Disk Lubricants for Spontaneous Adsorption and Grafting to Carbon Overcoat by UV Irradiation

Abstract

A molecular orbital study was performed to elucidate the π–π charge transfer interaction between perfluoropolyether (PFPE) lubricants possessing phenylic end-groups and the carbon overcoat of magnetic hard disks. It is revealed that the phenylic unit and the graphitic segment of the carbon attract each other leading to spontaneous adsorption. The strength of this interaction increases in the order of: an unsubstituted phenyl group < a phenoxy unit < a p-methoxy-phenoxy unit. A molecular dynamics calculation revealed that alkyl-phenyl ether, on capture of an electron, would dissociate to yield the phenoxide anion and the alkyl radical. It is thus predicted that PFPE lubricants with an end-group possessing a phenoxy unit would spontaneously adsorb on the carbon overcoat, and that irradiation of disks coated with such lubricant with short UV (185 nm), thus generating photo-electrons, would result in facile detachment of phenoxy groups and grafting of PFPE molecular chains to the carbon surface at the chain terminus. Four new PFPE lubricants, Z-SA1 and Z-SA2 based on the Fomblin Z type backbone, and D-SA1 and D-SA2 based on the Demnum backbone were synthesized, where SA1 and SA2 indicate end-groups possessing a phenoxy unit and a p-methoxy-pheoxy unit at the ω-position, respectively. Disks coated with these lubricants were tested for (1) spin-off rate, (2) diffusion over the disk surface, (3) facility for photo-grafting by UV, (4) water contact angle (before and after UV exposure), (5) the catalytic degradation, and (6) the on-track time-to-failure test. A TOF-SIMS study of disks coated with D-SA1 and D-SA2 was performed to elucidate the disposition of lubricant molecular chains due to spontaneous adsorption and the effect of UV irradiation. All the experimental results were found to be in good accord with predictions given by the molecular orbital study. In the time-to-failure test, disks coated with Z-tetraol, Z-SA1, and Z-SA2 were compared. The durability was found to increase in the order of Z-tetraol < Z-SA1 < Z-SA2.