Critical performance requirements for closed injection Pultrusion are low initial viscosity of the reactive mixture and no substantial polymerization at ambient temperature. On the contrary, it requires a very fast polymerization rate in the Pultrusion die to reach a high degree of curing. This concept is referred to in the industry as “snap cure” or “hockey stick” reactivity profile. While Polyurethane glass fiber closed injection has been practiced during the last 10 years, carbon fiber polyurethane Pultrusion have the added complexity of a lower carbon fiber filament diameter. A glass fiber filament diameter is on the order of 20-25µm, while a carbon fiber diameter is on the range of 5 to 7µm. This makes carbon fiber tow, which can contain 24K or 50K of these filaments very difficult to impregnate due to the lower intra-tow porosity (Darcy’s law), a fact that has limited Polyurethane carbon Pultrusion proliferation. Dow’s newly-developed low viscosity polyurethane system VORAFORCE™ TP1270EU/1300 was designed with these critical requirements in mind. In fact, a proper blend of polyols and the use of a low viscosity isocyanate achieved the required low initial viscosity. A systematic study on diverse catalyst and mold release agents and their interaction permitted Dow Scientists to optimize the reactivity profile of the Polyurethane system to enable carbon fiber Pultrusion.
But this development is not only about resin design. DowAksa with strong support of Dow focused on the creation of a disruptive closed injection system. The injection box (I-Box) is a fundamental part of the injection system and its design requires substantial know-how being one of the key elements of the novel process. Rheology and kinetics parameters were determined on Dow’s developed resin system and used by Dow’s computational modelers to simulate the fluid dynamics on different injection box designs and the curing kinetics on the Pultrusion die. Computational fluid dynamic models (CFD) and finite element analysis (FEA) were calibrated vs. process data and used for prediction on speeds and cure degree under different conditions [2] Figure 6 recreates how Dow and DowAksa engineers and scientists worked on predictive models and process data to design an optimum hardware to meet the stringent impregnation requirements of carbon fibers using a closed injection box system.
The significant challenge that Dow and DowAksa have overcome can be explained in the following practical example. In a pultruded laminate for spar cap containing about 70% of carbon fiber in volume, there are more than 10 million single carbon filaments. These filaments, are pulled continuously trough the injection box where they meet with the Polyurethane resin having a residence time in the Injection Box of typically less than one minute. The impregnation must be perfect; no dry spots are acceptable for the entire length of the coil as these could act as crack initiators. The length of the coils could be in the order of 280-300m and current throughput demand is in the order of several thousands of kilometers per week. Figure 7 shows the several hundred carbon bobbins unwinding from the creel and the carbon tows being directed towards the injection box. Figure 8 shows Scanning Electron Microscopy (SEM) pictures executed on the cross-section of the profiles that confirmed excellent wetting of the fibers. Online non-destructive analysis (NDT) continuously scan the production for dry spot detection, confirming excellent impregnation delivered consistently on millions of meters produced so far. This gives just a flavor of the enormous technical challenge DowAksa and Dow solved with the new technology.