Christian Heller

Photopolymers with tunable mechanical properties processed by laser-based high-resolution stereolithography

Stereolithography (SLA) is a widely used technique for the fabrication of prototypes and small series products. The main advantage of SLA and related solid freeform fabrication (SFF) techniques is their capability to fabricate parts with complex shapes with high resolution. Although the spectrum of available materials has been widened in recent years, there is still a lack of materials which can be processed with SLA on a routine basis. In this work, a micro-SLA (?SLA) system is presented which can shape a number of different photopolymers with resolutions down to 5 ?m in the xy-plane and 10 ?m in the z-direction. The system is capable of processing various specifically tailored photopolymers which are based on acrylate chemistry. The materials processed for this work range from hybrid sol?gel materials (ORMOCER) to photo-crosslinked elastomers and hydrogels. The elastic moduli of these materials can be tuned over several orders of magnitude and range from 0.1 MPa to 8000 MPa. The reactivity of these monomers is sufficient for achieving writing speeds up to 500 mm s?1 which is comparable to commercial SLA resins. Various test structures are presented which show the suitability of the process for fabricating parts required for applications in micro-mechanical systems as well as for applications in biomedical engineering. Using the presented system, internal channels with a diameter of 50 ?m and a length of 1500 ?m could be fabricated. It was also possible to manufacture a micro-mechanical system consisting of a fixed axe and a free spinning turbine wheel.

3D Printable Biophotopolymers for in Vivo Bone Regeneration

The present study investigated two novel biophotopolymer classes that are chemically based on non-toxic poly (vinyl alcohol). These vinylesters and vinylcarbonates were compared to standard acrylates in vitro on MC3T3-E1 cells and in vivo in a small animal model. In vitro, both vinylester and vinylcarbonate monomers showed about tenfold less cytotoxicity when compared to acrylates (IC50: 2.922 mM and 2.392 mM vs. 0.201 mM) and at least threefold higher alkaline phosphatase activity (17.038 and 18.836 vs. 5.795, measured at [10 mM]). In vivo, polymerized 3D cellular structures were implanted into the distal femoral condyle of 16 New Zealand White Rabbits and were observed for periods from 4 to 12 weeks. New bone formation and bone to implant contact was evaluated by histomorphometry at end of observation. Vinylesters showed similar rates of new bone formation but significantly less (p = 0.002) bone to implant contact, when compared to acrylates. In contrast, the implantation of vinylcarbonate based biophotopolymers led to significantly higher rates of newly formed bone (p < 0.001) and bone to implant contact (p < 0.001). Additionally, distinct signs of polymer degradation could be observed in vinylesters and vinylcarbonates by histology. We conclude, that vinylesters and vinylcarbonates are promising new biophotopolymers, that outmatch available poly(lactic acid) and (meth)acrylate based materials.

Poly(vinyl alcohol) based monomers for lithography-based 3D fabrication

Lithography based Solid Freeform Fabrication (SFF) methods (e.g. stereolithography allow the fabrication of cellular structures with defined pore sizes and geometries. Achievable wall thicknesses range down to 50 μm.

Biocompatible Phosphorus-based Monomers for Radical Polymerization

Novel biocompatible and biodegradable monomers based on phosphorus-containing vinyl esters and vinyl carbamates for radical photopolymerization were prepared. By photo-Differential Scanning Calorimetry (photo-DSC) the reactivity of the mono-, di- and trifunctional monomers was investigated. Furthermore, their cytotoxicity, mechanical properties and hydrolytic degradation behavior were evaluated, aiming at a future application of our compounds in the biomedical area.

Additive Manufacturing Technologies for the 3D Fabrication of Biocompatible and Biodegradable Photopolymers

High molecular weight vinyl esters and carbonates based on oligo(ethylene glycol), oligomeric fatty acids and poly(hexamethylene carbonate), as alternatives for potentially cytotoxic acrylate based monomers have been structured by Additive Manufacturing Technologies (AMTs) like Microstereolithography (μ-SLA), Digital Light Processing (DLP) and Two-Photon Induced Photopolymerization (TPIP). With these techniques feature resolutions down to 10 μm (μ-SLA and DLP) or even 200 nm (TPIP) can be obtained. This new class of monomers exhibits LC 50 values for cytotoxicity up to two orders of magnitude lower than acrylate references. Beside a high reactivity of the resin, the shrinkage and the mechanical properties of the final part material are another essential parameter. Low molecular weight monomers are very reactive and lead to densely cross-linked materials which suffer from high shrinkage and strains within the cured material. Therefore, mixtures of high molecular weight vinyl esters/carbonates with low molecular weight crosslinkers have been evaluated regarding their photoreactivity and mechanical properties.

New 3D-Biophotopolymers with Selective Surface-cell Interactions for Regenerative Medicine

Additive Manufacturing Technologies (AMTs) have become an appealing method for the fabrication of 3D cellular scaffolds for tissue engineering and regenerative medicine. To circumvent the use of (meth)acrylate based photopolymers, that suffer from skin irritation and sometimes cytotoxicity, new monomers based on vinyl esters, carbonates and carbamates were prepared. The new materials, giving poly(vinyl alcohol) upon hydrolysis, showed similar results compared to (meth)acrylate references concerning the photoreactivity and mechanical properties, yet being significantly less cytotoxic. To study the kinetics of hydrolytic degradation, the influence of the different polymerizable groups was investigated by hydrolysis of model compounds under alkaline conditions. We were able to show that the ester moiety of a vinyl ester based polymer could be used to immobilize alkaline phosphatase, therefore they exhibit the ability to immobilize enzymes for selective cell adhesion. Finally, 3D test structures by AMT techniques could be fabricated and in-vivo testing thereof proofed the biocompatibility of vinyl ester-based scaffolds.