Effect of ball-milling parameters on the rheological properties of mold powder slurry

In this study, mold powder slurries with high solid loading and low viscosity were prepared during the ball-milling process for improving the homogeneity and mechanical properties of granules after spray-drying. The effect of ball-milling parameters, such as solid loading, binder/dispersant content, and ball-milling time, on the flowability, dispersibility, stability, and rheological behavior of mold powder slurries was systematically investigated by rheology observation and sedimentation tests. As these parameters varied, the slurry exhibited the shear-thinning behavior of a non-Newtonian fluid with a shear rate range of 0–50 s^?1, which was adequately described by the Herschel-Bulkley model. The optimal parameters that optimized the flowability, dispersibility, and stability of the slurry, along with its rheological behavior, were chosen as follows: solid loading, 60 wt%; modified sodium carboxymethyl cellulose binder content, 1.0 wt%; sodium tripolyphosphate dispersant content, 0.5 wt%; ball-milling time, 60 min.     

Role of strontium substitution in spray drying of hydroxyapatite: A comparative study on physical properties

Spray drying (SD) has the ability to tailor granule size and morphology, thus, it is used for producing hydroxyapatite (HA) granules. Recently, Sr functionalized HA (SrHA) has been recommended owing to its improved biological properties. The aim of this article was to produce SrHA granules with the combination of nanoparticle synthesis and spray-drying. The effects of substitution on the physical properties of SrHA nanoparticles and spray-dried granules were investigated. TEM analyzes revealed that Sr substitution reduced the mean size of HA nanoparticles from 4.59 nm to 2.31 nm. Besides, Sr substitution increased the viscosity of the prepared slurry for spray drying, which may be attributed to the smaller nanoparticle sizes. The reduced nanoparticle size caused to the agglomeration of the SrHA more than the pure HA nanoparticles. Moreover the 16 mol % Sr substituted HA (16SrHA) slurry were quickly hardened, which hampered the feeding of the slurry to the SD system; eventually the atomizer was blocked. The increase in the viscosity increased the mean granule size of HA from 41.53 µm to 49.18 µm. HA and 8SrHA granules presented HA phase dominantly after the heat treatment at 1000°C, while, 16SrHA decomposed to TCP according to RAMAN and XRD investigations.     

Correlation between slurry properties and structures and properties of granules

Two types of granules were fabricated from a flocculated slurry (dispersant: 0.3 wt%) and a dispersed slurry (dispersant: 1.0 wt%), respectively. The slurry properties affected the packing density and morphology of the granules markedly; the granules obtained from the flocculated and dispersed slurries have spherical and dimpled shapes with densities 50.2 and 54.0%, respectively. A new crossed polarized microscopy showed a direct influence of slurry property on the packing structure of particles in the granules. The packing structure of particles affected the deformation behavior of granules; the loosely packed particles in the spherical granules make them easily deformable and the highly packed particles in the dimpled granules make them resistant against deformation.     

Synthesis and in vitro biodegradation of pure octacalcium phosphate spheres

Octacalcium phosphate (OCP) is a key precursor of biological apatite in hard tissues with excellent osteoconductive and biodegradable properties for bone regeneration. OCP spherical granules are expected to be useful as drug delivery carriers, since OCP has high specific surface area. Although there have been some reports of OCP sphere preparation, methods for preparing pure OCP spheres are limited. The objective of this study is the preparation of spherical granules of pure OCP and assessment of their in vitro biodegradation in physiological conditions. We successfully prepared spherical pure OCP granules with a size of ~500 µm without any organic additives by simple immersion of α-tricalcium phosphate spherical granules in pH 5.0 acetate buffered solutions at 60°C. The granules had core-shell structure composed of OCP crystals different particle size. The spherical granules showed 20%-40% in vitro degradation in physiological conditions; however, the phase transition of OCP was not significantly observed.     

