Forming and sintering of porous calcium-hexaaluminate ceramics with hydraulic alumina

We have developed a new eco-friendly fabrication process for porous ceramics using hydraulic alumina (HA) and water. In the present study, we fabricated porous calcium-hexaaluminate (CaAl₁₂O₁₉, CA6) ceramics using this new process. A boehmite gel 3-D network was formed by the hydration of HA in HA/CaCO₃ mixed slurry. The HA/CaCO₃ mixed slurry was hardened by the formation of this 3-D network. Even without the addition of an organic binder, green bodies containing the 3-D network demonstrated high compressive strength and retained their original shapes. Furthermore, the water acted as a fugitive material in the green bodies. Consequently, the open porosity of the CA6 ceramics could be controlled over a wide range of 42–62.7% by the addition of water (ratio of water to HA/CaCO₃ mixed powder: 0.4 to 1.6 by weight) without the use of organic fugitive materials. The results of evolved gas analysis-mass spectrometry measurements showed that the emissions from the hardened green body consisted mostly of water. Consequently, the new fabrication process for porous calcium-hexaaluminate ceramics was confirmed to be eco-friendly.     

Calcium-containing disk pattern from microspheres of chitosan with alginate

Microstructures bridge the molecular and the macroscopic scales. Disk-patterned microstructures obtained from microcapsules in this work are assembled through layer-by-layer which allowed depositing the natural polysaccharides chitosan (CS) and sodium alginate (SA) on porous CaCO₃ microparticles. Besides CS and SA assembled outside CaCO₃ microparticles, some CS and SA were also encapsulated by permeation in the pores of CaCO₃. During the dissolution of CaCO₃, the Ca^2 + cations from decomposed CaCO₃ were found to interact with alginate (AL) anions and to form Ca^2 +-AL scaffolds. The adhesion arising from the OH groups in polysaccharides to solid surfaces was attributed to the disk-patterned microstructures. The calcium content (2.290 × 10^− 10 mg) in each (CS/SA)₄ microstructure amounts to about 1% of the total mass of the CaCO₃ core. This work thus demonstrates the interaction between the decomposed core elements and the polysaccharides existing both inside and outside the porous cores. Such microstructures containing both Ca^2 + and natural polysaccharides have potential applications in biological and medical systems.     

Ultralight,Heat-Insulated,and Tough PVA Hydrogel Hybridized with SiO2@cellulose Nanoclaws Aerogel via the Synergy of Hydrophilic and Hydrophobic Interfacial Interactions

Lightweight porous hydrogels provide a worldwide scope for functional soft mateirals. However, most porous hydrogels have weak mechanical strength, high density (>1 g cm⁻³), and high heat absorption due to weak interfacial interactions and high solvent fill rates, which severely limit their application in wearable soft-electronic devices. Herein, an effective hybrid hydrogel-aerogel strategy to assemble ultralight, heat-insulated, and tough polyvinyl alcohol (PVA)/SiO₂@cellulose nanoclaws (CNCWs) hydrogels (PSCG) via strong interfacial interactions with hydrogen bonding and hydrophobic interaction is demonstrated. The resultant PSCG has an interesting hierarchical porous structure from bubble template (≈100 µm), PVA hydrogels networks introduced by ice crystals (≈10 µm), and hybrid SiO₂ aerogels (<50 nm), respectively. PSCG shows unprecedented low density (0.27 g cm⁻³), high tensile strength (1.6 MPa) & compressive strength (1.5 MPa), excellent heat-insulated ability, and strain-sensitive conductivity. This lightweight porous and tough hydrogel with an ingenious design provides a new way for wearable soft-electronic devices.     

Ultrahigh‐Water‐Content,Superelastic, and Shape‐Memory Nanofiber‐Assembled Hydrogels Exhibiting Pressure‐Responsive Conductivity

High‐water‐content hydrogels that are both mechanically robust and conductive could have wide applications in fields ranging from bioengineering and electronic devices to medicine; however, creating such materials has proven to be extremely challenging. This study presents a scalable methodology to prepare superelastic, cellular‐structured nanofibrous hydrogels (NFHs) by combining alginate and flexible SiO₂ nanofibers. This approach causes naturally abundant and sustainable alginate to assemble into 3D elastic bulk NFHs with tunable water content and desirable shapes on a large scale. The resultant NFHs exhibit the integrated properties of ultrahigh water content (99.8 wt%), complete recovery from 80% strain, zero Poisson's ratio, shape‐memory behavior, injectability, and elastic‐responsive conductivity, which can detect dynamic pressure in a wide range (>50 Pa) with robust sensitivity (0.24 kPa^?1) and durability (100 cycles). The fabrication of such fascinating materials may provide new insights into the design and development of multifunctional hydrogels for various applications.     

