Eike Volkmann

Mixed zirconia calcium phosphate coatings for dental implants: tailoring coating stability and bioactivity potential.

Enhanced coating stability and adhesion are essential for long-term success of orthopedic and dental implants. In this study, the effect of coating composition on mechanical, physico-chemical and biological properties of coated zirconia specimens is investigated. Zirconia discs and dental screw implants are coated using the wet powder spraying (WPS) technique. The coatings are obtained by mixing yttria-stabilized zirconia (TZ) and hydroxyapatite (HA) in various ratios while a pure HA coating served as reference material. Scanning electron microscopy (SEM) and optical profilometer analysis confirm a similar coating morphology and roughness for all studied coatings, whereas the coating stability can be tailored with composition and is probed by insertion and dissections experiments in bovine bone with coated zirconia screw implants. An increasing content of calcium phosphate (CP) resulted in a decrease of mechanical and chemical stability, while the bioactivity increased in simulated body fluid (SBF). In vitro experiments with human osteoblast cells (HOB) revealed that the cells grew well on all samples but are affected by dissolution behavior of the studied coatings. This work demonstrates the overall good mechanical strength, the excellent interfacial bonding and the bioactivity potential of coatings with higher TZ contents, which provide a highly interesting coating for dental implants.

Mechanical evaluation of calcium-zirconium-silicate (baghdadite) obtained by a direct solid-state synthesis route

Ca3ZrSi2O9 (baghdadite) has become a major research focus within the biomaterial community due to its remarkable in-vitro and in-vivo bioactivity. Although baghdadite seems to exhibit interesting biological properties, as yet there has been no data published concerning its mechanical properties. This lack of knowledge hinders targeting this novel bioactive material towards potential applications. In this study we prepare dense Ca3ZrSi2O9 bulk ceramics for the first time, allowing the evaluation of its mechanical properties including hardness, bending strength, Young׳s modulus, and fracture toughness. The preparation of baghdadite has been accomplished by a direct solid-state synthesis in combination with conventional sintering at 1350-1450°C for 3h. Our results show that samples sintered at 1400°C exhibit the best mechanical properties, resulting in a bending strength, fracture toughness, and hardness of 98±16MPa, 1.3±0.1MPam(0.5), and 7.9±0.2GPa. With a comparable mechanical strength to hydroxyapatite, but with an increased fracture toughness by 30% and hardness by 13% baghdadite is highly suitable for potential applications in non-load bearing areas (e.g. coatings or filler materials).

Characterization of Wet Powder-Sprayed Zirconia/Calcium Phosphate Coating for Dental Implants

PURPOSE Yttria-stabilized zirconia (TZ) is used for dental applications because of its low toxicity and beneficial mechanical properties, but it does not stimulate bone regeneration around the implant due to its bioinertness. Therefore, hydroxyapatite (HA) coatings are often utilized to increase the surface bioactivity and to achieve a better osseointegration. These coatings, however, are chemically nonstable and provide a weak bonding to the substrate surface. MATERIALS AND METHODS In this study, zirconia substrates were coated with a calcium phosphate/zirconia mixture to achieve ceramic coatings with a high bioactivity potential and a good mechanical stability. The coatings were obtained by wet powder spraying (WPS). Pure HA and TZ coatings were employed as reference materials. The coatings were characterized with regard to microstructure, surface roughness, and phase composition. Scratch tests were carried out to investigate the coating adhesion. The influence of the coating on the mechanical strength was evaluated with the ball on three balls test (B3B). In addition, zirconia dental implant screws were also coated and inserted in a biomechanical test block and bovine rip bone. RESULTS After sintering, the mixed coating exhibited a porous morphology with a surface roughness of about 4 μm and a total porosity of 17%. Phase analysis showed a transformation from TZ and HA to calcium zirconium oxide and tricalcium phosphate. Investigations of the bond strength confirmed a strong adhesion of the mixed coating to the substrate, while the biaxial fracture strength was only slightly affected. Insertion experiments confirmed the scratch test results and evidenced an intact mixed coating on the zirconia screw. CONCLUSIONS The present study revealed a higher stability and firm adhesion of the mixed coating compared with a pure calcium phosphate coating. We also successfully demonstrate the particular versatility of the WPS technique for dental implants by coating a complex curved surface.

