Abstract
The conventional sol-gel method used to synthesize monodispersed spherical silica nanoparticles produces particles with irregular shapes and low monodispersity. Microreactors show a promising new platform to synthesize nanomaterials due to their unique flow and mixing characteristics. In most known shear-based droplet generation microreactors, the effect of the flowing liquid’s physical properties on the reactor performance and product characteristics are not well investigated. Scaling-down the flow system was proven to change the flow behavior which will be dominated by the liquid apparent physical properties that are highly controllable. A new method to synthesize silica nanoparticles adapting the sol-gel approach in a microfluidic chip is proposed and experimentally tested in the present work. This work also analyzes changing the flowing reactants’ physical properties using nonionic surfactants with different concentrations on the reaction performance and nanoparticle size and properties. A custom-made microreactor, made from polydimethylsiloxane, was designed and then fabricated using a direct writing technique. The investigated surfactant concentration was within the range of 1 to 5 vol/vol%, respective to tetraethyl orthosilicate. A traditional bench-scale sole-gel method was also performed with the same reaction properties for comparison purposes. The obtained nanoparticles were characterized using transmission electron microscopy and EDX. The silica nanoparticles synthesized from a bench-scale system showed poor monodispersity and an irregular shape compared to the perfect spherical particles produced from the microflow system. The addition of surfactant reduced the coalescence of the droplet besides reducing the size of the droplets. Increasing the surfactant concentration reduces the silica nanoparticle size. The results showed that highly monodispersed silica nanoparticles with an average size of 5.76 ± 1.27 nm were synthesized using the microflow system comparing to silica nanoparticles with a mean size of 95 ± 4 nm produced from the bench-scale.
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.References
Iler RK (1979) The chemistry of silica: solubility, polymerization, colloid and surface properties, and biochemistry. New York
Oertel T, Helbig U, Hutter F, Kletti H, Sextl G (2014) Influence of amorphous silica on the hydration in ultra-high performance concrete. Cem Concr Res 58:121–130
Geszke-Moritz M, Moritz M (2016) APTES-modified mesoporous silicas as the carriers for poorly water-soluble drug. Modeling of diflunisal adsorption and release. Appl Surf Sci 368:348–359
Rajanna SK, Kumar D, Vinjamur M, Mukhopadhyay M (2015) Silica aerogel microparticles from rice husk ash for drug delivery. Ind Eng Chem Res 54(3):949–956
Liberman A, Mendez N, Trogler WC, Kummel AC (2014) Synthesis and surface functionalization of silica nanoparticles for nanomedicine. Surf Sci Rep 69(2–3):132–158
Wang J, Shah ZH, Zhang S, Lu R (2014) Silica-based nanocomposites via reverse microemulsions: classifications, preparations, and applications. Nanoscale 6(9):4418–4437
Guerrero-Martínez A, Pérez-Juste J, Liz-Marzán LM (2010) Recent progress on silica coating of nanoparticles and related nanomaterials. Adv Mater 22(11):1182–1195
Yue R, Meng D, Ni Y, Jia Y, Liu G, Yang J et al (2013) One-step flame synthesis of hydrophobic silica nanoparticles. Powder Technol 235:909–913