Processing and mechanical properties of hot-pressed zirconium diboride – zirconium carbide ceramics

ZrB₂ was mixed with 0.5 wt% carbon and up to 10 vol% ZrC and densified by hot-pressing at 2000 °C. All compositions were > 99.8% dense following hot-pressing. The dense ceramics contained 1–1.5 vol% less ZrC than the nominal ZrC addition and had between 0.5 and 1 vol% residual carbon. Grain sizes for the ZrB₂ phase decreased from 10.1 µm for 2.5 vol% ZrC to 4.2 µm for 10 vol% ZrC, while the ZrC cluster size increased from 1.3 µm to 2.2 µm over the same composition range. Elastic modulus was ~505 GPa and toughness was ~2.6 MPa·m^½ for all compositions. Vickers hardness increased from 14.1 to 15.3 GPa as ZrC increased from 2.5 to 10 vol%. Flexure strength increased from 395 MPa for 2.5 vol% ZrC to 615 MPa for 10 vol% ZrC. Griffith-type analysis suggests ZrB₂ grain pullout from machining as the strength limiting flaw for all compositions.     

Additive manufacturing of SiC-Sialon refractory with excellent properties by direct ink writing

Additive manufacturing of SiC-Sialon refractory with complex geometries was achieved using direct ink writing processes, followed by pressureless sintering under nitrogen. The effects of particle size of SiC powders, solid content of slurries and additives on the rheology, thixotropy and viscoelasticity of ceramic slurries were investigated. The optimal slurry with a high solid content was composed of 81 wt% SiC (3.5 µm+0.65 µm), Al₂O₃ and SiO₂ powders, 0.2 wt% dispersant, and 2.8 wt% binder. Furthermore, the accuracy of the structure of specimens was improved via adjustment of the printing parameters, including nozzle size, extrusion pressure, and layer height. The density and flexural strength of the printed SiC-Sialon refractory sintered at 1600 °C were 2.43 g/cm³ and 85 MPa, respectively. In addition, the printed SiC-Sialon crucible demonstrated excellent corrosion resistance to iron slag. Compared to the printed crucible bottom, the crucible side wall was minimally affected by molten slag.     

Preparation and characterisation of HA/TCP biphasic porous ceramic scaffolds with pore-oriented structure

Porous hydroxyapatite/tricalcium phosphate (HA/TCP) ceramic scaffolds with a uniform unidirectional pore structure were successfully fabricated by an ice-templating method by using Ca-deficient HA whiskers and phosphate bioglass. HA whiskers showed good dispersibility in the slurry and favoured the formation of interconnected pores in the scaffolds. Addition of bioglass powders enhanced the material sintering process and the phase transformation of Ca-deficient HA to β-TCP. Calcium-phosphate-based scaffolds with a composition from HA to an HA/β-TCP complex could be obtained by controlling the freezing moulding system and slurry composition. The fabricated scaffolds had a porosity of 75–85%, compressive strength of 0.5–1.0 MPa, and a pore size range of 130–200 µm.     

Preparation of dense spherical AlN fillers by aqueous granulation and post-sintering process

Herein, an innovative two-step method was proposed to prepare dense spherical aluminum nitride (AlN) fillers for the application of insulating encapsulants, involving spray granulation from AlN-based suspensions and subsequent sintering process to achieve full density. According to investigations on the dispersing ability of powders, the AlN-based aqueous suspensions with various solid loading were firstly prepared for spray granulation. It was indicated that a low-viscosity and high-concentration suspension could enhance the sphericity and uniformity of green granules and simultaneously facilitate the high green density. The spherical AlN green granules were further sintered with boron nitride (BN) powders, which played a role as the interval material to retain the spherical morphology and hinder the agglomerations of AlN granules. The distinct impacts of BN powders, sintering temperatures and additive species on the overall properties of resultant AlN fillers were further studied and rationally uncovered. Based on these results, spherical AlN granules with superior dispersion, low porosity and an average particle size of more than 40 µm were successfully fabricated via the newly-developed two-step method, showing promising potentiality for the application as thermal-conductive fillers.     

