Calcium phosphate (CaP) bioceramics are widely used in the field of bone regeneration, both in orthopedics and in dentistry, due to their good biocompatibility, osseointegration and osteoconduction. The aim of this article is to review the history, structure, properties and clinical applications of these materials, whether they are in the form of bone cements, paste, scaffolds, or coatings. Major analytical techniques for characterization of CaPs, in vitro and in vivo tests, and the requirements of the US Food and Drug Administration (FDA) and international standards from CaP coatings on orthopedic and dental endosseous implants, are also summarized, along with the possible effect of sterilization on these materials. CaP coating technologies are summarized, with a focus on electrochemical processes. Theories on the formation of transient precursor phases in biomineralization, the dissolution and reprecipitation as bone of CaPs are discussed. A wide variety of CaPs are presented, from the individual phases to nano-CaP, biphasic and triphasic CaP formulations, composite CaP coatings and cements, functionally graded materials (FGMs), and antibacterial CaPs. We conclude by foreseeing the future of CaPs.
Ti-6Al-4V alloy is the most commonly used alloy for dental and orthopedic implants. In order to improve osseointegration, different surface modification methods are usually employed, including self-assembled monolayers (SAMs). This study presents an investigation of both active (electroassisted) and passive (adsorption) approaches for the modification of Ti-6Al-4V using alkylphosphonic acid. The monolayers were characterized by cyclic voltammetry, double-layer capacitance, contact angle measurements, X-ray photoelectron spectroscopy, polarization modulation infrared reflection adsorption spectroscopy, electrochemical impedance spectroscopy, and corrosion potentiodynamic polarization measurements. It is shown that the electrochemically assisted monolayers, which are assembled faster, exhibit better control over surface properties, a superior degree of order, and a somewhat higher packing density. The electrosorbed SAMs also exhibit better blockage of electron transfer across the interface and thus have better corrosion resistance.
Calcium phosphates are of great interest for biomedical applications such as bone tissue engineering, bone fillers, drug and gene delivery, and orthopedic and dental implant coating. Here, the first electrochemically driven coating of medical implants using hydroxyapatite (HAp) nanoparticles (NPs) as building blocks is reported. This uncommon combination offers a simple, straightforward, and economic process with well controllable, pure, single‐phase HAp. Crystalline, pure HAp NPs are formed by precipitation reaction. The HAp NPs are dispersed by either citrate or poly(acrylic acid) to form pH sensitive dispersion. Controllable and homogeneous coating of medical implants is accomplished by altering the pH on the surface upon applying either a constant potential or current. The process involves protonation of the carboxylic acid moieties, which causes the irreversible aggregation of the HAp NPs due to diminishing the repulsive forces between the particles. Deposition is further demonstrated on a commercial dental implant. Moreover, the adhesion of the coating satisfies FDA and international standard requirements. A porous interconnected network of bone‐like HAp layer is formed during soaking in a simulated body fluid for 30 d and is similar to bone generation, and it therefore holds promise for further in vivo testing.
Freestanding flexible membranes based on biocompatible calcium phosphates are of great interest in regenerative medicine. Here, the authors report the first synthesis of well‐aligned biomimetic hexagonal bars of hydroxyapatite (HAp) on flexible, freestanding mesoporous graphene/single‐walled carbon nanotubes (MG/SWCNT) hybrid membranes. The chemical composition and surface morphology of the HAp coating resemble those of biological apatite. Nitrogen doping and oxygen plasma etching of the MG/SWCNT membranes increase the density of nucleation sites and yield more uniform coatings. This novel membrane favors the attachment and proliferation of human fetal osteoblast (hFOB) osteoprogenitor cells. When soaked in simulated body fluid, enhanced in vitro biomineralization occurs on the hybrid membranes. This hybrid membrane holds great promise in biomedical applications such as patches and strips for spine fusion, bone repair, and restoration of tooth enamel.
Calcium phosphate (CaP) ceramics are used in orthopedics and dentistry due to their excellent biocompatibility and osseointegration. Here, the electro-assisted deposition of CaP on two different self-assembled monolayers (SAMs), 2-mercaptoacetic acid (MAA) and 2mercaptoethanol (ME), were studied both at short (up to 3 min) and at long (2 hours) deposition periods on well-defined evaporated gold surfaces. It was found that the end group of the monolayer has a major effect on the growth of the CaP coating. The deposition was slower and less electrically efficient on MAA SAM, but surface cracking was essentially eliminated due to reduction of the crystallographic mismatch. The carboxylic acid may facilitate CaP growth by attracting Ca 2+ ions to the surface, which could explain the higher amount of side reactions occurring at the beginning of the deposition.
Calcium phosphate (CaP) ceramics are used in orthopedics and dentistry due to their excellent osseointegration and biocompatibility. The electrodeposition of CaP on titanium alloy covered with self-assembled monolayers (SAMs) was studied with respect to the influence of chain length, end-group charge, and anchoring group. SAMs with end-groups similar to the functional groups on the side chains of collagen were selected. This study is divided to three parts: (1) studying the effects of SAMs on the titanium substrate, (2) studying the process of nucleation and growth of the CaP on specific SAMs, and (3) characterizing the CaP coatings using various surface analytical techniques. It was concluded that the nucleation and growth behavior of CaP changed in the presence of the SAMs. Different surface energies and crystallographic phases were associated with this change. Although the nucleation remained progressive, the growth changed from three-dimensional on bare surfaces to two-dimensional on SAMs-covered surfaces. Moreover, the deposition kinetics was slower on SAMs-covered surfaces, with phases containing a higher Ca/P ratio. Examination of the coating revealed that different SAMs lead to different surface morphologies of the coating while maintaining its degree of crystallinity. Yet, the phase content changes from hydroxyapatite and octacalcium phosphate (HAp + OCP) on the bare electrode to OCP only on the SAMs-covered electrode. These changes may have a substantial effect on the in vivo behavior by changing the coating's solubility and surface morphology, thus affecting cell adhesion, proliferation, and differentiation processes.
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