Organic-inorganic Hybrid Resin Research Articles

Photolithographic additive manufacturing of high-entropy perovskite oxides from synthesized multimetallic polymeric precursors

In this work, the synthesis of high-entropy perovskite-type oxides from multimetallic polymeric precursors and their shaping by photolithographic additive manufacturing is investigated. Thermosets with well-controlled complex geometries are produced by digital light processing using the multimetallic organic-inorganic hybrid resin developed in this work and converted into ceramics by thermal debinding and sintering. The high-entropy perovskite-type oxides are produced at 1500 °C, they retain the printed geometry with high shape fidelity. The orthorhombic crystal structure is identified by the Rietveld refinement of high-resolution synchrotron X-ray data; elemental and spectroscopic characterizations suggest the composition Sr(Ti0.22Zr0.22Hf0.23Mn0.15Sn0.18)O2.85. The use of aqueous polyethylene glycol as a binder and porogen greatly reduces the formation of cracks and creates evenly distributed micropores, which leads to improved compressive strength of the specimens. The compressive strength of 0.94 MPa is highest for materials printed from the resins with 3 wt% PEG in the woodpile-like geometries.

Parameter investigation of an organic–inorganic hybrid resin for a 3D-printed microchannel heat exchanger

This study can act as a guideline for printing high-performance heat exchangers using diverse 3D printing technology for resin formulation.

Correction: Parameter investigation of an organic–inorganic hybrid resin for a 3D-printed microchannel heat exchanger

Correction for ‘Parameter investigation of an organic–inorganic hybrid resin for a 3D-printed microchannel heat exchanger’ by Sunjae Lee et al., React. Chem. Eng., 2024, 9, 2089–2097, https://doi.org/10.1039/D3RE00694H.

Assessing pyrolysis behavior of silicon-containing arylacetylene resin via experiments and ReaxFF MD simulations

Silicon-containing arylacetylene resin (PSA), a thermosetting organic-inorganic hybrid resin of high heat-resistance performs well in ablation process, whereas its pyrolysis behavior under high temperature has not been fully interpreted. Herein, the PSA pyrolysis process was in-depth investigated by experiments and ReaxFF molecular dynamics simulation (ReaxFF-MD). TG results show that the temperature of 5% weight loss (Td5) is above 600 ℃, and the residue at 900 ℃ surpass 85%, demonstrating PSA has excellent heat resistance and thermal stability. The on-line FTIR and out-line gas quantify analysis reveals that H2 and CH4 are dominant gaseous products, which are also unveiled by ReaxFF-MD simulation. Molecular reaction tracking indicates PSA pyrolysis is initiated by the cleavage of skeleton in benzene ring, the cleavage of C-C bond and C-Si bond in main chain at elevated temperature. Hydrogen abstraction reactions are primary formation pathways of CH4 and H2, together with conquering high energy barriers. The activation energy of PSA pyrolysis in experiments is 155 kJ/mol, agreeing well with that from ReaxFF MD simulations (144 kJ/mol), which further confirms the thermochemical stability of cured PSA that rich in highly crosslinked aromatic structure. Besides, the influence of silicon side-groups on PSA pyrolysis is screened by MD and results indicate that gases evolution depended largely on side-groups types and decreasing side phenyl groups in PSA is benefit for improving its thermal stability. This work deepens the understanding of PSA pyrolysis mechanism and provides theoretical guidance for improving its heat resistance.

SYNTHESIS OF SILICON NANOPARTICLES MODIFIED POLYESTER AS MATERIAL ACTIVE ELECTRODE ON A SECONDARY CELL BATTERY

After oxygen, silicon is the second most prevalent element. Despite their abundance, this element is not discovered by itself. Minerals like silicates and aluminum silicates are typically where you can find silicon compounds. This study uses synthesis composite organic-inorganic hybrid resin with a silicon nanoparticles intermediate. Silicon nanoparticles modified polyester can be used as an anode electrode on a secondary cell battery. The characterization XRD of SiNPs showed silicon but contained other impurities such as SiO2, Mg, and MgO. The characterization XRD of SiNPs-PE showed silicon, and a broad peak indicated polyester. The surface area shows SiNPs 70.550 m2 /g and SiNPs-PE 1.064 m2 /g. Pore size showed SiNPs 0.892 nm and SiNPs-PE 1.683 nm. Pore volume showed that SiNPs 0.142 cm3 /g and SiNPs-PE 0.002 cm3 /g. The characterization SEM shows a spherical shape for silicon and a solid surface that shows polyester. The electrical conductivity of SiNPs is 2140,673 µS/cm and resistance 4,671 Ω at 1 V, while the electrical conductivity of SiNPs-PE is 2752,294 µS/cm and resistance 3,633 Ω at 1 V.