Zhao M, Zheng L, Bai X, Li N, Yu L (2009) Fabrication of silica nanoparticles and hollow spheres using ionic liquid microemulsion droplets as templates. Colloids Surfaces A Physicochem Eng Asp 346(1–3):229–236
Lin CH, Chang JH, Yeh YQ, Wu SH, Liu YH, Mou CY (2015) Formation of hollow silica nanospheres by reverse microemulsion. Nanoscale 7(21):9614–9626
Dixit CK, Bhakta S, Kumar A, Suib SL, Rusling JF (2016) Fast nucleation for silica nanoparticle synthesis using a sol-gel method. Nanoscale 8(47):19662–19667
Jafarzadeh M, Rahman IA, Sipaut CS (2009) Synthesis of silica nanoparticles by modified sol-gel process: the effect of mixing modes of the reactants and drying techniques. J Sol-Gel Sci Technol 50:328–336
Rao KS, El-Hami K, Kodaki T, Matsushige K, Makino K (2005) A novel method for synthesis of silica nanoparticles. J Colloid Interface Sci 289:125–131
Park SK, Do KK, Kim HT (2002) Preparation of silica nanoparticles: determination of the optimal synthesis conditions for small and uniform particles. Colloids Surfaces A Physicochem Eng Asp 197(1–3):7–17
Van Blaaderen A, Van Geest J, Vrij A (1992) Monodisperse colloidal silica spheres from tetraalkoxysilanes: particle formation and growth mechanism. J Colloid Interface Sci 154(2):481–501
Fernandes RS, Raimundo IM, Pimentel MF (2019) Revising the synthesis of Stöber silica nanoparticles: a multivariate assessment study on the effects of reaction parameters on the particle size. Colloids Surfaces A Physicochem Eng Asp 577:1–7
Dabbaghian M, Babalou A, Hadi P, Jannatdoust E (2010) A parametric study of the synthesis of silica nanoparticles via sol-gel precipitation method. Int J Nanosci Nanotechnol 6(2):104–113
Lindberg R, Sjöblom J, Sundholm G (1995) Preparation of silica particles utilizing the sol-gel and the emulsion-gel processes. Colloids Surfaces A Physicochem Eng Asp 99(1):79–88
Lei Z, Xiao Y, Dang L, Lu M, You W (2006) Fabrication of ultra-large mesoporous carbon with tunable pore size by monodisperse silica particles derived from seed growth process. Microporous Mesoporous Mater 96(1–3):127–134
Giesche H (1994) Synthesis of monodispersed silica powders I. Particle properties and reaction kinetics. J Eur Ceram Soc 14(3):189–204
Khan SA, Günther A, Schmidt MA, Jensen KF (2004) Microfluidic synthesis of colloidal silica. Langmuir. 20:8604–8611
Watts P, Haswell SJ, Pombo-Villar E (2004) Electrochemical effects related to synthesis in microreactors operating under electrokinetic flow. Chem Eng J 101(1–3):237–240
Puntes VF, Krishnan KM, Alivisatos P (2001) Synthesis, self-assembly, and magnetic behavior of a two-dimensional superlattice of single-crystal ε-co nanoparticles. Appl Phys Lett 78(15):2187–2189
Puntes VF, Krishnan KM, Alivisatos AP (2001) Colloidal nanocrystal shape and size control: the case of cobalt. Science 291(5511):2115–2117
Wiles C, Watts P (2011) Recent advances in micro reaction technology. Chem Commun 47(23):6512–6535
Licklider L, Kuhr WG (1994) Optimization of online peptide mapping by capillary zone electrophoresis. Anal Chem 66(24):4400–4407
Kumar S, Nann T (2006) Shape control of II-VI semiconductor nanomaterials. Small 2(3):316–329
Zhou G, Lü M, Xiu Z, Wang S, Zhang H, Zhou Y et al (2006) Controlled synthesis of high-quality PbS star-shaped dendrites, multipods, truncated nanocubes, and nanocubes and their shape evolution process. J Phys Chem B 110(13):6543–6548
