Random stacking template of polymer spheres and water soluble particles to fabricate porous hydroxyapatite with interconnected pores

Particle stacking simulation is applied in the fabrication of porous hydroxyapatite (HA) ceramics to predict the relationship between the template preparation process and the porosity of porous ceramics. The stacking of multi-diameter spherical particles, such as polymer spheres and NaCl particles, in three-dimensional space is simulated by using continuous generation method. The porosity of porous HA is predicted by calculating the stacking density of large spheres (the ratio of large sphere volume and container volume). The model of three-dimensional random stacking spheres is implemented by using the C++ program. Porous HA ceramics with interconnected spherical pores were fabricated by slipcasting which the use of a polymer template. Templates were produced by randomly stacking polymer spheres and NaCl particles. The arithmetic average error between the porosity of porous HA ceramics and the stacking density of polymer spheres (large spheres) is 3.52%. Simulation results obtained by using the proposed method are consistent with the experimental results.     

Novel fabrication of hierarchically porous hydroxyapatite scaffolds with refined porosity and suitable strength

Based on extrusion deposition and foaming technique, a novel method for biological hydroxyapatite (HA) scaffolds was introduced in this paper. The scaffolds were primarily characterised by interconnected and hierarchically porous structures with high porosity, adjustable distribution of pore sizes, as well as considerable mechanical strength. In order to confirm that fine control of bulk porosity and mechanical strength was possible and feasible, further analysis of obtained scaffolds was carried out by field emission scanning electron microscope (FESEM), compressive test and calculation of volumetric shrinkage; in particular, the additional porosity resulting from the introduction of pore former was evaluated. The results indicated that this method can have a great potential to construct HA scaffolds of suitable quality for spongy bone in bone tissue engineering.     

壳聚糖-胶原多孔支架的制备研究

本研究的目的就是利用细胞亲和力较好的胶原与壳聚糖复合,制备具有较好细胞亲和力的组织工程复合支架。在研究中采用冷冻诱导相分离的方法制备了壳聚糖(Cs)和胶原溶胀液(Co)质量比为1：2、1：3、1：4、1：5的4种成分的复合多孔支架,并对支架的孔结构、吸水性、孔隙率和溶胀性等特性进行了评价。结果显示,制备的复合多孔支架孔隙率均在90％以上;不同成分的支架孔径大小不同,胶原含量越高,孔径越大;支架内部孔隙连通：残留的醋酸在超声波作用下用碱液中和并干燥后,支架浸入水中基本无溶胀,保持了原有的形貌。     

TBA-based freeze/gel casting of porous hydroxyapatite scaffolds

Porous ceramic scaffolds with a controlled “designer” pore structure have been prepared by the freeze/gel casting route using a TBA-based hydroxyapatite slurry system with 20–40 wt.% solid content. The products were characterized in terms of sintered microstructure, together with physical and mechanical properties. After sintering at 1050–1250 °C, the advantages of freeze casting and gel casting appeared in the pore structure and compressive strength of the ceramics, i.e., unidirectional aligned macro-pore channels developed by controlling the solidification direction of the TBA solvent used in the freeze casting together with small diameter (micron sized) isolated pores formed in the dense outer walls of the pore channels when processed by gel casting. The sintered porosity and pore size generally resulted in a high solid loading giving low porosity and small pore size, this leading to higher compressive strengths. The scaffolds obtained exhibited an average porosity and compressive strength in the range 41.9–79.3% and 35.1–2.7 MPa, respectively, depending on the processing conditions used.     

