Particle design for dry powder inhalation via binderless powder coating by pressure swing granulation

Novel formulation for dry powder inhalation (DPI) particularly appropriate for very dilute drug concentration was developed based on the pressure swing granulation (PSG) technology. PSG was applied to the granulation of excipient lactose particles and to the coating/dusting of lactose granules with fine model drug particles. Size distribution and granule strength as well as the dispersibility of the drug particles for DPI were found to be successful for practical use. The drug particles dispersed into the respirable aerodynamic size range of 1-7 μm from the E-haler® was 53.9% for 1% coating/dusting (i.e. 1% drug in product granules) and 46.3% for 2%. E-haler® was capable of emitting 89.8% and 83.2% of drug particles charged for cases for 1% and 2% coatings, respectively.     

Reactive spark plasma sintering of the hexacelcian barium aluminosilicate phase.

The barium aluminosilicate compound (BaAl₂Si₂O₈ or BAS) has been synthesized by powder reactive sintering within a Spark Plasma Sintering (SPS) device. The reaction paths between the precursors (alumina, silica and barium carbonate powders) have been deeply investigated at different temperatures from 900° to 1550°C in order to get at the end, the hexacelcian crystallographic form without any undesirable other compounds. Thanks to this approach, a 3 step thermal treatment is proposed to get a fully dense and nearly pure (98 wt%) BAS.     

Influence of spark plasma sintering conditions on microstructure,carbon contamination,and transmittance of CaF2 ceramics

Commercial CaF₂ powder was applied to fabricate transparent CaF₂ ceramics by spark plasma sintering under various sintering conditions. The low sintering temperatures and high pressures caused serious carbon contamination, while the soak time had less influence on the carbon concentration in the ceramics. The highest carbon contamination occurred to the CaF₂ ceramics sintered at 800 °C. A low sintering pressure suppressed carbon contamination but led to high porosity and large pore size. A high pre-loading pressure led to relatively high porosity and carbon concentration. Furthermore, the relatively fast densification in the edge region of the plates may cause the non-uniform distribution of porosity, thereby affecting the distribution of carbon concentration. The low pre-loading pressure and the high sintering pressure reduced porosity and carbon concentration to obtain dense transparent ceramic with uniform microstructure and high transmittance.     

Fabrication of powder components with internal channels by spark plasma sintering and additive manufacturing

A novel method of producing complex ceramic and metallic parts with designed internal channels is developed. The method utilizes a combination of the additive manufacturing technique of solvent jetting and spark plasma sintering (SPS.) The developed manufacturing approach brings benefits in producing complex shapes with internal channels. Along with geometric customization of the 3D printed mold, a major advantage of this method is the removal of the need for a long debinding process, usually necessary with other 3D printing methods, by using the SPS. High density ceramic and metallic complex parts with internal channels were successfully produced with close to theoretical densities. The conducted studies include the development of a model that can predict the evolution and/or distortions of the complex-shaped powder assembly during the sintering process. The model is based on the continuum theory of sintering formulations embedded in a finite element code.     

Drucker-Prager-Cap modelling of boron carbide powder for coupled electrical-thermal-mechanical finite element simulation of spark plasma sintering

The coupled electrical-thermal-mechanical finite element method in the continuum scale has been widely used to investigate the spark plasma sintering process. An accurate constitutive model of powder material is pivotal for precise continuum finite element simulation. In this study, the Drucker-Prager-Cap model, which is highly accurate in describing the densification behaviour of powder material, was adopted to numerically analyse the spark plasma sintering process of boron carbide powder. First, the parameters of the model were defined to be dependent on temperature and density for higher accuracy; they were determined by minimising the discrepancy between the simulated and experimental results. Based on a spark plasma sintering experiment with a cylindrical sample, the parameters of the Drucker-Prager-Cap model were identified at 1500 °C, 1600 °C, 1700 °C, 1800 °C, and 1900 °C. A coupled electrical-thermal-mechanical finite element simulation with the model was performed for spark plasma sintering of boron carbide powder at 1750 °C and 1850 °C. The temperature, stress, and relative density were investigated numerically. By comparing the model results with the temperature and relative density measured in the experiment, the continuum finite element method with the Drucker-Prager-Cap model was validated.     

Polycrystalline infrared-transparent MgO fabricated by spark plasma sintering

In the present research, polycrystalline magnesium oxide (MgO) bodies were fabricated using spark plasma sintering (SPS) at different temperatures and times from MgO nanopowder. Microstructural development, densification, and optical properties were investigated during SPS. The critical pressure of plastic deformation of the MgO compacts during sintering was also analyzed. The results showed that the plastic deformation phenomenon had a profound effect on the grain size and optical properties. In addition, the optical properties and microstructure of MgO bodies were strongly dependent on sintering temperature and time. Full-dense infrared-transparent magnesium oxide with a relative density of 99.99% was prepared at 1200 °C for 5 min under the pressure of 80 MPa. The spark plasma sintered MgO demonstrated the highest infrared transmittance of 72% in the 3–7 μm wavelength range, which was comparable with the values reported for MgO single crystal.     

