Molecular dynamics simulation of amine groups formation during
plasma processing of polystyrene surfaces

J 2020

Molecular dynamics simulation of amine groups formation during plasma processing of polystyrene surfaces

MICHLÍČEK, Miroslav, Satoshi HAMAGUCHI and Lenka ZAJÍČKOVÁ

Basic information

Original name

Molecular dynamics simulation of amine groups formation during plasma processing of polystyrene surfaces

Authors

MICHLÍČEK, Miroslav (203 Czech Republic, belonging to the institution), Satoshi HAMAGUCHI (112 Belarus) and Lenka ZAJÍČKOVÁ (203 Czech Republic, belonging to the institution)

Edition

Plasma Sources Science and Technology, Bristol, IOP Publishing, 2020, 0963-0252

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

21001 Nano-materials

Country of publisher

United Kingdom of Great Britain and Northern Ireland

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

URL

Impact factor

Impact factor: 3.584

RIV identification code

RIV/00216224:14310/20:00114427

Organization unit

Faculty of Science

DOI

http://dx.doi.org/10.1088/1361-6595/abb2e8

UT WoS

000583117500001

Keywords in English

amine functionalization; plasma treatment; plasma polymerization; molecular dynamics

Abstract

V originále

Plasma treatment and plasma polymerization processes aiming to form amine groups on polystyrene surfaces were studied in-silico with molecular dynamics simulations. The simulations were compared with two experiments, (i) plasma treatment in N2/H2 bipolar pulsed discharge and (ii) plasma polymerization in cyclopropylamine/Ar radio frequency (RF) capacitively coupled discharge. To model favorable conditions for the incorporation of primary amine groups, we assumed the plasma treatment as the flux of NH2 radicals and energetic NH3 ions, and the plasma polymerization as the flux of cyclopropylamine molecules and energetic argon ions. It is shown in both the simulation and the experiment that the polystyrene treatment by the bipolar pulsed N2/H2 plasmas with an applied voltage of about ±1 kV formed a nitrogen-rich layer of a thickness of only a few nm. The simulations also showed that, as the NH3 incident energy increases, the ratio of primary amines to the total number of N atoms on the surface decreases. It is because the energetic ion bombardment brakes up N–H bonds of primary amines, which are mostly brought to the surface by NH2 radical adsorption. Our previous experimental work on the CPA plasma polymerization showed that increased RF power invested in the plasma leads to the deposition of films with lower nitrogen content. The MD simulations showed an increase of the nitrogen content with the Ar energy and a limited impact of the energetic bombardment on the retention of primary amines. Thus, the results highlighted the importance of the gas-phase processes on the nitrogen incorporation and primary amines retention in the plasma polymers. However, the higher energy flux towards the growing film clearly decreases amount of hydrogen and increases the polymer cross-linking.

Links

GA18-12774S, research and development project

Name: Plazmové polymery připravené na nanovlákenných membránách pro inženýrství cévní tkáně

Investor: Czech Science Foundation

LQ1601, research and development project

Name: CEITEC 2020 (Acronym: CEITEC2020)

Investor: Ministry of Education, Youth and Sports of the CR

Citovat

MICHLÍČEK, Miroslav, Satoshi HAMAGUCHI and Lenka ZAJÍČKOVÁ. Molecular dynamics simulation of amine groups formation during plasma processing of polystyrene surfaces. Plasma Sources Science and Technology. Bristol: IOP Publishing, 2020, vol. 29, No 10, p. 1-13. ISSN 0963-0252. Available from: https://dx.doi.org/10.1088/1361-6595/abb2e8.

@article{1689017,
   author = {Michlíček, Miroslav and Hamaguchi, Satoshi and Zajíčková, Lenka},
   article_location = {Bristol},
   article_number = {10},
   doi = {http://dx.doi.org/10.1088/1361-6595/abb2e8},
   keywords = {amine functionalization; plasma treatment; plasma polymerization; molecular dynamics},
   language = {eng},
   issn = {0963-0252},
   journal = {Plasma Sources Science and Technology},
   note = {doc. Zajíčková - dle rozhodnutí ředitelů 5.3.2024},
   title = {Molecular dynamics simulation of amine groups formation during plasma processing of polystyrene surfaces},
   url = {https://iopscience.iop.org/article/10.1088/1361-6595/abb2e8},
   volume = {29},
   year = {2020}
}

TY  - JOUR
ID  - 1689017
AU  - Michlíček, Miroslav - Hamaguchi, Satoshi - Zajíčková, Lenka
PY  - 2020
TI  - Molecular dynamics simulation of amine groups formation during plasma processing of polystyrene surfaces
JF  - Plasma Sources Science and Technology
VL  - 29
IS  - 10
SP  - 1-13
EP  - 1-13
PB  - IOP Publishing
SN  - 09630252
N1  - doc. Zajíčková - dle rozhodnutí ředitelů 5.3.2024
KW  - amine functionalization
KW  - plasma treatment
KW  - plasma polymerization
KW  - molecular dynamics
UR  - https://iopscience.iop.org/article/10.1088/1361-6595/abb2e8
L2  - https://iopscience.iop.org/article/10.1088/1361-6595/abb2e8
N2  - Plasma treatment and plasma polymerization processes aiming to form amine groups on polystyrene surfaces were studied in-silico with molecular dynamics simulations. The simulations were compared with two experiments, (i) plasma treatment in N2/H2 bipolar pulsed discharge and (ii) plasma polymerization in cyclopropylamine/Ar radio frequency (RF) capacitively coupled discharge. To model favorable conditions for the incorporation of primary amine groups, we assumed the plasma treatment as the flux of NH2 radicals and energetic NH3 ions, and the plasma polymerization as the flux of cyclopropylamine molecules and energetic argon ions. It is shown in both the simulation and the experiment that the polystyrene treatment by the bipolar pulsed N2/H2 plasmas with an applied voltage of about ±1 kV formed a nitrogen-rich layer of a thickness of only a few nm. The simulations also showed that, as the NH3 incident energy increases, the ratio of primary amines to the total number of N atoms on the surface decreases. It is because the energetic ion bombardment brakes up N–H bonds of primary amines, which are mostly brought to the surface by NH2 radical adsorption. Our previous experimental work on the CPA plasma polymerization showed that increased RF power invested in the plasma leads to the deposition of films with lower nitrogen content. The MD simulations showed an increase of the nitrogen content with the Ar energy and a limited impact of the energetic bombardment on the retention of primary amines. Thus, the results highlighted the importance of the gas-phase processes on the nitrogen incorporation and primary amines retention in the plasma polymers. However, the higher energy flux towards the growing film clearly decreases amount of hydrogen and increases the polymer cross-linking.
ER  -

MICHLÍČEK, Miroslav, Satoshi HAMAGUCHI and Lenka ZAJÍČKOVÁ. Molecular dynamics simulation of amine groups formation during plasma processing of polystyrene surfaces. \textit{Plasma Sources Science and Technology}. Bristol: IOP Publishing, 2020, vol.~29, No~10, p.~1-13. ISSN~0963-0252. Available from: https://dx.doi.org/10.1088/1361-6595/abb2e8.

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