Emulsion Templating Research Articles

Design and engineering of 3D plasmonic superstructure based on Pickering emulsion templates for surface-enhanced Raman spectroscopy applications in chemical and biomedical sensing

The integration of Pickering emulsion as a versatile template facilitates the assembly of nanoscale and microscale NPs, leading to the formation of intricate 3D superstructures. These superstructures exhibit collective properties, including optical, electric, and catalytic functionalities, surpassing individual building block. This review comprehensively explores the design and engineering principles behind the creation of these multifaceted superstructures. The exploration begins with the fundamental aspects of surface chemistry governing nanoparticles, a crucial factor in directing their assembly behavior at the curved liquid–liquid emulsion interface. Emphasis is placed on understanding emulsion stability, a pivotal element guiding the formation of stable 3D architectures. The discussion extends to unraveling the underlying mechanisms promoting the formation of these 3D superstructures. The focus lies in elucidating the optical functionalities of these superstructures, particularly in the context of surface-enhanced Raman spectroscopy application. The surveyed literature showcases diverse Pickering emulsion-based strategies employed in the assembly of plasmonic nanoparticles into intricate superstructures, offering controlled architectures and unlocking unique potentials for chemical and biochemical sensing.

Investigating the Potential of CO2 Nanobubble Systems for Enhanced Oil Recovery in Extra-Low-Permeability Reservoirs.

Carbon Capture, Utilization, and Storage (CCUS) stands as one of the effective means to reduce carbon emissions and serves as a crucial technical pillar for achieving experimental carbon neutrality. CO2-enhanced oil recovery (CO2-EOR) represents the foremost method for CO2 utilization. CO2-EOR represents a favorable technical means of efficiently developing extra-low-permeability reservoirs. Nevertheless, the process known as the direct injection of CO2 is highly susceptible to gas scrambling, which reduces the exposure time and contact area between CO2 and the extra-low-permeability oil matrix, making it challenging to utilize CO2 molecular diffusion effectively. In this paper, a comprehensive study involving the application of a CO2 nanobubble system in extra-low-permeability reservoirs is presented. A modified nano-SiO2 particle with pro-CO2 properties was designed using the Pickering emulsion template method and employed as a CO2 nanobubble stabilizer. The suitability of the CO2 nanobubbles for use in extra-low-permeability reservoirs was evaluated in terms of their temperature resistance, oil resistance, dimensional stability, interfacial properties, and wetting-reversal properties. The enhanced oil recovery (EOR) effect of the CO2 nanobubble system was evaluated through core experiments. The results indicate that the CO2 nanobubble system can suppress the phenomena of channeling and gravity overlap in the formation. Additionally, the system can alter the wettability, thereby improving interfacial activity. Furthermore, the system can reduce the interfacial tension, thus expanding the wave efficiency of the repellent phase fluids. The system can also improve the ability of CO2 to displace the crude oil or water in the pore space. The CO2 nanobubble system can take advantage of its size and high mass transfer efficiency, among other advantages. Injection of the gas into the extra-low-permeability reservoir can be used to block high-gas-capacity channels. The injected gas is forced to enter the low-permeability layer or matrix, with the results of core simulation experiments indicating a recovery rate of 66.28%. Nanobubble technology, the subject of this paper, has significant practical implications for enhancing the efficiency of CO2-EOR and geologic sequestration, as well as providing an environmentally friendly method as part of larger CCUS-EOR.

