Este trabalho apresenta uma alternativa para a reciclagem dos resíduos de cromo da Indústria do Curtume incorporando-os na formulação de pigmentos cerâmicos. Inicialmente o resíduo de cromo foi tratado sendo realizada a extração de sais solúveis, cloretos, sulfatos, carbonatos e posterior calcinação para a eliminação de matéria-orgânica, tornando assim, viável sua utilização como pigmentos. Os ensaios realizados utilizaram as seguintes técnicas: fluorescência de raios X, espectroscopia por emissão de plasma atômico, espectrofotometria com difenilcarbazida, análises termodiferencial e termogravimétrica, difração de raios X, eletroforese capilar e microscopia eletrônica de varredura. Através destas análises foram feitos estudos das composições de pigmentos que favoreçam a incorporação do cromo a vidrados cerâmicos. A incorporação foi avaliada por testes de lixiviação ácida e identificação por eletroforese capilar e absorção atômica, confirmando teores abaixo dos limites especificados pela norma NBR10004. Foi possível incorporar até 10% do resíduo de cromo na produção de vidrados cerâmicos, resultando em boas características de cor e textura no vidrado final, mostrando o grande potencial de reciclagem dos resíduos de cromo da indústria do curtume como pigmentos cerâmicos. / In this work, an alternative for recycling the chromium waste from the leather industry, incorporating it to formulations of ceramic pigments was studied. Firstly, the characterization of chromium waste was performed, as well as the extraction of soluble salts, chlorides, sulfates, ad carbonates. After that, the calcination, for the elimination of the organic matter to turn viable the use of the waste as ceramic pigments was performed. The various stages were evaluated by: X-ray Fluorescence, Inductively Coupled Plasma-Atomic Emission Spectrometer, Atomic Absorption, Spectroscopy with Dyphenylcarbazide, Differential Thermal Analysis and Thermogravimetry, X-ray Diffraction, Capillary Electrophoresis and Scanning Electron Microscopy. The results indicated that it is possible the incorporation of the waste into the ceramic glazes. Leaching tests were performed with the developed glazes and the chemical compositions of the leachates were determined by capillary electrophoresis and atomic absorption, confirming amounts lower than the ones specified by the Brazilian standard NBR10004. It was possible to incorporate 10wt.% of chromium residue in the production of inorganic pigments, resulting in glazes with good characteristics of color and texture, showing the great potential of recycling chromium waste from the tannery industry in the fabrication of pigments for the Ceramic Tile Industry.

O couro vegetal é obtido através do revestimento de tecido de fibras celulósicas com látex de campo ou concentrado, extraído de seringueira (Hevea spp.). A produção do couro vegetal já ocorre atualmente, possibilitando manter os seringueiros da região norte do Brasil em sua atividade com melhor valor agregado ao produto, sendo ainda submetido ao processo de vulcanização associado à defumação. Adicionalmente, dá ao produtor de seringueira possibilidade de agregar valor ao seu produto e cria alternativa de matéria-prima com padrão de qualidade para a indústria da moda que trabalha exclusivamente com couro animal. Entretanto, há pouca informação científica e tecnológica sobre os processos de produção e métodos de avaliação do couro vegetal. O presente trabalho teve como objetivo avaliar a resistência à tração de couro vegetal produzido tecido de algodão impregnado com látex de diferentes cultivars de seringueira e submetido à vulcanização lenta. Amostras de látex de cinco cultivars de seringueiras GT 1, PR 107, PB 235, IAN 873 e RRIM 600, em campo de competição de clones do Campo Experimental do Departamento de Produção Vegetal da ESALQ/USP foram preparadas para vulcanização com mistura de aditivos padrões e utilizadas para impregnação de tecido de algodão cru, seguida de vulcanização lenta. Corpos de prova desses couros vegetais foram submetidos a teste de resistência à tração. O couro vegetal feito com látex do cultivar GT 1 apresentou maior resistência à tração que aquele feito com látex de RRIM 600, e os demais apresentaram resistências intermediárias. / The vegetal leather is made by coating cotton cloth with field or concentrated latex extracted from rubber trees (Hevea spp.). Currently, the production of vegetal leather already occurs in the Northern Brazil, associated with smoking and vulcanization, making possible to retain rubber tappers in the region. In addition, it permits rubber planters to aggregate some more values to its products and to create an alternative of raw material to the fashion industry, in replacement of animal leather. However, the product is not standardized and there is a lack of scientific and technological information about the production process and evaluation procedures. The objective of the present research was to evaluate the tension resistance of vegetal leather made of cotton cloth impregnated with latex of different rubber tree clones and submitted to vulcanization. Samples of latex from the rubber tree clones GT 1, PR 107, PB 235, IAN 873 e RRIM 600, cultivated at the Experimental Field of the Crop Production Department at ESALQ/USP, were prepared for vulcanization with standard mixture of addictives and used to coat cotton clothes followed by slowly vulcanization. Proof bodies of these vegetal leathers were submitted to tests tension resistance. The vegetal leather made of GT1 latex presented a tension resistance superior to that made of RRIM 600 latex, the others presented intermediate resistances.