Microstructural evolution of ZnO via hybrid cold sintering/spark plasma sintering

In this work, we demonstrate a hybrid cold sintering/spark plasma sintering (CSP-SPS) process to densify ZnO ceramic with controlled grain growth. The densification of ZnO is initially activated at 85 °C, and high densities (>98%) are achieved at 200–300 °C in only 5 min with a low assisted pressure of 3.8–50 MPa. The microstructure of ZnO grains experiences a mild coarsening from ~205–680 nm during the CSP-SPS. In comparison, a much higher temperature (>770 °C) is required to sinter ZnO ceramic via SPS, and the grain size exhibits an obvious overgrowth to ~10 µm. The calculated apparent activation energy of grain growth using CSP-SPS is 69.3 ± 6 kJ/mol, which is much lower than that of SPS samples with 296.8 ± 59 kJ/mol. In addition, the conduction mechanism of the CSP-SPS and SPS samples is investigated using impedance spectroscopy. Overall, CSP-SPS is promising for the fabrication of fine ceramics with mild sintering conditions.     

Reactive spark plasma sintering of exothermic systems: A critical review

Spark plasma sintering (SPS) is an efficient method for fabricating various bulk dense materials, including ceramics. Reactive spark plasma sintering (RSPS) of the exothermic reaction systems involves an initial powder mixture that allows chemical transformation with release of an additional energy during the SPS process. Thus, a deep understanding of the chemistry is critical for controlling the microstructure and thus the properties of the obtained materials. Recent publications have revealed that the RSPS is widely used for manufacturing of variety of materials including ultrahigh-temperature ceramics, high-entropy ceramics, and thermoelectrics. However, the thermodynamics and kinetics of the chemical reactions occurring during RSPS are not well understood. The goals of the present critical review are as follows: (i) to provide the fundamental definitions of chemistry related parameters of RSPS; (ii) to analyze the thermodynamics and kinetics of the RSPS processes; (iii) to emphases the influence of the microstructure of the consolidated media on the chemistry of RSPS; (iv) briefly overview recent publications on RSPS of ceramics. We also provide some recommendations for future work in the field of RSPS.     

Processing and mechanical properties of B4C-SiCw ceramics densified by spark plasma sintering

Homogenous distribution of whiskers in the ceramic matrix is difficult to be achieved. To solve this problem, B₄C-SiC_w powder mixtures were freeze dried from a slurry dispersed by cellulose nanofibrils (CellNF) in this work. Dense B₄C ceramics reinforced with various amounts of SiC_w up to 12 wt% were consolidated by spark plasma sintering (SPS) at 1800 °C for 10 min under 50 MPa. During this process, CellNF was converted into carbon nanostructures. As iron impurities exist in the starting B₄C and SiC_w powders, both thermodynamic calculations and microstructure observations suggest the dissolution and precipitation of SiC_w in the liquids composed of Fe-Si-B-C occurred during sintering. Although not all the SiC_w grains were kept in the final ceramics, B₄C-9 wt% SiC_w ceramics sintered at 1800 °C still exhibit excellent Vickers hardness (35.5 ± 0.8 GPa), flexural strength (560 ± 9 MPa) and fracture toughness (5.1 ± 0.2 MPa·m^1/2), possibly contributed by the high-density stacking faults and twins in their SiC grains, no matter in whisker or particulate forms.     

Effects of powder preparation and sintering temperature on consolidation of ultrafine WC-8Co tool material produced by spark plasma sintering

In this study, ultrafine tool materials were produced by spark plasma sintering using three sets of WC-8Co nanopowders mixed by different methods. Effects of powder preparation method and sintering temperature on the consolidation of WC-8Co cemented carbides were investigated. At sintering temperature of 1250 °C, cemented carbide sintered from the powder mixed by ultrasonic vibration method exhibited homogeneous microstructure, high relative density (99.1%), small average grain size (280 nm), and excellent mechanical properties (H_V: 18.8 GPa, K_IC: 11.4 MPa⋅m^1/2). However, cemented carbide sintered from heavily ball-milled powder (ball milling for 24 h) showed increased grain coalescence and microdefects as well as lower relative density of 94.6%. Moreover, its hardness decreased to 17.7 GPa due to the decrease in relative density. Furthermore, straight cracks along grain boundary became dominant, causing fracture toughness to decrease to 10.5 MPa⋅m^1/2. Additionally, high sintering temperature caused grain coarsening, which was detrimental to mechanical properties of cemented carbides.     