A critical study: Assessment of the effect of silica particles from 15 to 500 nm on bacterial viability

The current opinion on the toxicity of nanomaterials converges on a size-dependent phenomenon showing increasing toxicity with decreasing particle sizes. We demonstrate that SiO2 particles have no or only a mild effect on the viability of five bacterial strains, independently from the particle size. A two-hour exposure to 20 mg L(-1) of 15, 50 and 500 nm sized SiO2 particles neither alters bacterial adenosine triphosphate (ATP) levels nor reduces the number of colony forming units (CFU). Additionally, we tested the effect of Al2O3-coated LUDOX-CL (ACS 20) with a primary particle size of 20 nm. In contrast, these particles caused a significant reduction of ATP levels and CFU. Fluorescence microscopy revealed that ACS 20 induced a pronounced agglomeration of the bacteria, which led to underestimated counts in regard of CFU. Bactericide effects as indicated by decreased ATP levels can be explained by bactericide additives that are present in the ACS 20 suspension.

Enzyme-assisted calcium phosphate biomineralization on an inert alumina surface

In this study a bioinspired approach to induce self-mineralization of bone-like material on alumina surfaces is presented. The mineralizing enzyme alkaline phosphatase (ALP) is covalently immobilized by a carbodiimide-mediated chemoligation method. The enzymatic activity of immobilized ALP and its mineralization capability are investigated under acellular conditions as well as in the presence of human bone cells. Analytical, biochemical and immunohistochemical characterization show that ALP is efficiently immobilized, retains its activity and can trigger calcium phosphate mineralization on alumina at acellular conditions. In vitro cell tests demonstrate that ALP-functionalized alumina clearly boosts and enhances bone cell mineralization. Our results underpin the great potential of ALP-functionalized alumina for the development of bioactive surfaces for applications such as orthopaedic and dental implants, enabling a fast and firm implant osseointegration.

Combination of biological mechanisms for a concept study of a fracture-tolerant bio-inspired ceramic composite material

The biological materials nacre and wood are renowned for their impressive combination of toughness and strength. The key mechanisms of these highly complex structures are crack deflection at weak interfaces, crack bridging, functional gradients and reinforcing elements. These principles were applied to a more fracture-tolerant model material which combined porous stiff ceramic layers, manufactured by freeze casting, infiltrated and bonded by a polymer phase reinforced with fabric layers. In the hybrid composites, crack deflection occurred at the ceramic–fabric interface and the intact fabric layers served as crack-bridging elements. Fabric-reinforced epoxy layers stabilized the fracture behaviour and delayed catastrophic failure of the material. The influence of the different components was analysed by varying the ceramic, fabric and interface properties. More ductile fabrics lead to larger strain to failure and more crack bridging but reduced the composite strength and stiffness after initial cracking. Higher elastic mismatch between the components improved crack deflection and bridging but resulted in deterred load transfer and a lower strength. The stiffness and strength of the ceramic layers influenced the elastic properties of the laminar composite and the initial crack resistance. Flaw tolerance was increased with polymer infiltration. We show with our hybrid ceramic–fabric composite as a bio-inspired concept study how fracture toughness, work of fracture and tolerance for cracking can be tailored when the contributing factors, i.e. the ceramic, the fabric and their interface, are modified.

Magnesium-containing mixed coatings on zirconia for dental implants: mechanical characterization and in vitro behavior

An important challenge in the field of dental and orthopedic implantology is the preparation of implant coatings with bioactive functions that feature a high mechanical stability and at the same time mimic structural and compositional properties of native bone for a better bone ingrowth. This study investigates the influence of magnesium addition to zirconia-calcium phosphate coatings. The mixed coatings were prepared with varying additions of either magnesium oxide or magnesium fluoride to yttria-stabilized zirconia and hydroxyapatite. The coatings were deposited on zirconia discs and screw implants by wet powder spraying. Microstructure studies confirm a porous coating with similar roughness and firm adhesion not hampered by the coating composition. The coating morphology, mechanical flexural strength and calcium dissolution showed a magnesium content-dependent effect. Moreover, the in vitro results obtained with human osteoblasts reveal an improved biological performance caused by the presence of Mg2+ ions. The magnesium-containing coatings exhibited better cell proliferation and differentiation in comparison to pure zirconia-calcium phosphate coatings. In conclusion, these results demonstrate that magnesium addition increases the bioactivity potential of zirconia-calcium phosphate coatings and is thus a highly suitable candidate for bone implant coatings.

