Abstract Introduction After the advent of low-temperature thermoplastics, their prevalence in the manufacture of orthoses for upper limbs has been identified by several authors. The understanding of their properties by occupational therapists and other professionals working in this field is important in the process of selecting the thermoplastic, which follows a logic to match the material’s characteristics to the desired function for each orthosis. Objectives Systematize the characteristics of low-temperature thermoplastics and, from that, develop an instrument for carrying out practical empirical tests with the materials, to establish criteria for their handling and evaluation. Method Exploratory study consisting of the creation of testing procedures and, consequently, the development of a qualitative assessment instrument that values the practical experience of the professional who handles the material and evaluates each requirement. Results The created instrument includes 14 material characteristics, accompanied by a definition, a procedure with recommendations for the practical testing, and a field for filling in response alternatives. Conclusions The instrument considers important characteristics to be verified during the evaluation of materials and can direct the professional’s observations and records, aiding in clinical decision-making. This will be important to improve the quality of orthoses and other assistive technology devices made with these thermoplastics. In addition, the systematization of the practical evaluation of thermoplastic materials can assist in the development of health studies and research involving materials for orthoses.

Resumo Introdução Após o advento dos termoplásticos de baixa temperatura, sua prevalência na confecção de órteses para membros superiores é identificada por vários autores. A compreensão de suas propriedades, por parte do terapeuta ocupacional e de outros profissionais que atuam na área, é importante no processo de seleção do termoplástico, que segue uma lógica para combinar as características do material à função desejável para cada órtese. Objetivos Sistematizar as características dos termoplásticos de baixa temperatura e, a partir disso, elaborar um instrumento para realizar testes práticos empíricos com os materiais a fim de estabelecer critérios para o seu manuseio e avaliação. Método Pesquisa de caráter exploratório, constituindo a criação de procedimentos de teste e, consequentemente, a elaboração de um instrumento de avaliação de abordagem qualitativa e que valoriza a experiência prática do profissional, que manipula o material e avalia cada requisito. Resultados O instrumento criado contempla 14 caraterísticas do material, acompanhadas de uma definição, um procedimento com recomendações para o teste prático e um campo destinado ao preenchimento das alternativas de resposta. Conclusão O instrumento considera características importantes a serem verificadas durante a avaliação dos materiais e poderá direcionar o olhar e os registros do profissional, auxiliando o nas decisões clínicas. Isso será importante para melhorar a qualidade das órteses e de outros dispositivos de Tecnologia Assistiva confeccionados com esse grupo de materiais. Além disso, a sistematização da avaliação prática dos materiais termoplásticos poderá auxiliar no desenvolvimento de estudos da área da saúde e de pesquisas envolvendo materiais para órteses.

Abstract Mechanical recycling of biodegradable plastics has to be encouraged, since the consumption of energy and raw materials can be reduced towards a sustainable development in plastics materials. In this study, the evolution of thermal and mechanical properties, as well as structural changes of poly(hydroxybutyrate) (PHB) up to three extrusion cycles were investigated. Results indicated a significant reduction in mechanical properties already at the second extrusion cycle, with a reduction above 50% in the third cycle. An increase in the crystallinity index was observed due to chemicrystallization process during degradation by chain scission. On the other hand, significant changes in the chemical structure or in thermal stability of PHB cannot be detected by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analyses (TGA), respectively.

This paper presents the results of a study that aimed to monitor and evaluate biodegradation in soil, by the mass loss and the mechanical properties of plastic tubes. For this work, there were extruded and injected plastic tubes made of biodegradable polymer poly(hydroxybutyrate) - (PHB) and composite PHB/Wood Flour and PHB/Sisal Fiber, both with 20% fiber. There were used three biodegradation test devices for 30, 60 and 90 days. At the end of each test, the biodegraded samples were taken from soil, washed thoroughly with water, dried and weighed to evaluate the mass loss. Mechanical properties were evaluated using flexural tests before and after biodegradation in soil. Based on the results, it was observed that all the studied tubes lost mass over the biodegradation test, and the tubes of biodegradable composites lost more weight than pure PHB.