Bandulasena MV, Vladisavljević GT, Odunmbaku OG, Benyahia B (2017) Continuous synthesis of PVP stabilized biocompatible gold nanoparticles with a controlled size using a 3D glass capillary microfluidic device. Chem Eng Sci 171:233–243
Adamo CB, Junger AS, Bressan LP, da Silva JAF, Poppi RJ, de Jesus DP (2020) Fast and straightforward in-situ synthesis of gold nanoparticles on a thread-based microfluidic device for application in surface-enhanced Raman scattering detection. Microchem J 156:104985
Bressan LP, Robles-Najar J, Adamo CB, Quero RF, Costa BMC, de Jesus DP et al (2019) 3D-printed microfluidic device for the synthesis of silver and gold nanoparticles. Microchem J 146:1083–1089
Kolmykov O, Commenge JM, Alem H, Girot E, Mozet K, Medjahdi G et al (2017) Microfluidic reactors for the size-controlled synthesis of ZIF-8 crystals in aqueous phase. Mater Des 122:31–41
Stolzenburg P, Lorenz T, Dietzel A, Garnweitner G (2018) Microfluidic synthesis of metal oxide nanoparticles via the nonaqueous method. Chem Eng Sci 191:500–510
Gioria E, Signorini C, Wisniewski F, Gutierrez L (2020) Green synthesis of time-stable palladium nanoparticles using microfluidic devices. J Environ Chem Eng 8(5):104096
Dai J, Yang X, Hamon M, Kong L (2015) Particle size controlled synthesis of CdS nanoparticles on a microfluidic chip. Chem Eng J 280:385–390
Dashtimoghadam E, Mirzadeh H, Taromi FA, Nyström B (2013) Microfluidic self-assembly of polymeric nanoparticles with tunable compactness for controlled drug delivery. Polym (United Kingdom) 54(18):4972–4979
Ni M, Tresset G, Iliescu C (2017) Self-assembled polysulfone nanoparticles using microfluidic chip. Sensors Actuators B Chem 252:458–462
Baby T, Liu Y, Middelberg APJ, Zhao CX (2017) Fundamental studies on throughput capacities of hydrodynamic flow-focusing microfluidics for producing monodisperse polymer nanoparticles. Chem Eng Sci 169:128–139
Balbino TA, Serafin JM, Radaic A, de Jesus MB, de la Torre LG (2017) Integrated microfluidic devices for the synthesis of nanoscale liposomes and lipoplexes. Colloids Surfaces B Biointerfaces 152:406–413
Li Y, Lee RJ, Huang X, Li Y, Lv B, Wang T et al (2017) Single-step microfluidic synthesis of transferrin-conjugated lipid nanoparticles for siRNA delivery. Nanomed Nanotechnol Biol Med 13:371–381
Hao N, Nie Y, Xu Z, Closson AB, Usherwood T, Zhang JXJ (2019) Microfluidic continuous flow synthesis of functional hollow spherical silica with hierarchical sponge-like large porous shell. Chem Eng J 366:433–438
Jaouhari T, Zhang F, Tassaing T, Fery-Forgues S, Aymonier C, Marre S et al (2020) Process intensification for the synthesis of ultra-small organic nanoparticles with supercritical CO2 in a microfluidic system. Chem Eng J 397:125333
Hao N, Nie Y, Xu Z, Zhang JXJ (2019) Ultrafast microfluidic synthesis of hierarchical triangular silver core-silica shell nanoplatelet toward enhanced cellular internalization. J Colloid Interface Sci 542:370–378
Song Y, Hormes J, Kumar CSSR (2008) Microfluidic synthesis of nanomaterials. Small 4(6):698–711
Shestopalov I, Tice JD, Ismagilov RF (2004) Multi-step synthesis of nanoparticles performed on millisecond time scale in a microfluidic droplet-based system. Lab Chip 4(4):316–321
Hung LH, Choi KM, Tseng WY, Tan YC, Shea KJ, Lee AP (2006) Alternating droplet generation and controlled dynamic droplet fusion in microfluidic device for CdS nanoparticle synthesis. Lab Chip 6(2):174–178
