Artigos de couro estão associados com tendências de moda e sofisticação em produtos de consumo. No processamento do couro, a fase de acabamento consiste de um conjunto de operações e tratamentos, essencialmente de superfície, que conferem características finais ao produto. Os objetivos do acabamento são reduzir defeitos visíveis, modificar as propriedades superficiais e melhorar os atributos de uso. Nesta fase final, são aplicadas, dentre outros produtos, resinas, geralmente, poliacrilatos e poliuretanos, e algumas vezes caseínas e outros polímeros que formam filmes de recobrimento protetores sobre o couro. Nesse contexto, este trabalho visa a uma avaliação dos filmes formados com resinas comerciais utilizadas industrialmente no acabamento de couros, relacionando a composição destes materiais com características sensoriais, com resistência mecânica, através de testes de tração, com estabilidade à água ou a solvente orgânico, com análise de dureza, e através de caracterizações por infravermelho e DSC. Ensaios de tração mostraram que as resinas poliuretânicas, no geral, apresentam uma maior resistência à tração quando comparadas com resinas acrílicas, assim como os valores de tenacidade, indicando que esses filmes suportam um maior impacto para levar o material à ruptura. A adição de pigmentos diminui essa resistência, tanto em resinas acrílicas quanto em resinas poliuretânicas, enquanto que a produção de filmes compactos apresenta características intermediárias com relação aos componentes puros. Todos os filmes acrílicos testados apresentaram uma maior capacidade de alongamento. Com relação à dureza, as resinas que se mostraram mais flexíveis e com maior alongamento, foram as que apresentaram menor dureza. A estabilidade dos filmes com relação à água e solventes mostrou que os componentes solúveis em água e em solvente aumentam com a presença de pigmento e que a absorção de água é maior e de solvente é menor em filmes com pigmento, tanto para acrilatos quanto para poliuretanos. As caracterizações a partir de análise por FTIR e DSC indicaram os grupamentos químicos e picos de temperaturas característicos dos acrilatos e poliuretanos, respectivamente. / Leather goods are associated with fashion trends and sophistication in consumer products. In the leather processing, the finishing phase consists of a series of operations and treatments, essentially in surface, conferring its final characteristics. The objectives are to reduce visible defects, modify surface properties and improve the usage attributes In this final stage are applied, among other products, resins, generally polyacrylates and polyurethanes, sometimes casein and other polymers, which form protective coating films on leather. In this context, this paper evaluates the films formed with commercial polymeric resins used industrially in finishing leather, relating the composition of these materials with their sensory characteristics, with their strength by tensile testing, with its stability to water or organic solvent, with analysis of hardness and characterizations by IR and DSC. Tensile tests showed that the polyurethane resins in general have a higher tensile strength when compared with acrylic resins, as well as the toughness values, indicating that these films support a greater impact to bring the material to rupture. The addition of pigments decreases this resistance, for acrylic resins and polyurethane resins, while the production of compact film has intermediate characteristics with respect to the pure components. All acrylic films tested had a higher elongation. With respect to hardness, the resins that were more flexible and more stretching, showed the lowest hardness. The stability of the films with respect to water and solvents has shown that water soluble solvent components increased by the presence of pigment and the water absorption is higher and the solvent is lower in pigmented films to acrylates and polyurethanes. The characterizations from IR and DSC analysis indicated the chemical groups and characteristic temperatures peaks of acrylates and polyurethanes, respectively.

