Morphology and properties of foamed high crystallinity PEEK prepared by high temperature thermally induced phase separation.

Polyetheretherketone (PEEK) is a high-performance semi-crystalline thermoplastic polymer with outstanding mechanical properties, high thermal stability, resistance to most common solvents, and good biocompatibility. A high temperature thermally induced phase separation technique was used to produce PEEK foams with controlled foam density from PEEK in 4-phenylphenol (4PPH) solutions. Physical and mechanical properties, foam and bulk density, surface area, and pore morphology of foamed PEEK were characterized and the role of PEEK concentration and cooling rate was investigated. Porous PEEK with densities ranging from 110 to 360 kg/m3 with elastic moduli and crush strength ranging from 13 to 125 MPa and 0.8 to 7 MPa, respectively, was produced.

An approach for the scalable production of macroporous polymer beads.

A tubular co-flow reactor to produce macroporous polymer beads by polymerization of medium and high internal phase emulsion (M/HIPE) templates was developed. This reactor allows for improved production rates compared to tubing based microfluidic devices. Water-in-oil (W/O) M/HIPEs, containing methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA) monomers in the continuous phase, were injected into a re-circulating carrier phase. The continuous phase of the emulsion droplets was UV polymerized in situ, resulting in polyM/HIPE beads. The emulsion composition was adjusted to produce poly(MMA-co-EGDMA) porous polymer beads with a protective crust and an interconnected internal pore structure. HCl loaded beads were produced by adding the active ingredient into the dispersed emulsion phase, leading to HCl encapsulation in the porous structure of the beads after polymerization. Even after exposure to ambient conditions for 24 h, 60% of the HCl remained in the beads, indicating good encapsulation efficiencies. Thus, it is possible to use such macroporous beads as delivery vehicles.

High-Performance Polymer Foams by Thermally Induced Phase Separation.

Macroporous, low-density polyetheretherketone, polyetherketoneketone, and polyetherimide foams are produced using a high-temperature, thermally induced phase separation method. A high-boiling-point solvent, which is suitable to dissolve at least 20 wt% of these high-performance polymers at temperatures above 250 °C, is identified. The foam morphology is controlled by the cooling procedure. The resulting polymer foams have porosities close to 80% with surface areas up to 140 m2 g-1 and elastic moduli up to 97 MPa.

Emulsion and Foam Templating-Promising Routes to Tailor-Made Porous Polymers.

Emulsions, foams, and foamed emulsions have been used successfully as templates for the synthesis of macroporous polymers. Based on this knowledge this Minireview presents strategies to use, optimise, and upscale these templating methods to synthesise tailor-made porous polymers. The uniqueness of such polymers lies in the ability to tailor their structures and, therefore, their properties. However, systematic studies on structure-property relations are lacking mainly because the templating scientific community is "split into two": the polydisperse and monodisperse camps. Thus, it is time to build a bridge between the camps, that is, to synthesise porous polymers with very different structures from the same precursors to determine the relationship between the structure and the properties.

Porous Bioactive Nanofibers via Cryogenic Solution Blow Spinning and Their Formation into 3D Macroporous Scaffolds.

There is increasing focus on the development of bioactive scaffolds for tissue engineering and regenerative medicine that mimic the native nanofibrillar extracellular matrix. Solution blow spinning (SBS) is a rapid, simple technique that produces nanofibers with open fiber networks for enhanced cell infiltration. In this work, highly porous bioactive fibers were produced by combining SBS with thermally induced phase separation. Fibers composed of poly(d,l-lactide) (PLA) and dimethyl carbonate were sprayed directly into a cryogenic environment and subsequently lyophilized, rendering them highly porous. The surface areas of the porous fibers were an order of magnitude higher in comparison with smooth control fibers of the same diameter (43.5 m2·g-1 for porous fibers produced from 15% w/v PLA in dimethyl carbonate) and exhibited elongated surface pores. Macroporous scaffolds were produced by spraying water droplets simultaneously with fiber formation, creating a network of fibers and ice microspheres, which act as in situ macroporosifiers. Subsequent lyophilization resulted in three-dimensional (3D) scaffolds formed of porous nanofibers with interconnected macropores due to the presence of the ice spheres. Nanobioactive glass was incorporated for the production of 3D macroporous, bioactive, therapeutic-ion-releasing scaffolds with potential applications in non-load-bearing bone tissue engineering. The bioactive characteristics of the fibers were assessed in vitro through immersion in simulated body fluid. The release of soluble silica ions was faster for the porous fibers within the first 24 h, with confirmation of hydroxyapatite on the fiber surface within 84 h.