Influence of solid loading on the rheological,porosity distribution,optical and the microstructural properties of YAG transparent ceramic

Stable aqueous dispersed mixture of commercial Al₂O₃ and Y₂O₃ nano powders was prepared by ball mill. Ammonium poly meta acrylate (Dolapix CE64) and tetraethyl orthosilicate (TEOS) were added as dispersant and sintering aid, respectively. The effects of slurry solid loading on the fabrication of transparent polycrystalline YAG ceramics by slip casting method were investigated. The rheological properties of slurries with different solid loading (64, 70 and 76?wt%) were studied by measuring the viscosity and shear stress as a function of shear rate. The effect of solid loadings on the porosity distribution was examined. The specimens were vacuum-sintered at 1715?°C for 10?h. Slips with 64 and 70?wt% solid loading behaved as near-Newtonian and as non-Newtonian with thixotropic behavior at 76?wt% solid loading. The relative densities of the green bodies increased from 58.0?±?0.6% (SD?=?0.424) to 64.0?±?0.3% (SD?=?0.228) by increasing the solid loading from 64?wt% to 70?wt% and then decreased to 63.0?±?0.2% (SD?=?0.141) at 76?wt% solid loading. The results showed that the suitable solid loading for fabricating transparent YAG ceramics is 70?wt%. This sample had the narrowest pore size distribution (4–100?nm), homogenized surface fracture of green body, dense microstructure (99.990?±?0.005% final relative density, SD?=?0.003) and the average grain size of 6?µm. It had the highest in-line transmittance, which was approximately 77% at 1064?nm.     

Granule performance of zirconia/alumina composite powders spray-dried using polyvinyl pyrrolidone binder

Polyvinyl pyrrolidone (PVP) was used as a binder in spray-drying a slurry containing zirconia/alumina composite powder and its influence on granulation and granule deformability was compared with those of polyvinyl alcohol (PVA) and polyethylene glycol–hydroxyethyl cellulose cobinder (PEG–HEC). Although the most spherical solid granules were obtained from the slurry containing PEG–HEC, the granules containing PVP were the most deformable during compaction. It was apparent that a high-viscosity organic additive mixture added to the slurry resulted in highly spherical solid granules, and a low T_g of the mixture led to a high deformability. The flexural strengths of composites prepared from granules containing PVP, PEG–HEC, and PVA were 634, 578, and 468 MPa, respectively, which corresponds to the ascending order of T_g of the binders mixed with plasticizers.     

TiB2/Al2O3复合粉体的喷雾干燥造粒与特性研究

利用喷雾干燥技术对TiB_2/Al_2O_3复合粉体进行造粒,研究了浆料固相含量及粘结剂含量对喷雾干燥粉体颗粒形貌、结构、松装密度、流动性等的影响。结果表明：当浆料固相含量为47．6%,分散剂和粘结剂分别为固相质量的0．4%和1．0%时,浆料具有合适的粘度和最佳的分散稳定性,喷雾造粒得到的粉体为球形或近球形,具有较高的松装密度和流动性,能满足各种压制成型的需要。     

Effect of temperature and holding time on the densification of alumina obtained by two-step sintering

The two-step sintering technique is a process of controlling the sintering curve, which provides materials with higher density and smaller grain size when compared to conventional sintering. This technique was evaluated by optical dilatometry with three commercial alumina powders of different purity (92, 96 and 99 wt% of Al₂O₃) and particle size (between 0.73 and 2.16 µm). Different sintering conditions in the first (temperature, T1) and second (temperature, T2, and holding time, t2) steps were studied in order to evaluate the effect of these variables on densification and grain growth. Considering T1 as the temperature at which a relative density (D_rel) of 83% was achieved, and for the range of conditions tested, it was found that higher D_rel values and lower grain size of alumina were obtained with higher T2 and lower t2. Alumina with 99 wt% purity sintered at T1 of 1550 °C for 5 min and T2 of 1500 °C for 4 h showed the best relationship between higher densification (~96% relative density) and reduced grain size (0.94±0.15 µm). Thus, this work demonstrated that suppression of grain growth can also be obtained for commercial alumina.     