Improving the recycling and storage stability of enzyme by encapsulation in mesoporous CaCO3–alginate composite gel

Mesoporous CaCO₃ microparticle-doped alginate composite gels were prepared and studied as efficient carriers for enzyme immobilization. β-Glucuronidase (GUS) was immobilized by first pre-adsorption on CaCO₃ microparticles and then encapsulation in alginate beads. In this hybrid composite, alginate matrix effectively prevented the desorption of enzyme and inhibited the recrystallization of CaCO₃, while the impregnated CaCO₃ particles remarkably reduced the swelling of alginate hydrogel from 130% to 20%. As a result, GUS loading efficiency, recycling and storage stability were all significantly improved. Immobilized GUS retained 80% of its initial activity after seven recycles and 67% after storage for 27 days.     

Computational simulation of chemical dissolution‐front instability in fluid‐saturated porous media under non‐isothermal conditions

This paper primarily deals with the computational aspects of chemical dissolution‐front instability problems in two‐dimensional fluid‐saturated porous media under non‐isothermal conditions. After the dimensionless governing partial differential equations of the non‐isothermal chemical dissolution‐front instability problem are briefly described, the formulation of a computational procedure, which contains a combination of using the finite difference and finite element method, is derived for simulating the morphological evolution of chemical dissolution fronts in the non‐isothermal chemical dissolution system within two‐dimensional fluid‐saturated porous media. To ensure the correctness and accuracy of the numerical solutions, the proposed computational procedure is verified through comparing the numerical solutions with the analytical solutions for a benchmark problem. As an application example, the verified computational procedure is then used to simulate the morphological evolution of chemical dissolution fronts in the supercritical non‐isothermal chemical dissolution system. The related numerical results have demonstrated the following: (1) the proposed computational procedure can produce accurate numerical solutions for the planar chemical dissolution‐front propagation problem in the non‐isothermal chemical dissolution system consisting of a fluid‐saturated porous medium; (2) the Zhao number has a significant effect not only on the dimensionless propagation speed of the chemical dissolution front but also on the distribution patterns of the dimensionless temperature, dimensionless pore‐fluid pressure, and dimensionless chemical‐species concentration in a non‐isothermal chemical dissolution system; (3) once the finger penetrates the whole computational domain, the dimensionless pore‐fluid pressure decreases drastically in the non‐isothermal chemical dissolution system.     

Preparation and characterisation of controlled porosity alginate hydrogels made via a simultaneous micelle templating and internal gelation process

Controlled porosity alginate hydrogel monoliths were synthesised by simultaneous micelle templating (MT) and an internal gelation reaction. In water, the self assembling surfactant, cetyltrimethylammonium bromide (CTAB) formed non-spherical micelles that were used as a template for pore formation. The porous microstructure was assessed by mercury intrusion porosimetry (MIP), helium pycnometry, X-ray microtomography (XMT) and scanning electron microscopy (SEM), respectively. The MT hydrogels displayed relatively monodisperse pore size distributions (with pore sizes ranging from 32.5 μm to 164.0 μm), high total pore volumes (4.5–20.3 cm³/g) and high degrees of porosity (83–97%). Some control over pore size distributions was achieved by varying the surfactant concentration; higher surfactant concentrations, led to smaller pores with lower total pore volumes. Uniaxial compression testing revealed that hydrogels made via MT are stable in cell culture media for 28 days. Fourier transform infrared (FTIR) spectroscopy data, suggested that all surfactant could be removed from the final product by washing with ethanol and water, making these hydrogels potentially suitable for tissue engineering (TE) applications.     

A High Energy and Power Li‐Ion Capacitor Based on a TiO2 Nanobelt Array Anode and a Graphene Hydrogel Cathode

A novel hybrid Li‐ion capacitor (LIC) with high energy and power densities is constructed by combining an electrochemical double layer capacitor type cathode (graphene hydrogels) with a Li‐ion battery type anode (TiO₂ nanobelt arrays). The high power source is provided by the graphene hydrogel cathode, which has a 3D porous network structure and high electrical conductivity, and the counter anode is made of free‐standing TiO₂ nanobelt arrays (NBA) grown directly on Ti foil without any ancillary materials. Such a subtle designed hybrid Li‐ion capacitor allows rapid electron and ion transport in the non‐aqueous electrolyte. Within a voltage range of 0.0?3.8 V, a high energy of 82 Wh kg^?1 is achieved at a power density of 570 W kg^?1. Even at an 8.4 s charge/discharge rate, an energy density as high as 21 Wh kg^?1 can be retained. These results demonstrate that the TiO₂ NBA//graphene hydrogel LIC exhibits higher energy density than supercapacitors and better power density than Li‐ion batteries, which makes it a promising electrochemical power source.     

