Methods of making multilayer glass structure are described. The method involves providing first and second glass sheets, and a first enamel composition layer and at least one separation layer between the first and second glass sheets, and firing the glass sheets to sinter the first enamel composition to the first glass sheet. The separation layer is a black pigment separation layer, a refractory material separation layer, or an oxidizer separation layer. The separation layer can improve separation of the first and second glass sheets after the firing.