Com a utilização de filtros percoladores aeróbios, procurou-se promover a remoção de nitrogênio amoniacal do esgoto sanitário efluente de reator anaeróbio compartimentado, através do processo de nitrificação. O trabalho foi desenvolvido em duas fases; na primeira foi realizada a preparação da serragem de couro utilizando-se peneiramento e lavagens e a seguir iniciou-se a aplicação do esgoto sanitário em quatro filtros percoladores. Os filtros F1 e F2 foram operados com a mesma taxa de aplicação (1,91 'M POT.3'/'M POT.2'.dia) e diferentes meios suportes, sendo brita e serragem de couro do tipo wet blue respectivamente. Os filtros F3 e F4 foram preenchidos com serragem de couro e operaram com taxa de aplicação hidráulica de 4,00 e 6,00 'M POT.3'/'M POT.2'.dia . O filtro F3 apresentou melhores eficiências de remoção para todos os parâmetros, com eficiência média de remoção de NTK, 'N'-'NH IND.3' e DQO de 71%; sendo que a partir do sexagésimo quarto dia, esse filtro passou a apresentar 100% de remoção de NTK e 'N'-'NH IND.3'. Os filtros F1 e F2 podem ter tido problemas com a aeração, já que foram operados com menores taxas de aplicação hidráulica e deveriam apresentar melhores resultados. O filtro F4 apresentou baixas eficiências de remoção, provavelmente devido a maior taxa de aplicação hidráulica. / The aim of the work is to promote the ammoniacal nitrogen removal from anaerobic baffed reactor effluent using aerobic trickling filters, through the nitrification process. The research was developed in two phases; firstly the leather sawing was prepared through sieving and washing, later the domestic sewage was applied into four tricking filters. The F1 and F2 filters were operated with the same hydraulic loading (1,91 'M POT.3'/'M POT.2'.day) and different filter packing. For the F1 filter was used rock and for the F2 wet blue leather sawing. The F3 and F4 filters were filled with leather sawing and operated in a hydraulic loading of 4,00 and 6,00 'M POT.3'/'M POT.2'.day respectively. The F3 filter presented better removal efficiencies for all the parameters, with 70% of average removal efficiency of KTN (Kjeldahl Total Nitrogen), 'NH IND.3'-'N' (ammoniacal nitrogen) and COD (Chemical Oxygen Demand). From the 49th day on, this filter presented 100% of removal efficiency of KTN and 'NH IND.3'-'N'. The F1 and F2 filter were supposed to present better results due to the lower hydraulic loading, but it did not happen, probably because the aeration was not enough. The F4 filter presented low removal efficiency, possibly due to the higher hydraulic loading.

