Solid Freeform Fabrication of Aqueous Alumina–Poly(vinyl alcohol) Gelcasting Suspensions

Solid freeform fabrication of aqueous alumina–poly(vinyl alcohol) (Al₂O₃–PVA) gel-casting suspensions was conducted using a computer-controlled extrusion apparatus fitted with a two-nozzle delivery system. The impact of casting parameters on the shear rate profiles experienced during deposition was evaluated via conventional flow analysis and computer simulations. In addition, the influence of these parameters on line resolution/uniformity, printability, and as-cast component properties was studied using laser profilometry, optical microscopy, and scanning electron microscopy. Continuous printablity was achieved for tip diameters ranging from 0.254 to 1.370 mm for all mixing rates and suspension compositions studied. Printed lines were uniform with good edge definition, and line dimensions were independent of mixing rate for these process conditions. The Al₂O₃ volume fraction (φ_Al2O3) in the as-deposited layers depended on casting conditions and cross-linking agent concentration, where (φ_Al2O3 increased with decreased tip diameter and increased cross-linking agent concentration. The free-formed Al₂O₃ components exhibited uniform particle packing, with minimal macrodefects (e.g., slumping or staircasing) and no discernable microdefects (e.g., bubbles or cracking).     

Chemorheology of Aqueous-Based Alumina-Poly(vinyl alcohol) Gelcasting Suspensions

A new gelcasting system based on aqueous-based alumina-poly(vinyl alcohol) (PVA) suspensions cross-linked by an organotitanate coupling agent has been developed. The chemorheological properties of this system exhibited a strong compositional dependence. A sol-gel phase diagram was established, which yielded the critical titanium concentration ([Ti]_c) required for gelation at a given PVA volume fraction as well as the minimum PVA volume fraction (φ^min_PVA= 0.0245) and titanium concentration ([Ti]_min= 9.984 × 10^-4 g of Ti/mL) below which gelation was not observed irrespective of solution composition. The gelation time of suspensions of constant PVA volume fraction (φ^soln_PVA) decreased with increased cross-linking agent concentration, temperature, and solids volume fraction. The steady-state viscosity and elastic modulus of polymer solutions (φ^soln_PVA= 0.05) of varying [Ti] were well described by the percolation model, giving scaling exponents of 0.84 and 1.79, respectively. The steady-state elastic modulus of gelcasting suspensions, which provided a measure of their handling strength in the as-gelled state, increased with increased solids volume fraction.     

Rheology of Cross-Linked Chitosan–Alumina Suspensions Used for a New Gelcasting Process

The rheological behavior of a low-toxicity, aqueous, Al₂O₃–chitosan–2,5-dimethoxy-2,5-dihydrofuran (DHF) system was examined over a temperature range of 20°–98°C. At room temperature, a high-volume-fraction solids, shear-thinning suspension was produced. The suspension remained in a liquidlike state for ∼24 h. By contrast, at elevated temperatures, DHF became active as a cross-linking agent for chitosan, and a rapid transition from liquidlike to solidlike suspension behavior was apparent. The rate of gelation and the gel strength increased with increased temperature and increased DHF concentration. Gelation occurred at pH 1.4–4.5, which is a complex function of pH. At pH above ∼4, rapid gelation was not possible because of the low-pH solution conditions required for the cross-linking reaction. An examination of the strength and shape-forming properties of several Al₂O₃–chitosan–DHF systems showed them to be suitable for production of strong, reliable, complex-shaped ceramic components. In particular, small, dense Al₂O₃ pseudorotors were formed and found to be of sufficient strength for mold removal and subsequent handling. In all formulations examined, chitosan concentrations of <0.5 wt% (by weight of ceramic) were required; therefore, the need for a discrete binder burnout process was eliminated.     

氧化铝陶瓷凝胶注模成型工艺研究

本文介绍了氧化铝陶瓷的凝胶注模成型工艺。所制备的浓悬浮体的固相体积分数高达60vol%,粘度低于200mPa.S。脱脂后的坯体密度可达理论密度的62%,抗弯强度达19Mpa。研究了球磨时间、固相体积含量和助烧剂对悬浮体的粘度的影响,并研究了有机单体与交联剂的比例与含量对生坯抗弯强度的影响。     

Alumina Agglomerate Effects on Toughness-Curve Behavior of Alumina–Mullite Composites

Toughness-curve ( T -curve) behavior of composites of spherical, polycrystalline, coarse-grained, alumina agglomerates dispersed throughout a constant-toughness, fine-grained, 50–50 vol% alumina–mullite matrix has been evaluated as a function of agglomerate content for the range 15 to 45 vol%. T -curve behavior was evaluated using the indentation-strength method. Increasing alumina agglomerate content resulted in a progressive increase of large indentation load strengths with negligible change of plateau strength levels at small indentation loads. This behavior is consistent with underlying T -curves that rise to greater values and are shifted toward longer crack lengths with increasing agglomerate content, suggesting that both bridge spacing and bridge potency increase with increasing agglomerate content over the range tested. The proposed relationships between bridge spacing and agglomerate content, and bridge potency and agglomerate content, are rationalized in terms of residual stress considerations. The indentation-strength data also demonstrated that the composite containing the greatest alumina agglomerate content, 45 vol%, exhibited the greatest flaw tolerance.     