Polymeric hindered amine light stabilizers (polymeric HALS) have been extensively studied because they combine a high ability to protect the polymers against harmful effects of weathering with minimum physical loss. In this study a new polymeric N-methylated HALS was synthesized by the radical copolymerization of a cyclic tertiary amine with vinyl acetate (VAc). 4-Acryloyloxy-1,2,2,6,6-pentamethylpiperidine (APP), the cyclic tertiary amine, was prepared by the initial conversion of 2,2,6,6-tetramethyl-4-piperidinol derivatives via two different routes. The APP/VAc copolymer synthesized was characterized by size exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FTIR) and carbon-13 nuclear magnetic resonance (13C NMR). The photostabilizing performance, particularly the induction period of polypropylene (PP) films containing different concentrations of APP/VAc copolymer, when exposed to accelerated aging, was comparable to that of PP films compounded with commercial polymeric HALS.

Resumo Sistemas pró-degradantes fundamentados em estearatos de ferro e de manganês e o aditivo comercial d2w, fundamentado em sal orgânico de manganês, foram avaliados em filmes de polietileno de alta densidade (PEAD) em ambiente termooxidativo (estufa a 80 °C e ausência de luz). A degradação termooxidativa foi monitorada por propriedades mecânicas, espectroscopia de infravermelho e cromatografia por exclusão de tamanho. Os resultados mostram que ambos os metais aceleram a degradação termooxidativa do PEAD. Entretanto, o desempenho pró-degradante do estearato de manganês é significativamente superior ao do estearato de ferro. Para o ferro, a degradação aumenta com o aumento da concentração do metal, enquanto que o manganês apresenta valor máximo de degradação em função da concentração. O estado de oxidação do ferro não interfere no desempenho pró-degradante. O aditivo comercial d2wTM acelera, significativamente, a termooxidação do PEAD, mas seu desempenho é inferior ao estearato de manganês provavelmente em função do conjunto de estabilizantes adicionados ao produto comercial.

Abstract The evaluation of pro-degradant systems based on iron and manganese in the form of metallic stearate, and d2wTM commercial additive, based on organic salt of manganese, was carried out on films of high density polyethylene (HDPE) in thermal oxidative conditions (80 °C oven and absence of light). The thermo oxidative degradation was monitored by mechanical properties, by infrared spectroscopy and by size exclusion cromatography. The results show that both metals accelerate thermal oxidative degradation of HDPE. However, the pro-degrading performance of manganese is significantly higher than iron. Considering iron, the degradation increases with increasing concentration of the metal, while manganese presents the maximum value of degradation depending on the concentration. The oxidation state of iron does not interfere with pro-degrading performance. The commercial additive d2wTM significantly accelerates HDPE thermo-oxidation, but its performance is lower than manganese stearate as a function of the set of stabilizing additives to be added to the commercial product.

Neste trabalho, foi estudada a miscibilidade de misturas de um PHB constituído de frações de alta e baixa massa molar com um PLA de alta massa molar. Os materiais extrudados foram analisados pelas técnicas de calorimetria exploratória diferencial (DSC), espectroscopia dielétrica (DE) e análises dinâmico-mecânicas (DMA). A partir dos resultados observou-se o distinto comportamento cristalino das frações de PHB, assim como a miscibilidade parcial do PLA com o PHB de baixa massa molar.

In this work, the miscibility of a PHB formed by high and low molar mass fractions and a low molar mass PLA was studied. The extruded materials were analyzed by differential scanning calorimetry (DSC), dielectric spectroscopy (DS) and dynamic mechanical analysis (DMA). From these results, it was observed an unique behavior from the PHB fractions, and the partial miscibility of PLA onto low molar mass PHB.

