Use of fiber-reinforced composite framework and thermochromic pigment in maxillofacial prostheses

The purpose of this investigation was to evaluate the possibility to enhance certain qualities of facial prostheses. Polymethyl methacrylate is still being used as base mate¬rial or clip carrier material, but it is hard and heavy, and debonding of the silicone from the acrylic base material is a frequent problem. This thesis aims to evaluate the use of fiber-reinforced composite (FRC) as framework material for maxillofacial silicone prostheses. FRC has been used as reinforcement in removable and fixed partial dentures since the 1990s. This material is lightweight and can be fabricated to compress the margins of the prosthesis slightly, to keep it tightly against the skin during jaw movements and facial expressions. Additionally, the use of a thermochromic pigment, colorless in room temperature and red in a cold environment, was studied in order to evaluate the possibility of using this color changing pigment in facial prostheses to mimic the color change of facial skin in cold weather. The tensile bond strength between pre-impregnated, unidirectional FRC and maxillofacial silicone elastomer was studied. Three different bonding agents or primers were compared. Bond strength was improved by one of the primers and by roughening the surface. The effect of a skin compressing glass fiber-reinforced composite framework on facial skin blood flow was studied by using a face mask, constructed with a compression pad corresponding to the outer margin of a glass fiber-reinforced framework beam of a facial prosthesis. The skin blood flow of ten healthy volunteers, aged 23-25 years, was measured during touch, light, and moderate compression of the skin, by using laser Doppler imaging technique. None of the compressions showed any marked effects on local skin blood flow. There were no significant differences between blood flow during compression and at baseline. Maxillofacial silicone elastomer was colored intrinsically with conventional color pigments: a control group containing only conventional pigments was compared to two test groups with 0.2 wt% and 0.6 wt% thermochromic pigment added. The color of the material was measured with a spectrophotometer in room temperature and after storage in a freezer. The color stability of the maxillofacial silicone elastomer colored with thermo¬chromic pigment was evaluated by artificial aging. The color dif¬ference of the L* (lightness) and a* values (redness), comparing color after the samples were stored at room temperature and in a freezer (-19°C), was statistically significant for both 0.2 wt% and 0.6 wt% thermo¬chromic pigment groups. The differences in the b* values (yellowness) were statistically significant for the 0.6 wt% group. Exposure to ultraviolet (UV) radiation led to visually noticeable and statistically signifi¬cant color changes (ΔE) in all color values in both test groups. The specimens containing thermochromic pigment were very sensitive to UV radiation. In conclusion, a framework of fiber-reinforced composite can successfully be bonded to maxillofacial silicone elastomer, and a framework beam, compressing the facial skin, did not remarkably alter the skin blood flow on healthy, young adults. The thermochromic pigment showed color change in maxillofacial silicone elastomer. However, artificial aging showed that it was too sensitive to UV radiation to be used, as such, in maxillofacial prostheses.

Kaupallisten komposiittituotteiden materiaaliominaisuuksien määritys ja vertailu

Tässä kandidaatintyössä tutkittiin viiden kaupallisen puu-muovikomposiittituotteen säänkestävyyttä kolmen eri materiaaliominaisuuden avulla. Tuotteet olivat Suomessa markkinoilla olevia terassirakentamisen tuotteita ja niiltä mitattiin Charpy -iskulujuutta, veden absorptiokykyä ja värinmuutosta. Tuloksia verrattiin sekä keskenään, että muualla maailmassa tutkittujen kaupallisten tuotteiden kanssa. Tulosten perusteella havaittiin, että Suomen markkinoilla olevien tuotteiden säänkestävyys on erinomainen.

Ultraviolet light protection and weathering properties of wood-polypropylene composites

The main aim of this thesis is to study the effect of pigments on the weathering properties of wood-polypropylene composites (WPC). The studied properties are color change, water absorption, thickness swelling and Charpy impact strength. The impact of weathering and UV exposure on WPCs was studied by using pigments and minerals as protective agents. The study shows that the pigments and/or mineral fillers can be used to improve the weathering properties of WPCs. The effect of pigments was found to vary with the type of pigment and the method of weathering. The black pigment, an inorganic carbon black master-batch, was found to be the most effective one in reduction of the discoloration of WPCs. By preventing discoloration, and further reducing the degradation of the surface of the WPC, the pigments were found to reduce the decrease in the impact strength after weathering. As well as UV protection, the moisture resistance is a significant factor affecting the durability of WPCs. The addition of mineral fillers was found to improve the moisture-related properties, such as water absorption and thickness swelling, of WPC significantly. According to the findings, addition of pigments and mineral fillers to wood-polypropylene composites appears to be beneficial: color stability and moisture resistance can be enhanced especially in outdoor weathering. The combined effect of black pigment (carbon black master-batch) and wollastonite as a mineral filler was found to bring about the most effective properties against weathering.

Viologen based electroactive polymers and composites for durable electrochromic systems

Electrochromism, the phenomenon of reversible color change induced by a small electric charge, forms the basis for operation of several devices including mirrors, displays and smart windows. Although, the history of electrochromism dates back to the 19th century, only the last quarter of the 20th century has its considerable scientific and technological impact. The commercial applications of electrochromics (ECs) are rather limited, besides top selling EC anti-glare mirrors by Gentex Corporation and airplane windows by Boeing, which made a huge commercial success and exposed the potential of EC materials for future glass industry. It is evident from their patents that viologens (salts of 4,4ʹ-bipyridilium) were the major active EC component for most of these marketed devices, signifying the motivation of this thesis focusing on EC viologens. Among the family of electrochromes, viologens have been utilized in electrochromic devices (ECDs) for a while, due to its intensely colored radical cation formation induced by applying a small cathodic potential. Viologens can be synthesized as oligomer or in the polymeric form or as functionality to conjugated polymers. In this thesis, polyviologens (PVs) were synthesized starting from cyanopyridinium (CNP) based monomer precursors. Reductive coupling of cross-connected cyano groups yields viologen and polyviologen under successive electropolymerization using for example the cyclic voltammetry (CV) technique. For further development, a polyviologen-graphene composite system was fabricated, focusing at the stability of the PV electrochrome without sacrificing its excellent EC properties. High electrical conductivity, high surface area offered by graphene sheets together with its non-covalent interactions and synergism with PV significantly improved the electrochrome durability in the composite matrix. The work thereby continued in developing a CNP functionalized thiophene derivative and its copolymer for possible utilization of viologen in the copolymer blend. Furthermore, the viologen functionalized thiophene derivative was synthesized and electropolymerized in order to explore enhancement in the EC contrast and overall EC performance. The findings suggest that such electroactive viologen/polyviologen systems and their nanostructured composite films as well as viologen functionalized conjugated polymers, can be potentially applied as an active EC material in future ECDs aiming at durable device performances.