Content: ZnO nanoparticles were developed by 1:2 ratios of Zinc sulphate heptahydrate and Sodium hydroxide by using precipitation method. The structure, morphology of ZnO nanoparticles were investigated by using XRay Diffraction, Scanning Electron Microscopy and Transmission electron Microscopy. X-Ray Diffraction confirms the formation and average crystallite size of ZnO nanoparticles. Scanning Electron Microscopy studies shows the ZnO nanoparticles were in spherical in structure. These ZnO nanoparticles were used in different ratios along with conventional finishing formulations and coated on the leather surface. The performance properties such as water fastness, rub fastness and flexing resistance were evaluated. Application of ZnO nanoparticles in leather finishing showed significant improvement in overall performance properties than conventional finishing formulations. XRD confirms the formation of ZnO nanoparticles (wurtzite structure) at 36.67° (101) plane and the particles size was in the range of 43 nm. SEM image shows that the particles are in the spherical structure wheras EDAX investigate the stoichiometry and chemical purity of the samples to confirm the presence of zinc and oxygen. Optimum quantity up to 2-5 g/L of the season of ZnO nanoparticle is desirable for upgrading the value of leathers by improving color fastness to water, rub fastness and flexing resistance (wet & dry) properties significantly in cationic (wet), NC lacquer emulsions and PU top coat dispersions in finishing formulations. Take-Away: Optimum quantity up to 2-5 g/L of the season of ZnO nanoparticle is desirable for upgrading the value of leathers by improving color fastness to water, rub fastness and flexing resistance (wet & dry) properties significantly in cationic (wet), NC lacquer emulsions and PU top coat dispersions in finishing formulations.

Content: In this study, different acid proteases, which were produced from Aspergillus and Bacillus, were applied for wet-blue bating and their properties and bating effects were observed. The results showed that the acid protease produced Aspergillus had better bating effect and higher chromium tolerance than that of produced by Bacillus. Furthermore, how the acid protease influenced wet-blue microstructure was analyzed by SEM and Micro-CT. The enzymatic properties of acid protease was studied firstly.Zeta potential analysis showed that the isoelectric point (pI) of the protease was consistent with its pH value, which was at 3.0. By particle size analysis, it found that its particle size was 700 nm. In order to obtain the functional components, the molecular weight of the acidic protease was analyzed by Polyacrylamide gel Electrophoresis (SDS-PAGE). Different molecular weight components were obtained by separating the acidic protease with Tangential Flow Filtration (TFF) Technology. The characteristics of these components were determined such as enzyme types and their proportion. Afterwards, these different molecular weight components were used for wet-blue bating. The bating effluent was collected, and then, contents of Hydroxyproline (Hyp), Hyaluronic acid (HA), Desmosine (Des) and Chondroitin sulfate (CS) were analysed, which could be directly corresponding with the degradation of different proteins in wet-blue. Therefore, by characterizing and comparing the bating effect influenced with these different molecular weight components, the functional components of protease could be identified and further be separated and purified. Based on these results, this research is helpful to the development and study of the action of acid protease in the wet-blue bating process. Take-Away: Micro-CT as a new way to characterize the microstructure of leather; Identification and Separation of Effective Components of Acid Protease； Degradation Analysis of Main Components of Wet-Blue during bating process.