Background: Recommendations to restrict summer sunlight exposure to prevent skin cancer apparently conflict with requirements to protect bone health through adequate 25-hydroxyvitamin D (25[OH]D) levels, as provided by cutaneous ultraviolet (UV)B exposure. Furthermore, sunlight exposure promotes a feeling of euphoria that is felt to drive further sun-seeking behaviour. Objectives: My principal objective was to examine health risk (DNA damage) and health benefits (25[OH]D gain, and potential cutaneous photoprotection) following low-level summer sunlight exposures in people of light (phototype II) and darker (phototype V) skin. A further objective was to evaluate serum endocannabinoid levels, potential drivers of mood elevation, following these exposures, and to assess for evidence of tanning addiction in a cross-section of psoriasis patients who had received similar low dose UV exposures, as medical phototherapy. Methods: During wintertime, 10 white Caucasians and 6 South Asians aged 18 to 60 years, from Greater Manchester, UK, received a simulated summer's sunlight exposures, specifically 1.3 standard erythemal dose, thrice weekly for 6 weeks, whilst casually dressed. Serum and urine samples and skin colour measurements were taken at baseline, Monday, Wednesday and Friday of week 1 and then weekly, and buttock skin that had received differential UVR exposures was biopsied for immunohistochemical analysis. Phototype II individuals, who are at higher risk of sunburn, were subsequently challenged with 2X minimal erythema dose (MED) UVB on small areas of simulated summer-exposed and photoprotected skin. Separately, a link to an online tanning questionnaire survey was sent to all members of the National Psoriasis Foundation (USA) during my USA field trip. Results: The simulated summer resulted in 50% gain in 25(OH)D for both phototype groups, but significantly more cutaneous DNA damage (cyclobutane pyrimidine dimers, CPD) in phototype II than V (p<0.0001). There was no accumulation of cutaneous CPD after 6 weeks compared with a single UVR exposure in either group, while phototype V individuals had repaired a greater proportion of their CPD 24 hours after final UVR exposure (p<0.0001). Urinary oxidative DNA damage was higher in phototype II throughout the simulated summer (p=0.002) and unaffected by UVR. All individuals had significant skin darkening, and in phototype II, stratum corneum thickness increased significantly (p<0.05). This tanning response provided significant photoprotection against a pro-inflammatory UVB (2X MED) challenge, as shown by reduced erythema and neutrophil influx in skin exposed to the simulated summer than in photoprotected skin (p<0.05 for both). Serum endocannabinoid (2-arachidonoyl glycerol) levels increased significantly during the simulated summer in both phototype groups (p<0.01), peaking at week 2-3. The cross-sectional study of 1,832 psoriasis patients revealed 34% had used sunbeds; 11% of current users fulfilled diagnostic criteria for addictive-like tanning behaviour: female sex, younger age, younger age at psoriasis diagnosis, severe disease and prior phototherapy were significant risk factors for addiction. Discussion: These findings should assist public health guidance on safe sunlight exposure and highlight the need for distinct guidance targeted to different phototype groups. Furthermore, individuals with psoriasis, in particular those who previously received regular UVR exposure, are at high risk of tanning addiction that may be driven by the endocannabinoid system.

A indústria coureiro-calçadista, durante o processamento de peles, produz resíduos que, por causa do método de curtimento empregado, têm cromo na sua composição química. O objetivo geral deste trabalho é mostrar que é possível a reutilização do metal contido nas cinzas oriundas da incineração de aparas de couro como matéria prima na produção da liga ferro-cromo, livrando o meio ambiente de um resíduo perigoso. Trata-se de um estudo para a elaboração de uma liga com as características similares às de uma ferro-liga ferro-cromo alto carbono (FeCrAC) comercial. Uma análise termodinâmica foi realizada simulando o processo de redução do óxido de cromo com o objetivo de fundamentar e de fornecer as condições para a condução de experimentos. Ao nível de laboratório, em estágio preliminar, foi demonstrado que é possível a reutilização do cromo contido nas cinzas da incineração de aparas de couro na produção de uma liga ferro-cromo. Neste caso obteve-se uma liga com 28 % de cromo e 7% de carbono com uma recuperação metalúrgica de cromo de 69%. / The leather and shoe industry, during the process of leather tanning, produces residues that, because of the method used, have chromium in its chemical composition. The general objective of this work is to show that the recycling of the contained metal is possible as raw material for the iron-chromium alloy production, exempting the environment of a dangerous residue. This study is aimed at the production of an alloy with the similar characteristics to those of the commercial ferroalloy HCFeCr. A thermodynamic analysis was carried through, simulating the process of reduction of chromium oxide, to base and give the conditions for the experiments. At the laboratory level, in preliminary stage, it was demonstrated that the reutilization of chromium contained in ashes of the incineration of leather shavings for the production of one commercial ferroalloy HCFeCr is possible. In this case, an alloy with 28% of chrome and 7% of carbon was obtained, with a metallurgical chrome yield of 69%.