Improving adhesion and moisture permeability of UV/heat dual-curable adhesives using organic-inorganic hybrid resin

Seamless displays have attracted considerable attention because they simultaneously offer an immersive experience and one virtual screen. In this study, we prepared new UV/heat dual-curable adhesives containing organic–inorganic hybrid resin for narrow bezel display. The silane coupling groups contained in the organic–inorganic hybrid resin react with substrates, thereby improving adhesion strength and reducing moisture permeability of adhesives. The UV/heat curing ratio, adhesive strength, moisture permeability, and internal contamination of new adhesive were compared with those of conventional sealant. The proposed adhesive offered high adhesion, reduced moisture permeability, and low internal contamination level for a full screen display application.

Cold-Cured Epoxy-Based Organic⁻Inorganic Hybrid Resins Containing Deep Eutectic Solvents.

The development of improved cold-cured resins, to be used as either adhesives or matrices for FRP (fiber reinforced polymer) composites employed in the construction industry, has become the focus of several academic and industrial research projects. It is expected that the use of nano-structured organic–inorganic hybrid materials could represent a realistic alternative to commercial epoxy-based resins due to their superior properties, especially in terms of higher durability against: moisture, temperatures, harsh environments, and fire. In this context, organic–inorganic epoxy hybrids were synthesized by a modified sol–gel method without the addition of water. The experimental formulations were prepared starting from a mixture of a silane-functionalized epoxy resin, alkoxysilane components and a deep eutectic solvent (DES) based on a blend of choline chloride and urea. The latter was added in two different loads in order to analyze in depth its effect as a promoter for an effective dispersion of silica nano-phases, formed through hydrolysis and condensation reactions, into the cross-linked epoxy network. The produced formulations were cold-cured for different time spans in the presence of two hardeners, both suitable for a curing process at ambient temperature. In this first part of a wider experimental program, several analyses were carried out on the liquid (rheological and calorimetric) and cold-cured (calorimetric, thermogravimetric, dynamic-mechanical, flexural mechanical, and morphological) systems to evaluate and quantify the improvement in properties brought about by the presence of two different phases (organic and inorganic) in the same epoxy-based hybrid system.

Preparation and tribological behaviors of a novel organic-inorganic hybrid resin bonded solid lubricating coating cured by ultraviolet radiation

Here a novel organic-inorganic hybrid bonded solid lubricating coating with excellent tribological properties was prepared by an efficient and low-cost method of ultraviolet radiation technique. The nano-indentation and scratch tests were conducted to evaluate the mechanical properties of the hybrid coating with different inorganic content. In addition, the effects of polytetrafluoroethylene (PTFE) content and test conditions on tribological behaviors of the hybrid lubricating coatings were investigated. The experimental results show that the indentation hardness and elastic modulus of the hybrid coatings were improved synchronously by increasing the inorganic content in the binder formulations, and the hybrid coating containing 10 wt. % inorganic components presented better scratch resistance than others. Moreover, the best tribological properties were obtained when the mass ratio of PTFE to binder was 0.4. And the hybrid lubricating coating showed good resistance to the variation of sliding speed (frequency) and was susceptible to the load applied in present work.

Low-loss graded-index polymer crossed optical waveguide with high thermal resistance.

In this paper, crossed polymer waveguides with graded-index (GI) square cores are fabricated using the soft-lithography method. We experimentally demonstrate that the fabricated GI-core crossed waveguides exhibit a much lower insertion loss than conventional step index (SI)-core counterparts, which is almost independent of the cross angle. We also show in this paper that the crossed waveguides fabricated applying organic-inorganic hybrid resins show remarkably high thermal resistance compared to the waveguides fabricated utilizing an acrylate resin and a dopant system we previously reported.

Shape-memory behaviors of epoxy-functionalized polyhedral oligomeric silsesquioxane/epoxy organic–inorganic hybrid resin systems

A series of organic–inorganic hybrid resin systems are prepared using hydroepoxy, 1,3-bis(aminomethyl)cyclohexane, and epoxy-functionalized polyhedral oligomeric silsesquioxane (POSS-Ep). The thermomechanical properties and shape-memory behaviors of the hybrid materials are systematically investigated by differential scanning calorimetry, thermogravimetric analysis (TGA), dynamic mechanical analysis, bend test, and shape recovery test. Results indicate that the glass transition temperature ( Tg) and rubber modulus gradually increase as the POSS-Ep content increases. The thermal stabilities of the hybrid materials gradually increase with increasing POSS-Ep content. The bend strength of the hybrid materials increases firstly and then decreases as POSS-Ep content increases, showing an extreme value for the hybrid materials with 3.17 mol% POSS-Ep content. Finally, investigation of the shape-memory behavior of the hybrid materials reveals that full recovery can be observed after only several minutes when the temperature is equal to or above Tg. The shape recovery time decreases at first and then increases as POSS-Ep content increases at Tg, Tg + 10°C, and Tg + 20°C. These results are attributed to the increase in POSS-Ep content.