Content: Leather manufacturing involves discharge of large quantities of solid and liquid wastes. While efficient recycling methods and in-plant controls have considerably reduced the discharge of obnoxious liquid streams, satisfactory methods to the solid waste management still elude the leather manufacturers. Landfilling is an easy option for the disposal of solid wastes like chrome shavings and trimmings, but is subjected to stringent environmental regulations because of the presence of chromium in these materials. Considerable efforts have been made to recycle the chrome containing wastes by methods such as incineration, pyrolysis and alkaline or enzyme hydrolysis. These recycling processes, however, are seldom complete without further environmental problems. Unfortunately, in such recycling processes the inherent fibrous structure of these materials gets completely destroyed. Applications based on the fibrous nature of the shavings and trimmings are presently limited but various possibilities are being explored continuously. An efficient way of utilization of these fibrous waste materials may be to combine them in a suitable form with synthetic polymers to give composite materials. Short fiber reinforcement of polymers is an important area in polymer composites where both synthetic and natural fibers are effectively used. Footwear has become a basic necessity like food, shelter and clothes. Soles are bottom components of footwear and some important polymeric materials used in footwear fabrication are last, soles and Insoles. This research aims at reducing the solid waste (Chrome shavings) generated by leather industry and reusing them as low cost shoe components such as soles and insole material. In this research, the footwear components were prepared using chrome shaving (tannery solid waste), EPDM (ethylene propylene monomer rubber) and isoprene rubber with different inorganic oxide/hydroxide nano particle based fillers. In this study, soles are prepared by using strap cutting machine, two roll mill and compression moulding machine. The soling materials made characterised using FT-IR and SEM and tested for mechanical properties. Due to good mutual compatibility between Isoprene, EPDM and leather fibre with inorganic nano clay based fillers, the composites are well in terms of all the physic-mechanical behaviours like hardness, density, abrasion resistance and grain crack suitable for shoe sole application. Take-Away: 1. Ethylene propylene monomer rubber and leather fibre with inorganic nano clay based fillers, the composites are well in terms of all the physic-mechanical behaviours like hardness, density, abrasion resistance and grain crack suitable for shoe sole application. 2. An efficient way of utilization of these fibrous waste materials may be to combine them in a suitable form with synthetic polymers to give composite materials. Short fiber reinforcement of polymers is an important area in polymer composites where both synthetic and natural fibers are effectively used.

Content: The toxicity and unpleasant smell of hydrogen sulphide (H2S) gas is an issue for the leather industry that has been contained rather than eliminated in tannery practice. Completely eliminating H2S from tanneries while maintaining practical and economically feasible processing is still a big challenge to be addressed. Significant progress has, though, been made by introducing robust and reliable low sulphide unhairing systems based on selective soaking and specific enzymatic liming auxiliaries. These systems allow the reduction of sodium sulphide offers from the typical 2.5% to 1% of pelt weight. These lower levels reduce the amount of hydrogen sulphide gas released into the environment from the liming float, as well as the amount of sulphide that is carried over in the hide to subsequent processing steps. Overall, the H2S problem is not eliminated, but significantly reduced with this technology. In a further evolution of the technology, organic thio compounds can be used to fully or partially replace the already low levels of sulphide required, and thus allow to operate with offers well below 1%, or even completely without inorganic sulphide. Due to their reductive power, the organic thio compounds react with keratin in a similar way as inorganic sulphides, but they are oxidized much faster, which is advantageous for the effluent load. Alternatively to, or in combination with organic thio compounds, H2S scavengers can be used to reduce or eliminate hyrogen sulphide released from liming floats. Different types of scavengers are available, but the selection is limited for technical and economic reasons. The paper on hand shows how the release of hydrogen sulphide from beamhouse operations can be effectively controlled by a combination of technologies involving more effective unhairing with lower amounts of reductive agents, replacement of inorganic sulphide by organic thio compound and the use of H2S scavengers. Take-Away: - The release of toxic H2S from Beamhouse operations can be effectively controlled using modern unhairing technologies allowing to use no or low sulphide. - These modern unhairing systems are based on a combination of selective soaking, unhairing assisted by enzymes with specific activity and the use of organic thio compounds.

Content: A characteristic of leather is that if it is gradually heated in aqueous solution it reaches a temperature where sudden and irreversible shrinkage occurs. This phenomenon is related to the denaturalization of the collagen protein that conforms the hide and is known as leather shrinkage. Specifically, the internal bonds break thus causing a shortening of the skin that can be up to a 35% from its original length. Accordingly, one of the most used methods to check the quality of the leather tanning process is the determination of the contraction temperature according to the ISO 3380:2015 standard. This method measures the leather shrinkage when constantly increasing the sample temperature. The shrinkage temperature corresponds to the temperature when the sample suddenly contracts. The value of this temperature indicates the degree of collagen stability and therefore, when higher, the leather will have better quality and resistance. The process of leather shrinkage can be divided in different stages. Several authors discriminate temperature A1 (when the first fibre starts to shrinkage), temperature C (when there is a massive shrinkage) and finally temperature A2 (when the last fibres are contracted individually). The method that describes the ISO 3380:2015 standard uses a device where the determination of the shrinkage temperature is performed visually by the laboratory technician. Consequently, the method tends to be imprecise and subjective. It should also be noticed that the device proposed by the standard does not allow differentiation between the different stages of the contraction process. There are other methods to determine leather shrinkage temperature including differential scanning calorimetry, microscopic hot table, thermogravimetric analysis, differential thermal analysis and thermomechanical analysis. All these methods involve complex devices and are only suitable for specialized personnel. In this work, a new device is developed to precisely measure the leather shrinkage temperature and to distinguish the different contraction stages. In addition, the proposed device is simple, easy to use and inexpensive, which facilitates its use in any industry. The developed system consists basically of a load cell to measure the strength produced by the shrinkage of the leather. With the logged data during the test a strength versus temperature graph is built. By means of its interpretation, the different stages of shrinkage can be determined. Different mathematical analysis of the logged data is proposed to determine the shrinkage stages temperatures, thus achieving a high degree of certainty and repeatability. Take-Away: A new device, simple and inexpensive, is developed to precisely measure the leather shrinkage temperature and to distinguish the different contraction stages.