Orientador: Tsunao Matsumoto / Banca: Dib Gebara / Banca: Maria Lucia Ribeiro / Resumo: Os efluentes de curtume caracterizam-se por possuírem elevadas concentrações de compostos tóxicos, tais como: cromo, amônia, sulfatos e compostos orgânicos de baixa biodegradabilidade, por isso o tratamento desses efluentes é extremamente difícil. O presente trabalho tem como objetivo comparar a eficiência de tratamento de efluentes de curtume de duas linhas experimentais, em escala piloto, compostas por: reator UASB simplificado em forma de "Y" seguido de um Biofiltro Aerado Submerso (BF) e somente um BF, operadas simultaneamente, recebendo o mesmo efluente pré-tratado físico-quimicamente, por meio de um decantador de coluna e um floculador de manta de lodo. As linhas experimentais foram montadas junto à estação de tratamento de efluentes do curtume Fuga Couros Jales Ltda., na cidade de Jales-SP. O monitoramento das linhas de tratamento foi dividido em 4 etapas operacionais distintas: 1aetapa, a partida do sistema experimental, 2a etapa, adição do coagulante sulfato de alumino ferroso, 3a etapa, aumento da taxa de aeração nos BFs e 4a etapa, aumento do TDH nos reatores. Em cada etapa, foram analisados os seguintes parâmetros: alcalinidade total, acidez volátil, cromo total, DBObruta, DQObruta, fósforo total, nitrato e nitrito, nitrogênio total e amoniacal, oxigênio dissolvido, pH, sólidos, sulfato, sulfeto e temperatura. A eficiência média de remoção de DQO e DBO, na linha 1, foi de 66% e 73%, respectivamente. Na linha 2, a eficiência média de remoção de DQO foi de 47% e de DBO foi de 49%. A baixa eficiência de remoção de DQO, nas duas linhas, é devido as elevadas concentrações de sulfato afluentes ao tratamento biológico, resultando numa baixa relação DQO/SO4 2-, cerca de 1,2. Apesar da eficiência de remoção de DBO, na linha 1, estar próxima da porcentagem mínima estipulada na legislação estadual, cerca de 80%, o efluente das duas ...(Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The tanning effluents are characterized for its have high concentrations of toxicity compounds, such as: chromium, ammonia, sulfates and organic compound of low biodegradability, the treatment for those effluents is extremely hard. The present work has as objective compared the tanning effluents treatment efficiency of two lines experimental devices on pilot scale, composed for: line 1 - simplified UASB reactor on "Y" form following the Submerged Aerated Biofilter (BF) and line 2, only the BF reactor were operated simultaneously, receiving the same effluent pre-treated by physic-chemical devices, through a column settler and a sludge blanket flocculator. The experimental devices were installed in the tanning effluents treatment plant of the Fuga Couros Jales Ltd., at the Jales-SP city of. The treatment lines was monitoring on four different operational steps: 1st.step, start-up of the experimental system, 2nd step, addition of the coagulant ferrous aluminum sulfate in the pre-treatment devices, 3rd step, increase of the aeration rate in BFs and 4th step, increase the reactors HDT. On each step, the following parameters were analyzed: total alkalinity, volatile acidity, total chrome, BOD, COD, total phosphorous, nitrate and nitrite, total nitrogen and ammonia, dissolved oxygen, pH, solids, sulfate, sulfide and temperature. The COD and BOD removal efficiency average, in the line 1, was 66% and 73%, respectively. In the line 2, the removal efficiency average of the COD was 47% and the BOD was 49%. This low removal efficiency of COD, at two lines, is due the high sulfate inlet concentrations to the biological treatment, that resulting in a low COD/SO4 2- rate, about 1.2. In spite of the removal BOD efficiency, at line 1, reach the minimum state legislation requisite, about 80%, the effluent of the two treatment lines doesn't attempt the effluents discharges patterns, established by the environmental legislation. / Mestre