A comparative study of porous scaffolds with cubic and spherical macropores

Two kinds of polyester porous scaffolds having cubic and spherical macropores were fabricated, and a comparative study of their morphologies and mechanical properties were made in this paper. Poly(d,l-lactic-co-glycolic acid) (PLGA) scaffolds were prepared by room temperature compression molding and particulate leaching method based on cubic NaCl particles and paraffin spheres with a similar size range of 355-450 μm and a series of porosities (77-97%). Scanning electronic microscopy demonstrated that the spherical pore scaffolds exhibited better pore interconnectivity than the cubic pore ones. In compressive tests of both kinds of scaffolds, striking yield peaks were found at relatively low porosities, but just non-linear flexure behavior was observed at high porosities. The power-law relationships of compressive modulus and compressive strength versus porosity were confirmed in both foams. Comparison of the underlying scaling exponents reveals that the scaffolds with spherical pores are, at high porosities, with better compressive properties to a certain degree in contrast to those with cubic pores.     

In vitro behaviour of sol-gel interconnected porous scaffolds of doped wollastonite

Using the sol-gel method, two different three-dimensional (3D) porous interconnected scaffolds were prepared, whose compositions were MgO-K₂O-CaO-SiO₂ (MgO-K₂O-wollastonite) and Na₂O-K₂O-CaO-SiO₂ (Na₂O-K₂O-wollastonite). Scaffold sintering was performed at 950 °C for 8 h. The scaffolds were obtained and soaked in simulated body fluid for different times (6 h, 3 d, 7 d and 14 d) to study their in vitro behaviour. Scanning electron microscopy and energy-dispersive X-ray spectroscopy revealed the presence of both a hydroxyapatite-like microstructure and a nanostructure on the surface of 3D scaffolds. The presence of Na and K in the scaffolds resulted in the precipitation of a hierarchical hydroxyapatite-like layer composed of nanorods, approximately 200–400 nm in size. The presence of Mg and K ions in the composition caused the precipitation of particles with a nanorod morphology, approximately 50–100 nm in size. The addition of Na, K and Mg, K to the wollastonite resulted in scaffolds with mechanical strengths of 0.03 and 0.02 MPa, respectively.     

Highly porous fibrous mullite ceramic membrane with interconnected pores for high performance dust removal

Porous fibrous mullite ceramic membranes with different content of fibers were successfully fabricated by molding method for dust removal. The properties of the samples, such as microstructure, porosity, bulk density and mechanical behavior were analyzed. Owing to the highly porous three-dimensional structure of ceramic membranes, all the samples exhibited low density (lower than 0.64?g/cm³), high porosity (higher than 73%), low linear shrinkage (lower than 1.0%) and low thermal conductivity (lower than 0.165?W/mK). Significantly, the as-prepared porous ceramic membrane possessed of enhanced dust removal efficiency with almost 100% for 3–10?µm, 97% for 1.0?µm, 87% for 0.5?µm and 82% for 0.3?µm dust particles in diameter from dust-laden air passed through the test module. Moreover, the pressure drop was lower than 80?Pa when the airflow linear velocity reached 1.25?m?min^?1. The results indicated that the ceramic membranes prepared in this work were promising high efficiency dedusting materials for the application in gas filtration field.     

Formation mechanism of porous reaction-bonded silicon nitride with interconnected pores in the presence of MgO

In porous reaction bonded silicon nitride, whiskers normally grow in globular clusters as the dominant morphology and deteriorate the pore interconnectivity. However, the ceramic microstructure was significantly transformed with the addition of MgO; specifically, the morphology was modified to a combination of matte and hexagonal grains. Microstructural observation along with thermodynamic studies suggest that MgO interfered with the presence and nitridation of SiO_(g). Consequently, rather than being involved in the whiskers’ formation, surface silica instead reacted with volatile MgO to form intermediate products. Through these reactions, whisker formation was blocked, and a porous interconnected structure formed which was confirmed by 3D tomography. After heat-treatment at 1700 °C, β-Si₃N₄ crystallized in a glassy matrix containing magnesium. Resulting samples had an open-pore structure with porosity of 74–84 vol. %, and density of 0.48-0.75 g.cm^?3. Combination of high porosity and pore size of <40 μm led to compressive strengths of 1.1–1.6 MPa.     

