Isolating the effects of thixotropy in geopolymer pastes

The rheological properties of potassium-based geopolymers were investigated through a series of experiments intended to isolate the influence of shear rate, recovery time, and shear ramping on thixotropy for a greater understanding of geopolymer thixotropic properties within the context of the geopolymer setting reaction. It is shown that for thixotropic disruption to occur a critical shear rate of 100 s⁻¹ must be reached or surpassed, full thixotropic restructuring occurs at around 90–100 min of total undisturbed rest time, and that reaching a state of full thixotropic disturbance heavily depends on subjected processing parameters. In addition, a consistent crossover between the storage and loss modulus within 1–3 min of oscillation during cyclical oscillatory measurements greatly indicates the repeatability and reversibility of thixotropy in geopolymers and the potential for tailorable viscosity. Overall, it is found that geopolymer pastes exhibit strong evidence of thixotropy, which is favorable for additive manufacturing, and that allotted rest time before shear and shear rate greatly influence the overall rheological properties.     

Rheological assessment of metakaolin-based geopolymer composites through squeeze flow

Geopolymer (GP) composites show great potential as a replacement for ordinary Portland cement (OPC) in construction material, extrusion-based, and additive manufacturing. The rheological properties of highly viscous and reinforced systems have not yet been well studied, due to limitations in the current state of the art rheometers and viscometers, such as size and torque limits. In this study, the basic rheological properties of highly reinforced, geopolymer composites with potential for 3D printing are innovatively investigated with “squeeze flow” and “flow table” tests commonly used in civil engineering. Squeeze-flow rates of 0.1, 1.0, and 3.0 mm/s were assessed with varying sand weight percentages or basalt fiber lengths and compared to a conventional OPC mixture to differentiate the flow properties and deformation resistance of both materials. It is shown that the deformation resistance as a result of jamming increases with increasing solid reinforcement percentages, but that the overall effect of fiber size is somewhat inconclusive. In addition, the effect of squeeze-flow rate exhibits an increase in load required to initiate flow at lower squeezing rates, but, upon reaching a certain ratio of solids to liquid in the matrix, the results become variable.     

Comb Polymer Architecture Effects on the Rheological Property Evolution of Concentrated Cement Suspensions

We have studied the rheological behavior of concentrated cement suspensions in the absence and presence of comb polymers comprised of a polyacrylic acid (PAA) backbone and charge-neutral, poly(ethylene oxide) (PEO) teeth. These species possessed a uniform backbone molecular weight and graft density, with varying teeth molecular weight. Both PAA, a linear polyelectrolyte, and PAA/PEO comb polymers imparted initial stability to concentrated cement suspensions above a critical weight fraction, w * of 4 mg/(g of cement). Cement–PAA suspensions, however, set prematurely. Their rapid, irreversible stiffening stemmed from deleterious interactions between PAA and multivalent counterions in solution. Interestingly, the presence of PEO teeth comprised of only a few monomer units in length mitigated such interactions. The rheological property evolution of concentrated cement–PAA/PEO suspensions exhibited complex behavior ranging from the reversible gel-like response observed at short teeth lengths to a remarkable gel-to-fluid transition observed during the deceleratory period for systems comprised of longer PEO teeth. At longer hydration times, all cement–PAA/PEO suspensions exhibited initial elastic modulus values, G_i '∼ exp( t /τ_c) before the onset of the acceleratory period, followed by initial set. Their characteristic hydration time, τ_c, and set time depended strongly on the concentration of "free" carboxylic acid groups [COO⁻] arising from non-adsorbed polyelectrolyte species in solution.     

