Development of porous glass-fiber reinforced composite for bone implants. Evaluation of antimicrobial effect and implant fixation

Cranial bone reconstructions are necessary for correcting large skull bone defects due to trauma, tumors, infections and craniotomies. Traditional synthetic implant materials include solid or mesh titanium, various plastics and ceramics. Recently, biostable glass-fiber reinforced composites (FRC), which are based on bifunctional methacrylate resin, were introduced as novel implant solution. FRCs were originally developed and clinically used in dental applications. As a result of further in vitro and in vivo testing, these composites were also approved for clinical use in cranial surgery. To date, reconstructions of large bone defects were performed in 35 patients. This thesis is dedicated to the development of a novel FRC-based implant for cranial reconstructions. The proposed multi-component implant consists of three main parts: (i) porous FRC structure; (ii) bioactive glass granules embedded between FRC layers and (iii) a silver-polysaccharide nanocomposite coating. The porosity of the FRC structure should allow bone ingrowth. Bioactive glass as an osteopromotive material is expected to stimulate the formation of new bone. The polysaccharide coating is expected to prevent bacterial colonization of the implant. The FRC implants developed in this study are based on the porous network of randomly-oriented E-glass fibers bound together by non-resorbable photopolymerizable methacrylate resin. These structures had a total porosity of 10–70 volume %, of which > 70% were open pores. The pore sizes > 100 μm were in the biologically-relevant range (50-400 μm), which is essential for vascularization and bone ingrowth. Bone ingrowth into these structures was simulated by imbedding of porous FRC specimens in gypsum. Results of push-out tests indicated the increase in the shear strength and fracture toughness of the interface with the increase in the total porosity of FRC specimens. The osteopromotive effect of bioactive glass is based on its dissolution in the physiological environment. Here, calcium and phosphate ions, released from the glass, precipitated on the glass surface and its proximity (the FRC) and formed bone-like apatite. The biomineralization of the FRC structure, due to the bioactive glass reactions, was studied in Simulated Body Fluid (SBF) in static and dynamic conditions. An antimicrobial, non-cytotoxic polysaccharide coating, containing silver nanoparticles, was obtained through strong electrostatic interactions with the surface of FRC. In in vitro conditions the lactose-modified chitosan (chitlac) coating showed no signs of degradation within seven days of exposure to lysozyme or one day to hydrogen peroxide (H2O2). The antimicrobial efficacy of the coating was tested against Staphylococcus aureus and Pseudomonas aeruginosa. The contact-active coating had an excellent short time antimicrobial effect. The coating neither affected the initial adhesion of microorganisms to the implant surface nor the biofilm formation after 24 h and 72 h of incubation. Silver ions released to the aqueous environment led to a reduction of bacterial growth in the culture medium.

Unidirectional fiber-reinforced composite as an oral implant abutment material: Experimental studies of E-glass fiber/BisGMA-TEGDMA polymer in vitro

Fiber-reinforced composites (FRCs) are a new group of non-metallic biomaterials showing a growing popularity in many dental and medical applications. As an oral implant material, FRC is biocompatible in bone tissue environment. Soft tissue integration to FRC polymer material is unclear. This series of in vitro studies aimed at evaluating unidirectional E-glass FRC polymer in terms of mechanical, chemical, and biological properties in an attempt to develop a new non-metallic oral implant abutment alternative. Two different types of substrates were investigated: (a) Plain polymer (BisGMA 50%–TEGDMA 50%) and (b) Unidirectional FRC. The mechanical behavior of high fiber-density FRCs was assessed using a three-point bending test. Surface characterization was performed using scanning electron and spinning disk confocal microscopes. The surface wettability/energy was determined using sessile drop method. The blood response, including blood-clotting ability and platelet morphology was evaluated. Human gingival fibroblast cell responses - adhesion kinetics, adhesion strength, and proliferation activity - were studied in cell culture environment using routine test conditions. A novel tissue culture method was developed and used to evaluate porcine gingival tissue graft attachment and growth on the experimental composite implants. The analysis of the mechanical properties showed that there is a direct proportionality in the relationship between E-glass fiber volume fraction and toughness, modulus of elasticity, and load bearing capacity; however, flexural strength did not show significant improvement when high fiber-density FRC is used. FRCs showed moderate hydrophilic properties owing to the presence of exposed glass fibers on the polymer surface. Blood-clotting time was shorter on FRC substrates than on plain polymer. The FRC substrates also showed higher platelet activation state than plain polymer substrates. Fibroblast cell adhesion strength and proliferation rate were highly pronounced on FRCs. A tissue culture study revealed that gingival epithelium and connective tissue established an immediate close contact with both plain polymer and FRC implants. However, FRC seemed to guide epithelial migration outwards from the tissue/implant interface. Due to the anisotropic and hydrophilic nature of FRC, it can be concluded that this material enhances biological events related with soft tissue integration on oral implant surface.

