Synthesis and characterization of polyHIPE composites from CTAB-modified halloysite nanotube stabilized Pickering emulsions: Effect of CTAB immobilized nanotube on reducing surfactant usage

Öz

In this study, halloysite (HL) nanotubes were used as solid particles contributing to the stabilization of high internal phase emulsions (HIPEs) in the preparation of porous composites. PolyHIPEs were obtained by polymerization of the continuous phase of these HIPEs. Immobilization of cetyltrimethylammonium bromide (CTAB) on the HL surface was carried out using the adsorption in solution (SOL) technique. The stability of HIPE without nanofiller was achieved with the use of 5% surfactant by volume. However, the surfactant requirement for the emulsion stability of HIPE materials with organophilic HL fillers (0.25-1.00 wt%) was reduced to 1%. At constant CTAB-SOL-HL clay amounts, decreasing the surfactant concentration resulted in the formation of pores of different sizes, while increasing the amount of filler while keeping the surfactant concentration constant resulted in a decrease in pore size and improved size distribution. The highest adsorption values of cationic dye (Nile Blue) were exhibited by polyHIPE composites containing 0.50 and 1.00 wt% CTAB-SOL-HL, and about 100% more adsorption was obtained with 1% filler compared to pure polyHIPE. The use of CTAB-SOL-HL at 0.50 wt% and above, higher thermal degradation temperatures were achieved in the composites compared to pure polyHIPE. The use of HL nanotubes in the preparation of porous composites is of great importance in terms of possible engineering and environmental benefits in terms of both improving the thermal performance of the materials and taking an active role in the adsorption of the dye, as well as helping to ensure emulsion stability.

Anahtar Kelimeler

• Pickering emulsion
• PolyHIPE
• Silica nanotube
• Dye adsorption
• Thermal stability

Destekleyen Kurum

Yalova Üniversitesi BAPKO Birimi

Proje Numarası

2015/DR/061

Teşekkür

Bu çalışma 2015/DR/061 numaralı Yalova Üniversitesi BAPKO Lisansüstü Tez projesi kapsamında desteklenmiştir.

CTAB-modifiye haloysit nanotüp stabilize Pickering emülsiyonlardan poliHIPE kompozitlerinin sentezi ve karakterizasyonu: CTAB immobilize edilmiş nanotüp’ün surfaktan kullanımını azaltmadaki etkisi

Öz

Bu çalışmada, haloysit (HL) nanotüpleri, gözenekli kompozitlerin hazırlanmasında yüksek iç faz emülsiyonlarının (HIPE'ler) stabilizasyonuna katkıda bulunan katı partiküller olarak kullanılmıştır. Bu HIPE'lerin sürekli fazının polimerizasyonu ile poliHIPE'ler elde edilmiştir. HL yüzeyine setiltrimetilamonyum bromür (CTAB) immobilizasyonu, çözeltide adsorpsiyon (SOL) tekniği kullanılarak gerçekleştirilmiştir. Nanodolgu ihtiva etmeyen HIPE’nin kararlılığı hacimce %5 surfaktan kullanımı ile sağlanabilmiştir. Bununla birlikte, organofilik HL dolgulu (ağırlıkça %0,25-%1,00) HIPE malzemelerinin emülsiyon kararlılıkları için surfaktan gereksinimi %1’e düşmüştür. Sabit CTAB-SOL-HL kil miktarlarında, surfaktan konsantrasyonunun azaltılması farklı boyutlarda gözeneklerin oluşmasına neden olurken, surfaktan konsantrasyonu sabit tutulduğunda ise dolgu maddesi miktarının artırılması gözenek boyutunda bir azalmaya ve boyut dağılımının iyileşmesine neden olmuştur. En yüksek katyonik boya (Nile Blue) adsorpsiyon değerleri %0,50 ve %1,00 CTAB-SOL-HL içeren polyHIPE kompozitleri tarafından sergilenmiş ve %1 dolgu kullanımı ile saf poliHIPE'ye kıyasla yaklaşık %100 daha fazla adsorpsiyon elde edilmiştir. Ağırlıkça %0.50 ve üzerinde CTAB-SOL-HL kullanımı ile saf polyHIPE’ye nazaran, kompozitlerde daha yüksek ısıl bozunma sıcaklıklarına ulaşılmıştır. Gözenekli kompozitlerin hazırlanmasında HL nanotüplerin kullanımı, emülsiyon stabilitesinin sağlanmasına yardımcı olmasının yanı sıra hem malzemelerin termal performansının iyileştirilmesi hem de boyanın adsorpsiyonunda aktif rol alması açısından olası mühendislik ve çevresel faydalar açısından büyük önem taşımaktadır.