In Situ Rheological Investigation of the Coagulation in Aqueous Alumina Suspensions

Electrostatically stabilized alumina suspensions can be destabilized by the enzyme-catalyzed decomposition of urea (direct coagulation casting). Depending on the conditions, this reaction can shift the pH of a suspension to the buffer pH of the reaction products or increase the ionic strength at the buffer pH. The coagulation for both mechanisms was investigated using in situ rheological measurements. Using a vane tool in oscillation mode, the measuring conditions were optimized to find a reasonable method for time-dependent measurements. Constant parameters (stress or strain) proved to be unsuitable, because the linear viscoelastic region shifted considerably during the coagulation. Furthermore, the gel structure produced on coagulation via increase of ionic strength (Δ I ) was very sensitive to the oscillation. Therefore, for long-time experiments, a short continuous measurement with a low strain was followed by amplitude sweeps with increased intervals to determine the linear values of G ' and G ". In this way, the increase of the moduli G ' and G " could be followed for longer times, and it was possible to demonstrate two results. First, the final G ' of the network was about 10 times higher for Δ I -coagulated material than for suspensions coagulated via pH shift (ΔpH). Second, particle rearrangement processes took place in Δ I -coagulated networks even after the chemical changes were finished, whereas ΔpH-coagulated samples were "frozen-in" when approaching the isoelectric point and showed no further physical changes afterward.     

Cement Composition Effects on the Rheological Property Evolution in Concentrated Cement–Polyelectrolyte Suspensions

We have studied the rheological property evolution and hydration behavior of white and ordinary portland cement (type I) pastes and concentrated cement–polyelectrolyte suspensions. Cement composition had a marked effect on the elastic property evolution ( G '( t )) and hydration behavior of these suspensions in the presence of poly(acrylic acid)/poly(ethylene oxide) copolymer (PAA/PEO), even though their affinity to adsorb such species was nearly identical. Both white and ordinary portland cement pastes exhibited G '₀ values of ∼10⁴ Pa and fully reversible G '( t ) behavior until the onset of the acceleratory period ( t = 2 h), where the pastes stiffened irreversibly. In contrast, cement–PAA/PEO suspensions exhibited G '₀ values of ∼1 Pa and G '( t ) behavior comprised of both reversible and irreversible features. Interestingly, ordinary portland cement–PAA/PEO suspensions experienced a gel-to-fluid transition on high shear mixing at short hydration times (<1 h), and the particle network did not rebuild until ∼24 h of hydration. In sharp contrast, white portland cement–PAA/PEO suspensions remained weakly gelled throughout the initial stage of hydration even after high shear mixing. At longer hydration times (>1 h), both cement–PAA/PEO suspensions exhibited G ' _i ( t ) ∼ exp( t /τ_c) with τ_c values of 5.6 and 1.3 h for ordinary and white portland cement, respectively. Our observations suggest that hydration phenomena impact interparticle forces during early stage hydration and, ultimately, lead to initial setting through the formation of solid bridges at the contact points between particles within the gelled network.     

Rheology of simulated radioactive waste slurry and cold cap during vitrification

During the vitrification of radioactive waste in a Joule‐heated melter, aqueous melter feed slurry forms a cold cap, a reacting and melting material, which floats on the surface of the molten glass. The rheological behavior of the feed affects cold cap formation and shape, and is vital for modeling the feed‐to‐melt conversion process. We used slurry feed simulant and fast‐dried slurry solids representing the cold cap to investigate the rheological behavior of the feed as it transforms into glass. Both low‐temperature and high‐temperature rheometry were performed and a new scheme was applied to estimate the feed viscosity. This study shows that the conversion advances in four sequential stages that form distinct regions in the cold cap: (i) a fast‐spreading boiling slurry from which water evaporates, (ii) a porous solid region (viscosity > 10⁸ Pa s) containing reacting solids and molten salts, (iii) a plastic region in which glass‐forming melt connects the refractory solids (~10⁸ to ~10⁶ Pa s), and (iv) a viscous foam layer in which the viscosity drops from ~10⁵ to ~10¹ Pa s. The implications for the mathematical modeling of the cold cap are discussed.     

Dynamic Rheology of Agar Gel Based Aqueous Binders

Dynamic rheology was used to study the gelation behavior of agar gel based aqueous binders (1–3 wt%) for powder injection molding. Typical gelation temperatures, T _gel, and liquefaction temperatures, T _liq, were 36° and 78°C, respectively. The thermal history of the gels was found to influence T _gel and the asymptotic storage modulus, G '. A higher degree of undercooling (Δ T = T _gel− T _hold) enhanced the driving force for gelation. G ' master curves were created and revealed a relatively weak frequency dependence. G ' increased significantly with agar content. The shape of the gel's relaxation spectrum was found to be independent of agar content, indicating that the nature of the relaxation processes does not change significantly.     