In this work, the improvement of mechanical properties in biodegradable materials was obtained through the incorporation of natural and also biodegradable plasticizers and nucleation agents into the PHBV copolymer. PHBV production with different quantities of additives was obtained by extrusion followed by injection. The additives in the copolymer were efficient, resulting in an adequate processing due to the presence of nucleate and an improvement of the mechanical properties of the resulting material provided by the action of the plasticizer. The formulation with the minimum amount of additive content, 5% epoxidized cottonseed oil and 0.1% Licowax, was the most effective showing 35% reduction in the elastic modulus, and 18% in the PHBV crystallinity; 58% increase in impact resistance and 46% increase in elongation. Furthermore, it is important to emphasize that the natural additives were very efficient for biodegradation, showing a mass loss higher of pure PHBV.

O poli(hidroxibutirato) - PHB - e o poli(ácido lático) - PLA - são dois poliésteres termoplásticos com grande potencial para uso em aplicações industriais, sendo viáveis nos principais métodos de processamento e totalmente biodegradáveis. Porém, devido às suas propriedades mecânicas limitadas, necessitam de modificações para melhorar seu desempenho e tornarem-se industrialmente competitivos. Foram estudadas propriedades e características destes dois polímeros e suas misturas poliméricas, avaliando a possibilidade do uso na preparação de filmes finos por extrusão para embalagens. Verificou-se a possibilidade de produção de filmes finos de misturas PHB/PLA, através das técnicas de extrusão de filmes, planos e tubulares soprados. Porém, para viabilizar a produção industrial destes filmes, modificações devem ser realizadas no processo de produção e/ou no preparo da mistura polimérica através da aditivação, com o objetivo de reduzir a alta adesividade dos filmes durante o seu processamento.

Poly(hydroxybutyrate) - PHB - and poly(latic acid) - PLA - are thermoplastic polyesters with huge potential for industrial applications since they are fully biodegradable and can be processed by usual methods. However, due to their limited mechanical properties, they need to be modified to achieve better performance and become industrially competitive. The properties of both polymers and their mixtures were evaluated in order to investigate their application for thin films extrusion, for packages. PHB/PLA thin films were produced by extrusion and blow film techniques. To allow for an industrial production process, the preparation of the polymer blend should be changed in order to decrease their high adhesion during processing.

Os objetivos do estudo foram avaliar as propriedades físicas e a atividade antibacteriana de uma resina composta fotopolimerizável modificada com nanopartículas de prata. Discos foram produzidos com resina não modificada (grupo controle - GC) e resina modificada com nanopartículas de prata em duas concentrações 0,3 e 0,6% em massa (MR03 e MR06, respectivamente). Biofilmes de Streptococcus mutans e Lactobacillus acidophilus foram induzidos in vitro pela incubação dos discos em meio líquido com 20% de sacarose, seguida pela sonicação e contagem de células viáveis após 1, 4 e 7 dias. A rugosidade aritmética de todos os grupos foi avaliada por microscopia de força atômica (MFA). Os dados foram submetidos à ANOVA e ao Teste de Tukey (α=0,05%). Nos três períodos de tempo, o número de células viáveis foi estatisticamente mais baixo para MR03 e MR06, em comparação com GC, para ambas as espécies. MR03 e MR06 não apresentaram diferenças significantes. A análise por meio de MFA demonstrou que não houve diferença significante para a rugosidade entre os três grupos. MR03 apresentouse mais resistente em compressão do que GC, e o desempenho em compressão em MR06 foi estatisticamente pior do que em GC e MR03. Foi possível concluír que as resinas modificadas de MR03 inibiram o crescimento dos biofilmes, sem comprometimento da resistência à compressão e da rugosidade superficial.

The objectives of this study were to evaluate physical properties and antibacterial activity of a light-activated composite modified with silver nanoparticles. Discs were produced with unmodified resin (control group - CG) and modified resin with silver nanoparticles at two concentrations, 0.3% wt (MR03) and 0.6% wt (MR06). Streptococcus mutans and Lactobacillus acidophilus biofilms were induced in vitro by incubation of discs in a 20% sucrose medium, followed by sonication and counting of viable cells after 1, 4 and 7 days (n=9). The arithmetic roughness of all three groups was evaluated by atomic force microscopy (n=9). Compression assay was conducted in all groups to measure the compressive strength at failure and elasticity modulus (n=5). Data were subjected to ANOVA and Tukey's tests (α=0.05%). At all three time points the number of viable cells was statistically lower for MR03 and MR06 compared with CG, for both specimens. MR03 and MR06 showed no significant differences. Microscopic analysis demonstrated no significant differences for roughness among the three groups (p>0.05). The MR03 was stronger to compression than CG, and MR06 was statistically lower than CG and MR03. It was concluded that the MR03 were less conducive to biofilm growth, without compromising the strength in compression and surface roughness.

