Studies on the interactions between ZDOL perfluoropolyether lubricant and the carbon overcoat of rigid magnetic media

Current high performance magnetic storage devices, i.e., hard disk drives, typically operate at elevated temperatures of nominally 45-60 degrees C. As a consequence, understanding the thermal response of the materials used in the construction of the drive becomes imperative. In this report, we focus on the thermal behavior of a common perfluoropolyether lubricant (ZDOL) used on the carbon-overcoated, hard disk. In particular, we show that evaporative loss of this disk lubricant, as well as bonding of the lubricant to the carbon-overcoated disk, can occur at the temperatures encountered in the hard-disk drive. Surface energy measurements show that the interaction of the hydroxyl-terminated perfluoropolyether ZDOL occurs principally through the end-groups. On unannealed disks, the interaction between this "mobile" lubricant and the carbon overcoat is characterized by hydrogen bonding with the strength of these interactions being only slightly stronger than the intermolecular hydrogen bonding characteristic of bulk ZDOL. Upon annealing at temperatures in the range of 60-150 degrees C, the ZDOL lubricant becomes "bonded" to the disk. The surface energy of the bonded lubricant is substantially lower than the mobile lubricant reflecting the increased interaction strength that occurs as a result of bonding. Since the bonded state is the lower energy state, transitions from the mobile state to the bonded state are thermodynamically favored. The kinetics of this bonding transition, as well as the kinetics of lubricant evaporation were studied as a function of temperature. Using a model of two competing reaction channels, the activation energies for both lubricant bonding and lubricant evaporation were determined to be 3.6 kcal/mole and 5.4 kcal/mole respectively. Ab initio quantum chemical modelling was used to investigate possible interaction sites on the carbon surface. Both experiment and theory indicate that interaction of the hydroxyl-terminated ZDOL to the carbon overcoat occurs via hydrogen bonding to oxygenated species on the carbon overcoat, with a binding energy of 5-8 kcal/mole. An esterification reaction between the hydroxyl end-groups of ZDOL with carboxyl groups on the carbon surface as a result of annealing is shown to be consistent with the both the surface energy data and the kinetic data.