Eco-friendly, highly interpenetrated and slightly swollen pHEMA hydrogel foam for durable underwater superoleophobicity and emulsion separation

Despite the emergence of hydrogels as ideal candidates for preparing the superhydrophilic materials for emulsion separation, their structural stability and swelling still hinder their long-term use, mainly due to structure defects after swelling. Herein, differing from the common modification, the eco-friendly poly 2-hydroxyethyl methacrylate (pHEMA) hydrogel foam was designed and synthesized via a one-step strategy by using the high internal phase emulsion (HIPE) template method, which endowed it with a highly interpenetrated porous structure. Unlike the normal swellable hydrogels such as poly(N-isoproplyacrylamide) (PNIPAM) hydrogel, or modified hydrogel coatings, the pHEMA hydrogel foam displayed stable structure and underwater superoleophobicity after 20 d of immersion in water. The pHEMA hydrogel foam could separate different kinds of highly surfactant-stabilized oil-in-water (O/W) emulsions with a high separation efficiency of 99.3% for liquid paraffin emulsion obtained solely under gravity-driven. Additionally, it exhibited excellent antifouling performance and long-term acid/alkali tolerance over 100 h without decrease in emulsion separation efficiency (98.0%, oil/water ratio of 99:1) and permeation flux (over 2000 L·m−2·h−1) attributed to its stable bulky structure. Moreover, the pHEMA hydrogel foam demonstrated high cell viability of 96.87% and 95.96% after culturing the 3T3 clone A31 cells in the pHEMA hydrogel foam for 24 h and 48 h, respectively, indicating good biocompatibility. Hence, our work provides a new design to develop an eco-friendly bulk hydrogel foam that achieves stable structure and performance for emulsion separation.

Macroporous lignin adsorbents: A bio-sourced tool kit to defuse the Cr(VI) threat in wastewater

Amino-functionalised (triethylenetetramine) macroporous lignin monoliths were produced by curing an emulsion template containing untreated kraft black liquor with oxirane-crosslinkers. These lignin-based adsorbents were tested for the removal of Cr(VI) from water and synthetic waste water. A one-pot rout for their production is presented and their chemical and physical nature was investigated. Produced monoliths were tested in static and continuous adsorption experiments and chromium removal from water and synthetic wastewater was quantified via UV–vis spectroscopy. The nitrogen content of functionalised lignin monoliths reached up to 5.1 wt%, leading to adsorption capacities of up to 897 mg/g at pH = 2, as compared to non-functionalised lignin monoliths with a maximum adsorption capacity of 117 mg/g. The adsorption capacity of lignin monoliths produced is amongst the highest of bio-based materials presented in the literature.

Fabrication of thermo-responsive microcapsule pesticide delivery system from maleic anhydride-functionalized cellulose nanocrystals-stabilized pickering emulsion template

The overuse of pesticides has shown their malpractices. Novel and sustainable formulations have consequently attracted abundant attention but still appear to have drawbacks. Here, we use a maleic anhydride-functionalized cellulose nanocrystals-stabilized Pickering emulsions template to prepare thermo-responsive microcapsules for a pesticide delivery system via radical polymerization with N-isopropyl acrylamide. The microcapsules (MACNCs-g-NIPAM) are characterized by the microscope, SEM, FTIR, XRD, TG-DTG, and DSC techniques. Imidacloprid (IMI) is loaded on MACNCs-g-NIPAM to form smart release systems (IMI@MACNCs-g-NIPAM) with high encapsulation efficiency (~88.49%) and loading capability (~55.02%). The IMI@MACNCs-g-NIPAM present a significant thermo-responsiveness by comparing the release ratios at 35°C and 25°C (76.22% vs 50.78%). It also exhibits advantages in spreadability, retention and flush resistance on the leaf surface compared with the commercial IMI water-dispersible granules (CG). IMI@MACNCs-g-NIPAM also manifest a significant advantage over CG (11.12 mg/L vs 38.90 mg/L for LC50) regarding activity tests of targeted organisms. In addition, IMI@MACNCs-g-NIPAM has shown excellent biocompatibility and low toxicity. All the benefits mentioned above prove the excellent potential of IMI@MACNCs-g-NIPAM as a smart pesticide formulation.