Interparticle Potentials in Nonaqueous Silicon Nitride Suspensions

The rheological properties of nonaqueous silicon nitride suspensions are studied. Suspensions were prepared to volume fractions of solids of 0.21, 0.25, 0.29, and 0.33, and dispersed with phosphate ester in a mixture of solvents (methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone). Expanded viscosity curves were obtained by measuring under controlled rate and stress conditions, and the experimental data were fitted to the Cross model that provides the high shear limiting viscosity (η_∞). The evolution of viscosity with volume fraction of solids was fitted to the Krieger-Dougherty equation, to predict the maximum packing fraction (φ_m). The electrostatic pair potential was calculated based on the DLVO theory by evaluating the dielectric constant of the three-component solvent and the Hamaker constant of the Si₃N₄–solvent system. The surface potential was calculated by measuring the elastic modulus through dynamic rheological measurements. The steric potential was also evaluated from the available models. It has been observed that phosphate ester provides a purely steric stabilization at short separation distances (up to 9 nm), while electrostatic forces dominate at larger separation distances.     

Dispersion and Grinding of Oxide Powders into an Aqueous Slurry

The present paper deals with a comprehensive analysis of the dispersion behavior of oxide powders to determine accurate conditions for mixing and grinding dense slurries without the use of steric dispersing agents. The experimental support of the work was the synthesis of (Zr,Sn)TiO₄ microwave dielectric ceramics by the solid-state reaction of raw materials mixed and ground by attrition milling. Zeta potential measurements were performed on the raw materials versus pH to determine the optimum pH of the slurry, allowing a good dispersion of all the species: the absolute value of the zeta potential of every powder >20 mV, with all potentials having the same sign. During the grinding process, as the surface of the materials increases due to the breakup of the grains, surface reaction occurs with the dispersion liquid, and pH must be continuously adjusted to be maintained at an adequate level. We have correlated these characterizations of the optimal processing conditions with the rheological behavior of the slurries, thus providing an analysis of the flocculated or deflocculated state. When applied to synthesizing (Zr,Sn)TiO₄ microwave dielectric ceramics, these conclusions made it possible to produce reproducible resonators with a k = 37 dielectric constant and characterized by a quality factor, Q × F > 60 000 GHz measured at 3 GHz, the highest value reported for this composition.     

Setting and nanostructural evolution of metakaolin geopolymer

The nanostructural evolution during formation of geopolymers and its correlation with setting have not been well understood. In this study, penetration resistance and ultrasonic wave reflection tests were conducted to measure setting, and solid‐state ²⁷Al NMR and liquid‐state ²⁹Si NMR were used to examine nanostructural changes in a metakaolin geopolymer as a function of time. Aluminum was released rapidly during the first 10 hour after mixing and immediately condensed with silicate species in solution to form larger sized aluminosilicate oligomers, which then condensed to form large structural units. Our evidence suggests these units form near metakaolin particle surface. Smaller sized silicate ions in the sol phase then attach to these units to form a gel with a more interconnected network structure. The initial stage of this attaching process was seen to be associated with set, which in this mixture occurred at 15 hour.     

Direct-Write Fabrication of Pb(Nb,Zr,Ti)O3 Devices: Influence of Paste Rheology on Print Morphology and Component Properties

Lead niobium zirconate titanate (PNZT) pastes with tailored rheological properties have been developed for direct-write fabrication of thick-film capacitor elements in highly integrated, multifunctional electroceramic devices. Such pastes exhibited pseudoplastic behavior with a low shear apparent viscosity of roughly 1 × 10⁶ cP. On aging, the degree of shear thinning and the low shear apparent viscosity decreased. Pastes prepared from as-received powders attained printable, steady-state viscosities of ∼2 × 10⁵ cP after 50 days of aging. In contrast, pastes prepared from dispersant-coated powders showed no measurable rheological changes after 1 day of aging. Square elements were patterned on dense alumina substrates or Teflon sheets. Leveling behavior as a function of time for single line prints, and the resulting surface topographies of dried PNZT films were measured by laser profilometry. PNZT layers sintered at varying temperatures between 950° and 1050°C for 5 h in either air or a lead-rich atmosphere yielded porous microstructures as revealed by scanning electron microscopy (SEM). Such layers exhibited dielectric constants ( K ) of 1400–1570 at 1 kHz with dissipation factors ( D ) of less than 4.1%.     