Hydrometallurgical recovery of valuable metals from secondary raw materials

Wastes and side streams in the mining industry and different anthropogenic wastes often contain valuable metals in such concentrations their recovery may be economically viable. These raw materials are collectively called secondary raw materials. The recovery of metals from these materials is also environmentally favorable, since many of the metals, for example heavy metals, are hazardous to the environment. This has been noticed in legislative bodies, and strict regulations for handling both mining and anthropogenic wastes have been developed, mainly in the last decade. In the mining and metallurgy industry, important secondary raw materials include, for example, steelmaking dusts (recoverable metals e.g. Zn and Mo), zinc plant residues (Ag, Au, Ga, Ge, In) and waste slurry from Bayer process alumina production (Ga, REE, Ti, V). From anthropogenic wastes, waste electrical and electronic equipment (WEEE), among them LCD screens and fluorescent lamps, are clearly the most important from a metals recovery point of view. Metals that are commonly recovered from WEEE include, for example, Ag, Au, Cu, Pd and Pt. In LCD screens indium, and in fluorescent lamps, REEs, are possible target metals. Hydrometallurgical processing routes are highly suitable for the treatment of complex and/or low grade raw materials, as secondary raw materials often are. These solid or liquid raw materials often contain large amounts of base metals, for example. Thus, in order to recover valuable metals, with small concentrations, highly selective separation methods, such as hydrometallurgical routes, are needed. In addition, hydrometallurgical processes are also seen as more environmental friendly, and they have lower energy consumption, when compared to pyrometallurgical processes. In this thesis, solvent extraction and ion exchange are the most important hydrometallurgical separation methods studied. Solvent extraction is a mainstream unit operation in the metallurgical industry for all kinds of metals, but for ion exchange, practical applications are not as widespread. However, ion exchange is known to be particularly suitable for dilute feed solutions and complex separation tasks, which makes it a viable option, especially for processing secondary raw materials. Recovering valuable metals was studied with five different raw materials, which included liquid and solid side streams from metallurgical industries and WEEE. Recovery of high purity (99.7%) In, from LCD screens, was achieved by leaching with H2SO4, extracting In and Sn to D2EHPA, and selectively stripping In to HCl. In was also concentrated in the solvent extraction stage from 44 mg/L to 6.5 g/L. Ge was recovered as a side product from two different base metal process liquors with Nmethylglucamine functional chelating ion exchange resin (IRA-743). Based on equilibrium and dynamic modeling, a mechanism for this moderately complex adsorption process was suggested. Eu and Y were leached with high yields (91 and 83%) by 2 M H2SO4 from a fluorescent lamp precipitate of waste treatment plant. The waste also contained significant amounts of other REEs such as Gd and Tb, but these were not leached with common mineral acids in ambient conditions. Zn was selectively leached over Fe from steelmaking dusts with a controlled acidic leaching method, in which the pH did not go below, but was held close as possible to, 3. Mo was also present in the other studied dust, and was leached with pure water more effectively than with the acidic methods. Good yield and selectivity in the solvent extraction of Zn was achieved by D2EHPA. However, Fe needs to be eliminated in advance, either by the controlled leaching method or, for example, by precipitation. 100% Pure Mo/Cr product was achieved with quaternary ammonium salt (Aliquat 336) directly from the water leachate, without pH adjustment (pH 13.7). A Mo/Cr mixture was also obtained from H2SO4 leachates with hydroxyoxime LIX 84-I and trioctylamine (TOA), but the purities were 70% at most. However with Aliquat 336, again an over 99% pure mixture was obtained. High selectivity for Mo over Cr was not achieved with any of the studied reagents. Ag-NaCl solution was purified from divalent impurity metals by aminomethylphosphonium functional Lewatit TP-260 ion exchange resin. A novel preconditioning method, named controlled partial neutralization, with conjugate bases of weak organic acids, was used to control the pH in the column to avoid capacity losses or precipitations. Counter-current SMB was shown to be a better process configuration than either batch column operation or the cross-current operation conventionally used in the metallurgical industry. The raw materials used in this thesis were also evaluated from an economic point of view, and the precipitate from a waste fluorescent lamp treatment process was clearly shown to be the most promising.

