RESUMO
A custom-made prosthetic product is unique for each patient. Fossil-based thermoplastics are the dominant raw materials in both prosthetic and industrial applications; there is a general demand for reducing their use and replacing them with renewable, biobased materials. A transtibial prosthesis sets strict demands on mechanical strength, durability, reliability, etc., which depend on the biocomposite used and also the additive manufacturing (AM) process. The aim of this project was to develop systematic solutions for prosthetic products and services by combining biocomposites using forestry-based derivatives with AM techniques. Composite materials made of polypropylene (PP) reinforced with microfibrillated cellulose (MFC) were developed. The MFC contents (20, 30 and 40 wt%) were uniformly dispersed in the polymer PP matrix, and the MFC addition significantly enhanced the mechanical performance of the materials. With 30 wt% MFC, the tensile strength and Young´s modulus was about twice that of the PP when injection molding was performed. The composite material was successfully applied with an AM process, i.e., fused deposition modeling (FDM), and a transtibial prosthesis was created based on the end-user's data. A clinical trial of the prosthesis was conducted with successful outcomes in terms of wearing experience, appearance (color), and acceptance towards the materials and the technique. Given the layer-by-layer nature of AM processes, structural and process optimizations are needed to maximize the reinforcement effects of MFC to eliminate variations in the binding area between adjacent layers and to improve the adhesion between layers.
RESUMO
Cellulose nanofibrils (CNF) can be produced in the form of thin, transparent and flexible films. However, the permeability of such materials to oxygen and water vapor is very sensitive to moisture, which limits their potential for a variety of packaging and encapsulation applications. Diffusion barrier coatings were thus developed to reduce the access of water molecules to enzymatically pre-treated and carboxymethylated CNF substrates. The coatings were based on UV curable organic-inorganic hybrids with epoxy, tetraethylorthosilicate (TEOS) and 3-glycidoxypropyltrimethylenesilane (GPTS) precursors and additional vapor formed SiNx layers. A total of 14 monolayer and multilayer coatings with various thickness and hybrid composition were produced and analyzed. The water vapor transmission rate (WVTR) of the bilayer epoxy/CNF film was two times lower compared to that of uncoated CNF film. This was partly due to the water vapor permeability of the epoxy, a factor of two times lower than CNF. The epoxy coating improved the transparency of CNF, however it did not properly wet to the CNF surfaces and the interfacial adhesion was low. In contrast hybrid epoxy-silica coatings led to high adhesion levels owing to the formation of covalent interactions through condensation reactions with the OH-terminated CNF surface. The barrier and optical performance of hybrid coated CNF substrates was similar to that of CNF coated with pure epoxy. In addition, the hybrid coatings provided an excellent planarization effect, with roughness close to 1 nm, one to two orders of magnitude lower than that of the CNF substrates. The WVTR and oxygen transmission rate values of the hybrid coated CNF laminates were in the range 5-10 g/m2/day (at 38°C and 50% RH) and 3-6 cm3/m2/day/bar (at 23°C and 70% RH), respectively, which matches food and pharmaceutical packaging requirements. The permeability to water vapor of the hybrid coatings was moreover found to decrease with increasing the TEOS/GPTS ratio up to 30 wt% and then increase at higher ratio, and to be much lower for thinner coatings due to further UV-induced silanol condensation and faster evaporation of byproducts. The addition of a single 150 nm thick SiNx layer on the hybrid coated CNF improved its water vapor barrier performance by more than 680 times, with WVTR below the 0.02 g/m2/day detection limit.