A indústria coureiro-calçadista, durante o processamento de peles, produz resíduos que, por causa do método de curtimento empregado, têm cromo na sua composição química. O objetivo geral deste trabalho é mostrar que é possível a reutilização do metal contido nas cinzas oriundas da incineração de aparas de couro como matéria prima na produção da liga ferro-cromo, livrando o meio ambiente de um resíduo perigoso. Trata-se de um estudo para a elaboração de uma liga com as características similares às de uma ferro-liga ferro-cromo alto carbono (FeCrAC) comercial. Uma análise termodinâmica foi realizada simulando o processo de redução do óxido de cromo com o objetivo de fundamentar e de fornecer as condições para a condução de experimentos. Ao nível de laboratório, em estágio preliminar, foi demonstrado que é possível a reutilização do cromo contido nas cinzas da incineração de aparas de couro na produção de uma liga ferro-cromo. Neste caso obteve-se uma liga com 28 % de cromo e 7% de carbono com uma recuperação metalúrgica de cromo de 69%. / The leather and shoe industry, during the process of leather tanning, produces residues that, because of the method used, have chromium in its chemical composition. The general objective of this work is to show that the recycling of the contained metal is possible as raw material for the iron-chromium alloy production, exempting the environment of a dangerous residue. This study is aimed at the production of an alloy with the similar characteristics to those of the commercial ferroalloy HCFeCr. A thermodynamic analysis was carried through, simulating the process of reduction of chromium oxide, to base and give the conditions for the experiments. At the laboratory level, in preliminary stage, it was demonstrated that the reutilization of chromium contained in ashes of the incineration of leather shavings for the production of one commercial ferroalloy HCFeCr is possible. In this case, an alloy with 28% of chrome and 7% of carbon was obtained, with a metallurgical chrome yield of 69%.

Artigos de couro estão associados com tendências de moda e sofisticação em produtos de consumo. No processamento do couro, a fase de acabamento consiste de um conjunto de operações e tratamentos, essencialmente de superfície, que conferem características finais ao produto. Os objetivos do acabamento são reduzir defeitos visíveis, modificar as propriedades superficiais e melhorar os atributos de uso. Nesta fase final, são aplicadas, dentre outros produtos, resinas, geralmente, poliacrilatos e poliuretanos, e algumas vezes caseínas e outros polímeros que formam filmes de recobrimento protetores sobre o couro. Nesse contexto, este trabalho visa a uma avaliação dos filmes formados com resinas comerciais utilizadas industrialmente no acabamento de couros, relacionando a composição destes materiais com características sensoriais, com resistência mecânica, através de testes de tração, com estabilidade à água ou a solvente orgânico, com análise de dureza, e através de caracterizações por infravermelho e DSC. Ensaios de tração mostraram que as resinas poliuretânicas, no geral, apresentam uma maior resistência à tração quando comparadas com resinas acrílicas, assim como os valores de tenacidade, indicando que esses filmes suportam um maior impacto para levar o material à ruptura. A adição de pigmentos diminui essa resistência, tanto em resinas acrílicas quanto em resinas poliuretânicas, enquanto que a produção de filmes compactos apresenta características intermediárias com relação aos componentes puros. Todos os filmes acrílicos testados apresentaram uma maior capacidade de alongamento. Com relação à dureza, as resinas que se mostraram mais flexíveis e com maior alongamento, foram as que apresentaram menor dureza. A estabilidade dos filmes com relação à água e solventes mostrou que os componentes solúveis em água e em solvente aumentam com a presença de pigmento e que a absorção de água é maior e de solvente é menor em filmes com pigmento, tanto para acrilatos quanto para poliuretanos. As caracterizações a partir de análise por FTIR e DSC indicaram os grupamentos químicos e picos de temperaturas característicos dos acrilatos e poliuretanos, respectivamente. / Leather goods are associated with fashion trends and sophistication in consumer products. In the leather processing, the finishing phase consists of a series of operations and treatments, essentially in surface, conferring its final characteristics. The objectives are to reduce visible defects, modify surface properties and improve the usage attributes In this final stage are applied, among other products, resins, generally polyacrylates and polyurethanes, sometimes casein and other polymers, which form protective coating films on leather. In this context, this paper evaluates the