Microfluidic Templating of Spatially Inhomogeneous Protein Microgels

3D scaffolds in the form of hydrogels and microgels have allowed for more native cell‐culture systems to be developed relative to flat substrates. Native biological tissues are, however, usually spatially inhomogeneous and anisotropic, but regulating the spatial density of hydrogels at the microscale to mimic this inhomogeneity has been challenging to achieve. Moreover, the development of biocompatible synthesis approaches for protein‐based microgels remains challenging, and typical gelation conditions include UV light, extreme pH, extreme temperature, or organic solvents, factors which can compromise the viability of cells. This study addresses these challenges by demonstrating an approach to fabricate protein microgels with controllable radial density through microfluidic mixing and physical and enzymatic crosslinking of gelatin precursor molecules. Microgels with a higher density in their cores and microgels with a higher density in their shells are demonstrated. The microgels have robust stability at 37 °C and different dissolution rates through enzymolysis, which can be further used for gradient scaffolds for 3D cell culture, enabling controlled degradability, and the release of biomolecules. The design principles of the microgels could also be exploited to generate other soft materials for applications ranging from novel protein‐only micro reactors to soft robots.     

Fabrication of porous low crystalline calcite block by carbonation of calcium hydroxide compact

Calcium carbonate (CaCO₃) has been widely used as a bone substitute material because of its excellent tissue response and good resorbability. In this experimental study, we propose a new method obtaining porous CaCO₃ monolith for an artificial bone substitute. In the method, calcium hydroxide compacts were exposed to carbon dioxide saturated with water vapor at room temperature. Carbonation completed within 3 days and calcite was the only product. The mechanical strength of CaCO₃ monolith increased with carbonation period and molding pressure. Development of mechanical strength proceeded through two steps; the first rapid increase by bonding with calcite layer formed at the surface of calcium hydroxide particles and the latter increase by the full conversion of calcium hydroxide to calcite. The latter process was thought to be controlled by the diffusion of CO₂ through micropores in the surface calcite layer. Porosity of calcite blocks thus prepared had 36.8–48.1% depending on molding pressure between 1 MPa and 5 MPa. We concluded that the present method may be useful for the preparation of bone substitutes or the preparation of source material for bone substitutes since this method succeeded in fabricating a low-crystalline, and thus a highly reactive, porous calcite block.     

Solvent‐Assisted Micromolding of Biohybrid Hydrogels to Maintain Human Hematopoietic Stem and Progenitor Cells Ex Vivo

Array‐format cell‐culture carriers providing tunable matrix cues are instrumental in current cell biology and bioengineering. A new solvent‐assisted demolding approach for the fabrication of microcavity arrays with very small feature sizes down to single‐cell level (3 µm) of very soft biohybrid glycosaminoglycan–poly(ethylene glycol) hydrogels (down to a shear modulus of 1 kPa) is reported. It is further shown that independent additional options of localized conjugation of adhesion ligand peptides, presentation of growth factors through complexation to gel‐based glycosaminoglycans, and secondary gel deposition for 3D cell embedding enable a versatile customization of the hydrogel microcavity arrays for cell culture studies. As a proof of concept, cell‐instructive hydrogel compartment arrays are used to analyze the response of human hematopoietic stem and progenitor cells to defined biomolecular and spatial cues.     

Photodetachable Adhesion

Peeling from strong adhesion is hard, and sometimes painful. Herein, an approach is described to achieve both strong adhesion and easy detachment. The latter is triggered, on‐demand, through an exposure to light of a certain frequency range. The principle of photodetachable adhesion is first demonstrated using two hydrogels as adherends. Each hydrogel has a covalent polymer network, but does not have functional groups for bonding, so that the two hydrogels by themselves adhere poorly. The two hydrogels, however, adhere strongly when an aqueous solution of polymer chains is spread on the surfaces of the hydrogels and is triggered to form a stitching polymer network in situ, in topological entanglement with the pre‐existing polymer networks of the two hydrogels. The two hydrogels detach easily when the stitching polymer network is so functionalized that it undergoes a gel–sol transition in response to a UV light. For example, two pieces of alginate–polyacrylamide hydrogels achieve adhesion energies about 1400 and 10 J m^?2, respectively, before and after the UV radiation. Experiments are conducted to study the physics and chemistry of this strong and photodetachable adhesion, and to adhere and detach various materials, including hydrogels, elastomers, and inorganic solids.     

