Lignin has potential as a reinforcing filler and to become an alternative to carbon black in the rubber industry. This is because it is formed from cheaper materials with abundant annually renewable sources and has low weight, high biological efficiency, and wide ecological adaptability. The utilization of bio-filler in the rubber industry has garnered increasing attention from researchers due to increasing environmental concerns over the toxic effects of carbon black on health and the environment. This article is intended to summarize current efforts in the development of a green and sustainable rubber product. Instead of focusing on silica and alternative rubber matrix-like guayule and Russian dandelion, it looks at lignin, which also has potential as a reinforcing filler and can enable the development of competitive green rubber composites. Lignin has several special characteristics such as good mechanical, physico-chemical, biodegradability, and antioxidant properties and excellent thermal stability. However, the incorporation of lignin in a rubber matrix is not straightforward, and this needs to be overcome with certain suitable solutions because of the polarity of lignin molecules, which contributes to strong self-interactions. Consequently, chemical modification of lignin is often used to improve the dispersion of lignin in elastomers, or a compatibilizer is added to enhance interfacial adhesion between lignin and the rubber matrix. This review attempts to compile relevant knowledge about the performance of lignin-filled rubber composite using different approaches such as mixing method, surface modification, hybrid fillers, etc. This study is expected to gain significant interest from researchers globally on the subject of lignin-based rubber composites and the advancement of development in green rubber products.

After cellulose, lignin is the most commonly used natural polymer in green biomaterials. Pulp and paper mills and emerging cellulosic biorefineries are the main sources of technical lignin. However, only 2–5% of lignin has been converted into biomaterials. Making lignin-based polymer biocomposites to replace petroleum-based composites has piqued the interest of many researchers worldwide due to the positive environmental impact of traditional composites over time. In composite development, lignin is being used as a filler in commercial polymers to improve biodegradability and possibly lower production costs. As a natural polymer, lignin may have different properties depending on the isolation method and source, affecting polymer-based composites. The application has been affected by the characteristics of lignin and the uniform distribution of lignin in polymers. The review’s goal was to provide an overview of technical lignin extraction, properties, and its potential appropriate utilization. It was also planned to revisit the lignin-based composites’ preparation procedure as well as their composite characteristics. Solvent casting and extrusion methods are used to fabricate lignin from polymeric matrices such as polypropylene, epoxy, polyvinyl alcohol, polylactic acid, starch, wood fiber, natural rubber, and chitosan. Packaging, biomedical materials, automotive, advanced biocomposites, flame retardant, and other applications for lignin-based composites has existed. As a result, the technology is still being refined to increase the performance of lignin-based biocomposites in several applications. This review could assist explain lignin’s position as a composite additive, which could lead to more efficient processing and application strategies.

Commercial fillers, including carbon black (N550), halloysite nanotubes (HNTs), and precipitated silica, were replaced by recycled poly(ethylene terephthalate) powder (R‐PET) in natural rubber (NR) composites. Five different compositions of NR/N550/R‐PET, NR/HNTs/R‐PET, and NR/silica/R‐PET compounds, i.e., 100/20/0, 100/15/5, 100/10/10, 100/5/15, and 100/0/20 parts per hundred rubber (phr), were prepared on a two‐roll mill. The curing behavior, tensile properties, and morphological characteristics of the natural rubber composites were investigated. The results indicated that the replacement of carbon black, HNTs, and silica by R‐PET decreased the tensile strength and tensile modulus, such that NR/silica/R‐PET composites showed the lowest effect, followed by NR/HNTs/R‐PET and NR/N550/R‐PET composites. The negative effect on these properties can be explained by the decrease of crosslink density. The curing results revealed that with the replacement of carbon black by R‐PET, the scorch time and cure time decreased, but that the NR/HNTs/R‐PET and NR/silica/R‐PET composites exhibited the opposite trend. Scanning electron microscopy investigation of tensile fracture surfaces confirmed that the co‐incorporation of N550/R‐PET improved the dispersion of R‐PET and enhanced the interaction between the fillers and NR matrix more than R‐PET and silica/R‐PET hybrid fillers. J. VINYL ADDIT. TECHNOL., 2012. © 2012 Society of Plastics Engineers

