Preparation and mechanical characterization of halloysite containing styrene-butadiene rubber nanocomposites

Abstract

In this study, different SBR nanocomposites were prepared by adding pure halloysite (HNT) and thiol- and vinyl- modified HNT nanofillers to styrene-butadiene rubber (SBR) compounds at 3 phr. These nanocomposites were characterized in terms of rheological, mechanical, and morphological properties. The aging process and crosslinking density of the prepared nanocomposites were also investigated in the presence of HNT nanotubes. The sulfur curing characteristics of SBR vulcanizates were determined by moving die rheometer. It was found that the SBR nanocomposite including thiol- modified HNT had higher crosslinking density than the other nanocomposites prepared with pure HNT and vinyl- modified HNT. Also, all SBR nanocomposites containing pure and functionalized HNT showed better mechanical properties compared to the reference sample without nanofillers. This result showed the reinforcement effect of HNT in the SBR matrix. In addition, the crosslink density and mechanical strength of SBR/HNT nanocomposites increased with thermal aging process. This confirmed the post-cure effect.

Keywords

• Halloysite
• Nanocomposite
• Rubber
• Styrene-butadiene copolymer

Project Number

2018/DR/0007

Haloysit içeren stiren-bütadien kauçuk nanokompozitlerinin hazırlanması ve mekanik özelliklerinin incelenmesi

Abstract

Bu çalışmada, saf haloysit (HNT) ile tiyol ve vinil gruplarıyla fonksiyonlandırılmış HNT nanodolguları, stiren-bütadien kauçuk (SBR) karışımlarına 3 phr olacak şekilde eklenerek farklı SBR nanokompozitleri hazırlanmış ve bu nanokompozitler reolojik, mekanik ve morfolojik olarak karakterize edilmiştir. Hazırlanan nanokompozitlerin termal yaşlanma prosesleri ve çapraz bağ yoğunlukları da HNT nanotüpleri varlığında incelenmiştir. SBR nanokompozitleri kükürt ile vulkanize edilmiş ve pişme özellikleri döner kalıp reometresi ile belirlenmiştir. Tiyol ile modifiye edilmiş HNT nanodolgusu ile hazırlanan SBR nanokompozitinin, saf HNT ve vinil modifiyeli HNT içeren nanokompozitlere göre daha fazla çapraz bağ yoğunluğu içerdiği bulunmuştur. Ayrıca, saf ve fonksiyonlandırılmış HNT içeren tüm SBR nanokompozitlerinin, nanodolgu içermeyen kauçuk karışımına kıyasla daha iyi mekanik özellikler gösterdiği belirlenmiştir. Bu sonuç, SBR matrisinde bulunan HNT’nin takviye etkisini göstermiştir. Ayrıca, uygulanan termal yaşlanma sonrası SBR/HNT nanokompozitlerinin çapraz bağ yoğunlukları ile mekanik kuvvetleri artmıştır. Bu durum ise ısı etkisiyle ilave çapraz bağ oluşumunu ifade eden post-cure etkisini doğrulamıştır.

Keywords

• Haloysit
• Kauçuk
• Nanokompozit
• Stiren-bütadien kopolimeri

Supporting Institution

Yalova Üniversitesi BAPKO

Project Number

2018/DR/0007

References

1. De Matos CF, Zarbin AJ, Galembeck F (2019) Nanostructures and compatibility in rubber nanocomposites containing carbon nanofillers. In: Carbon-Based Nanofillers and Their Rubber Nanocomposites. Elsevier, pp 1-26.
2. Leblanc JL (2002) Rubber–filler interactions and rheological properties in filled compounds. Progress in Polymer Science 27(4):627-687.
3. Lu YL, Zhang LQ (2010) Physical properties of rubber-based nanocomposites. In: Physical Properties and Applications of Polymer Nanocomposites. Woodhead, pp 787-831.
4. Di Gianni A, Colucci G, Priola A, Conzatti L, Alessi M, Stagnaro P (2009) Exfoliated/intercalated rubber/organo‐montmorillonite nanocomposites: preparation and characterization. Macromolecular Materials and Engineering 294(10):705-710.
5. Acar SB, Tasdelen MA, Karaagac B (2023) The effect of POSS nanoparticles on crosslinking of styrene-butadiene rubber nanocomposites. Turkish Journal of Chemistry 47(2):417-425.
6. Murphy Z, Kent M, Freeman C, Landge S, Koricho E (2020) Halloysite nanotubes functionalized with epoxy and thiol organosilane groups to improve fracture toughness in nanocomposites. SN Applied Sciences 2(12):2130.
7. Liu M, Jia Z, Jia D, Zhou C (2014) Recent advance in research on halloysite nanotubes-polymer nanocomposite. Progress in Polymer Science 39(8):1498-1525.
8. Zhang Y, Tang A, Yang H, Ouyang J (2016) Applications and interfaces of halloysite nanocomposites. Applied Clay Science 119:8-17.