Cost-effective suspension formulation for flexible TiB2 tapes

The manufacturing of ultra-high temperature ceramic materials has significantly advanced over recent years, allowing for the development of new microstructures, architectures, shapes, and geometries to explore new properties and applications for these materials beyond aerospace. For example, titanium diboride (TiB₂) exhibits high electrical and thermal conductivity that could satisfy the needs of battery applications by tailoring its geometry, microstructure, and architecture. In this work, aqueous tape casting of TiB₂ has been investigated. Zeta potential measurements and suspension rheology were used to understand the role of dispersant, binder, and plasticizer in the suspension and their interaction with the surface chemistry of the TiB₂ particles to develop a stable, homogenous suspension, with minimum additive amounts (0%–2 wt%). Homogeneous, flexible, and strong TiB₂ tapes were prepared using suspensions with 30 vol% solids and characterized to compare different compositions, mixing methods, and thicknesses. The characterization shows the tailoring of the properties as a function of the controlled suspension formulation with a minimum amount of additives. Green tapes with 2 wt% dispersants, 1 wt% binder, and 2 wt% plasticizers had similar microstructure to those with half the plasticizer but quintuple Young's modulus (1.96 GPa). The effect on other relevant properties is also discussed.     

A constitutive equation for thixotropic suspensions with yield stress by coarse‐graining a population balance model

A population balance model appropriate for the shear flow of thixotropic colloidal suspensions with yield stress is derived and tested against experimental data on a model system available in the literature. Modifications are made to account for dynamic arrest at the onset of the yield stress, in addition to enforcing a minimum particle size below which breakage is not feasible. The resulting constitutive model also incorporates a structural based relaxation time, unlike existing phenomenological models that use the inverse of the material shear rate as the relaxation time. The model provides a reasonable representation of experimental data for a model thixotropic suspension in the literature, capturing the important thixotropic timescales. When compared to prevalent structure kinetics models, the coarse‐grained population balance equation is shown to be distinct, emphasizing the novelty of utilizing population balances as a basis for thixotropic suspension modeling. © 2016 American Institute of Chemical Engineers AIChE J, 63: 517–531, 2017     

Direct ink writing of hierarchical porous alumina-stabilized emulsions: Rheology and printability

Bio-inspired multi-scaled (hierarchical) porous structures have remarkable strength and stiffness-to-density properties. Direct ink writing (DIW) or robocasting, an additive manufacturing (or also commonly known as 3D printing) material extrusion technique is able to create near-net-shaped complex geometries. A new approach of combining DIW, colloidal particle-stabilized emulsion paste inks and partial densification to create tailored architectures of hierarchical porosity on three scales has been demonstrated. The printed and sintered ceramic lattice structures possess relatively high overall porosity of 78.7% (on average), comprising mainly (64.7%) open porosity. The effects of formulation (surfactant and oil concentrations, solids particle size, and mixing speed) on rheology and pore size and morphology have been investigated. The rheological properties (storage modulus, yield stress, and recovery of storage modulus) of the emulsions have been found to delineate the samples with good shape retention from those that slump. Additionally, the internal features of the sintered structures have been analyzed via X-ray tomography and scanning electron microscope. The role of emulsion stability on printability and the internal structure of the prints has been investigated.     