Radiation synthesis of PVP/alginate hydrogel containing nanosilver as wound dressing

Hydrogels with polyvinyl pyrrolidone (PVP) and alginate were synthesized and silver nanoparticles were incorporated in hydrogel network using gamma radiation. PVP (10?and 15?%) in combination with 0.5?and 1?% alginate was gamma irradiated at different doses of 25?and 40?kGy. Maximum gel percent was obtained with 15?% PVP in combination with 0.5?% alginate. The fluid absorption capacity for the PVP/alginate hydrogels was about 1881–2361?% at 24?h. Moisture vapour transmission rate (MVTR) of hydrogels containing nanosilver at 24?h was 278.44?g/(m²h). The absorption capacity and moisture permeability of the PVP/alginate–nanosilver composite hydrogel dressings show the ability of the hydrogels to prevent fluid accumulation in exudating wound. The hydrogels containing nanosilver demonstrated strong antimicrobial effect and complete inhibition of microbial growth was observed with 70?ppm nanosilver dressings. PVP/alginate hydrogels containing nanosilver with efficient fluid handling capacity and antimicrobial activity was found suitable for use as wound dressing.     

Spontaneous patterning and nanoparticle encapsulation in carboxymethylcellulose/alginate/dextran hydrogels and sponges

Novel polysaccharide sponges containing a network of capillaries and pore structures have been prepared by freeze drying of Ca²⁺ ion cross-linked sodium carboxymethylcellulose/sodium alginate hydrogels with or without addition of dextran. The iontropic gels consisted of capillaries, 5 to 40 µm in width, which comprised small pores, 1–25 µm in size. Gold, Fe₃O₄ or TiO₂ nanoparticles were encapsulated in the patterned gels and the mechanical strength of the resulting sponges investigated.     

Oriented Arrangement: The Origin of Versatility for Porous Graphene Materials

Macroscopic porous graphene materials composed of graphene sheets have demonstrated their advantageous aspects in diverse application areas. It is essential to maximize their excellent performances by rationally controlling the sheet arrangement and pore structure. Bulk porous graphene materials with oriented pore structure and arrangement of graphene sheets are prepared by marrying electrolyte‐assisted self‐assembly and shear‐force‐induced alignment of graphene oxide sheets, and the super elasticity and anisotropic mechanical, electrical, and thermal properties induced by this unique structure are systematically investigated. Its application in pressure sensing exhibits ultrahigh sensitivity of 313.23 kPa^?1 for detecting ultralow pressure variation below 0.5 kPa, and it shows high retention rate for continuously intercepting dye molecules with a high flux of ≈18.7 L m^?2 h^?1 bar^?1 and a dynamic removal rate of 510 mg m^?2 h^?1.     

Physical and mechanical properties of SEBS/polypropylene nanocomposites reinforced by nano CaCO3

In present study, styrene‐b‐(ethylene‐co‐butylenes)‐b‐styrene triblock copolymer (SEBS) and polypropylene (PP) are prepared. This mixing is followed by adding 3, 5 and 10 wt% of nano CaCO₃. The morphology and thermal behavior of PP/SEBS/nano‐CaCO₃ compounds are characterized by different methods. Scanning electron microscopy micrographs of cryo‐fractured PP/SEBS/nano‐CaCO₃ nanocomposites show that with increasing nano‐CaCO₃ loading, the aggregation becomes worse. However, followed by adding 5 wt% nano‐CaCO₃ into PP/SEBS nanocomposites, nano‐CaCO₃ is homogeneously dispersed in PP matrix. The photomicrograph of transmission electron microscopy confirms that SEBS/PP/nano‐CaCO₃ nanocomposites are formed, as low aggregations of calcium carbonate were well‐dispersed in polymer matrix. With a rise in nano‐filler content, the tensile and impact strength of PP/SEBS/CaCO₃ nanocomposite are fixed while the elastic modulus of PP/SEBS nanocomposites increases followed by adding nano‐CaCO₃ to polymer blend, which could be due to the acceptable nano‐CaCO₃ dispersion quality.     

