Polymers synthesized with plasma techniques are very interesting materials for electronic, optic, and bio compatible applications. Thin films of plasma polymers shows a good adhesion to metals, glass, or other polymers. But the supramolecular structure, the durability, and the chemical and mechanical behavior of these polymers is poorly understood. Therefore dielectric investigations are carried out to study the dynamic behavior of the plasma polymers. As polymer system allyl alcohol/alkene is chosen to get polymers with a defined concentration of hydroxyl groups. The dielectric investigations shows several relaxation processes and a dependency of the dielectric parameters from the ratio of allyl alcohol in the polymer is observed. This results indicated that the alkene monomers were assembled continuous into the polymer matrix.
The retention of chemical structure and functional groups during pulsed plasma polymerization was used for producing adhesion-promoting plasma polymer layers with high concentrations of exclusively one kind of functional groups, such as OH, NH2, or COOH. The maximum content of functional groups was 31 OH using allyl alcohol, 18 NH2 using allylamine, or 24 COOH per 100 C atoms using acrylic acid. To vary the density of functional groups, chemical co-polymerization with ethylene as 'chain-extending' co-monomer, or butadiene as 'chemical crosslinker' was initiated in the pulsed plasma. The composition of these co-polymers was investigated by XPS and IR spectroscopy. The concentrations of functional groups were measured by derivatizing with fluorine-containing reagents and using XPS. A set of plasma parameters was found to be a good compromise between a high number of functional groups and complete insolubility in water, ethanol or THF,which is needed for further chemical processing. Here, these monotype-functionalized surfaces were used in metal-polymer systems as adhesion-promoting interlayers to examine the influence of type and density of functional groups on adhesion. As expected, COOH- and OH-group-terminated interlayers showed maximum peel strengths to evaporated aluminium layers. The adhesion increased linearly with the number of OH groups to a maximum at about 27 OH per 100 C atoms. Higher concentrations of OH groups did not increase the peel strength further.
This new functionalization method consists of the deposition of very thin plasma polymer layers (20 to 100 nm) of functional group bearing monomers in pulsed plasma. With allylalcohol, a maximum of 30 OH groups per 100 C atoms was measured with a selectivity of about 90% and a significant stability at long-time exposure to air. Allylamine was used to produce primary amino groups, with a maximum of 18 NH2 groups per 100 C atoms. Side reactions were observed during the storage in air, such as oxidation of the amino groups. Carboxylic groups could be produced using acrylic acid with a maximum concentration of 24 COOH groups per 100 C atoms. The most prominent side reaction was the decarbonylation/ decarboxylation of the acid group during plasma deposition.___TAGSTART___BR___TAGEND___ The variation of the density of functional groups using the pulsed-plasma polymerization of functional-group-bearing monomers was possible by the chemically-initiated radical copolymerization with either a chain-extending monomer, such as ethylene, or a cross linker, such as butadiene, in plasma. The density of functional groups could be adjusted continuously (0 to 30 OH, 0 to 18 NH2 and 0 to 24 COOH groups per 100 C atoms).___TAGSTART___BR___TAGEND___ The successful application of these densely functionalized polymer surfaces for producing biocompatible surfaces and for use in metalpolymer composites is proposed.
Copolymers of acrylic acid and styrene (AA/S) were prepared by pulsed plasma deposition and their structures were studied in dependence on the duty cycle (DC) for a fixed composition of 1:1. As a result, low values of DC doses preserve the structure of monomers in the plasma deposited polymers while high DC leads to a higher degree of fragmentation and a loss in regular structure. Regarding plasma copolymerisation as a feasible method to finish surfaces with a definite number of functional groups it is necessary to characterize both, the chemical nature and the physical properties of the deposited layer. Therefore, a combination of different methods was employed for the characterization of thin plasma copolymer films (FTIR, dielectric spectroscopy, differential scanning calorimetry, X-ray photoelectron spectroscopy (XPS)). Special attention was paid on the unambiguous identification of COOH groups at the surface after derivatization with trifluoroethanol by XPS and in the volume by FTIR. The glass transition temperature of the copolymer system is lower than that for the both plasma deposited homopolymers and increases with the DC in difference to plasma deposited poly(acrylic acid). The dielectric measurements showed that the plasma deposited films were not thermally stable and underwent an undesired post-plasma chemical reaction. The results obtained by dielectric spectroscopy are discussed in detail in comparison with the data from FTIR and XPS measurements.
The outdoor weathering of polymers is mainly due to UV radiation, water, Pollution, humidity, temperature etc. To understand the effects of weathering, simulated tests need to be undertaken in lab scale. Such tests must be quite efficient and similar to the effects of natural weathering. This paper mainly focuses on the effects of UV radiation along with humidity on LDPE.
Artificial weathering of LDPE under dry conditions (<10% of relative humidity) by UV radiation was monitored
by dielectric spectroscopy. For an apolar polymer like LDPE, dielectric study yields information
about the change in structure and dynamics of the system. The fluctuations of the polar groups which
are generated as a result of photooxidation such as carbonyl groups can be monitored as characteristic
relaxation processes like the αc or β mode. The dielectric loss characterized by typical dielectric parameters
like the activation energy and dielectric strength are strongly dependent upon changes induced
by photooxidation in the amorphous and crystalline domains. This paper discusses in detail how the foil
reached its mechanical disintegration. It was found that initial stages of weathering induce chain scission
and/or crosslinking in the amorphous domains of the polymer and the motional processes in the crystalline
regions are not affected. After this induction period, an increase in the degree of crystallization was
observed by employing differential calorimetry. The increasing crystallinity is considered as one of the
reasons for embrittlement which finally leads to the complete loss of the structural integrity.
Polystyrene (PS) spin coated thin films were modified by O2 and Ar plasma as
well as by UV irradiation treatments. The modified PS samples were compared with
plasma polymerized and commercial polystyrene. The effects of plasma (O2 and Ar) and
UV irradiation treatments on the surface and the bulk properties of the polymer layers were
discussed. The surface properties were evaluated by X-ray Photoelectron Spectroscopy and
Contact angle measurements and the bulk properties were investigated by FTIR and
dielectric relaxation spectroscopy. As a result only one second treatment time was sufficient
to modify the surface. However, this study was also dedicated to understand the effect
of plasma and plasma irradiation on the deposited layers of plasma polymers. The
dielectric measurements showed that the plasma deposited films were not thermally stable
and underwent an undesired post-plasma chemical oxidation.
Copolymers of acrylic acid and styrene (AA/S) were prepared by pulsed plasma deposition technique. Their structure–property relationships were studied in dependence on the comonomer ratio. Both, the regularity of the structure and the composition of the thin copolymer films were investigated by bulk-sensitive (dielectric spectroscopy, FTIR, and differential scanning calorimetry) as well as surface-sensitive methods such as X-ray photoelectron spectroscopy (XPS). For an unambiguous identification of the functionality of the deposited films the COOH groups were estimated by derivatization with trifluoroethanol and subsequent XPS measurement as well as by the quantitative analysis of the FTIR data. As a result, the concentration of COOH groups on the surface and in the bulk is increasing with the fraction of AA in precursor mixture in a non-monotonous way but similar to the dependence obtained by conventional free radical polymerization.