2020, Lindemann, Inge, Gebel, Bernhard, Pilz, Stefan, Uhlemann, Margitta, Gebert, Annett

Due to their excellent biocompatibility, titanium and titanium–niobium alloys are especially interesting for biomedical applications. With regard to favorable near-net shape production, Ti powder synthesis is the key hurdle. Extensive research has been in progress for alternative synthesis methods since decades. Herein, an efficient alternative method to the conventional powder production process to prepare spherical powders with very small sizes (<45 μm) for high-strength materials is shown. Very fine, hydrogenated Ti and Ti–Nb alloy powders are stable in air and are synthesized by calciothermic reduction in hydrogen. The herein presented reduction using CaH2 starts directly from the oxides instead of chlorides. Correlations of size and morphology of the as-synthesized TiH2 and (Ti,Nb)H2 powders with the precursors (TiO2, Nb2O5, and CaH2) are illustrated and are used to tailor the desired powders.

2013, Zhuravleva, Ksenia, Bönisch, Matthias, Prashanth, Konda Gokuldoss, Hempel, Ute, Helth, Arne, Gemming, Thomas, Calin, Mariana, Scudino, Sergio, Schultz, Ludwig, Eckert, Jürgen, Gebert, Annett

We used selective laser melting (SLM) and hot pressing of mechanically-alloyed β-type Ti–40Nb powder to fabricate macroporous bulk specimens (solid cylinders). The total porosity, compressive strength, and compressive elastic modulus of the SLM-fabricated material were determined as 17% ± 1%, 968 ± 8 MPa, and 33 ± 2 GPa, respectively. The alloy’s elastic modulus is comparable to that of healthy cancellous bone. The comparable results for the hot-pressed material were 3% ± 2%, 1400 ± 19 MPa, and 77 ± 3 GPa. This difference in mechanical properties results from different porosity and phase composition of the two alloys. Both SLM-fabricated and hot-pressed cylinders demonstrated good in vitro biocompatibility. The presented results suggest that the SLM-fabricated alloy may be preferable to the hot-pressed alloy for biomedical applications, such as the manufacture of load-bearing metallic components for total joint replacements.

2016, Vehlow, David, Schmidt, Romy, Gebert, Annett, Siebert, Maximilian, Lips, Katrin Susanne, Müller, Martin

An improved interfacial drug delivery system (DDS) based on polyelectrolyte complex (PEC) coatings with controlled drug loading and improved release performance was elaborated. The cationic homopolypeptide poly(l-lysine) (PLL) was complexed with a mixture of two cellulose sulfates (CS) of low and high degree of substitution, so that the CS and PLL solution have around equal molar charged units. As drugs the antibiotic rifampicin (RIF) and the bisphosphonate risedronate (RIS) were integrated. As an important advantage over previous PEC systems this one can be centrifuged, the supernatant discarded, the dense pellet phase (coacervate) separated, and again redispersed in fresh water phase. This behavior has three benefits: (i) Access to the loading capacity of the drug, since the concentration of the free drug can be measured by spectroscopy; (ii) lower initial burst and higher residual amount of drug due to removal of unbound drug and (iii) complete adhesive stability due to the removal of polyelectrolytes (PEL) excess component. It was found that the pH value and ionic strength strongly affected drug content and release of RIS and RIF. At the clinically relevant implant material (Ti40Nb) similar PEC adhesive and drug release properties compared to the model substrate were found. Unloaded PEC coatings at Ti40Nb showed a similar number and morphology of above cultivated human mesenchymal stem cells (hMSC) compared to uncoated Ti40Nb and resulted in considerable production of bone mineral. RIS loaded PEC coatings showed similar effects after 24 h but resulted in reduced number and unhealthy appearance of hMSC after 48 h due to cell toxicity of RIS.

2020, Kruppke, Benjamin, Heinemann, Christiane, Gebert, Annett, Rohnke, Marcus, Weiß, Manuel, Henß, Anja, Wiesmann, Hans-Peter, Hanke, Thomas

Aiming at the generation of a high strontium-containing degradable bone substitute, the exchange of calcium with strontium in gelatin-modified brushite was investigated. The ion substitution showed two mineral groups, the high-calcium containing minerals with a maximum measured molar Ca/Sr ratio of 80%/20% (mass ratio 63%/37%) and the high-strontium containing ones with a maximum measured molar Ca/Sr ratio of 21%/79% (mass ratio 10%/90%). In contrast to the high-strontium mineral phases, a high mass loss was observed for the calcium-based minerals during incubation in cell culture medium (alpha-MEM), but also an increase in strength owing to dissolution and re-precipitation. This resulted for the former in a decrease of cation concentration (Ca + Sr) in the medium, while the pH value decreased and the phosphate ion concentration rose significantly. The latter group of materials, the high-strontium containing ones, showed only a moderate change in mass and a decrease in strength, but the Ca + Sr concentration remained permanently above the initial calcium concentration in the medium. This might be advantageous for a future planned application by supporting bone regeneration on the cellular level. © 2020 The Authors. Journal of Biomedical Materials Research Part A published by Wiley Periodicals LLC.