Chan EM, Alivisatos AP, Mathies RA (2005) High-temperature microfluidic synthesis of CdSe nanocrystals in nanoliter droplets. J Am Chem Soc 127(40):13854–13861
Lin Y, Jiang H-N, Lin Z-R, Wei K-Z (2013) Application in small-size and band-width of microstrip antenna for ferrocenyl organic magnet/BLT microceramics composites. Gongneng Cailiao/Journal Funct Mater 44(SUPPL.1):153–156
Mantzaris NV (2005) Liquid-phase synthesis of nanoparticles: particle size distribution dynamics and control. Chem Eng Sci 60(17):4749–4770
Liu ZM, Yang Y, Du Y, Pang Y (2017) Advances in droplet-based microfluidic technology and its applications. Chinese J Anal Chem 45(2):282–296
Poe SL, Cummings MA, Haaf MP, McQuade DT (2006) Solving the clogging problem: precipitate-forming reactions in flow. Angew Chemie Int Ed 45(10):1544–1548
Wacker JB, Lignos I, Parashar VK, Gijs MAM (2012) Controlled synthesis of fluorescent silica nanoparticles inside microfluidic droplets. Lab Chip 12(17):3111–3116
Xu L, Peng J, Yan M, Zhang D, Shen AQ (2016) Droplet synthesis of silver nanoparticles by a microfluidic device. Chem Eng Process Process Intensif 102:186–193
Chen X, Hu G (2015) Multiphase flow in microfluidic devices. Adv Mech 45(1):55–110
Zhao CX, He L, Qiao SZ, Middelberg APJ (2011) Nanoparticle synthesis in microreactors. Chem Eng Sci 66(7):1463–1479
Baret JC (2012) Surfactants in droplet-based microfluidics. Lab Chip 12(3):422–433
Kovalchuk NM, Roumpea E, Nowak E, Chinaud M, Angeli P, Simmons MJH (2018) Effect of surfactant on emulsification in microchannels. Chem Eng Sci 176:139–152
Morsy SMI (2014) Role of surfactants in nanotechnology and their applications. Int J Currr Microbiol Appl Sci 3(5):237–260
Bakshi MS (2016) How surfactants control crystal growth of nanomaterials. Cryst Growth Des 16(2):1104–1133
Abdulbari HA, Ling FWM, Hassan Z, Thin HJ (2018) Experimental investigations on biopolymer in enhancing the liquid flow in microchannel. Adv Polym Technol 37(8):3136–3145
Ling FWM, Heidarinik S, Abdulbari HA (2019) Organic additives for the enhancement of laminar flow in a brain-vessels-like microchannel assembly. Chem Eng Technol 42(9):1788–1796
Azlina HN, Hasnidawani JN, Norita H, Surip SN (2016) Synthesis of SiO2 nanostructures using sol-gel method. Acta Phys Pol A 129(4):842–844
Shah SIA, Kostiuk LW, Kresta SM (2012) The effects of mixing, reaction rates, and stoichiometry on yield for mixing sensitive reactions - part I: model development. Int J Chem Eng 750162:1–16
Qian JY, Li XJ, Gao ZX, Jin ZJ (2019) Mixing efficiency analysis on droplet formation process in microchannels by numerical methods. Processes 7(33):1–14
Harries N, Burns JR, Barrow DA, Ramshaw C (2003) A numerical model for segmented flow in a microreactor. Int J Heat Mass Transf 46(17):3313–3322
Dessimoz AL, Cavin L, Renken A, Kiwi-Minsker L (2008) Liquid-liquid two-phase flow patterns and mass transfer characteristics in rectangular glass microreactors. Chem Eng Sci 63(16):4035–4044
Kaminski TS, Garstecki P (2017) Controlled droplet microfluidic systems for multistep chemical and biological assays. Chem Soc Rev 46:6210–6226
Tice JD, Song H, Lyon AD, Ismagilov RF (2003) Formation of droplets and mixing in multiphase microfluidics at low values of the Reynolds and the capillary numbers. Langmuir 19(22):9127–9133
Joni IM, Nulhakim L, Vanitha M, Panatarani C (2018) Characteristics of crystalline silica (SiO2) particles prepared by simple solution method using sodium silicate (Na2SiO3) precursor. J Phys Conf Ser 1080:012006