Natural shellac-based microcapsules as lipase carriers for recyclable efficient Pickering interfacial biocatalysis

Enzyme is an important class of catalyst. However, the efficiency of enzyme-catalyzed reactions is constrained by the limited contact between the enzyme and its substrate. In this study, to overcome this challenge, lipase-loaded microcapsules were prepared from natural shellac and nanoparticles using the emulsion template method. These microcapsules can perform dual roles as stabilizers and enzyme carriers to construct a water-in-oil Pickering interfacial biocatalytic system. The results showed that the hydrolytic conversion of the microcapsules could reach 90% within 20 min, which was significantly higher than that of the traditional biphasic system. The catalytic activity was influenced by the oil-to-water volume ratio and the microcapsule content. The microcapsules remained highly catalytic efficiency even after storage for three months or seven cycles of reuse. These microcapsules were prepared without the use of any cross-linkers or harsh solvents. This green and efficient catalytic system has great application prospects in the food industry.

Preparation of Graphene Oxide/Polymer Hybrid Microcapsules via Photopolymerization for Double Self-Healing Anticorrosion Coatings.

In this work, graphene oxide (GO)/polymer hybrid microcapsule-loaded self-healing agents were prepared via the combination of the emulsion template method and photopolymerization technology. The incorporation of GO in the microcapsule shell not only improved the impermeability, mechanical property, and solvent resistance property of the microcapsules significantly but also endowed the microcapsules with photothermal conversion property. By incorporating GO/polymer hybrid microcapsules in water-borne epoxy resin, a novel kind of anticorrosion coating with a double self-healing property was successfully fabricated. When the coating was scratched, the linseed oil (LO) encapsulated in the microcapsules could fill the crack, and the photothermal conversion property of GO could promote the molecular chain movement of the damaged area under near-infrared (NIR) irradiation to realize the close of the crack. Based on the filling of LO and photothermal conversion-induced scratch narrowing, the "filling" and "close" double self-healing effect can be realized under temporal NIR irradiation, which could lead to the complete recovery of the scratched coating. The |Z|f=0.1Hz value of the damaged coating with GO/polymer microcapsules after double healing was comparable to that of the intact coating, which was about 4 orders of magnitude higher than that of the scratched blank coating and single self-healing coating. As to the neutral salt spray test, the scratched blank coating failed in protection after 100 h, while the healed composite coating did not show any corrosion after 300 h.

Quinizarin-based photoactive porous polymers from emulsion templates: Monoliths versus membranes in photobactericidal applications

The increasing challenge of antimicrobial resistance and the persistent threat of infectious diseases are strong incentives for development of novel materials that effectively and sustainably combat bacterial proliferation. Macroporous materials contribute to this endeavor, but the reported antibacterial porous polymers rely on the release of antibacterial agents, which carries the risk that their efficacy will diminish over time. This work reports a facile synthesis by emulsion templating polymerization of innovative photo-bactericidal macroporous polymers functionalized by a quinizarin photosensitizer that generates antibacterial reactive oxygen species under visible light. In brief, a monomethacrylated quinizarin (QMA) derivative, known for its ability to generate bactericidal singlet oxygen upon visible light irradiation, is copolymerized with a bio-based acrylated epoxidized soybean oil (AESO) under high internal phase emulsion (HIPE) conditions, resulting in 3D-interconnected quinizarin-functionalized macroporous monoliths. The QMA-functionalized polyHIPEs are also structured into membranes by photocuring thin layers of HIPEs to increase their external surface and promote interaction with light. Photobleaching tests show the ability of these materials to generate bactericidal singlet oxygen. Antibacterial tests also demonstrate the sustained antibacterial efficacy of the QMA-based porous membranes, providing a promising avenue for the development of next-generation antibacterial materials.

