Structural Unit Determination in Silica Nanoparticles Using Infrared Micro-Reflectance Spectroscopy

Abstract

A method based on infrared (IR) micro-reflectance measurements for the structural characterization of glassy nanomaterials is presented. Near-specular reflectance spectra of pressed pellets can be analyzed using a model relating the structure of silicate glasses to their dielectric response and an effective medium approximation to account for the effect of porosity. The integrated intensities of phenomenological bands attributed to $Q^{2}$ , $Q^{3}$ , and $Q^{4}$ structural units allow quantifying their relative populations. These values are in good agreement with those obtained with magic-angle spinning nuclear magnetic resonance, which serves as validation of the method and proves the feasibility of extracting quantitative information about glass structure from IR micro-reflectance experiments.

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Keywords

Infrared spectroscopy infrared microscopy sol-gel silica effective medium theories glass structure

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References

Singh

Agarwal

Bhattacharyya

Sharma

Ahalawat

. “Preparation of Silica Nanoparticles and its Beneficial Role in Cementitious Materials”. Nanomater. Nanotechnol. 2011. 1: 9.

Singh

L.P.

Bhattacharyya

S.K.

Kumar

Mishra

, et al. “Sol-Gel Processing of Silica Nanoparticles and their Applications”. Adv. Colloid. Interface. 2014. 214: 17–37.

J.C. Steinbach, F. Fait, H.A. Mayer, A. Kandelbauer. “Monodisperse Porous Silica/Polymer Nanocomposite Microspheres with Tunable Silica Loading, Morphology, and Porosity”. Int. J. Mol. Sci. 2022. 23(23): 14977.

J.G. Croissant, K.S. Butler, J.I. Zink, C.J. Brinker. “Synthetic Amorphous Silica Nanoparticles: Toxicity, Biomedical and Environmental Implications”. Nat. Rev. Mater. 2020. 5(12): 886–909.

S. Varshney, A. Nigam, S.J. Pawar, N. Mishra. “An Overview on Biomedical Applications of Versatile Silica Nanoparticles, Synthesized via Several Chemical and Biological Routes: A Review”. Phosphorus Sulfur Silicon Relat. Elem. 2022. 197(2): 72–88.

S. Bawaked, K. Narasimharao. “Structural and Catalytic Properties of Copper Silicate Nanomaterials”. Sci. Rep. 2020. 10(1): 1–12.

Greasley

S.L.

Page

S.J.

Sirovica

Chen

. et al. “Controlling Particle Size in the Stöber Process and Incorporation of Calcium”. J. Colloid. Interface Sci. 2016. 469: 213–223.

Hill

R.G.

Brauer

D.S.

. “Predicting the Bioactivity of Glasses Using the Network Connectivity or Split Network Models”. J. Non-Cryst. Solids. 2011. 357(24): 3884–3887.

Kamitsos

Patsis

Kordas

. “Infrared-Reflectance Spectra of Heat-Treated Sol-Gel-Derived Silica”. Phys. Rev. B. 1993. 48(17): 12499.

10.

Innocenzi

. “Infrared Spectroscopy of Sol–Gel Derived Silica-Based Films: a Spectra-Microstructure Overview”. J. Non-Cryst. Solids. 2003. 316(2-3): 309–319.

11.

A. Bertoluzza, C. Fagnano, M.A. Morelli, V. Gottardi, M. Guglielmi. “Raman and Infrared Spectra on Silica Gel Evolving Toward Glass”. J. Non-Cryst. Solids. 1982. 48(1): 117–128.

12.

Y.C. Fredholm, N. Karpukhina, R.V. Law, R.G. Hill. “Strontium Containing Bioactive Glasses: Glass Structure and Physical Properties”. J. Non-Cryst. Solids. 2010. 356(44-49): 2546–2551.

13.

Lutz

Täschner

Kurzhals

Heidemann

Hübert

. “Characterization of Silica Gels by

^{29}

Si MAS NMR and IR Spectroscopic Measurements”. Z. Anorg. Allg. Chem. 2009. 635: 2191–2196.

14.

Alessi

Agnello

Buscarino

Gelardi

. “Raman and IR Investigation of Silica Nanoparticles Structure”. J. Non-Cryst. Solids. 2013. 362: 20–24.

15.

Santos

C.N.