9. Acar SB, Ciftci M, Bouharras FE, Raihane M, Tasdelen MA (2021) In-situ preparation of halloysite nanotube-epoxy thermoset nanocomposites via light-induced cationic polymerization. European Polymer Journal 158:110682.
10. Bülbül Ş, Ergün ME (2022) Effect of mica powder-filled styrene-butadiene rubber compounds on crosslink density and mechanical properties. Thermal Science 26:3019-3028.
11. Acar SB, Tasdelen MA, Karaagac B (2021) Methacrylate-functionalized POSS influence on cross-linking and mechanical properties of styrene-butadiene rubber. Iranian Polymer Journal 30(7):697-705.
12. Yang JK, Park W, Ryu C, Kim SJ, Kim DI, Seo G,Chung CB (2020) Estimation of silica flocculation in SBR/BR compounds reinforced with different silica contents from their rheocurves. Journal of Applied Polymer Science 137(15):48559.
13. Khalifeh S, Tavakoli M (2019) Styrene butadiene rubber/epoxidized natural rubber/carbon filler nanocomposites: microstructural development and cure characterization. Iranian Polymer Journal 28(12):1023-1033.
14. Xu Z, Jerrams S, Guo H, Zhou Y, Jiang L, Gao Y, Wen S (2020) Influence of graphene oxide and carbon nanotubes on the fatigue properties of silica/styrene-butadiene rubber composites under uniaxial and multiaxial cyclic loading. International Journal of Fatigue 131:105388.
15. Jia ZX, Luo YF, Yang SY, Guo BC, Du Ml, Jia DM (2009) Morphology, interfacial interaction and properties of styrene-butadiene rubber/modified halloysite nanotube nanocomposites. Chinese Journal of Polymer Science 27(06):857-864.
16. Rybiński P, Janowska G, Plis A (2013) Thermal properties and flammability of ethylene-vinyl acetate rubbers (EVM) and their cross-linked blends with nitrile rubber (NBR). Thermochimica Acta 568:104-114.
17. Barghamadi M, Ghoreishy MHR, Karrabi M, Mohammadian‐Gezaz S (2021) Modeling of nonlinear hyper‐viscoelastic and stress softening behaviors of acrylonitrile butadiene rubber/polyvinyl chloride nanocomposites reinforced by nanoclay and graphene. Polymer Composites 42(2):583-596.
18. Abd‐El‐Messieh S, Abd‐El‐Nour K (2003) Effect of curing time and sulfur content on the dielectric relaxation of styrene butadiene rubber. Journal of Applied Polymer Science 88(7):1613-1621.
19. Khan M, Mishra S, Ratna D, Sonawane S, Shimpi NG (2020) Investigation of thermal and mechanical properties of styrene–butadiene rubber nanocomposites filled with SiO2–polystyrene core–shell nanoparticles. Journal of Composite Materials 54(14):1785-1795.
20. Harandi MH, Alimoradi F, Rowshan G, Faghihi M, Keivani M, Abadyan M (2017) Morphological and mechanical properties of styrene butadiene rubber/nano copper nanocomposites. Results in Physics 7:338-344.
21. Albdiry M, Yousif B (2013) Morphological structures and tribological performance of unsaturated polyester based untreated/silane-treated halloysite nanotubes. Materials & Design 48:68-76.
22. Peixoto AF, Fernandes AC, Pereira C, Pires J, Freire C (2016) Physicochemical characterization of organosilylated halloysite clay nanotubes. Microporous and Mesoporous Materials 219:145-154.
23. Raef M, Razzaghi-Kashani M (2019) The role of interface in gas barrier properties of styrene butadiene rubber-reduced graphene oxide composites. Polymer 182:121816.
24. He S, Bai F, Liu S, Ma H, Hu J, Chen L, Du X (2017) Aging properties of styrene-butadiene rubber nanocomposites filled with carbon black and rectorite. Polymer Testing 64:92-100.
25. Barghamadi M, Karrabi M, Ghoreishy MHR, Mohammadian‐Gezaz S (2019) Effects of two types of nanoparticles on the cure, rheological, and mechanical properties of rubber nanocomposites based on the NBR/PVC blends. Journal of Applied Polymer Science 136(25):47550.
26. Choi SS (2000) Influence of rubber composition on change of crosslink density of rubber vulcanizates with EV cure system by thermal aging. Journal of Applied Polymer Science 75(11):1378-1384.
27. Choi SS (2001) Influence of internal strain on change of crosslink density of natural rubber vulcanizates by thermal ageing. Polymer International 50(1):107-112.