Superhydrophobic hierarchically porous polymer modified by epoxidized soybean oil and stearic acid synergy for highly efficient sustainable oil-water separation

Environmental and human health are adversely affected by oil and organic wastewater pollution of water resources. However, it has always been difficult to develop an adsorption material that is multifunctional and able to remove multiple pollutants. A new hierarchically porous polymers have been synthesized using high internal phase emulsions (HIPE) template, and further modification by a physico-chemical synergy method of epoxidized soybean oil (ESO) coupled with stearic acid (STA). The modified polyHIPE (E/S-polyHIPE) exhibit superhydrophobic properties with water contact angle as high as 161.12°, and exhibit excellent robustness and chemical resistance. Oil/water mixtures can be separated using E/S-polyHIPE with a high separation efficiency (99.00–99.42 %), and it has a high oil absorption capacity (16–28 g/g) for a wide range of oil types. After 15 separation cycles, the E/S-polyHIPE exhibits excellent separation efficiency (＞ 97 %) because of its promising mechanical durability. E/S-polyHIPE still performed outstanding oil absorption capacity for floating oil, underwater oil, and emulsified oil, also it can be used as a continuous in-situ oil-water separator. An innovative approach to the fabrication of a sustainable multifunctional absorbent for oily wastewater is presented in this work, which illustrates the great potential for large-scale practical application.

Tailored Hollow Mesoporous Carbon Nanospheres from Soft Emulsions Enhance Kinetics in Sodium Batteries.

Mesoporous materials endowed with a hollow structure offer ample opportunities due to their integrated functionalities; however, current approaches mainly rely on the recruitment of solid rigid templates, and feasible strategies with better simplicity and tunability remain infertile. Here, we report a novel emulsion-driven coassembly method for constructing a highly tailored hollow architecture in mesoporous carbon, which can be completely processed on oil-water liquid interfaces instead of a solid rigid template. Such a facile and flexible methodology relies on the subtle employment of a 1,3,5-trimethylbenzene (TMB) additive, which acts as both an emulsion template and a swelling agent, leading to a compatible integration of oil droplets and composite micelles. The solution-based assembly process also shows high controllability, endowing the hollow carbon mesostructure with a uniform morphology of hundreds of nanometers and tunable cavities from 0 to 130 nm in diameter and porosities (mesopore sizes 2.5-7.7 nm; surface area 179-355 m2 g-1). Because of the unique features in permeability, diffusion, and surface access, the hollow mesoporous carbon nanospheres exhibit excellent high rate and cycling performances for sodium-ion storage. Our study reveals a cooperative assembly on the liquid interface, which could provide an alternative toolbox for constructing delicate mesostructures and complex hierarchies toward advanced technologies.

Integrating phase change materials and spontaneous emulsification: In-situ particle formation at oil–water interfaces

The properties of interfaces between two immiscible fluids, as engineered by interfacial materials, are crucial in various processes, including printing, coating, and multiphase flow in porous media. Interfacial materials, such as surface-active molecules and particles can be adsorbed from the bulk fluid phases to the interface or formed in-situ at the interface. In this study, we develop a methodology to form stiff silica-based particles in situ at the oil–water interface through coupling of phase change materials and spontaneous emulsification. This process is demonstrated by introducing a heptane micellar solution that spontaneously generates a microemulsion phase when in contact with an aqueous phase. Micron-sized droplets, consisting of an aqueous silicate precursor mixture, undergo a sol–gel reaction, leading to the generation of colloidal-sized particles. SEM micrographs and confocal images of dried samples, taken from the aqueous-heptane interface, reveal the formation of particles post-gelation. The in-situ formation of stiff particles can be characterized through the dynamics of evaporation, where a significant reduction in the heptane evaporation rate is observed. This particle generation method, utilizing phase change materials and emulsion templates, is spontaneous, energy-efficient, and enables particle formation at the interface at a predetermined time. Our findings offer valuable insights for the fabrication of interfacial materials with tailored properties and controlled timing.