Expanded Core/Shell Poly(vinyl acetate)/Poly(vinyl alcohol) Particles for Embolization

An improvement to a previously published suspension polymerization process for the production of spherical core/shell PVAc/PVA particles is described. To increase the settling time of the beads in the suspension, an expansion stage was introduced. The core/shell structure was obtained through the partial hydrolysis of the PVAc. The particle density was manipulated through addition of a solvent during the suspension polymerization stage and posterior expansion of the polymer beads obtained at the end of the process. This technique allows for effective reduction of the density of the final polymer beads. The expansion stage exerts also a beneficial effect on particle drying, avoiding particle aggregation during post‐polymerization processing of the polymer beads.

     

Poly(vinyl alcohol) and Polyamide‐66 Nanocomposites Prepared by Electrospinning

Summary: PVA and PA‐66 nanocomposite fibers with montmorillonite were prepared by electrospinning. Mixing of the components was conducted in two ways: polymer and montmorillonite were mixed with solvent, or monomer was polymerized in the presence of montmorillonite and was then dissolved in a solvent. Polymer/montmorillonite solutions were then electrospun on a non‐woven substrate. To the unaided eye, the coated area was either continuous coating or well‐defined spots. Characterization of the fiber structure and the particle size and distribution by SEM and elemental analysis showed the nanosized filler to be dispersed through the fiber network of the polymer/nanocomposite regardless of the preparation method. However, the clay particles within the fibers were smaller with the polymerization method than mixing in solvent. Only the PA‐66‐based nanocomposites exhibited large enough coating area on the substrate for measurements of contact angles and the time required for water penetration. Contact angles and the time required for water penetration were increased for most of the PA/nanoclay composites relative to the uncoated substrate.

SEM image of a typical fiber structure of a PVA/nanocomposite obtained by electrospinning under alkaline conditions.     

凝胶注模成形工艺制备高强度的氧化铝陶瓷

本文以氧化铝陶瓷为例,研究探讨了凝胶注模成形工艺中制备低粘度、高固相含量浓悬浮体的关键技术,讨论了分散剂因素对粘度的影响和不同固相含量对坯体强度的影响。     

Effect of Poly(vinyl alcohol) Adsorption on Binder Segregation during Drying

The effect of poly(vinyl alcohol) adsorption on segregation was quantitatively studied by a model experiment of one–dimension drying and simulated by a mathematical model. It was clear that the adsorption of PVA on alumina particle was a slow process, and the adsorbed binder was not desorbed at higher temperature. PVA segregation can significantly be limited by fully adsorbing the binder before drying. The simulation and experiments agreed very well. The effects of drying temperature, initial concentration of the binder, and thickness of specimen on the surface segregation are discussed quantitatively. Mathematical simulation has a great potential for predicting the segregation of soluble components during drying, especially for such cases as thin films and small granules where it is difficult to determine the distribution of the component directly.     

Thermal Decomposition of Polymer Mixtures Containing Poly(vinyl chloride)

Thermal decomposition of a series of 1 : 1 mixtures of typical polymer waste materials [polyethylene (PE), poly(propylene) (PP), polystyrene (PS), polyacrylonitrile (PAN), polyisoprene, poly(methyl methacrylate) (PMMA), polyamide‐6 (PA‐6), polyamide‐12 (PA‐12), polyamide‐6,6 (PA‐6,6), and poly(1,4‐phenylene terephthalamide) (Kevlar)] with poly(vinyl chloride) (PVC) was examined using thermal analysis and analytical pyrolysis techniques. It was found that the presence of polyamides and PAN promotes the dehydrochlorination of PVC, but PVC has no effect on the main decomposition temperature of polyamides. The hydrogen chloride evolution from PVC is not altered when other vinyl polymers or polyolefins are present. The thermal degradation of PAN is retarded significantly, whereas that of the other vinyl polymers is shifted to a slightly higher temperature in the presence of PVC. Among the pyrolysis products of PAN‐PVC mixture methyl chloride was found in comparable amount to the other gaseous products at 500°C pyrolysis temperature.     

Gelling of Alumina Suspensions Using Alginic Acid Salt and Hydroxyaluminum Diacetate

This paper proposes a novel direct casting method of alumina suspensions using alginic acid salt and the coagulation agent hydroxyaluminum diacetate (HADA). These two compounds allowed the consolidation of alumina suspensions through a simultaneous time-delayed physical and chemical gelation process. The physical gel was formed by the gradual release of aluminum and acetate ions from the HADA in water, while the chemical gel originated from the cross-linking of alginate molecules by the polyvalent aluminum ions. Wet alumina green bodies displayed enhanced mechanical properties with the addition of minimal contents of organic material (<0.1 wt%).     