Anahtar Kelimeler

• Pickering emülsiyon
• PoliHIPE
• Silika nanotüp
• Boya adsorpsiyonu
• Isıl kararlılık

Proje Numarası

2015/DR/061

Kaynakça

1. Lissant KJ, Peace BW, Wu SH, Mayhan KG (1974) Structure of high-internal-phase-ratio emulsions. J. Colloid Interface Sci. 47:416-423. https://doi.org/10.1016/0021-9797(74)90273-2
2. Menner A, Ikem V, Salgueiro M, Shaffer, MS, Bismarck A (2007) High internal phase emulsion templates solely stabilised by functionalised titania nanoparticles. Chemical Communications 41: 4274-4276. https://doi.org/10.1039/B708935J
3. Ikem VO, Menner A, Bismarck A (2008) High internal phase emulsions stabilized solely by functionalized silica particles. Angewandte Chemie International Edition 47(43):8277-8279. https://doi.org/10.1002/anie.200802244
4. Song X, Zhao Y, Wang H, Du Q (2009) Fabrication of polymer microspheres using titania as a photocatalyst and Pickering stabilizer. Langmuir 25(8): 4443-4449. https://doi.org/10.1021/la8039237
5. Silverstein MS (2014) PolyHIPEs: Recent advances in emulsion-templated porous polymers. Progress in Polymer Science 39(1):199-234. https://doi.org/10.1016/j.progpolymsci.2013.07.003
6. Cui, Threlfall M, van Duijneveldt JS (2011) Optimizing organoclay stabilized Pickering emulsions. Journal of Colloid and Interface Science 356(2):665-671. https://doi.org/10.1016/j.jcis.2011.01.046
7. Hermant MC, Klumperman B, Koning CE (2009) Conductive Pickering-poly (high internal phase emulsion) composite foams prepared with low loadings of single-walled carbon nanotubes. Chemical communications 19:2738-2740. https://doi.org/10.1039/B820638D
8. Ikem VO, Menner A, Horozov TS, Bismarck A (2010) Highly permeable macroporous polymers synthesized from pickering medium and high internal phase emulsion templates. Advanced Materials 22(32):3588-3592. https://doi.org/10.1002/adma.201000729

9. Abbasian Z, Moghbeli MR (2011) Preparation of highly open porous styrene/acrylonitrile and styrene/acrylonitrile/organoclay polymerized high internal phase emulsion (PolyHIPE) foams via emulsion templating. Journal of Applied Polymer Science 119(6):3728-3738. https://doi.org/10.1002/app.33086
10. Yang Y, Wei Z. Wang C. Tong Z (2013) Lignin-based Pickering HIPEs for macroporous foams and their enhanced adsorption of copper (II) ions. Chemical Communications 49(64): 7144-7146. https://doi.org/10.1039/C3CC42270D
11. Alikhani M, Moghbeli MR (2014) Ion-exchange polyHIPE type membrane for removing nitrate ions: preparation, characterization, kinetics and adsorption studies. Chemical Engineering Journal 239: 93-104. https://doi.org/10.1016/j.cej.2013.11.013
12. Rawtani D, Agrawal YK (2012) Multifarious applications of halloysite nanotubes: a review. Rev. Adv. Mater. Sci. 30(3): 282-295.
13. Kamble R, Ghag M, Gaikawad S, Panda B K (2012) Halloysite nanotubes and applications: a review. Journal of Advanced Scientific Research 3(02): 25-29.
14. Chen H, Zhao J, Wu J, Yan H (2014) Selective desorption characteristics of halloysite nanotubes for anionic azo dyes. RSC Advances 4(30):15389-15393. https://doi.org/10.1039/C3RA47561A
15. Tekay E, Nugay N, Nugay T, Şen S (2019) Revolution/rotation-type mixing-assisted masterbatch process for polypropylene-based high-impact ternary nanocomposites. Polymer Composites 40(1): 24-36. https://doi.org/10.1002/pc.24592
16. Mert HH, Şen S (2016) Synthesis and characterization of polyHIPE composites containing halloysite nanotubes. e-Polymers 16(6): 419-428. https://doi.org/10.1515/epoly-2016-0175
17. Menner A, Verdejo R, Shaffer M, Bismarck A (2007) Particle-stabilized surfactant-free medium internal phase emulsions as templates for porous nanocomposite materials: poly-pickering-foams. Langmuir 23(5): 2398-2403. https://doi.org/10.1021/la062712u
18. Palantöken S, Tekay E, Şen S, Nugay T, Nugay N (2016) A novel nonchemical approach to the expansion of halloysite nanotubes and their uses in chitosan composite hydrogels for broad-spectrum dye adsorption capacity. Polymer Composites 37(9): 2770-2781. https://doi.org/10.1002/pc.23473
19. Tekay E, Şen S (2022) High strength, tough/damping and creep resistant EVA/HNT nanocomposites via help of EVA-g-MA compatibilizer. Journal of Composite Materials 56(19): 2951-2962. https://doi.org/10.1177/00219983221107829