Direct Vat‐Photopolymerization 3D Printing of Hierarchically Porous SiC Loaded with Co/Ni Based Catalysts by Using Pickering Emulsions

AbstractHierarchically porous silicon carbide (SiC) is an important catalyst support widely used in various gas and liquid catalytic processes. Conventional approaches to fabricate such SiC have limited design flexibility and separated catalyst‐loading step is necessitated. Herein, a one‐step, direct vat‐photopolymerization 3D printing of hierarchically porous SiC loaded with Co/Ni based catalyst is demonstrated with Pickering emulsion as feedstock for the first time. Compared with normal ceramic slurries, Pickering emulsion dramatically increases the cure depth (by 50%) and emulsion stability, which allow continuous printing of complex SiC structures with uniform pore morphology. The resultant hierarchical porous SiC offered ≈40% better mechanical strength as compared with non‐hierarchical counterpart. By dissolving metal salts into aqueous phase in Pickering emulsions, complex architected structures with Co or Ni/Co in situ loaded in SiC matrix are printed. The metal salts are then thermally converted into oxides or silicates as catalysts anchored on SiC, exhibiting excellent catalytic activity and reusability. The emulsion templating strategy holds great facility to load various highly attractive materials such as high entropy oxides or functional fillers whilst reaping the benefits of vat photopolymerization for a myriad of applications in catalysis, batteries, and structural supports.

Optimizing shear-thickening fluid microencapsulation with high-temperature pickering emulsion for enhanced impact-resistant materials

Combining shear-thickening fluid (STF) with matrix material enables the creation of high-performance materials with enhanced impact resistance. However, effectively preventing STF leakage and avoiding potential reactions between the fluid and the matrix material remain notable challenges. Encapsulating STF through emulsion templating offers a viable solution to these issues. Traditional emulsion templating methods require adding extra solvents to STF to counteract the hindrance of shear-thickening on emulsification, accompanied with increased costs and environmental pollution, and difficulties in maintaining the integrity of core components. In this study, we developed STF microcapsules using a novel high-temperature Pickering double emulsion technique. Our investigation into the rheological properties of molecular sieve/diols suspensions demonstrates that the shear thickening effect could be controlled by particle concentration, surface charge of particles and solvent viscosity. Octadecyltrimethoxysilane-modified fumed silica and fumed silica were utilized as stabilizers for STF-in-paraffin primary emulsions and STF-in-paraffin-in-propylene glycol secondary emulsions, respectively. As temperature increased, droplet sizes of the primary emulsion were significantly reduced. The Pickering emulsion approach effectively preserves the STF composition by forming robust barriers at the emulsion interface with silica particles. Typical STF microcapsules were incorporated into a silicone rubber matrix, the composites exhibited a significant decrease in resilience and an enhanced impact resistance with a 20.9% reduction in maximum impact force. This study is the first to suggest the application of the high-temperature Pickering double emulsion technique for the microencapsulation of STF, offering a practical and scalable method without diluting the STF, thereby ensuring the controllability of the core components.

Magnetic Hyperporous Elastic Material with Excellent Fatigue Resistance and Oil Retention for Oil-Water Separation.

Oily wastewater has caused serious threats to the environment; thus, high-performance absorbing materials for effective oil-water separation technology have attracted increasing attention. Herein, we develop a magnetic, hydrophobic, and lipophilic hyperporous elastic material (HEM) templated by high internal phase emulsions (HIPE), in which free-radical polymerization of butyl acrylate (BA) and divinylbenzene (DVB) is employed in the presence of poly(dimethylsiloxane) (PDMS), lecithin surfactant, and modified Fe3O4 nanoparticles. The adoption of the emulsion template with nanoparticles as both stabilizers and cross-linkers endows the HEM with biomimetic hierarchical open-cell micropores and elastic cross-linked networks, generating an oil absorbent with outstanding mechanical stability. Compressive fatigue resistance of the HEM is demonstrated to endure 2000 mechanical cycles without plastic deformation or strength degradation. By exploiting the synergistic effect of hierarchical structures and low-surface-energy components, the resulting HEM also possesses excellent and robust hydrophobicity (water contact angle of 164°) and good oil absorption capacity, in which Fe3O4 nanoparticles lead to convenient magnetically controlled oil recyclability as well. Notably, the unique biomimetic microporous structure demonstrates superior oil retention capacity (>95% at 1000 rpm and >60% at 10,000 rpm) over the state-of-the-art porous materials for a diverse variety of oils to reduce the risk of secondary oil leakage, along with good recoverability by squeezing owing to the excellent compression resilience. These excellent performances of our HEM provide broad prospects for practical applications in oil-water separation, energy conversion, and smart soft robotics.