Traditional theories of industrial restructuring assign the most explanatory weight of the structural change phenomenon to increasing pressures via globalization and falling trade barriers. This thesis offers a new model of thinking about industrial restructuring that includes multiple stressors. The thesis focuses on three main drivers of structural change: market pressures, environmental regulation and changes in land use and land pricing, using two case studies of leather and footwear industrial clusters in Mexico, located in the cities of León and Guadalajara. Evidence of multiple drivers of structural change is found in the dissertation. Furthermore, responses to restructuring drivers in León and Guadalajara are found to be substantially different. Firms in the leather and footwear cluster in León have implemented countervailing strategies such as price competition, government lobbying, and more recently, investment in socio-economic research (competitiveness) projects. However, firms in the leather and footwear cluster in Guadalajara focused on a specific, high-end target market. At the larger, urban scale, footwear and its allied industries in the city of León resisted change and have tried to remain in operation while the city of Guadalajara has focused on a diversification strategy, attracting new (arguably more technically advanced) industries. This thesis offers empirical and theoretical advances. Empirically, it applies a firm demographics approach to the study of industrial clusters under multiple stressors. This approach has not been previously used on Mexican data. Theoretically, it demonstrates that future analyses of industrial complexes’ structural change can be strengthened through the use of an integrated assessment framework investigating the effect of multiple stressors (market forces, land pricing, technical change, environmental regulations, and consumer preferences) on industrial restructuring. / Science, Faculty of / Resources, Environment and Sustainability (IRES), Institute for / Graduate

L'exposition à la chaleur, notamment lors d'incendies est particulièrement dévastatrice et dans le cas d'objets du patrimoine elle entraine la destruction de tout ou partie de ces témoins du passé. Notre étude porte sur les effets de la chaleur sur le cuir, matériau largement présent dans les collections patrimoniales.A ce jour, aucune méthode de restauration permettant d'inverser les effets de la chaleur n'a été développée. Le premier objectif de notre étude est d'évaluer les effets d'une exposition à une chaleur sèche par une caractérisation systématique d'échantillons avant et après exposition à la chaleur. Des échantillons modèles, issus d'une même peau de veau de tannage végétal connu, ont été utilisés et caractérisés à différentes échelles structurales par un large ensemble de techniques physico-chimiques et biochimiques avant et après chauffage.Au-delà du brunissement et de la rétraction visible du cuir, la chaleur induit de nombreuses altérations au niveau de la structure du matériau, notamment, une perte de masse, une fonte des structures cristallines, une augmentation de l'hydrophobie ainsi qu'une rigidification. Une partie de ces changements sont attribués à l'agrégation protéique mise en évidence par cette recherche.Le second objectif était de développer une méthode de restauration innovante basée sur l'utilisation de molécules biologiques afin de respecter la nature de l'objet. Des enzymes de type protéase, capables de rompre les agrégats protéiques ont été utilisées. Un des défis est d'apporter suffisamment d'eau, nécessaire pour l'activité de l'enzyme, sans mouiller le cuir pour éviter tout dommage supplémentaire. Plusieurs supports d'application de la protéase ont été testés. Avec une émulsion enzymatique les résultats obtenus ne mettent en évidence ni coloration, ni rétraction et dans certains cas un gain de souplesse est observé. Des résultats encourageants ont également été obtenus dans le cas d'un cuir de veau historique (XIXe siècle). Des mesures complémentaires ont fait attribuer ces propriétés principalement à l'émulsion elle-même, cependant des mesures à plus long terme semblent mettre en évidence un effet positif de l'enzyme sur le gain de souplesse. Sous réserve de nouvelles caractérisations à des temps plus longs, le traitement élaboré pourrait constituer un nouveau support de restauration par voie biologique.Mots clefs : cuir - dénaturation thermique – agrégation protéique – bio-restauration – protéases / Heat, induced by fire, is particularly devastating for cultural heritage objects as it causes the destruction of all or part of these witnesses of the past. In this study, we focused on leather, a material largely present in heritage collections. Until now, no restoration method has been developed to treat the damaging effects of heat.The first aim of our study was to evaluate the effects of dry heat on leather samples through a systematic