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Highlights: [•] Deposition of organic molecules as alkaline (ALP) to induce mineralization of titanium surface. [•] The role of configurational deposition has been analyzed to detect the role of collagen to improve ALP retention. [•] Collagen is able to increase ALP retention and therefore mineral content after acellular mineralization. [•] A mixed structure of collagen and ALP produce a unique ECM-like mineralized pattern onto titanium. [ABSTRACT FROM AUTHOR]

Abstract: Electrostatic Spray Deposition (ESD) of biomedical calcium phosphate (CaP) coatings was investigated by in situ measurements of droplet sizes and velocities using Phase Doppler Anemometry. Processing parameters, related to the ESD-apparatus as well as the composition of the precursor solutions, were varied (deposition temperature, nozzle-to-substrate distance, nozzle geometry, and composition of the precursor solution). Thereafter, morphological characteristics of these ESD-derived CaP coatings were correlated with measured droplet characteristics. By varying physical apparatus-related parameters such as the nozzle-to-substrate distance and the deposition temperature, it was observed that electrosprayed butyl carbitol droplets did not shrink during droplet flight towards the heated substrate. Nevertheless, coatings with a different surface morphology were obtained, varying from microporous structures with coalesced pore walls to isolated rings on top of dense or grainy underlayers. The chemical composition of the precursor solutions and the mixing characteristics of the calcium and phosphate precursor components strongly influenced the initial droplet sizes, precipitation kinetics of the CaP solute, and subsequent coating morphology. Unique, reticular coatings can be deposited at a deposition rate of 3.2 μm/h, which have a graded structure consisting of a dense underlayer, a submicron-porous intermediate layer, and a roughened toplayer revealing droplet-derived features such as isolated rings or coalesced, hollow surface pits. [Copyright &y& Elsevier]

Abstract: The electrostatic spray deposition (ESD) technique was used for biomedical purposes in order to deposit calcium phosphate (CaP) coatings onto titanium substrates. The relationship between various deposition parameters and the chemical properties of deposited coatings was investigated in order to be able to deposit CaP coatings with tailored chemical characteristics. The results showed that the chemical properties of the coatings were determined by both physical, apparatus-related factors and chemical, solution-related parameters. By varying the processing parameters of the technique, several crystal phases and phase mixtures were obtained, ranging from carbonate-free phases such as meta- and pyrophosphates, monetite and various tricalcium phosphates to carbonate-containing phases such as various carbonate apatites and calcite. On the basis of these results, a chemical mechanism of coating formation was proposed. Essentially, the deposition of the various crystal phases was the result of an acid–base reaction between basic CO3 2− groups (originating from solvent decomposition reactions) and acidic HPO4 2− groups from an intermediate monetite (CaHPO4) phase of the CaP precipitate. The amount of carbonate incorporation (ranging from 0 to 15wt%) determined the crystal and molecular structure of the deposited coatings. [Copyright &y& Elsevier]

Abstract: In order to deposit biomedical calcium phosphate (CaP) coatings with a defined surface morphology, the electrostatic spray deposition (ESD) technique was used since this technique offers the possibility to deposit ceramic coatings with a variety of surface morphologies. A scanning electron microscopical study was performed in order to investigate the influence of several deposition parameters on the final morphology of the deposited coatings. The chemical characteristics of the coatings were studied by means of X-ray diffraction and Fourier-transform infrared spectroscopy. Regarding the chemical coating properties, the results showed that the coatings can be described as crystalline carbonate apatite coatings, a crystal phase which is similar to the mineral phase of bone and teeth. The morphology of CaP coatings, deposited using the ESD technique, was strongly dependent on the deposition parameters. By changing the nozzle-to-substrate distance, the precursor liquid flow rate and the deposition temperature, coating morphologies were deposited, which varied from dense to highly porous, reticular morphologies. The formation of various morphologies was the result of an equilibrium between the relative rates of CaP solute precipitation/reaction, solvent evaporation and droplet spreading onto the substrate surface. [Copyright &y& Elsevier]

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, β-TCP, Mg-substituted whitlockite, monetite, β/γ-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 Ca2+ cations in case of phosphate-deficient precursor solutions. [Copyright &y& Elsevier]

Abstract: Surface modification of implant materials with biomolecule coatings is of high importance to improve implant fixation in bone tissue. In the current study, we present two techniques for the deposition of biologically active enzyme coatings onto implant materials. The well-established thin film ElectroSpray Deposition (ESD) technique was compared with the SAW-ED technique that combines high-frequency Surface Acoustic Wave atomization with Electrostatic Deposition. By immobilizing the enzyme alkaline phosphatase (ALP) onto implant surfaces, the influence of both SAW-ED and ESD deposition parameters on ALP deposition efficiency and ALP biological activity was investigated. ALP coatings with preserved enzyme activity were deposited by means of both the SAW-ED and ESD technique. The advantages of SAW-ED over ESD include the possibility to spray highly conductive protein solutions, and the 60-times faster deposition rate. Furthermore, significantly higher deposition efficiencies were observed for the SAW-ED technique compared to ESD. Generally, it was shown that protein inactivation is highly dependent on both droplet dehydration and the applied electrical field strength. The current study shows that SAW-ED is a versatile and flexible technique for the fabrication of functionally active biomolecule coatings. [Copyright &y& Elsevier]

Electrostatic spray deposition (ESD) is a recently developed technique to deposit a calcium phosphate (CaP) coating upon substrates. With this technique, an organic solvent containing calcium and phosphate is pumped through a nozzle. Between the nozzle and substrate a high voltage is applied. As a consequence, droplets coming out the nozzle disperse into a spray, and this spray is deposited upon the substrate. When the solvent has evaporated, a coating is formed on the substrate. ESD allows for a variation in coating composition and morphology. Titanium alloy (TiAl6V4) substrates were coated with a CaP layer using two different methods; radio frequency magnetron sputtering, and ESD. These surfaces were characterized with X-ray diffraction, Fourier transform infrared spectroscopy, an universal surface tester, scanning electron microscopy, and energy dispersive spectrometry. Subsequently, bone marrow cells were isolated from rat femora and cultured 1, 4, 8, 14 and 16 days. Cell proliferation, alkaline phosphatase activity, and osteocalcin concentration were assayed. RT-PCR was done for collagen type I and osteocalcin. SEM was also performed to observe cellular behaviour during culture. Two separate runs of the experiment were performed. In the first run, osteoblast-like cells on both CaP coatings showed similar results in all assays. In the second run, proliferation and osteogenic expression had increased on ESD coatings. On basis of these results, we conclude that the novel ESD coating behaved similar to, or even better than the known RF magnetron sputter coating. Thus, ESD could be a valid addition to already existing CaP coating processes. [Copyright &y& Elsevier]