Physico-chemical modeling of high-frequency plasma modification of wood: from atomic mechanisms to engineering process optimization

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Abstract

A mathematical model of high-frequency low-temperature plasma surface modification of wood is presented, developed through the synergistic integration of molecular dynamics simulations and experimental spectroscopic data. The mechanism of oxygen ion (100 eV) bombardment of the cellulose surface has been simulated in detail, revealing the specific types of cleaved bonds — C-C, C-O, C-H, and OH — and the subsequent formation of macroradicals. A theoretical description of the key chemical reactions between these radicals and air plasma components is provided, explaining the formation of polar functional groups on the surface, namely hydroxyl (-OH), carbonyl (-C=O), and carboxyl (-COOH) groups. Experimental verification was carried out using FTIR and X-ray photoelectron spectroscopy (XPS), which quantitatively confirmed an 82,5 % increase in the O:C atomic ratio and a significant rise in oxidized functional groups following plasma treatment. A mathematical model describing the kinetics of C-C bond cleavage within the surface nanolayer as a function of discharge power and treatment time was developed. The optimal treatment duration was determined to be 10 minutes, beyond which the modification process plateaus. The model demonstrates high adaptability, enabling its recalibration for different functional groups and wood constituents (e.g., lignin, hemicellulose) as well as various technological parameters.

About the authors

Ruslan R. Safin

Kazan National Research Technological University

Author for correspondence.
Email: cfaby@mail.ru

Dr. Sci. (Tech.), Professor, Head of the Department of Architecture and Design of Wood Products

Russian Federation, 68, Karl Marx St., 420015, Kazan, Republic of Tatarstan

Ksenia V. Saerova

Kazan National Research Technological University

Email: senya97@inbox.ru

Cand. Sci. (Tech.), Associate Professor

Russian Federation, 68, Karl Marx St., 420015, Kazan, Republic of Tatarstan

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2. Fig. 1. Image of a cellulose macromolecule fragment (C — blue, O — purple, H — green) interacting with an oxygen ion (pink) with a kinetic energy of 100 eV in a low-pressure HF plasma at time: t = 0 fs (a); t = 10 fs (б); t = 50 fs (в); t = 100 fs (г)

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3. Fig. 2. Composition of cellulose macroradicals formed as a result of ion bombardment of cellulose with oxygen ion in low-pressure HF plasma

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4. Fig. 3. Mechanisms of polar functional groups formation as a result of interaction of cellulose macroradicals with components of plasma-forming gas of air

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5. Fig. 4. Fragments of the IR spectra of wood samples: the original (blue) and modified in HF plasma air (black)

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6. Fig. 5. XPS spectrum of the C 1s state of carbon and its peak deconvolution: a — thermally modified birch wood; б — thermally modified birch wood after high-frequency plasma treatment

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7. Fig. 6. The proportion of C-C bonds as a function of the total number of C-C bonds on the Smat surface area

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8. Fig. 7. Dependence of the number of remaining C-C bonds in the surface nanolayer of birch wood on high-frequency plasma treatment time, where Control denotes the untreated (reference) sample and 180, 210, 240 °C — indicate the thermal modification temperatures

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