2022, Pilz, Stefan, Gustmann, Tobias, Günther, Fabian, Zimmermann, Martina, Kühn, Uta, Gebert, Annett

The ß-type Ti-42Nb alloy was processed by laser powder bed fusion (LPBF) with an infrared top hat laser configuration aiming to control the Young’s modulus by creating an adapted crystallographic texture. Utilizing a top hat laser, a microstructure with a strong 〈0 0 1〉 texture parallel to the building direction and highly elongated grains was generated. This microstructure results in a strong anisotropy of the Young’s modulus that was modeled based on the single crystal elastic tensor and the experimental texture data. Tensile tests along selected loading directions were conducted to study the mechanical anisotropy and showed a good correlation with the modeled data. A Young’s modulus as low as 44 GPa was measured parallel to the building direction, which corresponds to a significant reduction of over 30% compared to the Young’s modulus of the Gaussian reference samples (67–69 GPa). At the same time a high 0.2% yield strength of 674 MPa was retained. The results reveal the high potential of LPBF processing utilizing a top hat laser configuration to fabricate patient-specific implants with an adapted low Young’s modulus along the main loading direction and a tailored mechanical biofunctionality.

2022, Hariharan, Avinash, Goldberg, Phil, Gustmann, Tobias, Maawad, Emad, Pilz, Stefan, Schell, Frederic, Kunze, Tim, Zwahr, Christoph, Gebert, Annett

Additive manufacturing of near β-type Ti-13Nb-13Zr alloys using the laser powder bed fusion process (LPBF) opens up new avenues to tailor the microstructure and subsequent macro-scale properties that aids in developing new generation patient-specific, load-bearing orthopedic implants. In this work, we investigate a wide range of LPBF parameter space to optimize the volumetric energy density, surface characteristics and melt track widths to achieve a stable process and part density of greater than 99 %. Further, optimized sample states were achieved via thermal post-processing using standard capability aging, super-transus (900 °C) and sub-transus (660 °C) heat treatment strategies with varying quenching mediums (air, water and ice). The applied heat treatment strategies induce various fractions of α, martensite (α', α'') in combination with the β phase and strongly correlated with the observed enhanced mechanical properties and a relatively low elastic modulus. In summary, our work highlights a practical strategy for optimizing the mechanical and corrosion properties of a LPBF produced near β-type Ti-13Nb-13Zr alloy via careful evaluation of processing and post-processing steps and the interrelation to the corresponding microstructures. Corrosion studies revealed excellent corrosion resistances of the heat-treated LPBF samples comparable to wrought Ti-13Nb-13Zr alloys.

2020, Vehlow, David, Wong, Jeremy P.H., Urban, Birgit, Weißpflog, Janek, Gebert, Annett, Schumacher, Matthias, Gelinsky, Michael, Stamm, Manfred, Müller, Martin

The proteasome inhibitor bortezomib (BZM) is one of the most potent anti-cancer drugs in the therapy of multiple myeloma. In this study, an adhesive drug delivery system (DDS) for BZM was developed. Therefore, we extended the present DDS concept of polyelectrolyte complex (PEC) nanoparticle (NP) based on electrostatic interactions between charged drug and polyelectrolyte (PEL) to a DDS concept involving covalent bonding between PEL and uncharged drugs. For this purpose, 3,4-dihydroxyphenyl acetic acid (DOPAC) was polymerized via an oxidatively induced coupling reaction. This novel chemo-reactive polyanion PDOPAC is able to temporarily bind boronic acid groups of BZM via its catechol groups, through esterification. PDOPAC was admixed to poly(l-glutamic acid) (PLG) and poly(l-lysine) (PLL) forming a redispersible PEC NP system after centrifugation, which is advantageous for further colloid and BZM loading processing. It was found that the loading capacity (LC) strongly depends on the PDOPAC and catechol content in the PEC NP. Furthermore, the type of loading and the net charge of the PEC NP affect LC and the residual content (RC) after release. Release experiments of PDOPAC/PEC coatings were performed at medically relevant bone substitute materials (calcium phosphate cement and titanium niobium alloy) whereby the DDS worked independently of the surface properties. Additionally, in contrast to electrostatically based drug loading the release behavior of covalently bound, uncharged BZM is independent of the ionic strength (salt content) in the release medium.