Weed Community in a Raw Sugarcane Renovation Area Submitted to Different Soil Managements

The objective of this study was to evaluate the weed community in a raw sugarcane renovation area with three soil managements and peanut sowing in succession. The experiment was conducted during the 2007/08 season on a raw sugarcane area harvested without prior burning in the last five cuts. A randomized block design with treatments arranged in a split plot and arranged in four replications was used. The main treatments consisted of three cropping systems: conventional tillage, minimum tillage and direct planting, and subplots consisted in the absence (resting) or presence of crop rotation with peanuts. After 135 days from planting peanuts and 180 days of sugarcane harvest, the number of weeds m-2 was counted and the shoot dry biomass of the weeds collected was determined. The data were interpreted by analysis of variance and the means were compared by Tukey's test at 5% probability so that phytosociological indices a, b, c e d were calculated. The use of soil conservation tillage and peanut in rotation with sugarcane in the renovation areas is effective in controlling weeds and suppression of weed species difficult to control like Cyperus rotundus, Commelina bengalensis, Urochloa plantaginea, and Digitaria nuda.

Through the looking glass: does our metadata make sense?

Esitys KDK-käytettävyystyöryhmän järjestämässä seminaarissa: Miten käyttäjien toiveet haastavat metatietokäytäntöjämme? / How users' expectations challenge our metadata practices? 30.9.2014.

Glass pipette-carbon fiber microelectrodes for evoked potential recordings

Current methods for recording field potentials with tungsten electrodes make it virtually impossible to use the same recording electrode also as a lesioning electrode, for example for histological confirmation of the recorded site, because the lesioning procedure usually wears off the tungsten tip. Therefore, the electrode would have to be replaced after each lesioning procedure, which is a very high cost solution to the problem. We present here a low cost, easy to make, high quality glass pipette-carbon fiber microelectrode that shows resistive, signal/noise and electrochemical coupling advantages over tungsten electrodes. Also, currently used carbon fiber microelectrodes often show problems with electrical continuity, especially regarding electrochemical applications using a carbon-powder/resin mixture, with consequent low performance, besides the inconvenience of handling such a mixture. We propose here a new method for manufacturing glass pipette-carbon fiber microelectrodes with several advantages when recording intracerebral field potentials

Energy and raw material consumption analysis of powder bed fusion: case study: CNC machining and laser additive manufacturing

Laser additive manufacturing (LAM), known also as 3D printing, is a powder bed fusion (PBF) type of additive manufacturing (AM) technology used to manufacture metal parts layer by layer by assist of laser beam. The development of the technology from building just prototype parts to functional parts is due to design flexibility. And also possibility to manufacture tailored and optimised components in terms of performance and strength to weight ratio of final parts. The study of energy and raw material consumption in LAM is essential as it might facilitate the adoption and usage of the technique in manufacturing industries. The objective this thesis was find the impact of LAM on environmental and economic aspects and to conduct life cycle inventory of CNC machining and LAM in terms of energy and raw material consumption at production phases. Literature overview in this thesis include sustainability issues in manufacturing industries with focus on environmental and economic aspects. Also life cycle assessment and its applicability in manufacturing industry were studied. UPLCI-CO2PE! Initiative was identified as mostly applied exiting methodology to conduct LCI analysis in discrete manufacturing process like LAM. Many of the reviewed literature had focused to PBF of polymeric material and only few had considered metallic materials. The studies that had included metallic materials had only measured input and output energy or materials of the process and compared to different AM systems without comparing to any competitive process. Neither did any include effect of process variation when building metallic parts with LAM. Experimental testing were carried out to make dissimilar samples with CNC machining and LAM in this thesis. Test samples were designed to include part complexity and weight reductions. PUMA 2500Y lathe machine was used in the CNC machining whereas a modified research machine representing EOSINT M-series was used for the LAM. The raw material used for making the test pieces were stainless steel 316L bar (CNC machined parts) and stainless steel 316L powder (LAM built parts). An analysis of power, time, and the energy consumed in each of the manufacturing processes on production phase showed that LAM utilises more energy than CNC machining. The high energy consumption was as result of duration of production. Energy consumption profiles in CNC machining showed fluctuations with high and low power ranges. LAM energy usage within specific mode (standby, heating, process, sawing) remained relatively constant through the production. CNC machining was limited in terms of manufacturing freedom as it was not possible to manufacture all the designed sample by machining. And the one which was possible was aided with large amount of material removed as waste. Planning phase in LAM was shorter than in CNC machining as the latter required many preparation steps. Specific energy consumption (SEC) were estimated in LAM based on the practical results and assumed platform utilisation. The estimated platform utilisation showed SEC could reduce when more parts were placed in one build than it was in with the empirical results in this thesis (six parts).