De Sousa Meneses

Montouillout

Echegut

. “Infrared Emissivity Spectroscopy of a Soda-Lime Silicate Glass Up to the Melt”, 2012. arXiv preprint arXiv:1201.5676.

16.

Naji

De Sousa Meneses

Guimbretière

Vaills

. “In Situ High-Temperature Probing of the Local Order of a Silicate Glass and Melt During Structural Relaxation”. J. Phys. Chem. C. 2015. 119(16): 8838–8848.

17.

D. De Sousa Meneses, M. Eckes, L. Del Campo, C.N. Santos, et al. “Investigation of Medium Range Order in Silicate Glasses by Infrared Spectroscopy”. Vib. Spectrosc. 2013. 65: 50–57.

18.

Prati

Joseph

Sciutto

Mazzeo

. “New Advances in the Application of FTIR Microscopy and Spectroscopy for the Characterization of Artistic Materials”. Acc. Chem. Res. 2010. 43(6): 792–801.

19.

Della Ventura

Marcelli

Bellatreccia

. “SR-FTIR Microscopy and FTIR Imaging in the Earth Sciences”. Rev. Mineral Geochem. 2014. 78(1): 447–479.

20.

Sato

Tomozawa

. “Anomalous Hydroxyl Diffusion Profile in Silica Glass”. J. Non-Cryst. Solids. 2003. 321: 66–72.

21.

Dalby

K.N.

King

P.L.

. “A New Approach to Determine and Quantify Structural Units in Silicate Glasses Using Micro-Reflectance Fourier-Transform Infrared Spectroscopy”. Am. Mineral. 2006. 91(11-12): 1783–1793.

22.

Looyenga

. “Dielectric Constants of Heterogeneous Mixtures”. Physica. 1965. 31(3): 401–406.

23.

Theiss

. “Optical Properties of Porous Silicon”. Surf. Sci. Rep. 1997. 29(3-4): 91–192.

24.

González de Arrieta

del Campo

De Sousa Meneses

. “Infrared Spectroscopy of CeO

_{2}

Nanoparticles Using Bergman’s Spectral Representation: Effects of Phonon Confinement and Lattice Strain”. Phys. Chem. Chem. Phys. 2021. 23(23): 13095–13105.

25.

De Sousa Meneses

Malki

Echegut

. “Optical and Structural Properties of Calcium Silicate Glasses”. J. Non-Cryst. Solids. 2006. 352(50-51): 5301–5308.

26.

De Sousa Meneses

Malki

Echegut

. “Structure and Lattice Dynamics of Binary Lead Silicate Glasses Investigated by Infrared Spectroscopy”. J. Non-Cryst. Solids. 2006. 352(8): 769–776.

27.

Bhattarai

Drabold

. “Vibrations in Amorphous Silica”. J. Non-Cryst. Solids. 2016. 439: 6–14.

28.

Ermini

I.M.

González de Arrieta

Fayon

Vespa

De Sousa Meneses

. “Static and Kinetic Study of the Structure and Dynamics of Vitreous Silica At High Temperatures by Infrared Emission Spectroscopy”. J. Non-Cryst. Solids. Paper submitted. 2023. https://doi.org/10.2139/ssrn.4596919

29.

Stöber

Fink

Bohn

. “Controlled Growth of Monodisperse Silica Spheres in the Micron Size Range”. J. Colloid. Interface Sci. 1968. 26(1): 62–69.

30.

Corrales

L.R.

. “Structure, Dynamics, and Electronic Properties of Lithium Disilicate Melt and Glass”. J. Phys. Chem. 2006. 125(11): 114702.

31.

M.A. Branch, T.F. Coleman, Y. Li. “A Subspace, Interior, and Conjugate Gradient Method for Large-Scale Bound-Constrained Minimization Problems”. SIAM J. Sci. Comput. 1999. 21(1): 1–23.

32.

Lippmaa

Maegi

Samoson

Engelhardt

Grimmer

. “Structural Studies of Silicates by Solid-State High-Resolution Silicon-29 NMR”. J. Am. Chem. Soc. 1980. 102(15): 4889–4893.

33.

Sindorf

D.W.

Maciel

G.E.

. “Silicon-29 NMR Study of Dehydrated/Rehydrated Silica Gel Using Cross Polarization and Magic-Angle Spinning”. J. Am. Chem. Soc. 1983. 105(6): 1487–1493.