放电等离子烧结合成单相MgAlON材料

以氮化铝、富铝镁铝尖晶石和氧化铝为原料 ,用放电等离子烧结 (SPS)技术合成了单相MgAlON,研究了其显微结构 ,并与用传统的无压烧结 (PLS)技术制备的单相MgAlON材料在显微结构和断裂行为上做了比较。结果表明 :用SPS法在 170 0℃保温 1min的条件下合成出的单相MgAlON材料 ,显微结构比用PLS法合成的更加均匀致密 ,且晶粒细小 ;前者的断裂模式主要是穿晶断裂 ,后者的断裂模式则主要是沿晶断裂。     

Synthesis and sintering at low temperature of a new nanostructured beta-Eucryptite dense compact by spark plasma sintering

The solid state reaction between kaolin and Li₂CO₃ with a 1:1 M composition has been studied in the temperature range 380°C-550 °C. The role played by Li₂CO₃ (basic medium) in the thermal transformation of the kaolin has been investigated by X-Ray diffraction, FESEM, TEM, MAS-NMR and XPS techniques. For the first time, a nanostructured high density β- Eucryptite (<10 nm) has been obtained by Spark Plasma Sintering (SPS) at 550 °C in high vacuum. The atmosphere used in sintering treatments has a determinant role in lithium migration and crystallization of β- Eucryptite. In the case of low vacuum treatments, an amorphous LiAlSiO₄ geopolymer type material was obtained. Due to exclusive properties and performances of β- Eucryptite based materials, the results reported in the present investigation open new perspectives for new nanostructured and amorphous functional materials with null thermal expansion, ionic conduction and remarkable mechanical properties.     

Microstructure and mechanical properties of B4C based ceramics with Fe3Al as sintering aid by spark plasma sintering

B₄C based ceramics were fabricated with different Fe₃Al contents as sintering aids by spark plasma sintering at relatively low temperature (1700 °C) in vacuum by applying 50 MPa pressure and held at 1700 °C for 5 min. The effect of Fe₃Al additions (from 0 to 9 wt%) on the microstructure and mechanical properties of B₄C has been studied. The composition and microstructure of as-prepared samples were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and electron probe microanalyzer (EPMA) equipped with WDS (wavelength dispersive spectrometry) and EDS. The mixtures of B₄C and Fe₃Al underwent a major reaction in which the metal borides and B₄C were encountered as major crystallographic phases. The sample with 7 wt% of Fe₃Al as a sintering aid was found to have 32.46 GPa Vickers hardness, 483.40 MPa flexural strength, and 4.1 MPa m^1/2 fracture toughness which is higher than that of pure B₄C.     

Coarse-grain CeO2 doped ZrO2 ceramic prepared by spark plasma sintering

In the present work, coarse grain cerium stabilized zirconia bulk ceramic was prepared by spark plasma sintering technique. The relatively high temperature of 2000 °C used for sintering led to enormous grain growth up to approximately 100 μm. Sintering at high temperatures and in the vacuum caused oxygen depletion and thus transformation from tetragonal to cubic phase during the sintering process. The tetragonal phase was recovered by annealing at 1400 °C in air. This led to a change in fracture behavior. Mostly transgranular fracture of the cubic phase was changed to intergranular fracture after recovering the tetragonal phase. On the intergranular fracture surface, twinning-like structure and structures similar to antiphase domain were observed.Mechanical properties represented by indentation hardness of prepared samples were evaluated.     

An optimized method for synthesizing phase-pure Ti3AlC2 MAX-phase through spark plasma sintering

So far many attempts have been made to synthesize phase-pure Ti₃AlC₂ MAX-phase. But still the challenge posed by the presence of TiC and Ti-Al based intermetallic transient impurity phases in the final product is a persisting problem. Spark plasma sintering (SPS) technique has been the most successful method to decrease the impurity content of the final product. Even so, synthesis of phase-pure Ti₃AlC₂ MAX-phase, without any TiC and Ti-Al based intermetallic impurities, has not been achieved and reported in literature with substantial evidences. Further, high purity Ti₃AlC₂ MAX-phase synthesized using SPS technique has shown lack of phase and microstructural stability above 1350°C temperature. In this work, we have reported an optimized method for producing phase-pure Ti₃AlC₂ MAX-phase (having more than 99 % purity) using commercial grade Ti, Al and C elemental powders through SPS technique. The final product also showed very good high temperature stability up to 1500°C under flowing Argon inert atmosphere.     

