote the first and prevent the second. Literature data are analysed from sintering maps (i.e. grain growth vs. densification). Sintering trajectories of hydroxyapatite produced by conventional pressureless sintering and non-conventional techniques, including two-step sintering, liquid phase sintering, hot pressing, hot isostatic pressing, ultrahigh pressure, microwave and spark plasma sintering, are presented. Whatever the sintering technique may be, grain growth occurs mainly during the last step of sintering, when the relative bulk density reaches 95% of the maximum value. Though often considered very advantageous, most assisted sintering techniques do not appear very superior to conventional pressureless sintering. Sintering of tricalcium phosphate or biphasic calcium phosphates is also discussed. The chemical composition of calcium phosphate influences the behaviour. Similarly, ionic substitutions in hydroxyapatite or in tricalcium phosphate create lattice defects that modify the sintering rate. Depending on their nature, they can either accelerate or slow down the sintering rate. The thermal stability of compounds at the sintering temperature must also be taken into account. Controlled atmospheres may be required to prevent thermal decomposition, and flash sintering techniques, which allow consolidation at low temperature, can be helpful.

Microstructure and related mechanical properties of hot pressed hydroxyapatite ceramics

Polycrystalline hydroxyapatite (HAP) ceramics were densified by hot pressing. The effects of thermal treatments and of a sintering additive (Na3PO4) on the microstructure, flexural strength and fracture toughness were investigated. Hot pressing without additive resulted in dense HAP having a small average grain size (below 0.5 μm). Spontaneous microcracking of the material was also noted. This originated from the thermal expansion anisotropy of HAP crystals. The presence of the sintering aid promotes grain growth. Dense materials exhibited mechanical properties depending on the microstructure. The highest values obtained were 137 MPa and 1.2 MPa % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaWaaOaaaeaaci% GGTbaaleqaaaaa!36FA!\[\sqrt \operatorname{m} \] for the flexural strength and fracture toughness, respectively. A decrease of both strength and toughness was observed with increasing average grain size. This behaviour is attributed to the weakening of the grain boundaries by either the development of initial microcracking or the Na3PO4 addition. It is concluded that hot pressing is very useful to elaborate dense HAP having good mechanical characteristics.

Processing, microstructure and toughness of Al2O3 platelet-reinforced hydroxyapatite

Abstract Experimental design has been used to analyse the processing of alumina platelet-reinforced hydroxyapatite ceramics. Composite materials were developed by slip casting and hot pressing. The most appropriate slurry composition allowing production of homogeneous composites was 65 wt% of powder and 3.1 wt% of deflocculant. HAP slurries containing up to 20 vol% of platelets had a quasi-Newtonian behaviour and a shear thinning flow was found at 30 vol% of alumina. A preferred orientation of platelets within the matrix was observed which led to anisotropic mechanical characteristics. Platelet incorporation induced strong toughening of the matrix. In comparison with the monolithic HAP (KlC⊥ = 0.75 (± 0.15) MPa √m; KlC// = 0.65 (± 0.20) MPa √m), the toughness increased up to 20 vol% of alumina content and reached maximum values of KlC⊥ = 2.95 (± 0.45) MPa ⊥m and KlC// = 1.95 (± 0.35) MPa ⊥m.

CHARACTERIZATION OF HOT PRESSED AL2O3-PLATELET REINFORCED HYDROXYAPATITE COMPOSITES

Hydroxyapatite reinforced with monocrystalline Al2O3 platelets was densified by hot pressing. The effect of volume fraction and size of platelets on the microstructure, strength and toughness was investigated. It was demonstrated that no phase degradation occured during thermal treatments. A better homogeneity of composite mixtures was achieved when large platelets had been used. In return, the incorporation of small platelets appeared more favourable to increase the mechanical characteristics although limiting effect induced by microstructural defects. The flexural strength can reach 140 MPa with an associated fracture toughness of 2.5 MPa % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaWaaOaaaeaaca% qGTbaaleqaaaaa!36F8!\[\sqrt {\text{m}} \] compared to 137 MPa and 1.2 MPa % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaWaaOaaaeaaca% qGTbaaleqaaaaa!36F8!\[\sqrt {\text{m}} \] for dense monolithic HAP. The observation of crack propagation allowed us to point out the mechanisms responsible of this toughening. Crack deflection on disk faces should be considered as the initiating phenomenon leading to platelet debonding, crack bridging or branching. Crack deflection and branching may also result in the formation of unbroken ligaments of material which bridge the crack.

Termal decomposition of carbonated calcium phosphate apatites

The thermal stability of AB-type carbonated calcium phosphate apatites prepared by precipitation from aqueous media was studied. The behavior of powders was investigated using temperature programmed XRD, infrared spectroscopy and thermogravimetry. In N2 atmosphere, two successive peaks of decarbonatation with maxima at about 700 and 950°C occurred. This behavior is explained by different substitution modes for carbonates in the apatite. The decarbonatation peaks were shifted to higher temperature under CO2 (around 900 and 1150°C). The analysis of the thermal stability allowed further densification of carbonate apatite ceramics without important carbonate loss.

Dynamic fatigue and degradation in solution of hydroxyapatite ceramics

Polycrystalline hydroxyapatite was densified by hot pressing. The dissolution process in aqueous solution and the effects of environment on dynamic fatigue resistance of the resulting HAP ceramics were investigated. Pure water or Ringers solution strongly enhances subcritical crack growth. The crack propagation exponent decreases from 22.5±2 in air to 10±4 in Ringers solution for materials densified at 98% of the theoretical value. The residual porosity ratio is also very detrimental for the mechanical reliability. Both fatigue resistance and immediate fracture strength are decreased, with values of only 14±4 for the propagation exponent and 40 MPa for the tensile strength (compared to 90 MPa at 98% relative density) for materials densified at 94% tested in air. The degradation in solution appears to be governed by uniform physico-chemical dissolution of crystalline HAP phase at the surface of the material. This dissolution is accompanied by a decohesion of grains located around residual pores which leads to the growth of local surface defects.

Calcination and sintering of hydroxyfluorapatite powders

Abstract A comparative study of calcination and sintering of hydroxyfluorapatite powders Ca 10 (PO 4 ) 6 (OH) x F 2− x substituted at various fluorine ratios has been carried out. Calcination led to the decrease of the specific surface area by particles coalescence. Superficial diffusion and gaseous phase transport appear as the main mechanisms of surface reduction. For densification a minimum was reached for x = 1 which corresponds to the minimum of FAP-HAP mixing enthalpy. Sintering is limited by the diffusion of hydroxide and fluorine ions.