Formation of Microcapsules of Pullulan by Emulsion Template Mechanism: Evaluation as Vitamin C Delivery Systems.

Pullulan is a polysaccharide that has attracted the attention of scientists in recent times as a former of edible films. On the other hand, its use for the preparation of hydrogels needs more study, as well as the formation of pullulan microcapsules as active ingredient release systems for the food industry. Due to the slow gelation kinetics of pullulan with sodium trimetaphosphate (STMP), capsules cannot be formed through the conventional method of dropping into a solution of the gelling agent, as with other polysaccharides, since the pullulan chains migrate to the medium before the capsules can form by gelation. Pullulan microcapsules have been obtained by using inverse water-in-oil emulsions as templates. The emulsion that acts as a template has been characterized by monitoring its stability and by optical microscopy, and the size of the emulsion droplets has been correlated with the size of the microcapsules obtained, demonstrating that it is a good technique for their production. Although some flocs of droplets form, these remain dispersed during the gelation process and two capsule size distributions are obtained: those of the non-flocculated droplets and the flocculated droplets. The microcapsules have been evaluated as vitamin C release systems, showing zero-order release kinetics for acidic pH and Fickian mechanism for neutral pH. On the other hand, the microcapsules offer good protection of vitamin C against oxidation during an evaluation period of 14 days.

A Journey from Structured Emulsion Templates to Multifunctional Aerogels

AbstractInterfacial jamming and assembly, facilitated by nanoparticle surfactant (NPS) complexation, demonstrate a remarkable efficacy in stabilizing multiphase systems, evident in structured liquid streams and structured Pickering emulsions. However, the utilization of structured liquid templates to tune multiple porosity levels of ultra‐flyweight aerogels is barely discussed. In this study, a structured Pickering emulsion is prepared through mixing an aqueous dispersion of graphene oxide (GO) with an organic (hexane) solution containing an active ligand. The emulsion is jetted into the same organic phase, resulting in “dual jamming”. This process produced worm‐like aerogels with porosity that can be precisely tailored at four different levels: i) voids between filaments, ii) cavities produced by evaporation of trapped hexane droplets, iii) pores generated from sublimation of water in the bulk of GO emulsion, and iv) microscopic regions trapped between GO flakes or fractures/holes within GO nanosheets. These aerogels exhibit ultra‐low density (1.67–2.3 mg cm−3), high compressibility, and shape recovery. The multi‐scale porosity, created by structural design, endows aerogels with a record‐level fluid sorption capacity (e.g., 615 g g−1 for chloroform). Additionally, the aerogels demonstrate an absorption‐dominant electromagnetic interference (EMI) shielding mechanism, achieving a remarkable specific EMI shielding (SSE/t) of 67 178 dB cm2 g−1.

Magnetic zinc oxide/silica microbeads for the photocatalytic degradation of azo dyes

Photocatalysis is a promising technique for the complete degradation of azo dyes that are present in wastewater. In this work, a new photocatalyst in the form of ZnO/Fe3O4/SiO2 hybrid microbeads was fabricated for the photocatalytic degradation of methylene blue. The microbeads were synthesised through self-assembly and subsequent agglomeration of nanoparticles within an aqueous phase of a water-in-oil emulsion template. Photocatalytic degradation experiments were conducted through exposure of a methylene blue solution to UV light. The hybrid microbeads performed better than ZnO powder at the same initial dye and ZnO concentration because of higher adsorption and degradation. The initial concentration of dye solution and catalyst dosage have a significant impact on the degradation. Higher degradation is seen with lower initial dye concentration and higher catalyst dosage. The presence of magnetic nanoparticles within the beads allows for their full recovery and reuse for degradation experiments. Complete degradation of dye was achieved using the new ZnO/Fe3O4/SiO2 microbeads.