Provitamin a activity of Brazilian carrots: leaves and roots, raw and cooked and their chemical composition

The purpose of this study was to determine through carotenoid analysis, the provitamin A value of two carrots (Daucus carota L.) cultivars (Brasilia and Beta3), leaves and roots, raw and submitted to two ways of cooking: boiling and microwave. Proximate analysis results are also presented for a better characterization of these vegetables (moisture, ash, lipids, proteins, fiber and total carbohydrates). The main carotenoids sources of provitamin A in this vegetable, both in leaves or roots was β-carotene and α-carotene. α-carotene shows half of the provitamin A value of β-carotene. Samples of the Brasilia cultivar presented the better provitamin A value both for leaves and roots. The results for raw samples of the Brasilia cultivar were 464.48 RE/100g for leaves and 606.42 RE/100g for roots. There were no significant losses of provitamin A with the boiling or microwave cooking methods used.

Provitamin a activity of raw and cooked Brazilian leaves

The purpose of this study was to determine, through beta-carotene analysis, the provitamin A value of three vegetables leaves ("serralha", celery and mint), raw and submitted to two ways of cooking: boiling and microwave. Samples of "serralha" presented the better provitamin A value beyond the three leaves analyzed: 1, 373 RE/100g for raw samples. Except for mint, it was observed a significant lost of provitamin A due the two ways of cooking.

Calcium bioavailability of raw and extruded amaranth grains

Calcium bioavailability of raw and extruded amaranth grains was assessed in a biological assay in rats. Rats were fed for 28 days on diets in which raw or extruded amaranth was the only calcium source, compared to a control diet with calcium carbonate. Calcium and phosphorous levels were determined in the rats' serum during the experimental period and in the bones at the end of the experiment. Amaranth extrusion increased its calcium bioavailability, assessed by tibia and femur weights and calcium and phosphorous content of the bones. Apparent calcium absorption index, the force needed to break the bones and bone densitometry of both extruded and raw amaranth were the same, though different from the control group. The results show that amaranth can be a complementary source of dietary calcium the bioavailability of which is favorably modified by the extrusion process.

Stability of volatile profile and sensory properties of passion fruit juice during storage in glass bottles

This study aimed at assessing the stability of passion fruit juice in glass bottles during a 120-day storage period, regarding its volatile compounds profile and sensory properties (aroma and flavor). Samples were obtained from a Brazilian tropical juice industry (Fortaleza, Brazil) and submitted to sensory and chromatographic analyses. The characteristic aroma and flavor of passion fruit were evaluated by a trained panel with a non-structured scale of 9 cm. The headspace volatile compounds were isolated from the product by suction and trapped in Porapak Q, analyzed through high-resolution gas chromatography and identified through gas chromatography-mass spectrometry (GC-MS). Twelve odoriferous compounds were monitored: ethyl butanoate, ethyl propanoate, 3-methyl-1-butanol, 3-methyl-2-butenol, (E)-3-hexenol, (Z)-3-hexenol, 3-methylbutyl acetate, benzaldehyde, ethyl hexanoate, hexyl acetate, limonene and furfural. The slight variations observed in the volatile profile were not enough to provoke significant changes in the characteristic aroma and flavor of the passion fruit juice.

