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Cold Plasma Systems and Their Application in Surface Treatments for Medicine

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Cold Plasma Systems and Their Application in Surface Treatments for Medicine molecules Review Cold Plasma Systems and Their Application in Surface Treatments for Medicine Francisco L. Tabares 1,* and Ita Junkar 2 1 Laboratorio Nacional de Fusion, CIEMAT, Av Complutense 40, 28040 Madrid, Spain 2 Department for Surface Engineering, Jožef Stefan Institute Jamova cesta 39, 1000 Ljubljana, Slovenia; [email protected] * Correspondence: [email protected] Abstract: In this paper, a review of cold plasma setups and the physical and chemical processes leading to the generation of active species is presented. The emphasis is given to the interaction of cold plasmas with materials used in medical applications, especially medical implants as well as live cells. An overview of the different kinds of plasmas and techniques used for generation of active species, which significantly alter the surface properties of biomaterials is presented. The elemental processes responsible for the observed changes in the physio-chemical properties of surfaces when exposed to plasma are described. Examples of ongoing research in the field are given to illustrate the state-of-the-art at the more conceptual level. Keywords: plasmas; RONS; atmospheric plasmas; plasma material interactions; plasma medicine 1. Introduction Citation: Tabares, F.L.; Junkar, I. In 1969, John R. Hollahan’s group experimentally demonstrated that with cold ammo- Cold Plasma Systems and Their nia plasmas or mixtures of nitrogen and hydrogen, amino groups (–NH2) were produced, Application in Surface Treatments for which, by adhering to the surface of different types of polymers, created materials compati- Medicine. Molecules 2021, 26, 1903. ble with blood [1]. Since then, the use of cold plasmas to optimize the interaction between https://doi.org/10.3390/ biological systems and different types of materials has been investigated, with the ultimate molecules26071903 goal of achieving biocompatible surfaces. Cold plasma treatment only affects the surface of the treated material. The physical, chemical, mechanical, electrical, and optical properties Academic Editor: Stefano Falcinelli of the interior of the material are not altered by the cold plasma. On the other hand, the use of different acids and chemical solvents can damage the surface of many plastics and, Received: 6 February 2021 if absorbed, affect the properties of the interior of the material. Accepted: 24 March 2021 Plasma is the predominant state of matter in the known universe (it is estimated Published: 28 March 2021 that up to 99% of matter is plasma), although not on our planet, where the conditions of pressure and temperature make normal the states of matter—solid, liquid, and gas—that Publisher’s Note: MDPI stays neutral in global terms are exotic. It is enough to add energy to the solid (in the form of heat or with regard to jurisdictional claims in published maps and institutional affil- electromagnetic radiation) for it to turn into a liquid state, from which gas is obtained iations. through an additional supply of energy. If we continue adding energy to the gas, we will partially or totally ionize it, that is, we will remove electrons from the atoms or molecules that constitute it. In this way, we reach a new state of matter, plasma, made up of free electrons, atoms and molecules (electrically neutral particles), and ions. The energy needed to generate plasma can be supplied in several ways: through heat from a combustion Copyright: © 2021 by the authors. process; through the interaction between laser radiation and a solid, a liquid, or a gas; or Licensee MDPI, Basel, Switzerland. through electrical discharges in gases, in which free electrons take energy field and lose it This article is an open access article distributed under the terms and through excitation and ionization processes of the atoms and molecules in the gas. conditions of the Creative Commons One of the peculiarities of plasmas is that they conduct electricity. On a macroscopic Attribution (CC BY) license (https:// scale, plasmas are, however, electrically neutral, since the number of positive and negative creativecommons.org/licenses/by/ charges is similar. Thus, the flame produced by burning candle wax in combination with 4.0/). oxygen from the air—a typical example of a plasma that is very little ionized—can conduct Molecules 2021, 26, 1903. https://doi.org/10.3390/molecules26071903 https://www.mdpi.com/journal/molecules Molecules 2021, 26, x FOR PEER REVIEW 2 of 17 Molecules 2021, 26, 1903 2 of 16 oxygen from the air—a typical example of a plasma that is very little ionized—can conduct electricity.electricity. A A graphical graphical overview overview of the of thedifferent different kinds kinds of plasmas of plasmas according according to their mi- to their microscopiccroscopic parameters parameters (electron (electron density density and temperature) and temperature) is displayed is displayed in Figure in Figure1 1 FigureFigure 1.1. Overview of of plasmas plasmas and and the the wide wide range range of oftheir their microscopic microscopic parameters parameters (electron (electron en- energy andergy electron and electron density). density). 