New copolymers from hindered amines and vinyl monomers were synthesized by radical chain polymerization. To obtain polymeric HALS, acrylamide-(1ATP) and acrylate-(4ATP) monomers, derivatives from 2,2,6,6-tetramethylpiperidine and 2,2,6,6-tetramethyl-4-piperidinol were synthesized. The radical chain polymerization of 1ATP with styrene (Sty) using 1-butanethiol (BTN) resulted in a copolymer with 95 units of Sty and 15 units of 1ATP. The radical chain polymerization of 1ATP and vinyl acetate (VAc) has produced only 1ATP homopolymer. In the chain polymerization of 4ATP with Sty or VAc, the hydrogen atom bonded to the nitrogen of 4ATP is labile enough to originate another radical at this site. The steric hindrance imposed by methyl groups on this bonding site hampers its reaction with other propagating species and the formation of a copolymer or network structure will be dependent on the size of the pendent group in the vinyl monomer.

A influência do sistema de envelhecimento artificial acelerado (EAA) na microestrutura e nas propriedades mecânicas das resinas compostas Z250, Filtek Supreme, 4 Seasons, Herculite, P60, Tetric Ceram, Charisma e Filtek Z100 foi investigada. Os compósitos foram caracterizados por espectroscopia de infravermelho com transformada de Fourier (FTIR) e análises térmicas (calorimetria exploratória diferencial - DSC e termogravimetria - TG). A microestrutura dos materiais foi analisada por microscopia eletrônica de varredura. Os dados de dureza superficial e resistência à compressão foram registados para as resinas e os valores médios foram submetidos ao teste de Kolmogorov-Smirnov (p>0,05), ANOVA e teste de Tukey (α=0,05). Os resultados mostraram diferenças significativas entre as marcas comerciais em termos de dureza (F=86,74, p<0,0001) e resistência à compressão (F=40,31, p<0,0001), mas o EAA não afetou as propriedades (dureza superficial: F=0,39, p=0,53, resistência à compressão: F=2,82, p=0,09) de qualquer uma das resinas. FTIR, DSC e análise de TG revelou que a polimerização da resina foi completa, e não houve diferenças entre os espectros e os perfis de curva térmica dos materiais obtidos, antes e depois de EAA. TG mostrou a ausência de compostos voláteis e evidenciou uma boa estabilidade térmica até 200 °C, e quantidades similares de resíduos foram encontradas em todas as resinas avaliadas, antes e depois de EAA. O tratamento de EAA não afetou significativamente a superfície das resinas. Portanto, independentemente do tipo de resina, o EAA não influenciou a microestrutura e as propriedades mecânicas.

The aim of this study was to investigate the influence of accelerated artificial aging (AAA) on the microstructure and mechanical properties of the Filtek Z250, Filtek Supreme, 4 Seasons, Herculite, P60, Tetric Ceram, Charisma and Filtek Z100. composite resins. The composites were characterized by Fourier-transform Infrared spectroscopy (FTIR) and thermal analyses (Differential Scanning Calorimetry - DSC and Thermogravimetry - TG). The microstructure of the materials was examined by scanning electron microscopy. Surface hardness and compressive strength data of the resins were recorded and the mean values were analyzed statistically by ANOVA and Tukey's test (α=0.05). The results showed significant differences among the commercial brands for surface hardness (F=86.74, p<0.0001) and compressive strength (F=40.31, p<0.0001), but AAA did not affect the properties (surface hardness: F=0.39, p=0.53; compressive strength: F=2.82, p=0.09) of any of the composite resins. FTIR, DSC and TG analyses showed that resin polymerization was complete, and there were no differences between the spectra and thermal curve profiles of the materials obtained before and after AAA. TG confirmed the absence of volatile compounds and evidenced good thermal stability up to 200 °C, and similar amounts of residues were found in all resins evaluated before and after AAA. The AAA treatment did not significantly affect resin surface. Therefore, regardless of the resin brand, AAA did not influence the microstructure or the mechanical properties.