Raw-appearing Restructured fish models made with Sodium alginate or Microbial transglutaminase and effect of chilled storage

Restructuring by adding Sodium Alginate or Microbial Transglutaminase (MTGase) using cold gelation technology make it possible to obtain many different raw products from minced and/or chopped fish muscle that are suitable for being used as the basis of new restructured products with different physicochemical properties and even different compositions. Special consideration must be given to their shelf-life and the changes that may take place during chilling, both in visual appearance and physicochemical properties. After chilled storage, the restructured models made with different muscular particle size and composition at low temperature (5 °C), it was observed that microbial growth limited the shelf-life to 7-14 days. Mechanical properties increased (p < 0.05) during that time, and higher values were observed in samples elaborated by joining small muscle particle size than in those elaborated by homogenization. There was no clear increase in the cooking yield and purge loss, and no significant colour change (p > 0.05) was detected during storage.

Effect of adding unconventional raw materials on the technological properties of rice fresh pasta

The aim of this study was to develop fettuccini type rice fresh pasta by cold extrusion. To produce the pasta, a 2² Central Composite Rotational Design was used, in which the effects of the addition of pre-gelatinized rice flour - PGRF (0-60%) and modified egg albumin - MEA (0-10%) were studied. The dependent variables were the results of the cooking test and of the instrumental texture. The optimum cooking time for all of the formulations of rice fresh pasta was 3 minutes. MEA had a greater effect on increasing the weight of the pasta when compared to that of PGRF. It was found that with the addition of PGRF increase in loss of solids in cooking water, whereas MEA exerted the opposite effect on this parameter. Moreover, the maximum value of MEA (10%) had an optimum effect on pasta firmness, while PGRF had a negative effect on this parameter. The maximum values of PGRF and MEA reduced the stickiness of the pasta. Based on these results and on the parameters considered as most important, the rice pasta with the best technological characteristics was that with the maximum levels of MEA (10%) and no addition of PGRF (0%). This product was submitted to sensory and microbiological analyses, with good results.

The kinetics of lipase activity and hydrolytic rancidity of raw, parboiled, and extruded rice bran during storage

The main problem related to rice bran use is that it goes rancid right after its production. The objective of the present study was to apply a mathematical model to evaluate the kinetics of the lipase activity and hydrolytic rancidity of the raw rice bran (RRB), extruded rice bran (ERB), and parboiled rice bran (PRB) stored in low density polyethylene bags at room temperature for 180 days. Extrusion and parboiling were efficient in preventing free fatty acid formationin ERB and PRB.Extrusion reduced the velocity constant of lipase activity as compared to that of RRB while parboiling increased it, and both decreased the lipase activity after equilibrium from 150 days. The extrusion and parboiling treatments increased the velocity constants for the liberation of free fatty acids although the equilibrium was reached with reduced production of free fatty acids in relation to the production of raw rice bran after 150 days ofstorage. Extrusion proved the best treatment under the storage temperature conditions of rice bran from cultivar BRS Primavera.

Adhesion and production of degrading enzymes by bacteria isolated from biofilms in raw milk cooling tanks

Biofilms in milk cooling tanks compromise product quality even on farms. Due to the lack of studies of this topic, this study evaluated the microbiological conditions of raw milk cooling tanks on farms and characterized the microorganisms isolated from these tanks. Samples were wiped off with sterile swabs from seven milk cooling tanks in three different points in each tank. Mesophiles and psychrotrophic counts were performed in all samples. The isolation of Pseudomonas spp., Bacillus cereus and atypical colonies formed on selective media were also performed, totalizing 297 isolates. All isolates were tested for protease and lipase production and biofilm formation. Of the total isolates, 62.9% produced protease, 55.9% produced lipase, and 50.2% produced biofilm. The most widespread genus inside the milk cooling tank was Pseudomonas since it was not possible to associate this contamination with a single sampling point in the equipment. High counts of microorganisms were found in some cooling tanks, indicating poor cleaning of the equipment and providing strong evidences of microbial biofilm presence. Moreover, it is worth mentioning the milk potential contamination with both microbial cells and their degrading enzymes, which compromises milk quality.