UV excimer laser and low temperature plasma treatments of polyamide materials

Abstract

Polyamides have found widespread application in various industrial sectors, for example, they are used in apparel, home furnishings and similar uses. However, the requirements for high quality performance products are continually increasing and these promote a variety of surface treatments for polymer modification. UV excimer laser and low temperature plasma treatments are ideally suited for polyamide modification because they can change the physical and chemical properties of the material without affecting its bulk features. This project aimed to study the modification of polyamides by UV excimer laser irradiation and low temperature plasma treatment. The morphological changes in the resulting samples were analysed by scanning electron microscopy (SEM) and tapping mode atomic force microscopy (TM-AFM). The chemical modifications were studied by x-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and chemical force microscopy (CEM). Change in degree of crystallinity was examined by differential scanning calorimetry (DSC). After high-fluence laser irradiation, topographical results showed that ripples of micrometer size form on the fibre surface. By contrast, sub-micrometer size structures form on the polyamide surface when the applied laser energy is well below its ablation threshold. After high-fluence laser irradiation, chemical studies showed that the surface oxygen content of polyamide is reduced. A reverse result is obtained with low-fluence treatment. The DSC result showed no significant change in degree of crystallinity in either high-fluence or low-fluence treated samples. The same modifications in polyamide surfaces were studied after low temperature plasma treatment with oxygen, argon or tetrafluoromethane gas. The most significant result was that the surface oxygen content of polyamide increased after oxygen and argon plasma treatments. Both treatments induced many hydroxyl (-OH) and carboxylic acid (-COOH) functional groups, which increased water absorption. However, after tetrafluoromethane plasma treatment it was found that the -CF, -CF2 and -CF3 groups were introduced to the polyamide surface and this enhanced the hydrophobicity of the fabric. Suggested explanations are given of the mechanisms that produce the structure of the polyamide after the processes of laser irradiation (both high- and low-fluence) and plasma treatment. The fundamental approach used in modelling was considered the temperature profile of the material during the treatment. The development of high-fluence induced structures was caused by elevated temperatures in the subsurface volume and preexisting stress caused by fiber extrusion. The structure formation under LF laser irradiation was determined by thermal effect accompanied by the optical phenomenon of interference. Ripple structures formed by plasma were closely related to physical or chemical etching. Possible applications of plasma and laser technologies in the textile and clothing industries are considered. Oxygen plasma seems to be the best candidate to improve the wettability of the fabric, while tetrafluoromethane plasma can be applied to produce a water repellent surface. Surface treatments including CF4 plasma, high-fluence and low-fluence laser treatments produce a deeper color in disperse dyed fabrics using the same amount of dyestuff as chemicals like leveling agents and dyestuff can be reduced during the textile manufacturing process. UV laser and low temperature plasma modification processes are promising techniques for polymer/fabric surface modification and have industrial potential as they are environmentally friendly dry processes which do not involve any solvents.