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: Consumers perceive leather as a durable and natural product. To support this positive image, car manufacturers have set demanding performance profiles addressing wear, emissions and sustainable manufacture. Poor performance of auto leather becomes visible as the polymeric finishing coat wears off or cracks over time. Therefore ageing property is seen as a representative key performance parameter and is determined by checking how flexible and strong a polymer coating remains after leather has been exposed to light, heat and humidity for a given time. Ageing of leather is complex to determine and depends on various parameters and requires a full system approach . In a first step different type of crusts (wet-blue, wet-white) were prepared and finished with a standard polyurethane coating. It turned out that the selection of the right fat liquors and tanning agents as well as the presence of vegetable tannins play an important role. On top of this the effective use of proper protective chemicals like anti-oxidants is needed. In a second approach the polymer coating itself was studied and optimized with regard to aged flexing and abrasion. Parameters like polymer type, crosslinking, application technology, coating thickness and impact of additives were investigated and tested when applied on the best crust leathers selected from part 1 of this work. Results show that not only is the right selection of polymers critical but also so is the way the coat is being applied . Furthermore coating thickness greatly defines wear (abrasion), lightfastness and ageing properties. Additives like dulling agents, levelers, feel agents, waxes ,fillers although needed can weaken the integrity of the polymer matrix and consequently reduce physical and chemical fastness properties. This may also apply to a certain extent to protective additives such as anti-oxidants and UV stabilizers, but when used properly their advantages outweigh the potential disadvantages. As to application, special emphasis is given to transfer coating technology which can provide advantages in application and quality consistency but also with regards to fastness properties such as wear and ageing. Take-Away: - crust leather has a critical impact on performance of finishing coat of automotive leathers and requires careful selction of products and use of protective chemical - polymer selection and use of protective chemical play an important role for achieving good aged flexing performance - type of application of finishing coat on auto leather further determines the performance of coating

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: Fine hair is the biggest seasonal challenge for bovine leather production in the United States. The origin, timing and severity of the fine hair problem can be unpredictable and vary from year to year. Seasonal changes on the hair growth cycle are prompted by the lower temperature from fall to winter; the cow hair increases in amount, length and thickness. This problem is very old and has increased in intensity due to changes in the leather manufacturing process, cattle breeding conditions and breed diversity. The amount of fat and thickness of the hide also play important roles. The extent of the problem has not been documented and is not fully understood by the scientific community. The presence of fine hair (residual hair) on the wet blue and final leather are a cause of downgrading the leather. If the wet blue has fine hair, it cannot be removed in further processing in crust or finishing. Some leather types can tolerate more fine hair than others. In this paper we will conduct a scientific evaluation of the fine hair on American bovine hides, wet blue and finished leathers through cross sections and stains, optical and electron microscope observations. We will include measurements of hair thickness and hair depth inside the hide. The work will compare sulfide and oxidative unhairing of winter hides, characterize and show the details of the fine hair through cross sections, and offer indicative measures to minimize the problem. Information from the largest wet blue manufacturer in the US with four tanneries will provide insight on the fine hair seasonality, types of breeds and cattle displacement temperature ranges and will discuss adaptive changes needed in the “Winter” time to control the fine hair. Take-Away: 1) scientific review and evaluation of the problem of fine hair though cross sections and stains, optical and electron microscopy observations 2) evaluate the fine hair on sulfide and oxidative unhairing; providing indicative measures to minimize the problem 3) characterize the seasonality of the fine hair problem regarding the types of breeds, displacement temperature ranges and adaptative changes to control the fine hair