Enhanced cell adhesion on bioinert ceramics mediated by the osteogenic cell membrane enzyme alkaline phosphatase.

Functional bone and dental implant materials are required to guide cell response, offering cues that provide specific instructions to cells at the implant/tissue interface while maintaining full biocompatibility as well as the desired structural requirements and functions. In this work we investigate the influence of covalently immobilized alkaline phosphatase (ALP), an enzyme involved in bone mineralization, on the first contact and initial cell adhesion. To this end, ALP is covalently immobilized by carbodiimide-mediated chemoligation on two highly bioinert ceramics, alpha-alumina (Al2O3) and yttria-stabilized zirconia (Y-TZP) that are well-established for load-bearing applications. The physicochemical surface properties are evaluated by profilometry, zeta potential and water contact angle measurements. The initial cell adhesion of human osteoblasts (HOBs), human osteoblast-like cells (MG-63) and mesenchymal stromal cells (hMSCs) was investigated. Cell adhesion was assessed at serum free condition via quantification of percentage of adherent cells, adhesion area and staining of the focal adhesion protein vinculin. Our findings show that after ALP immobilization, the Al2O3 and Y-TZP surfaces gained a negative charge and their hydrophilicity was increased. In the presence of surface-immobilized ALP, a higher cell adhesion, more pronounced cell spreading and a higher number of focal contact points were found. Thereby, this work gives evidence that surface functionalization with ALP can be utilized to modify inert materials for biological conversion and faster bone regeneration on inert and potentially load-bearing implant materials.

Synthesis and mechanical evaluation of Sr-doped calcium-zirconium-silicate (baghdadite) and its impact on osteoblast cell proliferation and ALP activity.

For the first time the successful preparation of Sr doped baghdadite (Ca3-x Sr x ZrSi2O9 x  =  0.1 and 0.75) is shown. Sr-doped as well as pure baghdadite are prepared via a versatile solid-state synthesis and conventional sintering at 1400 °C. XRD measurements and crystal structure refinements reveal that a substitution of Ca atoms with Sr and a high purity (>99%) is achieved. The physical, mechanical, and biological properties of these novel bioceramics are presented in relation to the dopant concentration. Incorporating Sr into the baghdadite crystal caused only minor changes to the grain size and the mechanical properties. The characteristic strength ranges from 145 to 168 MPa and a Weibull modulus of 4.9 to 9.2 is observed. Other mechanical properties like fracture toughness and hardness vary from 1.23  ±  0.07 MPam(0.5) to 1.31  ±  0.12 MPam(0.5) and 7.3  ±  0.6 GPa to 8.0  ±  0.7 GPa, respectively. The in vitro cellular response of human osteoblasts showed an increase in the cell proliferation and a significantly higher alkaline phosphatase (ALP) activity with an increase in the Sr content. From the improved biological properties and the suitable mechanical performance we conclude that this material is a highly promising candidate for bone replacement material and bioactive implant coatings.

Development and Validation of Oxide/oxide CMC Combustors within the HiPOC Program

In the framework of the High Performance Oxide Ceramics program (HiPOC), three different oxide/oxide ceramic matrix composite (CMC) materials are studied for a combustion chamber application in continuation of the work reported in Gerendas et al. [1]. A variation in the micro-structural design of the three CMC materials in terms of different fiber architecture and matrix processing are considered in a first work stream. By modification of the matrix and the fiber-matrix interface as well as the application of an environmental barrier coating (EBC), the high temperature stability is enhanced. Furthermore, design concepts for the attachment of the CMC component to the metal structure of the engine are finalized in a second work stream. Issues like sealing of cooling leakage paths, allowance for the different thermal expansion and the mechanical fixation are addressed. An interim standard of the mechanical attachment scheme is studied on a shaker table. Also the friction coefficient between the metallic and ceramic components is analyzed in order to set the proper tightening torque. The manufacturing of the CMC combustor is improved in several iterations in order to achieve a high quality material with optimized fiber architecture. Afterwards, two CMC materials are selected for the combustion testing and the finalized design of the metallic and CMC components is manufactured. A fit check is performed prior to EBC application and laser drilling of the effusion holes in order to evaluate the impact of the manufacturing tolerances on the function of the sealing and attachment scheme and to correct small issues at this stage. First results from the validation testing in a high-pressure tubular combustion rig up to a Technology Readiness Level 4 (TRL4) are reported.Copyright