Ceramic Near-Net Shaped Processing Using Highly-Loaded Aqueous Suspensions
Ceramic materials offer great advantages over their metal counterparts, due to their lower density, higher hardness and wear resistance, and higher melting temperatures. However, the use of ceramics in applications where their properties would offer tremendous advantages are often limited due to the difficulty of forming them into complex and near-net shaped parts. Methods that have been developed to injection-mold or cast ceramics into more complicated shapes often use significant volume fractions of a carrier (often greater than 35 vol.% polymer), elevated temperature processing, or less-than-environmentally friendly chemicals where a complex chemical synthesis reaction must be timed perfectly for the approach to work. Furthermore, the continuing maturation of additive manufacturing methods requires a new approach for flowing/placing ceramic powders into useful designs. This thesis addresses the limitations of the current ceramic forming approaches by developing highly-stabilized and therefore high solids loading ceramic suspensions, with the requisite rheology for a variety of complex and near-net shaped forming techniques. Silicon nitride was chosen as a material of focus due to its high fracture toughness compared to other ceramic materials. Designing ceramic suspensions that are flowable at room temperature greatly simplifies processing as neither heating nor cooling are required during forming. Highly-loaded suspensions (>40 vol.%) are desired because all formed ceramic bodies have to be sintered to remove pores. Finally, using aqueous-based suspensions reduces any detrimental effect on the environment and tooling. The preparation of highly-loaded suspensions requires the development of a suitable dispersant through which particle-particle interactions are controlled. However, silicon nitride is difficult to stabilize in water due to complex surface and solution chemistry. In this study, aqueous silicon nitride suspensions up to 45 vol.% solids loading were dispersed using commercially available comb-type copolymer. These copolymers are used as superplasticizers in the concrete industry and are referred to as water-reducing admixtures (WRAs). Four different WRA dispersants were examined and chemical analysis determined that each was made up of a sodium salt of polyacrylic acid (PAA-Na) backbone with neutral polyethylene oxide (PEO) side chains that afford steric stabilization. The general structures of the WRAs were compared to each other by measuring the relative areas of their prominent FTIR peaks and calculating a PAA-Na/PEO peak ratio. Suspensions were made with as-received silicon nitride powders with 5 wt.% aluminum oxide and 5 wt.% yttrium oxide added as sintering aids. Three of the four WRA dispersants studied were able to produce suspensions with 43 vol.% solids loading and 5 vol.% polymer dispersant, while exhibiting a yield-pseudoplastic behavior for shear rates up to 30 s-1. At higher solids loading (45 to 47 vol.%), a shift to shear thickening behavior was observed at a critical shear rate for these WRAs. Those WRAs with a lower PAA-Na/PEO peak ratio displayed better stabilization and diminished shear thickening behavior. The vol.% of the dispersant was optimized, producing yield-pseudoplastic suspensions containing 45 vol.% solids loading with yield stresses less than 75 Pa, no shear thickening behavior, and viscosities less than 75 Pa-s for shear rates in the range of 1 to 30 s-1. Using suspensions prepared with two of the WRAs investigated in this work, silicon nitride near-net shaped parts were formed via a novel injection molding process by loading each suspension in a syringe and injecting them at a controlled rate into a mold. Each suspensions had carefully tailored yield-pseudoplastic rheology such that they can be injection molded at room temperature and low pressures (< 150 kPa). Four suspensions were studied; two different commercially available concrete water-reducing admixtures (WRAs) were used as dispersants with and without a polymer binder (Polyvinylprolidone, PVP) added for rheological modification and improved green body strength. Test bars formed via this process were sintered to high densities (up to 97% TD) without the use of external pressure, and had complete conversion to the desirable β-Si3N4 phase with high flexural strengths up to 700 MPa. The specimen sets with the smallest average pore size on the fracture surface (77 μm) had the highest average flexural strengths of 573 MPa. The hardness of all specimens was approximately 16 GPa. The water-based suspensions, ease and low cost of processing, and robust mechanical properties obtained demonstrate this as a viable process for the economical and environmentally friendly production of Si3N4 parts. Finally, additive manufacturing was also used as a method to overcome ceramic forming difficulties and to create near-net shaped dense components via room-temperature direct ink writing. In this processes, highly loaded aqueous alumina suspensions were extruded in a layer-by-layer fashion using a low-cost syringe style 3D printer. With alumina as a model material, the effect of solids loading on rheology, specimen uniformity, density, microstructure, and mechanical properties was studied. All suspensions contained a polymer binder (~5 vol.%), dispersant, and 51 to 58 vol.% alumina powder. Rheological measurements indicated all suspensions to be yield-pseudoplastic, and both yield stress and viscosity were found to increase with increasing alumina solids loading. Shear rates ranging from 19.5 to 24.2 s-1, corresponding to viscosities of 9.8 to 17.2 Pa·s, for the 53 – 56 vol.% alumina suspensions were found to produce the best results for the 1.25 mm tip employed during writing. All parts were sintered to greater than 98% of true density, with grain sizes ranging from 3.2 to 3.7 μm. The average flexure strength, which ranged from 134 to 157 MPa, was not influenced by the alumina solids loading. In limited study, additive manufacturing of silicon nitride suspensions stabilized with a WRA has been established. These processing routes have been proven as low-cost and viable means for producing robust ceramic parts, both of which can be tailored to many systems to expand the use of ceramics materials. Further studies on utilizing the flow stress behavior during both injection molding and direct ink writing could be beneficial in creating ceramic materials with carefully tailored microstructure to increase mechanical performance.
Youngblood, Purdue University.
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