2022, Schell, Frederic, Alamri, Sabri, Hariharan, Avinash, Gebert, Annett, Lasagni, Andrés Fabián, Kunze, Tim

Complex repetitive periodic surface patterns were produced on a near-beta Ti-13Nb-13Zr alloy, using two-beam Direct Laser Interference Patterning (DLIP) employing a picosecond-pulsed laser source with wavelengths of 355 nm, 532 nm and 1064 nm. Different types of Laser-induced periodic surface structures (LIPSS) are produced, including low and high spatial frequency LIPSS, which are observed frequently on top of the line-like DLIP microstructures, as well as quasi-periodic microstructures with periods greater than the laser wavelength. The feature size of the fabricated LIPSS features could be tuned as function of the utilized laser process parameters.

2022, Günther, Fabian, Hirsch, Franz, Pilz, Stefan, Wagner, Markus, Gebert, Annett, Kästner, Markus, Zimmermann, Martina

Lattices based on triply periodic minimal surfaces (TPMS) have recently attracted increasing interest, but their additive manufacturing (AM) is fraught with imperfections that compromise their structural integrity. Initial research has addressed the influence of process-induced imperfections in lattices, but so far numerical work for TPMS lattices is insufficient. Therefore, in the present study, the structure–property relationships of TPMS lattices, including their imperfections, are investigated experimentally and numerically. The main focus is on a biomimetic Schoen I-WP network lattice made of laser powder bed fusion (LPBF) processed Ti-42Nb designed for bone tissue engineering (BTE). The lattice is scanned by computed tomography (CT) and its as-built morphology is examined before a modeling procedure for artificial reconstruction is developed. The structure–property relationships are analyzed by experimental and numerical compression tests. An anisotropic elastoplastic material model is parameterized for finite element analyses (FEA). The numerical results indicates that the reconstruction of the as-built morphology decisively improves the prediction accuracy compared to the ideal design. This work highlights the central importance of process-related imperfections for the structure–property relationships of TPMS lattices and proposes a modeling procedure to capture their implications.

2022, Alberta, Ludovico Andrea, Vishnu, Jithin, Hariharan, Avinash, Pilz, Stefan, Gebert, Annett, Calin, Mariana

This study aims to develop novel low-modulus, corrosion-resistant Ti-based alloys with enhanced antimicrobial properties for bone-related implant applications. Novel β-type (Ti–45Nb)-based alloys with minor additions of the antibacterial elements Ga and/or Cu (up to 4 wt.%) were produced by a two-step casting process followed by homogenization treatment. Three nominal compositions (Ti–45Nb)96-4 Ga, (Ti–45Nb)96–4Cu and (Ti–45Nb)96-2 Ga–2Cu (wt.%) were prepared based on alloy design approach using [Mo]eq and electron per atom (e/a) ratio. The influence of Ga and/or Cu addition on the phase constitution, mechanical response and corrosion characteristics in simulated body fluids (PBS, 37.5 °C) has been investigated. X-ray diffraction studies displayed a single β phase structure for all alloys, with an observed lattice contraction evidenced by the reduction of lattice parameters during Rietveld analysis. Homogenous equiaxed microstructures with grain sizes ranging from 55 μm up to 323 μm were observed for (Ti–45Nb)96-4 Ga, (Ti–45Nb)96-2 Ga–2Cu and (Ti–45Nb)96–4Cu alloys. The alloys displayed excellent plasticity with no cracking, or fracturing during compression tests. Their tensile strength, Young's modulus, maximum tensile strain and elastic energy were measured in the ranges of 544–681 MPa, 73–78 GPa, 17–28% and 2.5–3.7 MJ/m3, in the order (Ti–45Nb)96-4 Ga > (Ti–45Nb)96-2 Ga–2Cu > (Ti–45Nb)96–4Cu. In addition, it has been observed that micro-alloying Ti–Nb alloy with Ga and/or Cu posed no deleterious effect on the corrosion resistance in simulated body fluid conditions. The improvement in strength of the developed alloys has been discussed based on grain boundary and solid-solution strengthening, whereas the improved plasticity is attributed to work hardening.