characterization. Model samples from a calf skin vegetable tanned in known conditions were used and the consequences of heat exposure was characterized at different structural scales using a range of physical, chemical and biochemical methods.Besides the visible browning and shrinkage of leather, heat induces many changes including a loss of mass, the melt of the crystalline regions, an increase in both hydrophobicity and rigidity. Some of these changes result from the protein aggregation induced by exposure to heat and evidenced by our research.Our second goal was to develop an innovative restoration method based on the use of biological molecules in order to respect the nature of the object. Enzymes such as proteases, able to hydrolyze protein aggregates, were used. One of the challenges was to provide the water necessary for the enzyme activity without wetting the leather surface in order to avoid further damage of the leather. Several enzyme supports were tested. The use of an enzymatic emulsion reveals neither darkening nor retraction and in some cases a flexibility gain is observed. Encouraging results were also obtained in the case of an ancient book cover made from calfskin and dated from the nineteenth century. Additional measurements lead to attribute its effect mainly to the emulsion itself, however longer-term measurements appear to show a positive effect of the enzyme on the flexibility gain. Although further characterizations on the long term are required, the treatment may constitute a new support for leather bio-restoration.Keywords: leather – thermal denaturation – protein aggregation – bio-restoration - proteases

M.Com. (Business Management) / Please refer to full text to view abstract

O processo produtivo do couro leva à geração de resíduos sólidos que, por não possuírem boas características de utilização, acabam sendo dispostos em Aterros de Resíduos Industriais Perigosos (ARIP). Por ação microbiológica são degradados lentamente e produzem chorume e biogás (CH4 e CO2), o que pode se prolongar por muitos anos e há necessidade de monitoramento contínuo. Estes resíduos sólidos são em sua maioria farelo de couro wet-blue, um resíduo cromado originário da operação de rebaixamento para padronização e ajuste da espessura de couros, além dos lodos cromados provenientes das estações de tratamento de efluentes dos curtumes. O objetivo deste trabalho foi avaliar a produção de biogás por resíduos de curtume (farelo de rebaixamento e lodo biológico de ETE de curtume), o efeito do tratamento enzimático do farelo de rebaixamento para acelerar sua decomposição e aumentar a produção de biogás e, realizar um levantamento das condições (construção e operação) de ARIPs localizados nas proximidades de Porto Alegre. Os estudos sobre produção de biogás foram avaliados através da realização de experimentos em biorreatores de bacada, utilizando colágeno, farelo de couro wet-blue e lodo com cromo do tratamento biológico de ETE de curtume (inóculo). A avaliação do volume de biogás gerado foi realizada com a utilização de um frasco tipo Mariotte. A composição de metano, dióxido de carbono, oxigênio e nitrogênio foi determinada através de cromatografia gasosa. Os materiais utilizados foram caracterizados quanto ao seu teor de umidade, cinzas, cromo e nitrogênio, e os materiais após o experimento finalizado foram filtrados e caracterizados em relação à massa residual, teor de cromo e nitrogênio. Na primeira série de experimentos foi realizado o prétratamento enzimático térmico para hidrólise do colágeno e resultou em um aumento de 78,3% na produção de biogás e de 76,5% de metano em relação ao colágeno não tratado, porém, a enzima ativa em contato com o inóculo retardou o início da geração de biogás em no mínimo 14 dias. Assim, a inativação da enzima após o tratamento de hidrólise, através de um choque térmico, foi aplicada nos seguintes experimentos utilizando farelo do rebaixamento de couro wet-blue como substrato, resultando para o pré-tratamento enzimático térmico um aumento de 58% na produção de biogás e de 62,4% na produção de metano em relação ao farelo não tratado. Na terceira série de experimentos utilizando somente lodo, foi observado que conforme a quantidade de lodo utilizado é aumentada, o volume de biogás produzido também aumenta. A avaliação do levantamento dos ARIPs foi realizada através da elaboração e aplicação de um questionário com 23 perguntas, a pesquisa mostrou que todos estão em conformidade com a norma brasileira ABNT NBR 10.157/87, que o tipo de resíduo disposto afeta diretamento a produção de chorume e, que tem havido redução da disposição de resíduos de couro wet-blue. / The leather production process leads to generation of solid waste that by not having good characteristics for use, end up disposed of in Hazardous Industrial Waste Landfills (HIWLs). Through microbiological action it’s slowly degraded and produce leachate and biogas (CH4 and CO2), which can