Mechanical properties of porous, electrosprayed calcium phosphate coatings.

Mechanical properties of calcium phosphate coatings (CaP), deposited using the electrostatic spray deposition (ESD) technique, have been characterized using a range of analytical techniques, including tensile testing (ASTM C633), fatigue testing (ASTM E855), and scratch testing using blunt and sharp scratch styli. Moreover, a simple explantation procedure was successfully introduced using ESD-coated, threaded dental implants to characterize the mechanical performance of CaP coatings qualitatively under conditions that mimic clinical situations as close as possible. Generally, all analysis techniques revealed that ESD coatings need to be crystallized in order to ensure interfacial adhesion to the substrate and sufficient mechanical strength of the superficial reticular structure. Crystalline carbonated hydroxyapatite coatings (CHA, heat-treated at 700 degrees C) were resistant to fatigue as well as to plastic ploughing deformation by means of various scratch styli, and the fragile surface structure of ESD coatings was maintained to a large extent after unscrewing CHA-coated dental implants from femoral condyles of goat cadavers. From these experiments, it was concluded that interfacial adhesion of crystalline CHA ESD coatings to the titanium substrate was sufficient, but that mechanical strength of the superficial architecture of ESD coatings need to be optimized for applications where high shear and compressive stresses are imposed onto the rather fragile coating surface of reticular ESD morphologies.

Influence of deposition parameters on chemical properties of calcium phosphate coatings prepared by using electrostatic spray deposition.

The electrostatic spray deposition (ESD) technique offers the possibility of depositing calcium phosphate (CaP) coatings onto various substrate materials with defined chemical and morphological properties. The relationship between physical, apparatus-related deposition parameters, and the chemical characteristics of ESD coatings was investigated by means of X-ray diffraction, Fourier transform infrared spectroscopy, and energy dispersive spectroscopy to be able to deposit CaP coatings with tailored chemical properties. The results showed that the chemical characteristics of CaP coatings, deposited with use of the ESD technique, were strongly dependent on the deposition temperature, the nozzle-to-substrate distance, the liquid flow rate, and the geometry of the spraying nozzle. By investigating the influence of the deposition temperature, information could be obtained on the formation mechanism of CaP coatings-and specifically the biologically interesting carbonate apatite phase-using the ESD technique. CaP coatings were not formed merely because of solvent evaporation; a chemical reaction was needed to synthesize the coatings. This reaction involved thermal decomposition of the organic solvent butyl carbitol into carbonate ions via formation of intermediate oxalate ions. The amount of carbonate incorporation, and consequently, the Ca/P ratios of the deposited coatings, was shown 1) to decrease with increasing nozzle-to-substrate distance, 2) to decrease with increasing liquid flow rate, and 3) to decrease by making use of a novel two-component nozzle geometry.

Influence of precursor solution parameters on chemical properties of calcium phosphate coatings prepared using Electrostatic Spray Deposition (ESD).

A novel coating technique, referred to as Electrostatic Spray Deposition (ESD), was used to deposit calcium phosphate (CaP) coatings with a variety of chemical properties. The relationship between the composition of the precursor solutions and the crystal and molecular structure of the deposited coatings was investigated by means of X-ray diffraction (XRD), Fourier-Transform Infrared Spectroscopy (FTIR) and Energy Dispersive Spectroscopy (EDS). It was shown that the relative Ca/P ratio in the precursor solution, the absolute precursor concentration, the acidity of the precursor solution and the type of Ca-precursor strongly influenced the chemical nature of the deposited CaP coatings. Various crystal phases and phase mixtures were obtained, such as carbonate apatite, beta-TCP, Mg-substituted whitlockite, monetite, beta/gamma-pyrophosphate, and calcite. It was shown that carbonate plays an essential role in the chemical mechanism of coating formation. Carbonate is formed due to a decomposition reaction of organic solvents. Depending on deposition conditions, carbonate anions (a) react with acidic phosphate groups, (b) are incorporated into apatitic calcium phosphate phases, and (c) react with excessive Ca(2+) cations in case of phosphate-deficient precursor solutions.

Electrostatic spray deposition (ESD) of calcium phosphate coatings.

Using electrostatic spray deposition (ESD), thin calcium phosphate layers were deposited onto commercially pure cp-Ti substrates. ESD is a thin-film technique that enables the deposition of inorganic thin films onto metallic substrates using a simple and cheap experimental set-up. The results show that coating structure and morphology can be tailored by choosing the appropriate combination of deposition parameters. Scanning electron microscopy revealed that various surface morphologies, ranging from dense to very porous coatings, can be obtained. Particularly interesting was a unique reticular coating morphology characterized by a three-dimensionally interconnected pore network. X-ray diffraction (XRD) and Fourier transform infrared spectrometry (FTIR) analyses showed that crystalline carbonate apatite coatings were formed after heat treatment of as-deposited ESD coatings.

Osteoclastic resorption of biomimetic calcium phosphate coatings in vitro.

A new biomimetic method for coating metal implants enables the fast formation of dense and homogeneous calcium phosphate coatings. Titanium alloy (Ti6Al4V) disks were coated with a thin, carbonated, amorphous calcium phosphate (ACP) by immersion in a saturated solution of calcium, phosphate, magnesium, and carbonate. The ACP-coated disks then were processed further by incubation in calcium phosphate solutions to produce either crystalline carbonated apatite (CA) or octacalcium phosphate (OCP). The resorption behavior of these three biomimetic coatings was studied using osteoclast-enriched mouse bone-marrow cell cultures for 7 days. Cell-mediated degradation was observed for both carbonated apatite and octacalcium phosphate coatings. Numerous resorption lacunae characteristic of osteoclastic resorption were found on carbonated apatite after cell culture. The results showed that carbonated apatite coatings are resorbed by osteoclasts in a manner consistent with normal osteoclastic resorption. Osteoclasts also degraded the octacalcium phosphate coatings but not by classical pit formation.

Lithium dynamics in LiMn2O4 probed directly by two-dimensional (7)Li NMR.

LiMn2O4 has been studied using magic-angle-spinning nuclear magnetic resonance (MAS NMR). 1D MAS NMR shows three Li resonances assigned to different crystallographic sites. At low temperatures an extra peak appears, indicating charge ordering of Mn3+ and Mn4+. Direct observation of the lithium dynamics was possible using rotor-synchronized 2D exchange NMR. A millisecond time scale exchange of lithium starts around 285 K between the 8a and the 16c site. At 380 K lithium even starts to hop between more than two sites. The activation energies and Li jump rates are derived and are in agreement with those determined macroscopically.