Scratch, wear and corrosion resistant organic inorganic hybrid materials for metals protection and barrier

Abstract Polysiloxanes are widely used as protective barriers to delay erosion/corrosion and increase chemical inertness of metal substrates. In the present work, a high molecular weight methyl phenyl polysiloxane resin was designed to manufacture a protective coating for Fe 430 B structural steel. Methyl groups feature very small steric hindrance and confer ductility to the Si–O–Si backbone of the organic inorganic hybrid resin, thus allowing the achievement of high thickness. Phenyl groups feature larger steric hindrance, but they ensure stability and high chemical inertness. Visual appearance and morphology of the coatings were studied by field emission scanning electron microscopy and contact gauge surface profilometry. Micro-mechanical response of the coatings was analyzed by instrumented progressive load scratch, while wear resistance by dry sliding linear reciprocating tribological tests. Lastly, chemical inertness and corrosion endurance of the coatings were evaluated by linear sweep voltammetry and chronoamperometry in aggressive acid environment. The resulting resins yielded protective materials, which feature remarkable adhesion to the substrate, good scratch resistance and high wear endurance, thus laying the foundations to manufacture long lasting protective barriers against corrosion and, more in general, against aggressive chemicals.

Reinforcing Epoxy Resin with Polydopamine-Coated Al(OH)<sub>3</sub>: A Biomimetic Method to Constructing Organic-Inorganic Hybrid Materials

A facile biomimetic method was developed to enhance the interfacial interaction in organic-inorganic hybrid materials. By mimicking mussel adhesive proteins, a monolayer of polydopamine (PD) was constructed on surface of Al (OH)3 particles through a controllable coating pathway. The modified Al (OH)3 (PD-Al (OH)3) was incorporated into an epoxy resin. It is found that the strong interfacial interactions brought by the polydopamine benefits the effective interfacial stress transfer, leading to greatly improved flexural properties of the organic-inorganic hybrid resin.

Flame retardancy and thermal stability of organic–inorganic hybrid resins based on polyhedral oligomeric silsesquioxanes and montmorillonite clay

Organic–inorganic hybrids were prepared by incorporation of two polyhedral oligomeric silsesquioxanes, trisilanolisobutyl POSS (TSP) and isobutylAluminum POMS (AlP), and an organoclay (OC), in an epoxy–amine system.Differential scanning calorimetry revealed the great catalytic power of AlP. OC also showed catalytic power, but to a lesser extent. The storage modulus increased with lower POSS contents, due to the nanoreinforcing effect of POSS core. At higher concentration, the modulus strongly decreases due to POSS aggregation. The glass transition temperature was barely affected by the POSS, whereas OC addition decreased it. POSS and OC supplied greater thermal stability in high temperature regions, and the char residue increased with filler concentration because silicon species are formed. POSS addition improved the flame retardancy because of a multilayered carbonaceous silicate structure formation. The presence of metal atoms in AlP composites might contribute to stabilization through secondary chemical reactions.

Enhanced light output from vertical light-emitting diodes with an imprinted highly refractive polymer layer

Hexagonal arrays of submicron polymer patterns with a high refractive index were fabricated on a vertical light-emitting diode (LED) device by means of nanoimprint lithography (NIL) to improve the light extraction efficiency. An organic-inorganic hybrid resin containing a polymeric titanium dioxide precursor was spin-coated on the n-GaN top layer of a vertical LED wafer. The coated layer was then imprinted for 10 min with an elastomeric polydimethylsiloxane stamp at 200 °C and 5 atm. The NIL process formed pillar patterns on the n-GaN layer of the vertical LED wafer. The pillar patterns have a high refractive index ( n ≈ 2.0) in the visible wavelength range; they also have a diameter of 200 nm and a pitch of 700 nm. The light output power of the patterned vertical LED device is 28% greater than that of a non-patterned vertical LED device with a driving current of 350 mA. The I–V characteristics of the vertical LED device confirm that the patterning process induces no electric degradation.

