Turning lignin into treasure: An innovative filler comparable to commercial carbon black for the green development of the rubber industry.

Driven by the global carbon neutrality action, biomass-derived functional materials have been applied in many fields to alleviate the pressure brought by the depletion of fossil energy. However, due to the complex structure, lignin faces many difficulties in its high-value utilization. The second largest biomass in the world has become the largest "natural waste". In this paper, the lignin-based biochar-silica (LB-S) hybrid nanoparticles were prepared via a combination of two-step acid precipitation and carbonization using lignin black liquor extracted from xylose residue and sodium silicate as raw materials. The effects of carbonization temperature and lignin-based biochar (LB) content on the reinforcing properties of LB-S were studied. The results show that the particle size, specific surface area, pore characteristics, and surface polarity of LB-S all affect the mechanical properties of the final vulcanizates. The reinforcement performance of the best sample (LMB500-S) with "high structure" characteristics can be comparable to that of commercial carbon black (CB) N550. This study shows that LMB500-S hybrid nanoparticles with economic benefits possess the potential to completely replace commercial CB, which can turn lignin waste into treasure and promote the green development of traditional rubber industry in the context of carbon neutrality.

He Z ，Li Y ，Liu C ，Yang J ，Qian M ，Zhu Y ，Wang X ... -  《-》

Converting waste lignin into nano-biochar as a renewable substitute of carbon black for reinforcing styrene-butadiene rubber.

Industrial waste lignin was commonly burnt or discharged into river in the past. However, in this study, lignin has been converted into high value-added nano-biochar as a renewable reinforcing filler of styrene-butadiene rubber (SBR) by a simple high-temperature carbonization treatment. Herein, the physicochemical change in lignin before and after carbonization was investigated. It was found that lignin-derived biochar (LB) consisted of vesicle-like primary nanoparticles which were closely packed to form "high-structure" irregular fragments with a high specific surface area (83.41 m2/g). When incorporating LB into SBR, the tensile properties of LB/SBR composites were significantly improved. At the filler loading of 40 phr, the tensile strength and elongation at break of the rubber composite were improved up to 7.1-folds and 2.4-folds of pristine SBR, respectively. Compared to commercial carbon black (CB) N330, the LB showed a similar reinforcing effect on SBR. However, the analysis on the morphology, stress-strain behavior and dynamic mechanical behavior suggested distinct reinforcing mechanisms for LB- and CB-filled rubber composites, due to the difference in the surface properties and structural characteristic of fillers. This work showed the application potential of LB as a renewable substitute of CB in rubber industry and brought environmental and economic benefits for the disposal of lignin.

Jiang C ，Bo J ，Xiao X ，Zhang S ，Wang Z ，Yan G ，Wu Y ，Wong C ，He H ... -  《-》

Self-assembled lignin-silica hybrid material derived from rice husks as the sustainable reinforcing fillers for natural rubber.

Biomass derived fillers have been developed as sustainable substitution of carbon black (CB) used in rubber industry to reduce the dependence on fossil fuels. Lignin is the abundant component of biomass, but has poor reinforcing performance due to its huge particle size. In this work, we prepared a lignin/silica (LS) hybrid material from rice husks via a facile self-assembly method. The formation of LS cut lignin macromolecules into fragments and resulted in a small average particle size of 320 nm. When LS was filled into the natural rubber to substitute 10 phr CB, both filler-filler interaction and filler-rubber interaction were enhanced compared with the single use of CB. In consequence, the obtained 10LS/40CB/NR vulcanizates showed overall improvement in tensile strength, tear strength and abrasion resistance compared with the 50CB/NR vulcanizates. For the sustainable development of rubber industry, the natural LS hybrid material with low production cost is a promising reinforcing filler for the partial replacement of CB.

Xue B ，Wang X ，Yu L ，Di B ，Chen Z ，Zhu Y ，Liu X ... -  《-》

Controllable conversion of biomass to lignin-silica hybrid nanoparticles: High-performance renewable dual-phase fillers.

Due to the complex network of aromatic units, lignin is difficult to achieve high-value applications in the industrial field, becoming the largest "natural waste". In this paper, dual-phase fillers with excellent rubber reinforcement were prepared from lignin and sodium silicate through the method of controllable two-step acid precipitation without any complicated modification. During the formation of hybrid nanoparticles, silica nanoparticles were formed as templates in the first step, and then lignin was used as coating agent to bind with silica. The size and morphology of products could be easily adjusted by changing acid precipitation conditions. The L60SS hybrid nanoparticles with the best reinforcement performance showed the ability to replace carbon black (CB) in a high proportion. In addition, LSRH-S hybrid nanoparticles made from rice husk black liquor had similar physical and chemical properties and excellent reinforcement properties to L60SS. Even if the ratio of each component of the raw material was different, the product could be flexibly controlled by the two-step acid precipitation to obtain the expected properties. The wide applicability of this method in many extraction processes based on alkaline procedures was proved, and it provided a basis for the process design of comprehensive utilization of biomass. This work will promote the application of lignin in high-value fields, and the sustainable development of the rubber industry by utilizing agricultural waste was achieved.

He Z ，Li Y ，Liu C ，Li Y ，Qian M ，Zhu Y ，Wang X ... -  《-》

Synergistic Effect of Partial Replacement of Carbon Black by Palm Kernel Shell Biochar in Carboxylated Nitrile Butadiene Rubber Composites.

Zainal Abidin Z ，Mamauod SNL ，Romli AZ ，Sarkawi SS ，Zainal NH ... -  《Polymers》