films formed with commercial polymeric resins used industrially in finishing leather, relating the composition of these materials with their sensory characteristics, with their strength by tensile testing, with its stability to water or organic solvent, with analysis of hardness and characterizations by IR and DSC. Tensile tests showed that the polyurethane resins in general have a higher tensile strength when compared with acrylic resins, as well as the toughness values, indicating that these films support a greater impact to bring the material to rupture. The addition of pigments decreases this resistance, for acrylic resins and polyurethane resins, while the production of compact film has intermediate characteristics with respect to the pure components. All acrylic films tested had a higher elongation. With respect to hardness, the resins that were more flexible and more stretching, showed the lowest hardness. The stability of the films with respect to water and solvents has shown that water soluble solvent components increased by the presence of pigment and the water absorption is higher and the solvent is lower in pigmented films to acrylates and polyurethanes. The characterizations from IR and DSC analysis indicated the chemical groups and characteristic temperatures peaks of acrylates and polyurethanes, respectively.

Lignosulfonates are abundantly available by-products of the paper industry. In the vast majority of applications on leather lignosulfonates are physically blended with other chemistries to augment filling properties of the resulting products. We targeted to decrease the molecular weight of lignosulfonates using fungi to achieve increased application possibilities and to improve tanning properties. We screened various basidiomycotes for their capability to modify the molecular weight of calcium lignosulfonates and identified five species that actually polymerized the chosen lignosulfonate further. Only Irpex consors was found to depolymerize calcium lignosulfonate in surface and later in liquid cultures in our hands. We achieved a six fold reduction of the molecular weight determined by size exclusion chromatography.

Content: Leather manufacturing is classified as water, energy and waste intensive by the Industrial Emissions Directive (2010/75/EU). Tannery effluents, if not properly treated, cause significant damage to soil and water bodies. Over 85% of world leather production involves the traditional chrome tanning process (TCTP). The use of chrome (Cr) in the industrial processing of animal hides poses serious environmental and health problems due to the use of hazardous chemicals, the production of solid/liquid waste and air emissions. LIFE GOAST aims at demonstrating the benefits of a new tanning technology on a semi-industrial scale; the project started on July 2017 and is an ongoing investigation, and involves the competences of three direct actors in the leather industry such as GSC Group spa as chemical supplier, Conceria Pasubio as tannery and Mediochiampo as waste-water treatment agency, in conjunction with the expertise of Università di Venezia, thus forming together a model of leather industry. The technical feasibility of LIFE GOAST implementation, as well as its social and economic impact, have been monitored and compared with the TCTP in order to demonstrate the reduced environmental impacts of the new process, while producing comparable or better quality leather. The LIFE GOAST team demonstrated that it was possible to treat collagen with the GOAST technology to give stabilised collagen to be used in the leather industry. A series of leather swatches were realised in accordance with the new protocol in order to obtain preliminary information on chemical oxygen demand COD of the effluents and technical feasibility of the process. The results were remarkable: COD values were lower than TCTP and it was possible to obtain soft and firm grain leather despite a shrinkage temperature lower than chromium process. However, these preliminary results allowed to process bigger pieces of leather (quarter, half and entire) to demonstrate that the technology was reproducible and in line with the small trials. The investigation is still ongoing and the team is fully committed to focus on the objectives of the project. Take-Away: Novel and alternative tanning systems to traditional chrome tanning.

