Study of polymer treatment with tetrafluoromethane plasma: Reactivity of fluorinated species on model surfaces

Polyolefins and their model molecules, some n-alcanes, have been modified by a tetrafluoromethane microwave plasma. The chosen molecules are high-density polyethylene (HDPE) and hexatriacontane (HTC), low-density polyethylene (LDPE) and paraffin, and polycaprolactone (PCL) and octadecyl octadecanoate (ODO). It has been found, except for paraffin, that the model surfaces have the same behavior as the corresponding polymers. Plasma modification is described as the sum of two mechanisms: degradation and fluorination. These reactions seem to be competitive and parallel. Degradation and fluorination rates are dependent on treatment time and are practically independent on substrate position. A domain of fluorination exists near the edge of plasma, whatever the substrate in or outside plasma. © 1993 John Wiley & Sons, Inc.     

Characterization of Polypropylene Surface Treated in a CO2 Plasma

The polypropylene modification in CO₂ plasma mainly contributes to degradation, functionalization, and cross-linking. The degradation, whose rate is depending on CO₂ dissociation and oxygen atom formation, is a quite slow reaction and it is associated with surface topography alteration, especially of the amorphous phase of the polypropylene. The surface roughness increases with the treatment duration and the amorphous phase is more degraded than the crystallized part. The functionalization, corresponding to an increase of the surface energy (57.3 mJ m ^{– 2} in 30 s), and to an oxidation (23 oxygen at.%) with the appearance of alcohol, ketone, and acid functions is a much faster phenomenon. Cross-linking takes also place during this type of treatment and will reinforce the stability of the modified surface.     

Interaction Mechanisms Between Ar–O<Subscript>2</Subscript> Post-Discharge and Stearic Acid II: Behaviour of Thick Films

We study the interaction of thick films (~4 mm) of stearic acid (SA), a C₁₈ alkane skeleton with an acid function, with late Ar–O₂ post-discharge. Contrary to what is observed with thin films of SA (~2–3 μm) which are efficiently etched (part I), only functionalization is observed over the first 2 h of treatment with a plasma source operated in the continuous mode, whatever the temperature. The heat released by surface reactions affects non-linearly the temperature of the substrate. Pulsing the source at a frequency ranging from 0.1 to 1 kHz slows down the functionalization process but does not allow any etching of the material. On the contrary, the SA can be etched as thick films by pulsing the oxygen flow rate at a frequency below 50 mHz. By pulsing the reactive gas, the time averaged value of the [O]/[O₂] ratio is decreased, limiting the functionalization processes due to oxygen atoms, and the mean temperature is lowered, decreasing the diffusion length of O₂ (and/or possibly O₂*) species in the SA which are responsible for the scission of C–C bonds of radicals.     

Relationship between ammonia sensing properties of polyaniline nanostructures and their deposition and synthesis methods

The ammonia absorption properties of polyaniline nanostructures are studied in terms of sensitivity, response and recovery times and stability. These characteristics are obtained by measuring, at room temperature, the absorbance variations at 632 nm. The nanostructures are synthesized either by interfacial or rapid or dropwise polymerizations with the oxidant-to-monomer mole ratio equals to 0.5 or 1. The influence of the deposition method (in-situ or drop-coating technique) as well as the nature of the dopant (HCl, CSA or I₂) on the gas detection properties are also studied. The results show a strong dependence of the morphology on the deposition method, the in-situ technique leads to the best sensitivity and response time. For this deposition method, the nanostructures sensitivity, response time and regeneration rate depend on the synthesis method, the dopant and the mole ratio. The ageing effect after 8 months under ambient conditions and the mechanism of interaction between the polyaniline nanostructures and ammonia molecules are also presented.     

Characterization of CO2 Plasma and Interactions with Polypropylene Film

The interactions between CO₂ plasma, less degrading than O₂ plasma, and polymeric surfaces are studied. CO₂ discharge and the relationships between the density of plasma reactive species are analyzed by optical emission spectroscopy and mass spectrometry. The optical emission spectrum was identified and five principal systems of carbon monoxide were assigned: the 4th and 3rd positive systems, Angstrom and 3A systems. Other systems dealing with ionized species CO⁺ ₂ and CO⁺ were also found. Mass spectrometry showed that the carbon monoxide and atomic oxygen were created through CO₂ dissociation by electronic impact. The detected molecular oxygen coming from the atomic oxygen recombination was associated with the power. The study of plasma/polymer interface showed the consumption of ionized species, the appearance of atomic hydrogen due to methyl groups transformation into exomethylene groups onto the polypropylene surface, and a degradation mechanism dependent on atomic oxygen density in the plasma phase.     