last several years and requires continuous monitoring. These solid wastes are mostly wet-blue leather shaving, a chromed waste from the operation of standardizing and to adjust the thickness of the leather, besides the chromed sludge from the effluent treatment system of tanneries. The aim of this study was to evaluate the production of biogas by tannery waste (wet-blue leather shavings and biological sludge from tannery’s WWTP), the effect of enzymatic treatment of the wet-blue leather shavings to accelerate its decomposition and increase biogas production, and conduct the survey about conditions (construction and operational) of HIWLs located near Porto Alegre. Studies on biogas production were evaluated by conducting experiments on bench top bioreactors using collagen, wet-blue leather shavings, chromed sludge from biological treatment of tannery’s WWTP and inoculum. The evaluation of the volume of biogas produced was performed using a Mariotte flask type. The composition of methane, carbon dioxide, nitrogen and oxygen was determined by gas chromatography. The materials used were characterized regarding its moisturet, ash, chromium and nitrogen content, and the materials of the finished experiment were filtered and characterized in relation to the residual mass, chromium and nitrogen content. The first series of experiments carried out the thermal enzymatic pretreatment for hydrolysis of collagen and resulted in a 78.3% increase in biogas production and 76.5% of methane compared to untreated collagen, however, the active enzyme in contact with the inoculum delayed the beginning of biogas generation at least 14 days. Thus, inactivation of the enzyme after hydrolisis treatment, by a heat shock, was applied in the following experiments using wet-blue leather shavings as the substrate, resulting for the thermal enzymatic pretreatment an increase of 58% in the production of biogas and 62.4% in the production of methane compared to untreated leather. In the third series of experiments using only sludge it was observed that as the amount of sludge used increased, the volume of biogas also increased. The evaluation of HIWLs survey was conducted through the development and application of a questionnaire with 23 questions, the survey showed that all are in accordance with the Brazilian standard ABNT NBR 10.157/87, the type of waste disposed directly affects leachate production and there has been a large reduction of disposal of wet-blue leather wastes.

Content: The original substance of a book binding provides information about the place of origin, storage and user history of the book, why the preservation of this material in its original form is of crucial importance for research in the field of bookbinding. In a current research project in cooperation with FILK Freiberg, a newly sustainable treatment for historical aged leather book covers will be developed. The aim is to introduce a long-term mild care agent to boost leather flexibility, which will remain in the structure and to stabilize the pH value at the optimal level with the buffer introduced in the form of deacidification agent. Preliminary research showed, that ageing processes of vegetable tanned calf leather, which has been mainly used for leather book bindings in the past centuries, haven’t been fully explored yet. Further, essential characterization methods like the determination of the acid content and methods for accelerated aging tests are not yet defined for leather. For a systematic development and evaluation of the newly treatment, the project had to be focused on these topics first. Oxidation and acid-catalyzed hydrolysis have an enormous impact on the state of the leather. Both take place simultaneously and affect each other. It could be shown that the damage by acid hydrolysis is much more dominant than the damage by oxidation. Since oxidation plays only a minor role and can be slowed down only preventively by storage conditions, the project focused on the hydrolysis as the significant degradation mechanism. The aim of accelerated ageing was to reproduce as precisely as possible observed and identified degradation mechanisms in the natural aged leather. Therefore, a two-step aging process has been developed. The first stage is to introduce the acid into the material that is to be used to simulate the acid catalyzed hydrolytic degradation. The second step is to verify the effectiveness of the newly developed care products by comparing treated and untreated leathers at this stage of aging. The aging was evaluated by optical / haptic tests, shrinking temperature, mechanical properties, hot water solubility, pH value and differential number. Regarding the leather characterization, the determination of the exact amount of acid introduced by the artificial aging is of great importance for the development of the aging method as well as for the pH adjustment of the leather. For the method development, an acid-base titration was selected, which allows quantitative results of the acid content in the examined material. The developed method is easy to carry out and allows the measurements of different sample quantities (0,1 g - 1,0 g). Take-Away: - acid-catalyzed hydrolysis is the dominant degradation mechanism, oxidation plays a minor role - acid-base tritration allows quantitative results of the acid content in the examined material - development of an accelerated ageing method