1eV 1eV = 11,500 = 11,500◦C. °C. TheThe values of of density density and and electronic electronic temperature, temperature, two two of the of themain main parameters parameters that that characterizecharacterize plasmas, plasmas, cover cover a awide wide spectrum. spectrum. Thus, Thus, the theelectron electron density density varies varies between between 1 3 25 3 1electron/cm electron/cm and3 and 10 10 electrons/cm25 electrons/cm; that3; thatis, it is,even it even exceeds exceeds the concentration the concentration of electrons of electrons inin metals.metals. On the the other other hand, hand, the the average average free free path path of ofthe the particles particles in a in plasma, a plasma, that thatis, the is, the averageaverage distance covered covered before before a aparticle particle collides collides with with another another particle particle in the in plasma the plasma can can range from tens of millions of kilometers to just a few microns. range from tens of millions of kilometers to just a few microns. Classifying the diversity of types of plasmas that exist in nature or that can be gener- Classifying the diversity of types of plasmas that exist in nature or that can be gen- ated artificially is not easy, since it is risky to choose isolated parameters that serve as erated artificially is not easy, since it is risky to choose isolated parameters that serve as criteria to establish the differences. Despite these difficulties, we can venture into a first criteria to establish the differences. Despite these difficulties, we can venture into a first classification of the types of plasmas, one that considers their thermal equilibrium, that is, classificationwhether or not of the the temperature types of plasmas, or the average one that energy considers of the their particles thermal that equilibrium,make it up is that is,the whether same for or each not type the temperatureof particle. All or particles the average have the energy same of temperature the particles (thermal that make equi- it up islibrium) the same for forstellar each interior type plasma of particle. or for All its particlesterrestrial haveanalogs, the deuterium-tritium same temperature fusion (thermal equilibrium)plasmas and the for impurities stellar interior generated plasma in experimental or for its terrestrial controlled analogs, nuclear deuterium-tritiumfusion devices, fusionlike the plasmas JET and andthe ITER. the impurities These plasmas generated are also in called experimental hot or thermal controlled plasmas nuclear since the fusion devices,temperature like inside the JET them and reaches the ITER. millions These of plasmasdegrees (10 are7 °C–10 also called9 °C), the hot same or thermal for the elec- plasmas 7 ◦ 9 ◦ sincetrons theas for temperature heavy species inside [2]. them reaches millions of degrees (10 C–10 C), the same for theWhen electrons the gas as pressure for heavy is low species or the [2 electrical]. voltage applied in the discharge is high, the electronsWhen the in the gas plasma pressure acquire, is low in orthe the time electrical between voltagecollisions applied with other in theplasma discharge par- is high,ticles, the kinetic electrons energies in thehigher plasma thanacquire, the energy in theassociated time between with the collisions random thermal with other move- plasma particles,ment of the kinetic neutral energies particles higher (atoms thanand molecules) the energy of associated the plasma. with We can the then random attribute thermal movementsome degree of of the thermal neutral equilibrium particles deviation (atoms and to plasmas, molecules) since of electrons, the plasma. ions, and We canneu- then attributetral particles some have degree different of thermal “temperatures” equilibrium or average deviation kinetic to energies plasmas, (in since the case electrons, of non- ions, andMaxwellian neutral particlesdistributions), have differentrather common “temperatures” for plasmas or averageproduced kinetic at low energies pressure (in and the case ofwith non-Maxwellian a small degree of distributions), ionization. rather common for plasmas produced at low pressure and withNonthermal a small degreeplasmas, of also ionization. known as cold plasmas, are characterized by the fact that the temperatureNonthermal of plasmas, heavy species also known(neutralas particles cold plasmas, and ions) are is close characterized to room temperature by the fact that the temperature
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