Fabrication of cell patches using biodegradable scaffolds with a hexagonal array of interconnected pores (SHAIPs)

Cell patches are widely used for healing injuries on the surfaces or interfaces of tissues such as those of epidermis and myocardium. Here we report a novel type of porous scaffolds made of poly(d,l-lactic-co-glycolic acid) for fabricating cell patches. The scaffolds have a single layer of spherical pores arranged in a unique hexagonal pattern and are therefore referred to as “scaffolds with a hexagonal array of interconnected pores (SHAIPs)”. SHAIPs contain both uniform pores and interconnecting windows that can facilitate the exchange of biomacromolecules, ensure homogeneous cell seeding, and promote cell migration. As a proof-of-concept demonstration, we have created skeletal muscle patches with a thickness of approximately 150 μm using SHAIPs. The myoblasts seeded in the scaffolds maintained high viability and were able to differentiate into multi-nucleated myotubes. Moreover, neovasculature could efficiently develop into the patches upon subcutaneous implantation in vivo.     

Preparation and performance of hydroxyapatite/Ti porous biocomposite scaffolds

Hydroxyapatite/titanium (HA/Ti) porous biocomposite scaffolds were prepared via a powder metallurgical method using NH₄HCO₃ as the pore-forming agent. The scaffolds induced HA formation and showed high bioactivity, and their porosity and compressive strength could be regulated by changing the NH₄HCO₃ dosage. When the NH₄HCO₃ dosage was 40.0%, the porosity was 67.0 ± 0.8%, and compressive strength was 19.0 ± 0.6 MPa, indicating the corresponding scaffold was an ideal choice for spongy bone repair.     

A novel fabrication procedure for producing high strength hydroxyapatite ceramic scaffolds with high porosity

Hydroxyapatite (HA) scaffolds were fabricated using the space holder method with a pressureless sintering process in a systematically developed manner at different fabrication stages to increase the strength of the scaffold at high porosity. Polyvinyl alcohol (PVA) and Polymethyl methacrylate (PMMA) were used as binders and space holder agents, respectively. The physical properties of the HA scaffolds were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), linear shrinkage test, and porosity measurements. The mechanical properties of the HA scaffolds were analyzed using compressive strength measurements. The results revealed that the HA scaffold met the expected quality requirements with a compressive strength of 2.2 MPa at a porosity of 65.6% with pore sizes distributed in the range of 126–385 μm. The shrinkage of the scaffold diameter occurred by 20.27%, this diameter shrinkage predominantly to the shrinkage of the HA scaffold caused by sintering. Besides, suspect that a higher PMMA concentration causes pore size shrinkage upon sintering. The formation of pore interconnections was evidenced by SEM observations and the ‘translucent light method’ developed in this study. The results of the scaffold phase test using XRD showed that the final scaffold consisted only of the HA phase, as the PVA and PMMA phases burned out during the sintering process.     

Facile fabrication of near-infrared light-responsive shape memory nanocomposite scaffolds with hierarchical porous structures

In this work, the near-infrared (NIR) light-responsive shape memory scaffolds with hierarchical porous structures are designed and facilely formed by freeze drying of 3D printed viscous gel-like pickering emulsions, which are stabilized by hydrophobically modified graphene oxide (g-GO) and silica nanoparticles, and contain thermo-responsive poly(d , l -lactic acid-co-trimethylene carbonate) (PLMC) in the oil phase. The prepared scaffolds display an interconnected filament structure with hierarchical pores and high porosity. The incorporation of g-GO nanoparticles into PLMC matrix prompts that the scaffold shape memory can be triggered by NIR light with fast shape recovery. Moreover, the in vitro mineralization experiment shows that the scaffolds have biological activity, and the drug release study demonstrates that the scaffolds can be used as drug carriers with efficient drug release capacity. Furthermore, cell culture assays based on mouse bone mesenchymal stem cells exhibit that the scaffolds own good cytocompatibility. Therefore, the facile preparation and remote activation of the shape memory nanocomposite scaffolds with hierarchical porous structure and multifunctionality represents a highly attractive candidate as minimally invasive implantation scaffolds for bone tissue engineering applications.     