PHB was characterized after different industrial processes by Differential Scanning Calorimetry (DSC), Fourier Transform Infrared Spectroscopy (FTIR), Melt Flow Index (MFI), Complex Dielectric Relaxation (CDR) and Size Exclusion Chromatography (SEC). Some properties of PHB were investigated before and after processing, in order to understand how temperature and other extrusion or injection conditions affect the polymer degradation. All the processed samples showed an increasing in the melt flow index, a decreasing of the dynamic crystallization temperature, and a reduction in the molar mass, suggesting some degradation. The molar mass reduction after processing, predicted when only thermal degradation is considered, was calculated in function of the kinetic parameters, such as constant thermal degradation and residence time during the industrial processing. It was found that the real molar mass reduction was higher than the theoretical value, indicating an important contribution of the shearing of polymeric chains during processing in the PHB degradation.

Tests simulating exposure to severe weather conditions have been relevant in seeking new applications for particleboard. This study aimed to produce particleboards with residues of CCB (chromium-copper-boron oxides) impregnated Pinus sp. and castor oil-based polyurethane resin, and to evaluate their performance before and after artificial accelerated aging. Panels were produced with different particle mass, resin content and pressing time, resulting eight treatments. Particles moisture and size distribution were determined, beyond panel physical and mechanical properties, according to NBR14810-3: 2006. After characterization, treatments B and G (small adhesive consumption and better mechanical performance, respectively) were chosen to artificial aging tests. Statistical results analysis showed best performances were achieved for waterproof aged samples, of both B and G treatments. As example, in treatment B, MOR and MOE values were 23 MPa and 2,297 MPa, samples before exposure; 26 MPa and 3,185 MPa, 32 MPa and 3,982 MPa for samples after exposure (non-sealed and sealed), respectively.

The ever increasing accumulation of plastic waste in the environment has motivated research on polymers that degrade rapidly after being discarded as possible substitutes for conventional inert plastics. Biodegradable polymers can be an alternative, since they have non-toxic residual products and low environmental permanence. Poly (hydroxybutyrate) is a biodegradable polymer with a strong potential for industrial purposes, but its thermal instability and fragility limit its applications. Thus, an alternative to improve the processability and properties of poly (hydroxybutyrate) is to mix it with another polymer, not necessarily a biodegradable one. In this work, different mixtures of poly(hydroxybutyrate) or PHB and polypropylene or PP were extruded and injected. After processing, the blends were studied and their miscibility, mechanical properties and degradability in different soils were analyzed. The main results indicated that the PHB/PP blends had better mechanical properties than pure PHB, as well as improved immiscibility and higher degradation in alkaline soil. The poly-hydroxybutyrate/polypropylene blends showed a tendency for lower crystallinity and stiffness of the polymer matrix, proportional to the amount of polypropylene in the blends, rendering them less stiff and fragile. The degradation tests showed that both pure PHB and blends with 90% PHB and 10% PP were degraded, with loss of their mechanical properties and weight.

Blends of starch and zein plasticized with glycerol were prepared by melting processing in an intensive batch mixer connected to a torque rheometer at 160 °C. The resulting mixtures were compression molded and then characterized by scanning electron microscopy, differential scanning calorimetry, wide-angle X ray diffraction and water-absorption experiments. The blends were immiscible, showing two distinct phases of starch and zein. The water uptake at equilibrium and its diffusion coefficient were determined. The water uptake at equilibrium decreased with increasing zein content. The diffusion coefficient fell sharply on addition of 20% zein and remained constant as zein content was increased. No appreciable effect of zein on starch crystallization was observed by X ray diffraction. The use of zein in thermoplastic starch compositions causes a decrease in the water sensitivity of these materials and lower its melt viscosity during processing making zein a suitable and very promising component in TPS compositions.