High-performance and high-precision Al2O3 architectures enabled by high-solid-loading,graphene-containing slurries for top-down DLP 3D printing

To date, obtaining the high-solid-loading Al₂O₃ slurry and overcoming the trade-off between high solid loading and printing accuracy and strength of printed green bodies to achieve high-performance and precision Al₂O₃ ceramic parts by DLP 3D printing remain challenging. In this study, an Al₂O₃ slurry with high solid loading of 60 vol% was developed through dispersant optimisation for top-down DLP 3D printing. Graphene was innovatively introduced during slurry fabrication to decouple the printing accuracy and strength of green bodies from such high solid loading. Simultaneously, graphene addition could considerably reduce slurry fluidity, thereby facilitating its coordination with top-down DLP. With 0.07 wt% graphene addition, the dimension deviations of printed green bodies improved from 90 to 880 µm to ≤ 70 µm, and the bending strength increased by 17.75%. High-performance and precise Al₂O₃ ceramic components with low sintering shrinkages were prepared. The density and microhardness were 99.7% and 18.61 GPa, respectively.     

Preparation of Na-beta″-alumina film by tape casting process

This study focused on the preparation of Na-beta″-alumina film by a tape casting process. The effects of solvent, dispersant, binder, plasticizer contents, as well as milling time on the rheological properties of the slurry were investigated. The dispersion of the ceramic powder in the slurry was optimized by ball milling an azeotropic mixture of methyethylketone (MEK) and ethanol (EtOH) as the solvent, 2 wt% triethanolamine as the dispersant, 7 wt% PVB as the binder for 4 h. Green Na-beta″-alumina thick films with thickness of 100–300 μm and homogeneous microstructure were obtained and further sintered at 1600 °C to obtain a relatively dense membrane with a thickness of ca. 100 μm. The conductivity of the sintered ceramic was comparable to that obtained by the conventional isostatic pressing and sintering method.     

Development and characterization of ceftriaxone-loaded P3HB-based microparticles for drug delivery

In this study, polymer-based microparticles are used to improve the therapeutic properties of ceftriaxone (CEF) and render them safer. Poly-3-hydroxybutyrate (P3HB) and poly-3-hydroxybutyrate/polyethylene glycol (P3HB-PEG)-based microparticles were prepared by two methods: a double emulsification technique and spray-drying. The microparticles were characterized in terms of size and zeta potential, morphology, total drug loading and drug release. The microparticles had spherical shapes with diameters of a size range from 0.74 to 1.55?µm (emulsification technique) and from 3.84 to 6.51?µm (spray-drying); CEF encapsulation efficiency was around 63% and 49% for these methods respectively. The CEF release from microparticles obtained by spray-drying reached 100% after 150?h, while for microparticles obtained by emulsification technique the total release of CEF did not exceed 34% after 312?h. The release profiles could be best explained by Zero order kinetics model, Higuchi and Korsmeyer-Peppas models, as the plots showed high linearity. Antibacterial activity of the microparticles was evaluated against gram-positive and gram-negative bacterial strains. In general, CEF encapsulation in polymeric microparticles preserves the therapeutic efficacy of the CEF and provides its prolonged effect.     

Comparison of spray freeze dried nanozirconia granules using ultrasonication and twin-fluid atomisation

Granulation of nanostructured 3 mol% yttria stabilised zirconia using spray freeze drying was investigated to achieve flowable and crushable granules for subsequent die pressing. Commercial nanosuspension consisting of ∼16 nm particles was concentrated to ∼55 wt% solids content via a patented technique, followed by spraying into liquid nitrogen using either a vibrating ultrasonic probe or a twin-fluid atomizer and freeze dried to yield spherical granules. Control of the granule size fractions was investigated by changing the amplitude and the feeding rate of the nanosuspension during ultrasonication, whilst the flow rate of compressed air used for spraying was varied during twin-fluid atomisation. Granules retaining good crushability for pressing were in a size range of 125–250 μm, which were achieved with ∼60 wt% yields using the atomisation route, whilst a maximum of 35 wt% of granules in this size range were produced in previous research using ultrasonication.     