Replica Mold for Nanoimprint Lithography from a Novel Hybrid Resin

The use of durable replica molds with high feature resolution has been proposed as an inexpensive and convenient route for manufacturing nanostructured materials. A simple and fast duplication method, involving the use of a master mold to create durable polymer replicas as imprinting molds, has been demonstrated using both UV- and thermal nanoimprinting lithography (NIL). To obtain a high-durability replicating material, a dual UV/thermal-curable, organic-inorganic hybrid resin was synthesized using a sol-gel-based combinatorial method. The cross-linked hybrid resin exhibited high transparency to UV light and resistance to organic solvents. Molds made of this material showed good mechanical properties (Young's modulus=1.76 GPa) and gas permeability. The low viscosity of the hybrid resin (approximately 29 cP) allowed it to be easily transferred to relief nanostructures on transparent glass substrates using UV-NIL at room temperature and low pressure (0.2 MPa) over a relatively short time (80 s). A low surface energy release agent was successfully coated onto the hybrid mold surface without destroying the imprinted nanostructures, even after O2 plasma treatment. Nanostructures with feature sizes down to 80 nm were successfully reproduced using these molds in both UV- and thermal-NIL processes. After repeating 10 imprinting cycles at relatively high temperature and pressure, no detectable collapse or contamination of the replica surface was observed. These results indicate that the hybrid molds could tolerate repeated UV- and thermal-NIL processes.

Synthesis of 3-dimensional periodic nanostructures in an interference field of UV laser light

In 2000, Campbell et al. (Nature 404:53, 2000) have shown that three-dimensional periodic nanostructures can be obtained from UV laser interference irradiation of photoresist for 6 nanosecond single pulse. We have developed a similar experiment for photolytic gas phase decomposition and for photopatternable organic–inorganic hybrid resins.

Synthesis of hybrid resins via polysiloxane with methacryloyloxy groups

A polysiloxane derivative with methacryloyloxy groups (MPS) that was obtained from the reaction of polymeric tributylstannyl ester of silicic acid and (3-methacryloyloxypropyl)dimethylchlorosilane was demonstrated to be a useful inorganic component for the preparation of organic–inorganic hybrid resins as nanocomposites. The copolymerizations of MPS with common monomers such as styrene, acrylonitrile, and methyl methacrylate proceeded readily at room temperature under UV irradiation to give the corresponding resins in good yields. The resins obtained from MPS and methyl methacrylate showed good transparency, hardness in a scratch test, and resistance to toluene but had poor flexibility. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1–7, 2001

Synthesis of hybrid resins via polysiloxane with methacryloyloxy groups

A polysiloxane derivative with methacryloyloxy groups (MPS) that was obtained from the reaction of polymeric tributylstannyl ester of silicic acid and (3-methacryloyloxypropyl)dimethylchlorosilane was demonstrated to be a useful inorganic component for the preparation of organic–inorganic hybrid resins as nanocomposites. The copolymerizations of MPS with common monomers such as styrene, acrylonitrile, and methyl methacrylate proceeded readily at room temperature under UV irradiation to give the corresponding resins in good yields. The resins obtained from MPS and methyl methacrylate showed good transparency, hardness in a scratch test, and resistance to toluene but had poor flexibility. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1–7, 2001

Synthesis of Polysiloxane Having Methacryloyloxy Group from Tributylstannyl Ester of Silicic Acid and Silane Coupling Agent

Polysiloxane derivative (MPS), obtained from the reaction of polymeric tributylstannyl ester of silicic acid (PTBS) and (3-methacryloyloxypropyl)dimethylchlorosilane (1a), was shown to be a useful inorganic component for the preparation of organic-inorganic hybrid resin as a nanocomposite. Copolymerization of MPS containing methacryloyloxypropyl groups with the common monomer such as styrene, acrylonitrile, or methyl methacrylate proceeded readily at room temperature under UV irradiation to give the corresponding resins (HR). The resins obtained from MPS and methyl methacrylate showed a good transparency and resistance in scratch test, but a poor flexibility. The gels consisted of analogous structure to HR were obtained from PTBS, 1a, and the monomer by one-pot procedure, in which substitution and polymerization proceeded simultaneously.

Synthetic application of tributylstannyl ester of silicic acid: Synthesis and polymerization of polysiloxane having methacryloyloxypropyl groups

Polymeric tributylstannyl ester of silicic acid (PTBS) was demonstrated to be a useful intermediary compound for the preparation of polysiloxane derivative (MPS), which possessed methacryloyloxypropyl groups. The reaction of PTBS and (3-methacryloyloxypropyl)dimethylchlorosilane (1a) proceeded readily at room temperature under neutral conditions to give MPS with the elimination of tributyltin group. The reaction conducted in the presence of 1a and trimethylchlorosilane (1b) was effective for the preparation of MPS containing the both silyl groups, in which the content of methacryloyloxy groups could be controlled. The obtained MPS polymerized readily under UV irradiation to afford the organic–inorganic hybrid resin (MSR) as a kind of organically modified silica gel. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4226–4232, 1999