Content: Sustainability and transparency of the leather industry are increasingly important factors for the sector’s clients as well as final consumers, looking for quality products that are also sustainable in all tiers of the production process. In this sense, certification and labelling processes are tools that grant visibility to the positive practices of manufacturers and their suppliers. In Brazil, through an unprecedented tanneries initiative conducted by the Centre for the Brazilian Tanning Industry (CICB), a certification for the leather production process was created. The Brazilian Leather Certification of Sustainability (CSCB) counts on the participation of the various links in the production chain. Using the concept of the sustainability tripod, CSCB considers the results of tanneries in economic, environmental and social aspects. A sustainable tannery develops its activities with positive economic results, seeking to reduce inherent environmental impact of its activities, providing better working conditions to employees and respecting the surrounding community. Since the starting point of its creation (2012), CSCB has reached many results concerning process’ improvements in the industry, quitting wastage and getting efficiency in indicators. As the CSCB practices are inside more than 20 tanneries all over Brazil (some of them amongst the biggest in the country, covering a big part of the Brazilian leather production, which is one the hugest in the world) these findings are extremely important and must be shared with whole industry. The certification process is based on implementation and compliance with principles, criteria, and indicators established by standards developed by the Brazilian Association of Technical Standards (ABNT) and audited by certification institutes accredited by The National Metrology, Quality, and Technology Institute (Inmetro), signatory to the mutual recognition agreement within the framework of the International Accreditation Forum (IAF) and the International Laboratory Accreditation Cooperation (ILAC). These agreements guarantee the international validation and recognition of CSCB. Tanneries are certified according to how well they meet the standards, being granted an identification seal for sustainable processes, guaranteeing the transparency of Brazilian leather suppliers. Take-Away: Sustainability as a tool for efficiency in the leather industry Results on the last years of work of the Brazilian Leather Certification of Sustainability (CSCB) Sustainability indicators on Brazilian tannery work

Content: The retanning process is considered as one of the most important processes in leather making, and it plays an important role in the modern leather industry. The fibre structure of hide or skin is not uniform and the retanning agent improves the properties of leather by filling the empty part of wet-blue leather. It could contribute to further stabilization of collagen fibres and give better handle properties to leather such as fullness and elasticity. In a conventional leather retanning process, retanning materials used include both inorganic salt like basic chromium salt, zirconium salt and aluminum salt and organic materials such as vegetable tanning agent, synthetic tanning agent, resin retanning and aldehyde tanning agent. Extract from the barks of Acacia seyal (Talh bark), widely distributed in Sudan, has been evaluated for its utilization in the retanning of the leather and presented in this paper. Barks of talh have been extracted for 1 hour with distilled water (1:10 w/v) at temperature above 80˚C. The talh extract prepared has been used for the retanning of wet blue leathers. The effectiveness of talh extract in retanning of wet blue leathers has been compared with mimosa retanning. The organoleptic properties of the leathers viz. softness, fullness, grain smoothness, grain tightness (break), general appearance, uniformity of dyeing of talh retanned leather have been evaluated in comparison with mimosa retanned leathers. Talh retanning resulted in leathers with good grain tightness. Dyeing characteristics of talh retanned leathers have been found to be better than mimosa retanned leathers. Also physical strength characteristic and shrinkage temperature and economic viability were noted. The effluent arising from this retanning system has been analyzed for its environmental impact. Take-Away: Organoleptic properties physical strength characteristic Shrinkage temperature