Enhanced densification of thin tape cast Ceria-Gadolinium Oxide (CGO) layers by rheological optimization of slurries

Optimized CGO-based slurries are formulated and shaped into thin dense layers via a tape-casting process. The formulation is adjusted with respect to the rheological behaviour. The internal structure and flow properties of slurries are explored with the aim of identifying the required conditions to obtain thin dense CGO layers at reduced sintering temperatures (1200 °C). We demonstrate a correlation between the rheological properties of the slurries, the sintering behaviour and the microstructure of the resulting tapes. Remarkably, a dense CGO layer less than 20 µm thick is obtained with a non-congested slurry, having optimized ceramic loading and liquid-like behaviour.     

Influences of solid content of slurry on the microstructure of CaO crucible prepared by slip casting

CaO crucible was prepared from Ca(OH)₂ slurry via a slip-casting method in order to avoid hydration problem caused by free CaO during preparation process. The effect of solid content of Ca(OH)₂ slurry on microstructure of CaO crucible was investigated. It was found that the rheological property of the slurry was significantly improved when the solid content of the slurry within a certain range. The change of solid content of slurry affects the microstructure of the final products. When the solid content of the slurry was 71 wt%, the manufactured CaO crucible was of smallest mean pore size (2.58 μm) after 1600°C heating treatment. The heated CaO sample was of lower apparent porosity (4.1%) and higher bulk density (2.93 g/cm³). And the size distributions of most CaO grains are between 10 and 40 μm.     

Evaluation of crushing strength of spray-dried MgAl2O4 granule beds

The crushing strengths of four different experimental magnesium aluminate spinel (MgAl₂O₄) granule beds were monitored with the axial die pressing test after heat treatments. Precursor, magnesium hydroxide (Mg(OH)₂) and magnesium oxide (MgO) as Mg precursor and aluminium oxide hydroxide Al(O)OH and α-Al₂O₃ as Al precursor, were used for experimental granules, which were manufactured via a dispersion manufacturing and spray-drying process. After spray-drying, granules were heat treated in air at 1000, 1100, 1200, 1300 and 1400 °C. In order to understand the potential effect of precursor, phase structure, morphology, particle size distribution and density of granules on crushing strength behaviour, scanning X-ray diffraction (XRD) was used together with electron microscopy (SEM) and laser diffraction (LDPA) for characterisation. All precursor mixtures formed spherical granules during the spray-drying process and pure spinel phase structure during heat treatment. The crushing strength test results indicated that the Al precursor clearly affected the crushing strength behaviour of experimental granule beds. The highest strength was observed for granule beds with Al(O)OH) as Al and Mg(OH)₂ as Mg precursor.     

Whey Protein-Pullulan (WP/Pullulan) Polymer Blend for Preservation of Viability of Lactobacillus acidophilus

In this study, whey protein isolate-pullulan (WP/pullulan) microspheres were developed to entrap the probiotic Lactobacillus acidophilus NRRL-B 4495 by spray-drying technique. Microcapsules were analyzed for physicochemical characteristics including morphology, particle size, moisture content, water activity, dissolution time, and color properties. Results revealed that microcapsules were spherical in shape and obtained particle sizes between 5 and 160 µm, with an average size of around 50 µm. Blending pullulan with WP provided enhanced survival of probiotic bacteria during spray drying with a final viable cell number of 8.81 log CFU/g of microcapsule. Encapsulated probiotics were also found to have significantly (p ≤ 0.05) higher survived cell numbers compared to free probiotics under detrimental gastrointestinal conditions. Moreover, dissolution analysis suggested that protein-polysaccharide powdered microcapsules showed pH-sensitive dissolution properties in simulated gastric juice and simulated intestinal juice.