Antagonistic effects between magnetite nanoparticles and a hydrophobic surfactant in highly concentrated Pickering emulsions.

Herein we present a systematic study of the antagonistic interaction between magnetite nanoparticles (Fe3O4) and nonionic hydrophobic surfactant in Pickering highly concentrated emulsions. Interfacial tension measurements, phase behavior, and emulsion stability studies, combined with electron microscopy observations in polymerized systems and magnetometry, are used to support the discussion. First, stable W/O highly concentrated emulsions were obtained using partially hydrophobized magnetite nanoparticles. These emulsions experienced phase separation when surfactant is added at concentrations as low as 0.05 wt %. Such phase separation arises from the preferential affinity of the surfactant for the nanoparticle surfaces, which remarkably enhances their hydrophobicity, leading to a gradual desorption of nanoparticles from the interface. W/O emulsions were obtained at higher surfactant concentrations, but in this case, these emulsions were mainly stabilized by surfactant molecules. Therefore, stable emulsions could be prepared in two separate ranges of surfactant concentrations. After polymerization, low-density macroporous polymers were obtained, and the adsorption and aggregation of nanoparticles was analyzed by transmission electron microscopy. The progressive displacement of the nanoparticles was revealed: from the oil-water interface, in which aggregated nanoparticles were adsorbed, forming dense layers, to the continuous phase of the emulsions, where small nanoparticle aggregates were randomly dispersed. Interestingly, the results also show that the blocking temperature of the iron oxide superparamagnetic nanoparticles embedded in the macroporous polymers could be modulated by appropriate control of the concentrations of both surfactant and nanoparticles.

Hierarchical polymerized high internal phase emulsions synthesized from surfactant-stabilized emulsion templates.

In building construction, structural elements, such as lattice girders, are positioned specifically to support the mainframe of a building. This arrangement provides additional structural hierarchy, facilitating the transfer of load to its foundation while keeping the building weight down. We applied the same concept when synthesizing hierarchical open-celled macroporous polymers from high internal phase emulsion (HIPE) templates stabilized by varying concentrations of a polymeric non-ionic surfactant from 0.75 to 20 w/vol %. These hierarchical poly(merized)HIPEs have multimodally distributed pores, which are efficiently arranged to enhance the load transfer mechanism in the polymer foam. As a result, hierarchical polyHIPEs produced from HIPEs stabilized by 5 vol % surfactant showed a 93% improvement in Young's moduli compared to conventional polyHIPEs produced from HIPEs stabilized by 20 vol % of surfactant with the same porosity of 84%. The finite element method (FEM) was used to determine the effect of pore hierarchy on the mechanical performance of porous polymers under small periodic compressions. Results from the FEM showed a clear improvement in Young's moduli for simulated hierarchical porous geometries. This methodology could be further adapted as a predictive tool to determine the influence of hierarchy on the mechanical properties of a range of porous materials.

Macroporous polymers obtained in highly concentrated emulsions stabilized solely with magnetic nanoparticles.

Magnetic macroporous polymers have been successfully prepared using Pickering high internal phase ratio emulsions (HIPEs) as templates. To stabilize the HIPEs, two types of oleic acid-modified iron oxide nanoparticles (NPs) were used as emulsifiers. The results revealed that partially hydrophobic NPs could stabilize W/O HIPEs with an internal phase above 90%. Depending upon the oleic acid content, the nanoparticles showed either an arrangement at the oil-water interface or a partial dispersion into the oil phase. Such different abilities to migrate to the interface had significant effects on the maximum internal phase fraction achievable and the droplet size distribution of the emulsions. Highly macroporous composite polymers were obtained by polymerization in the external phase of these emulsions. The density, porosity, pore morphology and magnetic properties were characterized as a function of the oleic acid content, concentration of NPs, and internal phase volume of the initial HIPEs. SEM imaging indicated that a close-cell structure was obtained. Furthermore, the composite materials showed superparamagnetic behavior and a relatively high magnetic moment.

