Exploring molecular changes at the surface of polypropylene after accelerated thermomolecular adhesion treatments

A central composite rotatable design (CCRD) method was used to investigate the performance of the accelerated thermomolecular adhesion process (ATmaP), at different operating conditions. ATmaP is a modified flame-treatment process that features the injection of a coupling agent into the flame to impart a tailored molecular surface chemistry on the work piece. In this study, the surface properties of treated polypropylene were evaluated using X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). All samples showed a significant increase in the relative concentration of oxygen (up to 12.2%) and nitrogen (up to 2.4%) at the surface in comparison with the untreated sample (0.7% oxygen and no detectable nitrogen) as measured by XPS. ToF-SIMS and principal components analysis (PCA) showed that ATmaP induced multiple reactions at the polypropylene surface such as chain scission, oxidation, nitration, condensation, and molecular loss, as indicated by changes in the relative intensities of the hydrocarbon (C₃H₇⁺ , C₃H₅⁺ , C₄H₇⁺, and C₅H₉⁺), nitrogen and oxygen-containing secondary ions (C₂H₃O⁺, C₃H₈N⁺, C₂H₅NO⁺, C₃H₆NO⁺, and C₃H₇NO⁺). The increase in relative intensity of the nitrogen oxide ions (C₂H₅NO⁺ and C₃H₇NO⁺) correlates with the process of incorporating oxides of nitrogen into the surface as a result of the injection of the ATmaP coupling agent.

Tailoring the surface chemistry of carbon fiber and E-glass composites for improved adhesion

The main challenges in the manufacture of composite materials are low surface energy and the presence of silicon-containing contaminants, both of which greatly reduce surface adhesive strength. In this study, carbon fiber (CF) and E-glass epoxy resin composites were surface treated with the Accelerated Thermo-molecular adhesion Process (ATmaP). ATmaP is a multiaction surface treatment process where tailored nitrogen and oxygen functionalities are generated on the surface of the sample through the vaporization and atomization of n-methylpyrrolidone solution, injected via specially designed flame-treatment equipment. The treated surfaces of the polymer composites were analyzed using XPS, time of flight secondary ion mass spectrometry (ToF-SIMS), contact angle (CA) analysis and direct adhesion measurements. ATmaP treatment increased the surface concentration of polar functional groups while reducing surface contamination, resulting in increased adhesion strength. XPS and ToF-SIMS showed a significant decrease in silicon-containing species on the surface after ATmaP treatment. E-glass composite showed higher adhesion strength than CF composite, correlating with higher surface energy, higher concentrations of nitrogen and CO functional groups (from XPS) and higher concentrations of oxygen and nitrogen-containing functional groups (particularly C₂H₃O⁺ and C₂H₅NO⁺ molecular ions, from ToF-SIMS).