Effects of microwave sintering on the properties of porous hydroxyapatite scaffolds

Microwave sintering was used to process porous hydroxyapatite scaffolds fabricated by the extrusion deposition technique. The effects of microwave sintering on the microstructure, phase composition, degradation, compressive strength and biological properties of the scaffolds were investigated. After rapid sintering, scaffolds with controlled structure, high densification and fine grains were obtained. A significant increase in mechanical strength was observed relative to conventional sintering. The scaffolds (55–60% porosity) microwave sintered at 1200 °C for 30 min exhibited the highest average compressive strength (45.57 MPa). The degradation was determined by immersing the scaffolds in physiological saline and monitoring the Ca²⁺concentration. The results indicated that the microwave-sintered scaffolds possessed higher solubility than conventionally sintered scaffolds, as it released more Ca²⁺ at the same temperature. Furthermore, an in vitro MC3T3-E1 cell culturing study showed significant cell adhesion, distribution, and proliferation in the microwave-sintered scaffolds. These results confirm that microwave sintering has a positive effect on the properties of porous hydroxyapatite scaffolds for bone tissue engineering applications.     

Preparation of the reticulated hydroxyapatite ceramics using carbon-coated polymeric sponge with elongated pores as a novel template

This paper proposes a novel, simple way to improve the compressive strength of reticulated porous hydroxyapatite (HA) ceramics using carbon-coated polymeric sponges with elongated pores as a novel template. This template allowed samples to have two interconnected pore networks with a preferential orientation, in which an addition pore network was newly formed by removing the carbon-coated polymeric struts, while preserving the pre-existing pore network. The compressive strength of the sample was as high as 2.9 ± 0.3 MPa with a porosity of 76% when tested parallel to the direction of pore elongation. In addition, the in vitro cell test using a pre-osteoblast cell line revealed the samples to have good biocompatibility.     

Effects of nano-alumina content on the formation of interconnected pores in porous purging plug materials

The physical properties and microstructure of porous purging plug materials added with different nano-alumina contents and firing temperatures were investigated by means of X-ray diffraction, scanning electron microscopy, air permeability, pore size distribution, mean pore size, apparent porosity, bulk density, and cold crushing strength (CCS) tests. The results showed that the addition of nano-alumina had a great effect on the physical properties and microstructure of the porous purging plug materials. With increasing nano-alumina content in the composition, the main phase was α-Al₂O₃ in all compositions and the mean pore size, apparent porosity and air permeability all increased due to the increased number of pores and pore size of the specimens which facilitated the formation of interconnected pores. When the sintering temperature was changed from 1550 °C to 1650 °C, some of the smaller pores vanished due to solid phase sintering, which reduced the apparent porosity, and some open pores connected to form interconnected pores, which promoted increased air permeability. In addition, the strength and porosity were found to follow the relationship σ = σ₀ exp (-b P). When the apparent porosity increased, the CCS decreased, and vice versa.     

Fabrication and compressive strength of porous hydroxyapatite scaffolds with a functionally graded core/shell structure

A novel type of porous hydroxyapatite (HA) scaffolds with a functionally graded core/shell structure was fabricated by freeze casting HA/camphene slurries with various HA contents into fugitive molds containing a graphite template with three-dimensionally interconnected pores for the creation of a highly porous core. All the fabricated samples had functionally graded core/shell structures with 3-D periodic pore networks in a core surrounded by a relatively dense shell. The overall porosity of the sample decreased from 60 to 38 vol% with increasing HA content in the HA/camphene slurry from 20 to 36 vol% due to a decrease in porosity in both the core and shell regions. In addition, the compressive strength was improved remarkably from 12 ± 1.1 to 32 ± 3.0 MPa. The in vitro cell test using a pre-osteoblast cell line showed that the samples had good biocompatibility.     

