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This article presents an atomic force microscopy (AFM) study of the initial stage of the photografting of glycidyl methacrylate (GMA) onto high-density polyethylene (HDPE) surface and the microstructure of the grafted chains. The grafting was carried out in acetone, dichloromethane and tetrahydrofuran (THF), as well as without solvent. Granular structures were found on the surface of the samples grafted in the solvents. The height of the granules increased linearly with their diameter. Each granule was thought to be a single grafted chain with a highly branched (or superbranched) microstructure. The grafting density on HDPE was quite small when the grafting was carried out in the solvents. The grafted chains were more branched when grafting was carried out in THF than when the grafting was carried out in acetone and dichloromethane. The bulk (no solvent) grafting of GMA onto HDPE was much faster and more uniform than that carried out in the solvents. The thickness of the bulk grafted materials was a few nanometers after 30
s irradiation, and possibly, the grafting density was much higher and the grafted polymers were much less branched than those produced in solvent.