Optical emission from tetrafluoromethane plasma and its relationship to surface modification of hexatriacontane

The optical emission from tetrafluoromethane plasma (2% argon included) has been studied by emission spectroscopy. The evolution ofCF ^*,CF ₂ ^* , andF emissions has been followed during the treatment of an organic surface. An-alkane, hexatriacontane, has been used as a model for high density polyethylene surface and treated in different plasma conditions. We found that the evolution of fluorinated species emissions in the plasma gas phase is not only a measurement of the reactive species concentrations, but also an indication of the surface modifications. The surface properties, such as surface energy and surface roughness are correlated to the emission intensity of reactives species in the plasma gas phase. A mild exposure to the plasma can result in a great decrease of surface energy corresponding to the fluorination. The surface roughness only changes under drastic plasma conditions.     

Integrated SU-8 photonic gas sensors based on PANI polymer devices: Comparison between metrological parameters

In this work, we have designed and developed three families of integrated photonic sensors for ammonia detection. These photonic sensors are integrated onto single-mode TE₀–TM₀ SU-8 polymer planar waveguides and based on a polyaniline (PANI) sensitive polymer material. The first family relies on the deposit of a PANI–polymethyl methacrylate (PMMA) composite sensitive layer on a given SU-8 waveguide. The second family relies on a PMMA passive layer deposited on the SU-8 waveguide before applying the PANI sensitive layer on the PMMA passive layer. The third family takes advantage of a PANI layer deposited by plasma technique directly onto the SU-8 waveguide. The working principle of such sensors is based on the optical intensity modulation induced within the single-mode waveguide owing to the interaction between the evanescent field and the sensitive layer. The sensing proprieties of these integrated photonic sensors to ammonia gas at room temperature were characterized and the comparison between these different families of photonic sensors is presented. Experimental results show that the sensor based on new plasma–PANI as sensitive layer has the better metrological parameters.     

Azobenzene-containing monolayer with photoswitchable wettability

A compact monolayer containing azobenzene has been prepared on silicon substrates. The elaboration route consisted of covalent grafting of freshly synthesized azobenzene moieties onto an isocyanate-functionalized self-assembled monolayer (SAM). The highly packed and ordered isocyanate-functionalized SAM and the azobenzene-functionalized SAM were monitored and characterized by contact angle measurements and X-ray reflectivity (XR). Photoswitching of the wettability of the film induced by the reversible cis-trans isomerization of the azobenzene chromophores is experimentally shown from water and olive oil contact angle measurements.     

A Better Understanding of the Very Low-Pressure Plasma Polymerization of Aniline by Optical Emission Spectroscopy Analysis

In the wavelength range from 200 up to 1000 nm, optical emission from electronically excited fragments (CN, CH, NH, C₂, H₂, N₂, N₂⁺, and H-Balmer) is detected when aniline plasmas are generated in a multi-dipolar microwave reactor. The optical emission spectrum monitored in very low-pressure conditions (~?1 mTorr) shows important characteristics. The H_α, H_β and CN species are the most radiating systems and according to the NH/N₂ intensity ratio, two different operating regimes are observed suggesting a change in the reaction pathways. These two regimes are correlated to changes of the plasma characteristics (electron temperature and density) deduced from Langmuir probe measurements. The plasma thermodynamic state is quantified by implementing numerical simulation codes for synthetic spectra calculations. The rovibrational temperatures (T_r, T_v) are determined for some neutral species (CN, CH). The obtained values of T_r and T_v show the non-local thermodynamic equilibrium of the vibrational and rotational states (T_r?<?T_v). Moreover, the very low pressure aniline-based plasmas deviate substantially from the Boltzmann distribution. Correlation between the optical emission data and the solid phase analysis allows proving that the in situ characterization of the plasma phase is an important predictive tool of physico-chemical properties of the film. From these correlated data, we deduce preponderant chemical reaction pathways which help to better understand the plasma generation. Relative contributions of the dehydrogenation of C–H and N–H groups are established in order to deduce the leading initiation reaction for H-Balmer line formation.