Highly loaded hydroxyapatite microsphere/ PLA porous scaffolds obtained by fused deposition modelling

The goal of the work was the manufacturing of hydroxyapatite microsphere/polylactic acid (PLA) scaffolds by means of fused deposition modelling (FDM). Micrometer-sized hydroxyapatite spheres synthesized by spray drying (sdHA), were dispersed in PLA by extrusion compounding. Composite filaments were obtained from extrusion which were used in FDM 3D printing for the production of macroporous scaffolds. The sdHA microspheres were used in the composite in order to improve the biomimicry and the bioactivity of the 3D printed scaffold to increase the bone regeneration capacity. Morphological, thermal, physical and mechanical characterizations were performed on the 3D printed composites. Pure PLA scaffolds were 3D printed and used as a reference.Thermal analyses, TGA and DSC evidenced that the glass transition temperature and the degree of crystallinity of PLA were not influenced by the presence of sdHA. Morphological analysis showed a smooth surface of the printed samples when pure PLA was used. A rough surface was found on the PLA/sdHA composites, confirming, the homogeneous dispersion of the ceramic phase in the polymeric matrix. The higher porosity of the composite samples compared to PLA ones, most likely caused a decrease of the mechanical performances of the PLA/sdHA scaffolds. Composite scaffolds displayed stiffness values compatible with that of bone tissue.     

Formation of porous alumina with oriented pores

Adopting the theories describing the bubble forming in the metal–hydrogen solidification process, porous alumina with oriented pores was prepared by combining a foaming method with sol-gel technology. The bubble forming process in the sol-gel is different from that in the metal–hydrogen system. Samples were calcined at temperature from 800 to 1200C. The volume-shrinkage and compressive-strength increased with increasing calcination temperature. The porous alumina exhibited a bimodal pore structure when prepared below 1200°C.     

Conductivity of porous materials with spheroidal pores

Models predicting the conductivity of porous materials with spheroidal insulating pores are summarized and a new model, based on our exponential relation, is proposed. Using the well-known single-inclusion solution for spheroids, Maxwell coefficients (“intrinsic conductivities”) are calculated in dependence of the pore aspect ratio for isotropic microstructures with randomly oriented spheroidal pores, and implemented into the three traditional effective medium approximations (Maxwell-type, self-consistent, differential) and our exponential relation. As expected, all models predict that prolate pore shape has a very small influence on the porosity dependence, while oblate pores affect the porosity dependence of conductivity significantly. However, the self-consistent predictions are linear and imply spurious percolation thresholds, whereas Maxwell-type and differential models (power-law relations) are known to provide predictions that are unrealistically high for the special case of spherical pore shape. Thus, our exponential relation seems to be currently the most suitable relation for implementing the single-inclusion solution for spheroids.     

Influence of sodium on the properties of sol-gel derived hydroxyapatite powder and porous scaffolds

This study investigates the properties of sol-gel derived sodium (Na)-doped hydroxyapatite (HA) powder. Different amounts of Na (1, 5, 10 and 15 mol%) were prepared and the sintered bodies were characterized to determine the current phases, microstructural evolution and mechanical properties. X-ray diffraction analysis reveals that a phase pure HA of crystallite sizes, which varied from 35 nm to 65 nm, was obtained in the synthesized powder after calcining from 500 °C to 1000 °C. Scanning electron microscopy examination shows evidence of larger particle sizes, particularly in samples that contain higher amounts of Na concentration. The resultant powders were subsequently used to prepare porous NA-doped HA bodies through a polymeric sponge method. The addition of 5% Na resulted in a porous body with 27% porosity and was beneficial in enhancing the compressive strength of HA 17-fold compared with undoped HA. The prepared scaffold also shows suitable pore interconnectivity with pore sizes that vary between 100 and 300 µm which is suitable for use as porous bone substitutes.