This paper addresses nano‐sized titanium dioxide (TiO2) reinforced natural rubber composites. Micro‐sized TiO2 is simultaneously prepared to make a comparison with the composites containing nano‐sized TiO2. To improve the dispersion of TiO2, this study also suggests a new method of incorporating TiO2. Aqueous dispersions of micro‐ and nano‐sized TiO2 at the loadings of 0, 2, 4, 6, and 8 parts by weight per hundred parts of resin were dispersed in natural rubber latex, and then the resulting compounds were dried prior to mixing it with other ingredients on a two‐roll mill. By applying this technique, the homogeneity of the compound is significantly improved. This can be clearly seen from the enhancement of tensile properties and morphological characteristics where the optimum loading was found at 6 parts by weight per hundred parts of resin of micro‐ and nano‐sized TiO2. Adding TiO2 results in delayed scorch times and curing times wherein the curing process of filled compounds is shorter than the unfilled compound. J. VINYL ADDIT. TECHNOL., 23:200–209, 2017. © 2015 Society of Plastics Engineers

Kraft lignin was modified by using hydroxymethylation to enhance the compatibility between rubber based on a blend of natural rubber/polybutadiene rubber (NR/BR) and lignin. To confirm this modification, the resultant hydroxymethylated kraft lignin (HMKL) was characterized using Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopy. It was then incorporated into rubber composites and compared with unmodified rubber. All rubber composites were investigated in terms of rheology, mechanical properties, aging, thermal properties, and morphology. The results show that the HMKL influenced the mechanical properties (tensile properties, hardness, and compression set) of NR/BR composites compared to unmodified lignin. Further evidence also revealed better dispersion and good interaction between the HMKL and the rubber matrix. Based on its performance in NR/BR composites, hydroxymethylated lignin can be used as a filler in the rubber industry.

Sepiolite reinforced epoxidized natural rubber (ENR) composites were prepared by incorporation different loadings of sepiolite. Curing characteristics, mechanical properties, morphology and thermal stability of sepiolite-filled ENR composites were studied. Adding sepiolite into ENR has resulted in remarkable improvement of curing characteristics, mechanical properties and thermal stability. This is attributed to the unique structure of sepiolite itself. It gives a greater interaction between hydroxyl and/or siloxane groups of sepiolite and epoxide segment of ENR. The mechanical properties are very good agreement to the SEM micrographs where more surface roughness is observed upon the addition of sepiolite. Further evidence was found for the thermal decomposition temperature of the composites. The obtained thermogravimetric profiles indicate that their thermal stability was clearly enhanced irrespective of sepiolite loadings. POLYM.

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The performance of rubber composite relies on the compatibility between rubber and filler. This is specifically of concern when preparing composites with very different polarities of the rubber matrix and the filler. However, a suitable compatibilizer can mediate the interactions. In this study, composites of natural rubber (NR) with halloysite nanotubes (HNT) were prepared with maleated natural rubber (MNR) and modified palm stearin (MPS) as dual compatibilizers. The MPS dose ranged within 0.5–1.5 phr, while the MNR dose was fixed at 10 phr in all formulations. It was found that the mixed MNR/MPS significantly enhanced modulus, tensile strength, and tear strength of the composites. The improvements were mainly due to improved rubber-HNT interactions arising from hydrogen bonds formed in the presence of these two compatibilizers. This was clearly verified by observing the Payne effect. Apart from that, the MPS also acted as a plasticizer to provide improved dispersion of HNT. It was clearly demonstrated that MNR and MPS as dual compatibilizers improved rubber-HNT interactions and reduced filler-filler interactions, which then improved tensile and tear strengths, as well as dynamical properties. Therefore, the mix of MNR and MPS had a great potential to compatibilize non-polar rubber with HNT filler.