This review addresses the production of nano-particles and the processing of particles injected in atmospheric pressure electrical discharges (APED). The mechanisms of formation and the evolution of particles suspended in gases are first presented, with numerical and experimental facilities. Different APED and related properties are then introduced for dc corona, streamer and spark filamentary discharges (FD), as well as for ac filamentary and homogeneous dielectric barrier discharges (DBD). Two mechanisms of particle production are depicted in APED: when FD interact with the surface of electrodes or dielectrics and when filamentary and homogeneous DBD induce reactions with gaseous precursors in volume. In both cases, condensable gaseous species are produced, leading to nano-sized particles by physical and chemical routes of nucleation. The evolution of the so-formed nano-particles, i.e. the growth by coagulation/condensation, the charging and the collection are detailed for each APED, with respect to fine powders production and thin films deposition. Finally, when particles are injected in APED, they undergo interfacial processes. Non-thermal plasmas charge particles for electro-collection and trigger heterogeneous chemical reactions for organic and inorganic films deposition. Heat exchanges in thermal plasmas enable powder purification, shaping, melting for hard coatings and fine powders production by reactive evaporation.

https://iopscience.iop.org/article/10.1088/0022-3727/39/2/R01/pdf

Nucleation and aerosol processing in atmospheric pressure electrical discharges: powders production, coatings and filtration

Plasma polymers deposited from n-heptylamine onto silicon wafers have been found to form a porous microstructure when immersed in water and other solvents, with pores of dimensions and densities that vary considerably between coatings deposited under different plasma conditions. This solvent-induced pore formation was found to correlate with the observed percentage of extractable material. With low radio frequency (rf) power inputs, the resultant softer coatings possess considerably more extractable material than coatings deposited at higher applied power levels. The porosity is thus proposed to result from the formation of voids created by the extraction of soluble low-molecular-weight polymeric material, which produces shrinkage stress that the coating, firmly attached to the substrate, cannot relieve by macroscopic contraction. The microscopic contraction of plasma polymer volume creates voids that appear to span the entire film thickness. The effect of aging plasma polymers in air was also investigated. For films deposited at low power it led to reduced extraction of soluble material and different pore morphology, whereas for films deposited at higher rf power levels, the extracted amounts and pore formation were the same for aged coatings. It was also found that the density of surface amine groups was lower for films deposited under the two lowest power settings, in contrast to the commonly held belief that the use of minimal applied rf power aids retention of functional groups. These porous plasma polymer coatings with surface groups suitable for further interfacial chemical immobilization reactions may be useful for various membrane and biotechnology applications.

Solvent-induced porosity in ultrathin amine plasma polymer coatings.

Primary amine-based plasma polymer films (NH 2 -PPF) were synthesized using plasma polymerization of allylamine in continuous wave (CW) and pulsed radio-frequency (RF) modes. Plasma chemistry, studied by residual gas analysis mass spectrometry, revealed that the precursor fragmentation is a function of the equivalent power (P eq ) dissipated in the discharge, independently of the plasma mode used. X-ray photoelectron spectroscopy combined with time-of-flight secondary ion mass spectrometry suggests as the precursor fragmentation in the plasma increases: (i) a decrease of the primary amine concentration in the NH 2 -PPF (%NH 2 ) and (ii) an increase of the cross-linking degree. For a given P eq , similar to the precursor fragmentation in the plasma, the NH 2 -PPF characteristics were found to be independent of the plasma mode used. Therefore, the main advantage of using pulsed RF processes over CW ones is the possibility to work at very low P eq which enables low precursor fragmentation, optimization of %NH 2 , and reduction of the film cross-linking degree. The chemical composition and the cross-linking degree of the NH 2 -PPF synthesized by allylamine plasma polymerization can thus be tailored by adjusting the equivalent RF power injected in the plasma.

Synthesis of Allylamine Plasma Polymer Films: Correlation between Plasma Diagnostic and Film Characteristics

The pulsed plasma polymerization of allylamine and cyclopropylamine is investigated to study the influence of the precursor chemical structure on the process selectivity toward the primary amine groups. Both systems are compared under similar mean powers injected in the discharges (Pmean). The results reveal an increase in the precursor fragmentation in the plasma and a decrease in the primary amine content of the film (%NH2 )a sPmean increases. Nevertheless, below a critical Pmean value, different behaviors are observed depending on the precursor, cyclopropylamine being less plasma-fragmented than allylamine. As a result, plasma polymer films (PPF) synthesized from cyclopropylamine yield the largest %NH2. These results are rationalized with the help of theoretical calculations pointing to a preferential opening of the cyclopropylamine ring structure. Cyclopropylamine activation in the plasma can thus be achieved without fragmentation reactions, lead

https://docnum.umons.ac.be/Access/WebOpenAccess/GetDocument.aspx?GuidTicket=791e611b-1556-4415-aa64-2933e9a94917

Deposition of Functional Organic Thin Films by Pulsed Plasma Polymerization: A Joint Theoretical and Experimental Study

Summary:Inthisstudy,microstructuredsurfacesareproduc-ed by a spatial arrangement of different functional domainsby a combination of plasma polymerization and photo-lithography.Two differentkinds ofproteinandcell adhesivepatterns have been alternated with non-fouling areas. Non-foulingpatternsaremadeofpoly(ethyleneoxide)(PEO)-likepolymers obtained by pulsed plasma polymerization ofdiethylene glycol dimethyl ether, which leads to coatingswith a high concentration of ethylene oxidegroups (>70%).Fouling surfaces are composed of PEO coatings with a lowconcentration of ethylene oxide groups ( 40%) and ﬁlmscontaining amino groups (from allylamine monomer) ob-tained by plasma polymerization. High pattern ﬁdelity isdemonstrated by ellispometry measurements, whereas XPSand ToF-SIMS analyses have been used to characterize thesurfaces. Experiments with a model protein (bovine serumalbumin) and cells (L929 mouse ﬁbroblasts) on patternedsurfaces show that proteins and cells only adhere on thepatterns, whereas the background stays uncovered.Optical image showing the selective proliferation of L929mouseﬁbroblastcellsaftercultureonapulsedPEO-like/PALmicropatterned surface.

Functional Micropatterned Surfaces by Combination of Plasma Polymerization and Lift-Off Processes

Summary: Thin films of plasma-polymerized allylamine (PPAA) have been deposited onto polyethylene powders (PE) and polystyrene (PS) beads by using a low-pressure 13.56 MHz plasma in a fluidized bed reactor. Chemical derivatization using a set of three different blocking agents has allowed quantitative measurement of the relative percentages of primary, secondary, and tertiary amines. Under optimized conditions, it is possible to incorporate up to 110 nmol of amine groups per gram of powder and with a selectivity of 75% for primary amines. Moreover, our data clearly show that for films deposited at 10 W the selectivity for primary amines is at a maximum, but this is at the expense of resistance to washing. A power of 20 W corresponds to an optimum value since both the amount of primary amines and the degree of resistance of the coating to solvents reach maximum values.

Distribution of the primary (I), secondary (II), and tertiary (III) amine groups on plasma-polymerized allylamine films deposited on polyethylene powders.

Plasma Deposition of Allylamine on Polymer Powders in a Fluidized Bed Reactor

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Plasma Deposition of Allylamine on Polymer Powders in a Fluidized Bed Reactor