Rheology of cubic particles in a concentrated colloidal dispersion suspending medium

The flow behavior of mixtures of micron‐sized cubic particles suspended in a concentrated colloidal dispersion is investigated across a broad range of cubic particle concentrations. In the semi‐dilute regime, the qualitative shape of the dynamic moduli and flow curves reflect those of the underlying colloidal dispersion medium. These curves are superimposed with the underlying colloidal dispersion using shift factors that are found to be larger than those obtained in a recent study of suspensions of non‐colloidal spherical particles in the same colloidal dispersion medium. At higher concentrations of cubic particles, deviations from this shifting procedure are apparent. Scaling calculations suggest depletion interactions are responsible for the increase in the low shear viscosity and confinement of the underlying colloidal dispersion can be expected to enhance the shear thickening behavior at high shear stresses. The results of this study provide guidance for formulating suspensions through control of particle shape and mixture concentration. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1091–1101, 2017     

Effect of 2-Phosphonobutane-1,2,4-tricarboxylic Acid Adsorption on the Stability and Rheological Properties of Aqueous Nanosized 3-mol%-Yttria-Stabilized Tetragonal-Zirconia Polycrystal Suspensions

2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA) was evaluated as a dispersant for nanosized 3-mol%-Y₂O₃-stabilized tetragonal-ZrO₂ polycrystal (3Y-TZP) suspensions. The adsorption of PBTCA was characterized using the decolorization method of ferric 5-nitrosalicylate complexes. Maximum adsorption of the dispersant on the 3Y-TZP powder was found to occur at pH 3.0. At pH >3.0, the adsorbed amount decreased with increased pH. Semiquantitative analysis using auger electron spectroscopy showed that PBTCA adsorbed irreversibly on the powder. The surface charge of the powder was evaluated by measuring the zeta-potential in dilute powder suspensions. The suspension was most effectively stabilized at high pH by the high charge induced by the adsorption of PBTCA. Rheological properties of the suspension were evaluated as a function of dispersant amount and solids loading. The optimum amount of dispersant increased with increased solids loading for solids loading >20 vol%. A stable suspension of 35 nm 3Y-TZP particles with a solids loading as high as 32 vol% was obtained using PBTCA as dispersant, in contrast to 28 vol% when using ammonium polyacrylate (NH₄PAA). Theoretical calculations of the interaction between 3Y-TZP particles showed that the stabilization of the suspensions was attributed to a combination of the electrostatic repulsion and a steric barrier caused by the adsorbed PBTCA. Induced coupling plasma analysis showed that PBTCA could be completely burned out during sintering, which confirmed its suitability as a dispersant for 3Y-TZP.     

聚乙烯吡咯烷酮对PESA-H2O-SiC悬浮液流变性能的影响

研究了聚乙烯吡咯烷酮(PVP)对聚环氧琥珀酸(PESA)稳定的水基碳化硅(SiC)悬浮液流变性能的影响.结果表明,在pH值为9.0时,添加一定比例的少剂量的二元分散剂即可改善SiC悬浮液的分散性.当分散剂总添加量为0.4wt％,PESA与PVP的质量之比为3∶1时,悬浮液的流变性最佳.固含量为40vo1％时,PESA稳定的SiC悬浮液完全絮凝,而添加PVP作为第二分散剂可使体系较好的分散.此外,添加二元分散剂PESA/PVP显著提高了SiC悬浮液的抗电解质性能.     

Properties and characterization of alumina platelet reinforced geopolymer composites

Geopolymers are porous, amorphous, alkali-aluminosilicate hydrate materials formed at room temperature via a solution process. Geopolymer based on metakaolin had a relatively homogeneous microstructure that offered consistent behavior but suffered from dehydration cracking and large densification shrinkages when heated. It was found that by reinforcing a metakaolin geopolymer of composition (K₂O·Al₂O₃·4SiO₂·11H₂O) with 50 µm diameter alumina platelets, dehydration cracking could be prevented, and shrinkage could be reduced by an order of magnitude. Samples were reinforced with 30, 50, and 70 wt% of alumina platelets. Although the properties of the 30 and 50 wt% conditions were better than those of unreinforced geopolymer, those samples still showed warping, cracking, and strength losses on heating. The 70 wt% samples did not warp or crack when heated to temperatures of up to 1500°C. The room-temperature 4-point flexural strength of these samples remained at around 20 MPa regardless of heat treatments. The in situ measured flexural strength increased to almost 40 MPa at 600°C, and remained higher than 20 MPa until 1200°C. Samples subjected to propane-torch thermal shock heating and subsequent quenching did not crack or fragment. Dilatometry, X-ray diffraction, and scanning electron microscopy were used for additional characterization. Given these properties, this material showed promise as a castable refractory.