Mourhly A, Khachani M, El Hamidi A, Kacimi M, Halim M, Arsalane S (2015) The synthesis and characterization of low-cost mesoporous silica SiO2 from local pumice rock. Nanomater Nanotechnol 5(35):1–7
Dubey RS, Rajesh YBRD, More MA (2015) Synthesis and characterization of SiO2 nanoparticles via sol-gel method for industrial applications. Mater Today Proc 2(4–5):3575–3579
Ghosh P, Juvekar VA (2002) Analysis of the drop rest phenomenon. Chem Eng Res Des 80(7):715–728
Marsh BM, Iyer K, Cooks RG (2019) Reaction acceleration in electrospray droplets: size, distance, and surfactant effects. J Am Soc Mass Spectrom 30(10):2022–2030
Sagitani H (1981) Making homogeneous and fine droplet O/W emulsions using nonionic surfactants. J Am Oil Chem Soc 58:738–743
Bahloul B, Lassoued MA, Sfar S (2014) A novel approach for the development and optimization of self emulsifying drug delivery system using HLB and response surface methodology: application to fenofibrate encapsulation. Int J Pharm 466(1–2):341–348
Li C, Mei Z, Liu Q, Wang J, Xu J, Sun D (2010) Formation and properties of paraffin wax submicron emulsions prepared by the emulsion inversion point method. Colloids Surfaces A Physicochem Eng Asp 356(1–3):71–77
Lim C, Basri M, Omar D, Abdul Rahman M, Salleh A, Raja Abdul Rahman R (2011) Physicochemical characterization of nonionic surfactants in oil-in-water (O/W) nano-emulsions for new pesticide formulations. Int J Appl Sci Technol 1(5):131–142
Patil GA, Bari ML, Bhanvase BA, Ganvir V, Mishra S, Sonawane SH (2012) Continuous synthesis of functional silver nanoparticles using microreactor: effect of surfactant and process parameters. Chem Eng Process Process Intensif 62:69–77
Hecht LL, Wagner C, Landfester K, Schuchmann HP (2011) Surfactant concentration regime in miniemulsion polymerization for the formation of MMA nanodroplets by high-pressure homogenization. Langmuir 27(6):2279–2285
Nikam V, Kotade K, Gaware V, Dolas R, Dhamak K, Somwanshi S et al (2011) Eudragit a versatile polymer: a review. Pharmacologyonline 1:152–164
Rao JP, Geckeler KE (2011) Polymer nanoparticles: preparation techniques and size-control parameters. Prog Polym Sci 36(7):887–913
Harivardhan Reddy L, Vivek K, Bakshi N, Murthy RSR (2006) Tamoxifen citrate loaded solid lipid nanoparticles (SLN™): preparation, characterization, in vitro drug release, and pharmacokinetic evaluation. Pharm Dev Technol 11(2):167–177
Giannone G, Santi M, Ermini ML, Cassano D, Voliani V (2020) A cost-effective approach for non-persistent gold nano-architectures production. Nanomaterials 10(8):1600
Dobhal A, Kulkarni A, Dandekar P, Jain R (2017) A microreactor-based continuous process for controlled synthesis of poly-methyl-methacrylate-methacrylic acid (PMMA) nanoparticles. J Mater Chem B 5(18):3404–3417
Acknowledgments
The authors appreciate the financial support from Toray Science Foundation, Japan [19/G34].
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
ESM 1
(DOCX 2931 kb)
Rights and permissions
About this article
Cite this article
Ling, F.W.M., Abdulbari, H.A. & Sim-Yee, C. Investigating the effect of nonionic surfactant on the silica nanoparticles formation and morphology in a microfluidic reactor. J Flow Chem 11, 737–750 (2021). https://doi.org/10.1007/s41981-021-00139-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s41981-021-00139-4