High Degree Of Crosslinking Research Articles

Composite nanofiltration membrane with tannic acid coordinated collagen fibers for enhanced molecule separation

Biomass-based membranes have attracted increasing attentions due to their cheap and sustainable advantages. In this work, a novel thin-film composite (TFC) nanofiltration (NF) membrane was fabricated through a facial interfacial polymerization (IP) process by initiate the crosslinking reaction between collagen fibers (CFs) and tannic acid (TA). The increased TA concentrations endowed the TFC membrane with a higher crosslinking degree, a thicker active layer and a rougher top surface. At optimized condition with 0.60 mg TA decoration, the TFC-3 membrane exhibited a high water permeability of 23.49 L m−2 h−1 bar−1 with high rejections above 98.0% for congo red, reactive blue 19, coomassie blue G-250, and methyl blue. Furthermore, the membrane preserved remarkable salt retentions (93.3% for Na2SO4, 83.4% for MgSO4, 36.2% for MgCl2, and 26.4% for NaCl) and satisfying operation stability. This facial fabrication method offered a new insight to employ biomass for molecular precise separation.Graphical abstract

Stepwise UV crosslinking in solvent: A novel method to enhance the solvent resistance of poly(aryl ether ketone) membranes

In this contribution, the viability of using UV to give separation membranes a high crosslinking degree and broad-spectrum solvent resistance was investigated. A series of poly(aryl ether ketone) polymers suitable for UV crosslinking were first designed. And a unique photocrosslinking method, stepwise UV crosslinking in solvent, was developed by understanding photochemical reactions and molecular dynamics. This method does not require the introduction of additional photoinitiators and crosslinking agents, and the membrane preparation is a green and efficient process with a theoretical 100% atomic utilization rate. Combining this method with the special polymer structure design, a solvent-resistant nanofiltration membrane that can withstand strong polar aprotic solvents can be obtained. The molecular weight cut off of the membrane in N,N-dimethylformamide was 300 g/mol, and the permeance was 1.154 L m−2 h−1 bar−1. This separation effect even exceeded that of most composite membranes. After testing, the membranes prepared using this method had the ability to maintain functional stability at 80 °C in N,N-dimethylformamide for one month. The excellence of membrane performance and the flexibility of regulatory methods both reveal the enormous potential of this method.

Polyol grafted thin film nanocomposite membrane: Enhanced pervaporation performance for isopropanol dehydration

Isopropanol is used as a cleaning agents especially in the semiconductor industry. Thus, recycling, and purifying alcohol can reduce the overall cost of production. To improve the separation performance of the thin-film nanocomposite (TFN) membrane, nanozeolite (NZ) was embedded in polyamide layer followed by post-treatment of polyols. The polyamide layer was fabricated through interfacial polymerization of diethylenetriamine (DETA) and trimesoyl chloride (TMC). NZ was dispersed in TMC in order to be embedded on the separation layer. Afterwards, the membrane was simultaneously post-treated using polyols. Different types of polyols were introduced: d-sorbitol (DST), erythritol (ERT), and pentaerythritol (PET). A higher number of hydroxyl groups can provide a denser separation layer. Their chemical structures also affects the reaction rate, where more linear structures (DST and ERT) had better reaction and crosslinking with acyl chloride. High reaction rate of DST gives the roughest surface and high crosslinking degree. Compared to other polyols, Using DST in post-treatment exhibited the highest separation performance. It had a permeation flux of 3,098 g·m−2·h−1 and 99.9 wt% water concentration in permeate (feed = 70 wt% aqueous isopropanol solution at 25℃). Therefore, post-treatment using polyols can further enhance the separation efficiency of TFN membranes with a stable performance over a long period of time.

Monomeric glutaraldehyde fixation and amino acid detoxification of decellularized bovine pericardium for production of biocompatible tissue with tissue-guided regenerative potential

