Polydimethylsiloxane Microdomains Formation at the Polythiourethane/Air Interface and Its Influence on Barnacle Release.

In this study, polydimethylsiloxane (PDMS)/polythiourethane (PTU) composite reinforced with tetrapodal shaped micro-nano ZnO particles (t-ZnO) was successfully produced by a versatile, industrially applicable polymer blending process. On the surface of this composite, PDMS is distributed in the form of microdomains embedded in a PTU matrix. The composite inherited not only good mechanical properties originating from PTU but also promising fouling-release (FR) properties due to the presence of PDMS on the surface. It was shown that the preferential segregation of PDMS domains at the polymer/air interface could be attributed to the difference in the surface free energy of PDMS and PTU. The PDMS microdomains at the PTU/air interface significantly reduced the barnacle adhesion strength on the composite. Both the pseudo- and natural barnacle adhesion strength on the composite was approximately 0.1 MPa, similar to that on pure PDMS. The pseudo-barnacle adhesion on reference surfaces AlMg3 and PTU reached approximately 4 and 6 MPa, respectively. Natural barnacles could not be removed intact from AlMg3 and PTU surfaces without breaking the shell, indicating that the adhesion strength was higher than the mechanical strength of a barnacle shell (approximately 0.4 MPa). The integrity of PDMS microdomains was maintained after 12 months of immersion in seawater and barnacle removal. No surface deteriorations were found. In short, the composite showed excellent potential as a long-term stable FR coating for marine applications.

Development and Characterization of Mechanically Durable Silicone-Polythiourethane Composites Modified with Tetrapodal Shaped ZnO Particles for the Potential Application as Fouling-Release Coating in the Marine Sector.

Ecological considerations strongly necessitate the development of environmentally friendly antifouling paints. A promising alternative to biocide containing antifouling paints are fouling-release coatings, which are non-toxic and designed to prevent permanent attachment of marine organisms to the surface, due to their low surface energy. However, these coatings suffer from insufficient mechanical properties, which make them unsuitable for mechanically stressed surfaces e.g., on ship hulls. To overcome those obstacles, polydimethylsiloxane (PDMS)-polythiourethane (PTU) composites modified with tetrapodal shaped micro-nano ZnO particles (t-ZnO) were produced and characterized by evaluating the surface energy, mechanical properties, and fouling-release performance. Among all variations, PTU/1 wt.% PDMS composites with 1 wt.% t-ZnO particles possess superior properties for applications as fouling-release coatings for maritime purposes.

Sacrificial Template Synthesis and Properties of 3D Hollow-Silicon Nano- and Microstructures.

Novel three-dimensional (3D) hollow aero-silicon nano- and microstructures, namely, Si-tetrapods (Si-T) and Si-spheres (Si-S) were synthesized by a sacrificial template approach for the first time. The new Si-T and Si-S architectures were found as most temperature-stable hollow nanomaterials, up to 1000 °C, ever reported. The synthesized aero-silicon or aerogel was integrated into sensor structures based on 3D networks. A single microstructure Si-T was employed to investigate electrical and gas sensing properties. The elaborated hollow microstructures open new possibilities and a wide area of perspectives in the field of nano- and microstructure synthesis by sacrificial template approaches. The enormous flexibility and variety of the hollow Si structures are provided by the special geometry of the sacrificial template material, ZnO-tetrapods (ZnO-T). A Si layer was deposited onto the surface of ZnO-T networks by plasma-enhanced chemical vapor deposition. All samples demonstrated p-type conductivity; hence, the resistance of the sensor structure increased after introducing the reducing gases in the test chamber. These hollow structures and their unique and superior properties can be advantageous in different fields, such as NEMS/MEMS, batteries, dye-sensitized solar cells, gas sensing in harsh environment, and biomedical applications. This method can be extended for synthesis of other types of hollow nanostructures.

Biaxial flexural strength of new Bis-GMA/TEGDMA based composites with different fillers for dental applications.

OBJECTIVE: The aim of this study was to evaluate whether the mechanical properties of the modern dental composites can be improved by using tetrapodal ZnO particles as fillers in a Bis-GMA/TEGDMA matrix. Another aim was to test whether the mechanical properties of the composite are influenced by functionalization of the ZnO particles with lauric acid to achieve antibacterial activity. METHODS: Different filler materials and particle shapes (spherical zirconia, spherical zinc oxide, tetrapodal zinc oxide) were used to produce Bis-GMA/TEGDMA based composites with a filler content of 40wt.-% and 60wt.-%, respectively. In addition, functionalization with lauric acid was investigated. For the biaxial flexural strength testing 104 test disks (N=8) with a diameter of 15mm and a thickness of 1.5mm were produced. RESULTS: Functionalization with lauric acid resulted in a decrease in biaxial flexural strength for all filler materials. The biaxial flexural strength decreased when using a higher filler content with spherical particles but increased when using tetrapodal zinc oxide particles. SIGNIFICANCE: A higher durability of the composites using tetrapodal zinc oxide particles. An antibacterial functionalization with lauric acid cannot be recommended as the mechanical stability of the composite will be reduced.

Complex shaped ZnO nano- and microstructure based polymer composites: mechanically stable and environmentally friendly coatings for potential antifouling applications.

Since the prohibition of tributyltin (TBT)-based antifouling paints in 2008, the development of environmentally compatible and commercially realizable alternatives is a crucial issue. Cost effective fabrication of antifouling paints with desired physical and biocompatible features is simultaneously required and recent developments in the direction of inorganic nanomaterials could play a major role. In the present work, a solvent free polymer/particle-composite coating based on two component polythiourethane (PTU) and tetrapodal shaped ZnO (t-ZnO) nano- and microstructures has been synthesized and studied with respect to mechanical, chemical and biocompatibility properties. Furthermore, antifouling tests have been carried out in artificial seawater tanks. Four different PTU/t-ZnO composites with various t-ZnO filling fractions (0 wt%, 1 wt%, 5 wt%, 10 wt%) were prepared and the corresponding tensile, hardness, and pull-off test results revealed that the composite filled with 5 wt% t-ZnO exhibits the strongest mechanical properties. Surface free energy (SFE) studies using contact angle measurements showed that the SFE value decreases with an increase in t-ZnO filler amounts. The influence of t-ZnO on the polymerization reaction was confirmed by Fourier transform infrared-spectroscopy measurements and thermogravimetric analysis. The immersion tests demonstrated that fouling behavior of the PTU/t-ZnO composite with a 1 wt% t-ZnO filler has been decreased in comparison to pure PTU. The composite with a 5 wt% t-ZnO filler showed almost no biofouling.

Study of tetrapodal ZnO-PDMS composites: a comparison of fillers shapes in stiffness and hydrophobicity improvements.

ZnO particles of different size and structures were used as fillers to modify the silicone rubber, in order to reveal the effect of the filler shape in the polymer composites. Tetrapodal shaped microparticles, short microfibers/whiskers, and nanosized spherical particles from ZnO have been used as fillers to fabricate the different ZnO-Silicone composites. The detailed microstructures of the fillers as well as synthesized composites using scanning electron microscopy have been presented here. The tensile elastic modulus and water contact angle, which are important parameters for bio-mimetic applications, of fabricated composites with different fillers have been measured and compared. Among all three types of fillers, tetrapodal shaped ZnO microparticles showed the best performance in terms of increase in hydrophobicity of material cross-section as well as the stiffness of the composites. It has been demonstrated that the tetrapodal shaped microparticles gain their advantage due to the special shape, which avoids agglomeration problems as in the case for nanoparticles, and the difficulty of achieving truly random distribution for whisker fillers.