Currently, the functional monomer 10-methacryloyloxy-decyl-dihydrogen-phosphate (10-MDP) was documented to chemically bond to zirconia ceramics. However, little research has been conducted to unravel the underlying mechanisms. This study aimed to assess the chemical interaction and to demonstrate the mechanisms of coordination between 10-MDP and zirconium oxide using 1H and 31P magic angle spinning (MAS) nuclear magnetic resonance (NMR) and two dimensional (2D) 1H → 31P heteronuclear correlation (HETCOR) NMR. In addition, shear bond-strength (SBS) tests were conducted to determine the effect of 10-MDP concentration on the bonding effectiveness to zirconia. These SBS tests revealed a 10-MDP concentration-dependent SBS with a minimum of 1-ppb 10-MDP needed. 31P-NMR revealed that one P-OH non-deprotonated of the PO3H2 group from 10-MDP chemically bonded strongly to zirconia. 1H-31P HETCOR NMR indicated that the 10-MDP monomer can be adsorbed onto the zirconia particles by hydrogen bonding between the P=O and Zr-OH groups or via ionic interactions between partially positive Zr and deprotonated 10-MDP (P-O−). The combination of 1H NMR and 2D 1H-31P HETCOR NMR enabled to describe the different chemical states of the 10-MDP bonds with zirconia; they not only revealed ionic but also hydrogen bonding between 10-MDP and zirconia.

Tribochemical silica coating (TSC) is commonly used to pretreat zirconia surfaces prior to luting. Although many studies demonstrate an adhesion-promoting effect of TSC on zirconia, its actual interaction mechanism has not been fully elucidated. We therefore characterized the ultrastructure of TSC-treated zirconia and tested shear-bond strength. STEM/EDS disclosed a micro-roughened zirconia surface partially covered with fused Al and Si, while residual unfused silica particles could also still be detected. TSCtreated zirconia having received the solely silane primer exhibited a significantly lower shear-bond strength than zirconia on which the combined 10-MDP/silane primer was applied. SEM fracture analysis revealed residual silica particles on both the zirconia and cement sides. Correlative ultrastructural and chemical surface characterization revealed that TSC deposited an inhomogeneous silica layer on the zirconia surface, which explains why the solely silane coupling agent was less effective than the combined 10-MDP/ silane ceramic primer for bonding to zirconia pretreated by TSC.