High-pressure spark plasma sintering of silicon nitride with LiF additive

High-pressure spark plasma sintering of Si₃N₄ with Y₂O₃, Al₂O₃ and LiF additives was employed to fabricate high quality dense ceramics comprising approximately 92% α-Si₃N₄ phase and 8% β-Si₃N₄ phase. The relatively high pressure applied (up to 650 MPa) had a substantial effect on densification by enhancing particle rearrangement, making it possible to obtain dense Si₃N₄ at a significantly lower sintering temperature (1350 °C). Consequently, virtually no α to β phase transformation transpired during the liquid phase sintering process. The LiF additive had an indispensable influence on the densification process by lowering the viscous glass formation temperature, which also contributed to enhanced particle rearrangement. The nearly fully dense samples (theoretical density ≥99%) obtained displayed a good combination of mechanical properties, namely elastic modulus (304–316 GPa), hardness (1720–1780 HV2) and fracture toughness (6.0 MPa m^1/2).     

Microstructure and mechanical properties of SiC-SiC joints joined by spark plasma sintering

The development of reliable joining technology is of great importance for the full use of SiC. Ti₃SiC₂, which is used as a filler material for SiC joining, can meet the demands of neutron environment applications and can alleviate residual stress during the joining process. In this work, SiC was joined using different powders (Ti₃SiC₂ and 3Ti/1.2Si/2C/0.2Al) as filler materials and spark plasma sintering (SPS). The influence of the joining temperature on the flexural strength of the SiC joints at room temperature and at high temperatures was investigated. Based on X-ray diffraction and scanning electron microscopy analyses, SiC joints with 3Ti/1.2Si/2C/0.2Al powder as the filler material possess high flexural strengths of 133 MPa and 119 MPa at room temperature and at 1200 °C, respectively. The superior flexural strength of the SiC joint at 1200 °C is attributed to the phase transformation of TiO₂ from anatase to rutile.     

Joining of C/SiC composites by spark plasma sintering technique

CVD–SiC coated C/SiC composites (C/SiC) were joined by spark plasma sintering (SPS) by direct bonding with and without the aid of joining materials. A calcia-alumina based glass–ceramic (CA), a SiC + 5 wt% B₄C mixture and pure Ti foils were used as joining materials in the non-direct bonding processes. Morphological and compositional analyses were performed on each joined sample. The shear strength of joined C/SiC was measured by a single lap test and found comparable to that of C/SiC.     

Fabrication of nanostructured non-stoichiometric TiO2-x by spark plasma sintering for enhancing its thermoelectric properties

In this study, nanostructured non-stoichiometric TiO_2-x compacts were prepared by the in-situ reduction of rutile titanium oxide (TiO₂) powder with urea powder via spark plasma sintering (SPS). The crystal structure and particle size of the prepared compacts were examined. The XRD patterns revealed that TiO₂ could be reduced easily by the urea powder to obtain non-stoichiometric TiO_2-x, and the compacts still possessed rutile crystal structures. The average particle sizes of the compacts were less than 250 nm, successfully obtaining the non-stoichiometric TiO_2-x with uniform nanostructures at the sintering temperature of 1073 K. In addition, nanostructured TiO_2-x compacts with Magnéli phase Ti_nO_2n-1 (n = 2, 4, 8) were fabricated by varying the volume fraction of Ti powder in a urea environment via SPS. The results suggested that addition of Ti powder contributed to the formation of Magnéli phases Ti_nO_2n-1, and the value of n decreased with an increase in the volume fraction of the Ti powder. Furthermore, the thermoelectric properties of the compacts sintered with and without Ti powder were both investigated. The TiO₂–U13.3-Ti10 compact displayed the highest power factor of 5.04 μWcm⁻¹K⁻² at 973 K. A lower thermal conductivity was achieved by TiO₂–U13.3-Ti10 compact in the temperature range of 373–973 K, approximately 3 Wm⁻¹K⁻¹, due to the nanostructures and Magnéli phases. The highest ZT value of 0.146 was obtained for the TiO₂–U13.3-Ti10 compact at 973 K, achieving a reasonable enhancement of thermoelectric properties.     

Micro-hydrothermal reactions mediated grain growth during spark plasma sintering of a carbonate-containing hydroxyapatite nanopowder

A carbonate-containing hydroxyapatite nanopowder was consolidated by spark plasma sintering at the temperatures ranging from 650 to 1100 °C. It was found that the water released by dehydroxylation was trapped inside the nanopores in the densified HAp bodies over 900 °C. Based on the analysis by the X-ray diffraction, Fourier-transform infrared spectrometry and scanning electron microscope, the water-nanopore system was evaluated and its effect on the grain growth was also investigated. It was revealed that the water existed inside the closed nanopores most probably resulted in the formation of local micro-hydrothermal environments inside bulk HAp ceramics during SPS. Therefore, the grain growth was enhanced by the local micro-hydrothermal reactions activated above 900 °C. In addition, abnormal grain growth was also observed when a higher temperature or higher heating rate was employed, which may be attributed to the local highly active hydrothermal reactions.