Surface Chemistry of Various Poly(vinyl butyral) Polymers Adsorbed onto Alumina

Organic polymeric materials, often used as ceramic processing aids to assist in the fabrication of green bodies, are thought to be of a temporary nature, nature, being easily removed by thermolysis at temperatures between 250° and 600°C. The interaction of various poly(vinyl butyral) binders with fine, high-purity alumina powder was investigated using variable-temperature Fourier-transform infrared spectroscopy and thermal gravimetric analysis. It was found that there was interaction between the functionality of the polymers and the surface of the alumina powders. If these interactions are strong enough to persist to initial sintering temperatures, the polymers would not then be merely innocuous temporary processing aids, but could have an effect on the development of ceramic microstructures.     

Poly(acrylic acid)–poly(vinyl alcohol) copolymers with superabsorbent properties

Biodegradable polyacrylates were produced by a series of novel copolymerization and/or crosslinking techniques using poly(vinyl alcohol) (PVA) moieties modified by the incorporation of olefinic structures. PVA was modified by a tosylation and/or detosylation reaction. The functionalized PVA was copolymerized and/or crosslinked with acrylic acid or its partially neutralized form to give crosslinked polyacrylates that could swell in water. Their swelling behavior was determined under load. Degradation studies were performed in α-chymotrypsin, trypsin, and papain solutions. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 817–829, 1998     

Rheological Characterization of Synergistic Mixtures of Carrageenan and Locust Bean Gum for Aqueous Gelcasting of Alumina

Previous works have shown that carrageenan can be successfully used in the aqueous gelforming of powders, because carrageenan forms a firm gel, similar to that formed by agarose, but at a much lower cost. In this work, the synergistic effect of carrageenan with locust bean gum is studied. The rheological behavior of 2 wt% solutions of these polysaccharides and their mixtures are measured under mixing conditions (60°C) and by recording the viscosity and elastic modulus on cooling. The effect of the addition of these solutions to 50 vol% alumina slurries up to a concentration of 0.5 wt% is studied. Although gelling time increases, the resulting gels are stronger than for carrageenan alone. Gelcast alumina bodies with green and sintered densities of 57% and 97.6% of theoretical have been obtained.     

卤化聚乙烯醇的研究

通过将聚乙烯醇（PVA）直接卤化取代,筛选出Cl,Br等卤化剂,催化剂,并优选出合适的体系,使其既保持PVA的高阻氧性,又能保证加工性时的热稳定性。     

Poly(vinyl alcohol)–lignin blended resin for cellulose‐based composites

Wood has limitations in strength because of its biostructural defects, including vessels. To overcome this limitation, composite materials can be innovated by breaking wood down into cellulose and lignin and reassembling them for bio‐originating strong structural materials. In this study, an ecofriendly resin was developed that was suitable for cellulose‐based composites. To overcome the low dimensional stability of lignin and to increase its interactions with cellulose, it was blended with poly(vinyl alcohol) (PVA). The PVA–lignin resin was characterized with scanning electron microscopy, Fourier transform infrared spectroscopy, thermal analysis, mechanical tensile testing, and lap‐shear joint testing. The adhesion properties of the PVA–lignin resin increased with increasing PVA content. PVA played the role of synthetic polymer and that of linker between the cellulose and lignin, like hemicellulose does in wood. The PVA–lignin resin exhibited a high miscibility, mechanical toughness, and good adhesion properties for nanocellulose composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46655.     

Fully Green Poly(vinyl alcohol)/Tea Polyphenol Composites and Super Anti‐Ultraviolet and ‐Bacterial Properties

Several fully green composites are prepared by taking the tea polyphenols (TP) with various percentages to blend with poly(vinyl alcohol) (PVA). The as‐prepared PVA/TP composite with only 5% TP shows superb anti‐UV properties even after water washing, the presented UV protection factor (UPF) value is still greater than that of the standard values reported by Australia and New Zealand (AS/NZS 4399‐1996). Moreover, the UPF value of those PVA/TP composites is found capable of furthermore enhancement by increasing the TP percent. This PVA/TP composite also shows good antibacterial and biodegradability while it is kept with certain mechanical properties to fit required application cases.     

Poly(vinyl alcohol) functionalization with aldehydes in organic solvents: Shining properties of poly(vinyl acetals)

Poly(vinyl alcohol) has been functionalized with aldehydes in tetrahydrofuran (THF) with a good control of the grafting. A wide library of poly(vinyl acetals) could be obtained in order to study some structure/property correlations. The influence of the aldehyde nature on the functionalization rates has been studied, in particular for optical properties by measurement of the shininess for further applications in the cosmetic field. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40677.     

Polymerization and Rheological Behavior of the Thermoresponsive Gelcasting System Based on N‐isopropylacrylamide

Recently, we developed an efficient method for rapid drying and improving relative density of the gelcast green body. In this work, polymerization and rheological behavior of the thermoresponsive gelcasting system based on N‐isopropylacrylamide were investigated. To initiate reaction of the system with 4 mL/L of catalyst, 0.25–0.5 mg/mL of initiator is considered optimal in the optimized temperature range 15–20°C. Suspensions with 40–55 vol.% solid loading still show shear‐thinning behavior, which is favorable for mixing, degassing, and casting. The final storage moduli of consolidated suspensions are approximately 10⁴ Pa, which is sufficiently high for gelcast green bodies.