Inkjet printing of polymer solutions and the role of chain entanglement

Abstract

The influence of polymer concentration, going from the dilute through the overlap into the concentrated regime, during drop on demand inkjet printing is investigated for a range of cellulose ester (CE) polymers from visual examination of ligament stretching as a function of applied wave form. The physical behaviour of the polymer fluids in drop formation is indicative of the dominance of viscoelastic effects within the timescale of the process, in preventing ligament break-up at the pinch point compared with a water–glycerol–isopropanol blend Newtonian fluid of similar viscosity. This has previously been described in terms of the polymer chain undergoing a coil–stretch transition at the strain rates experienced in the inkjet process. When formulated at the coil overlap concentration all polymers showed qualitatively similar behaviour with respect to time and length of ligament at rupture irrespective of polymer molecular weight. Beyond the overlap concentration the ligament rupture time continues to increase with increasing elasticity of the solution but the ligament rupture length decreases rapidly. In this regime chain entanglement becomes important, dramatically increasing the elastic nature of the ligament. Additionally it is proposed that in the case of weakly associating polymers such as cellulose esters, the effective relaxation time is further increased due to the possibility that on chain extension intramolecular H-bonds are broken and may reform as intermolecular associations whilst the polymer chains are extended. These intermolecular associations act as physical crosslinks, thereby creating a transient network structure. This network structure is capable of having a finite large viscosity. Once the strain is removed the network will decay as the chains return to the more thermodynamically stable coil state.