Content: Developing novel tanning agents from renewable biomass is regarded as an effective strategy for sustainable leather industry. In this study, a series of dialdehyde carboxymethyl cellulose (DCMC) were prepared by periodate oxidation of carboxymethyl cellulose (CMC) with varying degrees of substitution (DS: 0.7, 0.9 and 1.2). The structural properties of DCMC were characterized. Size Exclusive Chromatography measurements showed that CMC underwent severe degradation during periodate oxidation, resulting in the decline of weight-average molecular weight from 250,000 g/mol to around 13,000 g/mol. FT-IR analysis illustrated that aldehyde group was successfully introduced into DCMC. The aldehyde group content of DCMC decreased from 8.38 mmol/g to 2.95 mmol/g as the DS rose from 0.7 to 1.2. Interestingly, formaldehyde was found to be produced in DCMC, and its content was 159.4, 151.7 and 38.4 mg/L, respectively when the DS of CMC was 0.7, 0.9 and 1.2, respectively. Further analysis by HPLC found that fructose was formed during oxidative degradation, and was subsequently oxidized to generate formaldehyde. This was in accordance with the fact that higher DS resulted in lower formaldehyde content in DCMC. The whole reaction mechanism is still under investigation at the moment. Tanning trials showed that the shrinkage temperature and thickening rate of DCMC tanned leather decreased as the DS increased. This should be due to the difference in aldehyde content of DCMC. Leather tanned by DCMC-0.7 (DS of CMC was 0.7) had the highest shrinkage temperature of 81°C and thickening rate of 76%. It was noteworthy that the formaldehyde content in DCMC tanned leather was only 0.11-0.40 mg/kg even though DCMC contained a small amount of formaldehyde. In general, we hope the work on dialdehyde tanning agent derived from CMC could provide some essential data for the development of sustainable tanning material and process. Take-Away: 1. Higher degree of substitution (DS) of CMC resulted in lower aldehyde group content of DCMC. 2. The formaldehyde content of DCMC was negatively correlated with DS. 3. The tanning performance of DCMC with lower DS was better.

Content: It is acknowledged that conventional chrome tanning in leather processing discharges significant amounts of chromium, dissolved solids and chlorides. The recycling technology is one of the effective solutions to reduce the environmental impact of chrome tanning waste water at source. In this work, a novel closed recycling technology of chrome tanning wastewater was applied in the tanning process of the goat skins at a pilot scale level. The properties of chrome tanning liquors obtained by the recycling technology and the resultant crust were analyzed. The results show that this close recycling process works well. The contents of Cr2O3, total organic carbon, ammonia nitrogen and chloride ion in the waste water tend to accumulate with the increase of recycling times, and finally reach a balance after 5 times of recycling. The obtained leather sample is full, soft and having a shrinkage temperature comparable to that of conventional chrome tanned leather. SEM images indicate that the resulting leather samples by this recycling technology show fine and clean grain and well-dispersed fibrils. TG and DSC results show that the thermal stability of wet blue leathers tanned by the circular process are similar to those tanned by conventional chrome tanning process. Compared with conventional chrome tanning technology, water, salt and chrome tanning agent are saved in this process, and the zero emission of chrome tanning wastewater is realized. The cleaner production technology exhibits promising application prospect for its economic and environmental benefits. Take-Away: 1. A novel closed recycling technology of chrome tanning wastewater was applied in the tanning process of the goat skins at a pilot scale level. 2. The chrome tanning liquors obtained by the recycling technology and the resultant crust were analyzed. 3. Water, Sodium chloride and chrome tanning agent are saved by the closed recycling technology, and the zero emission of chrome tanning wastewater is realized.