Macroporous Polymers with Hierarchical Pore Structure from Emulsion Templates Stabilised by Both Particles and Surfactants.

Inspired by natural porous materials, such as wood, bamboo and spongy bone consisting of individual structural units that are hierarchically arranged to optimise mechanical properties such as strength and toughness, synthetic macroporous polymers with enhanced physical properties were created by emulsion templating. Hierarchical poly(merised) high internal phase emulsions (HIPE) were created from HIPEs stabilised simultaneously by particles and a surfactant. In these HIPEs, surfactant stabilised and particle stabilised water droplets coexist, which upon polymerisation of the minority oil phase gives rise to macroporous polymers with a hierarchical pore structure. An improvement of the mechanical properties of our hierarchically structured macroporous polymers at equal porosity was observed, due to a more efficient packing of pores in a configuration that improves mechanical strength despite the presence of interconnecting pore throats. Moreover, the permeability of the hierarchically structured polyHIPEs are exceeding those measured for conventional polyHIPEs made from surfactant only stabilised HIPEs.

High-porosity macroporous polymers sythesized from titania-particle-stabilized medium and high internal phase emulsions.

Particle-stabilized high internal phase emulsions have been used to synthesize tough and very high porosity macroporus polymers with a closed-cell pore structure. In this study, we show that Pickering water-in-oil emulsion templates with up to an 85 vol % internal phase can be stabilized by only 1 wt % of titania particles with their surfaces suitably modified by the adsorption of 3.5 +/- 0.5 wt % oleic acid. The pore structure and mechanical properties of the resulting macroporous polymers were tailored by altering the internal phase volume ratio of the emulsion template and the titania particle concentration used to stabilize the emulsion templates. The pore size and pore size distributions increase with increasing internal phase volume of the emulsion template as well as decreasing titania particle concentration used to stabilize the emulsion template. The mechanical properties, namely, Young's modulus and the crush strength of the macroporous polymers, increased with decreasing porosity and increasing foam density. The toughest macroporous polymer had the lowest porosity but also the smallest pore size and narrowest pore size distribution.

Particle-stabilized surfactant-free medium internal phase emulsions as templates for porous nanocomposite materials: poly-Pickering-Foams.

We report on the successful use of particle-stabilized Medium Internal Phase Emulsion (MIPE) templates for the synthesis of porous polymer foams. In this case, carbon nanotubes (CNTs) were used to stabilize the minority phase as the continuous phase, through adsorption at the interface. The addition of the CNTs not only provides processing advantages (no need for traditional non-ionic molecular surfactants) but also enhances the mechanical and electrical properties of the final polyFoams. This approach allows the manufacture of both closed- and open-celled porous polymer foams in a one-pot process with porosities up to 66%.

High internal phase emulsion templates solely stabilised by functionalised titania nanoparticles.

Porous polymer foams (poly-Pickering-HIPEs) have been synthesised from stable high internal phase emulsion templates solely stabilised by low concentrations of functionalised titania nanoparticles.

A new route to carbon black filled polyHIPEs.

A series of carbon black filled polyHIPEs was synthesised following a new preparation protocol. 1 wt% carbon black was dispersed in the monomer mixture. In order to enhance the stability of the suspension, polymer grafting of carbon black was performed by initiating the polymerisation prior to emulsifying the formulation. All of the carbon black filled polymer foams synthesised the new preparation protocol have the characteristics usually observed for polyHIPEs. Carbon black particles are incorporated into the pore walls without affecting the pore structure of the polyHIPEs. The new preparation protocol positively influenced the properties of the resulting polyHIPEs namely the pore interconnectivity is increased and a water permeability of up to 2.3 D is achieved.