Porous bioactive calcium carbonate implants processed by starch consolidation

Macroporous calcium carbonate (CaCO₃) materials with porous structures suitable for implantation purposes were prepared in the present work. A new “direct consolidation” technique that uses starch granules as consolidator agent and as pore formers, combined with other larger organic inclusions, enabled us to tailor the porous microstructure for the intended application. Pore sizes as large as several hundreds of micrometers could be generated without matrix cracking, due to the high solid loading of the starting suspensions.The macroporous CaCO₃ bodies fabricated exhibit an accentuated bioactivity even for short soaking time periods. The crystalline calcium phosphate phases precipitate preferentially in the pores, pore boundaries, or in other strained sites at the surface of the samples.     

Influence of CaCO3 pore-forming agent on porosity and thermal conductivity of cellulose acetate materials prepared by non-solvent induced phase separation

Thermal insulation materials with a low thermal conductivity are indeed demanded because they play the main role in the enhancement of energy conservation in various industries, especially lightweight constructive materials. Therefore, tubular cellulose acetate (CA) materials were firstly prepared by non-solvent induced phase separation (NIPS). In the NIPS process, the concentration of CA was varied in a range of 20–40?wt%. Also, the temperature of water used as a non-solvent was studied from 5?°C up to 50?°C. According to the FE-SEM results, the 30?wt% CA solution at 20?°C provides tubular CA materials with a higher porous structure than an original CA material but the pore size is quite larger than the mean free path of air leading to achieve a material with high thermal conductivity. To overwhelmed such a problem, the calcium carbonate (CaCO₃) was used to be pore forming agents in order to decrease pore size of prepared CA sheet materials. The amount of CaCO₃ particles in the CA sheet materials was varied as 50 and 60?wt% to investigate its effect on porosity and thermal conductivity of the prepared materials. As the results, the CA sheet materials prepared using NIPS process and after removing 60?vol% CaCO₃ have an enlargement of pores with a size lower than the mean free path of air. They exhibit high porous materials leading to the reduction of their thermal conductivity, which has the lowest value about 0.043?W/mK. Consequently, the CA materials are potentially applied for constructive materials in order to reduce energy consumption in buildings.     

Hydrophobic Hydrogels with Fruit‐Like Structure and Functions

Normally, a polymer network swells in a good solvent to form a gel but the gel shrinks in a poor solvent. Here, an abnormal phenomenon is reported: some hydrophobic gels significantly swell in water, reaching water content as high as 99.6 wt%. Such abnormal swelling behaviors in the nonsolvent water are observed universally for various hydrophobic organogels containing omniphilic organic solvents that have a higher affinity to water than to the hydrophobic polymers. The formation of a semipermeable skin layer due to rapid phase separation, and the asymmetric diffusion of water molecules into the gel driven by the high osmotic pressure of the organic solvent–water mixing, are found to be the reasons. As a result, the hydrophobic hydrogels have a fruit‐like structure, consisting of hydrophobic skin and water‐trapped micropores, to display various unique properties, such as significantly enhanced strength, surface hydrophobicity, and antidrying, despite their extremely high water content. Furthermore, the hydrophobic hydrogels exhibit selective water absorption from concentrated saline solutions and rapid water release at a small pressure like squeezing juices from fruits. These novel functions of hydrophobic hydrogels will find promising applications, e.g., as materials that can automatically take the fresh water from seawater.     

Effect of starting PMMA content on microstructure and properties of gel casting BN/Si3N4 ceramics with spherical-shaped pore structures

By gel casting with polymethylmethacrylate microbeads (PMMA) as pore-forming agent, porous boron nitride/silicon nitride (BN/Si₃N₄) composite ceramics were successfully prepared. The obtained ceramic shows bimodal hierarchical structures that composed of spherical-shaped micro pores depending on PMMA content and irregular sub-micro pores formed by the stacking of ceramic particles. Porosity of the porous BN/Si₃N₄ ceramics can be well controlled from 53.0 to 60.6 % by the PMMA content from 10 to 40 wt%, as well as the mechanical and dielectric properties. Effect of PMMA content on phase composition and the relationship between microstructure and the basic properties of the porous BN/Si₃N₄ ceramics was discussed in detail. Microstructure analysis reveals that the sub-micro pores acted as channels between micro pores. BN particles have a relatively denser distribution on the wall of spherical-shaped micro pores with a window between micro and sub-micro pores, and resulting in a half-closed micro pore structure, which is meaningful for material design with concentration of BN particles on the wall of pore structure.