Fabrication of microcapsules with graphene/organic hybrid shell based on Pickering emulsions for self‐healing anti‐corrosive coatings

AbstractDuring the utilization of organic coatings, microcracks may arise as a result of external environmental influences and inherent aging, significantly diminishing the coating's lifespan. In this study, we employed the Pickering emulsion template method combined with interfacial polymerization to fabricate graphene oxide/polyurethane/polyaniline (GO/PU/PANI) organic–inorganic hybrid shell microcapsules utilizing isophorone diisocyanate (IPDI) as the core material. The capsules exhibited an average particle diameter of 3.11 μm and an encapsulation rate of 78.19%. Subsequently, these prepared capsules were incorporated into a photocurable resin to obtain a self‐healing corrosion‐resistant coating. Scanning electron microscopy analysis demonstrated that even with just 5% addition of microcapsules, nearly complete repair could be achieved. The tensile strength and flexural strength of the self‐healing material containing 5% microcapsules were measured at 84.8 MPa and 193 MPa respectively. These values represented only a marginal decrease in tensile strength by 2.75% and flexural strength by 5.39%, compared to the substrate without capsule addition. Remarkably, after immersing the repaired coating in a NaCl solution with a concentration of 5 wt% for up to 250 hours, the alternating current impedance value remained stable at approximately 6.9 × 105 Ω·cm2. This outstanding corrosion resistance can be attributed to synergistic effects between PANI and IPDI within the coating system, thereby expanding its potential applications under harsh conditions.

Functionally Gradient Macroporous Polymers: Emulsion Templating Offers Control over Density, Pore Morphology, and Composition.

Gradient macroporous polymers were produced by polymerization of emulsion templates comprising a continuous monomer phase and an internal aqueous template phase. To produce macroporous polymers with gradient composition, pore size, and foam density, we varied the template formulation, droplet size, and internal phase ratio of emulsion templates continuously and stacked those prior to polymerization. Using the outlined approach, it is possible to vary one property along the resulting macroporous polymer while retaining the other properties. The elastic moduli and crush strengths change along the gradient of the macroporous polymers; their mechanical properties are dominated by those of the weakest layers in the gradient. Macroporous polymers with gradient chemical composition and thus stiffness provide both high impact load and energy adsorption, rendering the gradient foam suitable for impact protective applications. We show that dual-dispensing and simultaneous blending of two different emulsion formulations in various ratios results in a fine, bidirectional change of the template composition, enabling the production of true gradient macroporous polymers with a high degree of design freedom.

Emulsion template – based porous silicones with piezocapacitive response

Porous silicones were prepared by thiol-ene photoaddition or hydrolysis - condensation cross-linking in emulsion template in the presence of a pyridyl-modified siloxane oligomer as surfactant, at room temperature. Hexamethyldisiloxane (HMDS) was tested as alternative, more eco-friendly solvent in competition with toluene. Variations in the composition of silicone precursors, thus in cross-linking density and method, allowed tuning of mechanical properties. The piezocapacitive response of the porous silicones was investigated, focusing on the dielectric material as potential sensing element in capacitive pressure sensors. The capacitance variation showed linearity on wide pressure domains, roughly between 2 and 300 kPa, depending on the mechanical properties of the porous monoliths. A direct correlation between sensitivity and Young's modulus was found, which allows tuning of the sensing behavior. The softest material, prepared with a binary mixture of silicone precursors, exhibited a sensitivity of 8.7 × 10−3 kPa−1 on 9–29 kPa pressure range. A porous silicone – MWCNT composite showed spectacular increase in sensitivity, with maximum value of 0.747 kPa−1 and 0–7.5 kPa sensing range when compressed at 30%. Gauge factors of 29.2 in the compressive strain range of 13–30% and as high as 88.8 in the compressive strain range of 25–50% were found.