The effect of monomeric glutaraldehyde fixation and amino acid detoxification on biocompatibility and tissue-guided regenerative potential of decellularized bovine pericardium was evaluated. The degree of cross-linking, porosity, enzymatic degradation, alpha-galactosyl content, the efficacy of detoxification, and cytotoxicity towards human epithelial cells were assessed. Tissue was subcutaneously implanted for eight weeks in male juvenile Sprague-Dawley rats, and mechanical properties, host cell infiltration, and calcification were evaluated. Three groups were compared i) decellularized tissue, ii) decellularized, monomeric glutaraldehyde fixed and amino acid detoxified tissue, and iii) commercial glutaraldehyde fixed non-decellularized tissue (Glycar®) (n = 6 rats per group). The fixation process gave a high degree of cross-linking (>85%), and was resistant to enzymatic degradation, with no significant effect on porosity. The detoxification process was effective, and the tissue was not toxic to mammalian cells in vitro. Tissue from both decellularized groups had significantly higher (p < 0.05) porosity and host cell infiltration in vivo. The process mitigated calcification. A non-significant decrease in the alpha-galactosyl content was observed, which increased when including the alpha-galactosidase enzyme. Mechanical properties were maintained. The fixation and detoxification process adequately removes free aldehyde groups and reduces toxicity, preventing enzymatic degradation and allowing for host cell infiltration while mitigating calcification and retaining the mechanical properties of the tissue. This process can be considered for processing decellularized bovine pericardium with tissue-guided regeneration potential for use in cardiovascular bioprostheses; however, methods of further reducing antigenicity, such as the use of enzymes, should be investigated.

The effect of media to reduce irradiation dose in crosslinking of self-assembled molecular layers

The present study aims to investigate the possibility of reducing the absorbed dose required to prepare a polymer nanocoating for surface functionalization by modifying the irradiation medium. We have studied the crosslinking of elaidic acid (EA), an unsaturated trans fatty acid, on oxidised copper by gamma irradiation. Three different irradiation media were compared: water purged with N2, water purged with N2O, and air purged with N2. Contact angle measurements were used to determine the hydrophobicity of the surface. The coatings were investigated by electrochemical measurements: The degree of crosslinking was indirectly determined by polarization measurements, while the behaviour of the coatings was studied by electrochemical impedance spectroscopy. The results showed that crosslinking can be achieved in all media studied. The highest dose of 110 kGy is required when irradiation is performed in oxygen-free air, while much lower doses of 40 kGy are required when irradiation is performed in water that has been purged with both gases used. The highest degree of crosslinking is achieved when irradiation is performed in air, while the degree of crosslinking when irradiated in water is highly dependent on the gas used. If N2O is used, the degree of crosslinking is significantly higher. The surface of the coatings is more hydrophobic when polymer coatings are present on the surface, regardless of the irradiation medium.

Mechanism of Accelerated Deterioration of High-Temperature Vulcanized Silicone Rubber under Multi-Factor Aging Tests Considering Temperature Cycling.

High-temperature vulcanized silicone rubber (HTV-SR) employed for composite insulators is continuously subjected to a complex environment of alternating heat, corona discharge, humidity, etc. These stresses (especially alternating heat) complicate the aging mechanism of HTV-SR, which lacks systematic investigation. In this paper, a multi-factor aging platform considering temperature cycling, moisture, and corona discharge is established. Specifically, four temperature-cycling settings are employed, each of which lasts for 15 cycles. The surface morphology, hydrophobicity, and chemical, mechanical, and electrical properties of aged samples are methodically characterized. Experimental results show that the aging degree is correlated to the range of temperature cycling, which is attributed to diverse crosslink-degradation degrees with different temperature differences. Under a large temperature difference (70 °C), HTV-SR possesses a high crosslinking degree and a low degradation degree, making the material hard but easy to crack with alternating thermal stress. Then, severe defects and water condensation emerge on the HTV-SR surface, which promote the diffusion of corona products and water molecules into the material. The subsequent rise in crosslinking density caused by in-depth oxidation further exacerbates the aging of the material. Consequently, it brings about poor hydrophobicity, high interfacial polarization, and shallow trap energy levels in HTV-SR. This work provides a detailed analysis of the aging mechanism of HTV-SR in a simulated on-site environment.

Application of Modified Styrene-Acrylic-Rubber-based Latex Binder to LiCoO&lt;sub&gt;2&lt;/sub&gt; Composite Electrodes for Lithium-ion Batteries

A new combination of styrene acrylic rubber (SAR) and sodium carboxymethylcellulose was developed as a water-borne binder for LiCoO2 composite electrodes operating at high voltages. Four novel SAR-based latex binders were synthesized with butyl acrylate or 2-ethylhexyl acrylate monomer and styrene via copolymerization with low and high crosslinking degrees. Composite electrodes prepared using lower-crosslinking-degree SAR binders became more stretchable and flexible. Surface analysis using electron microscopy and X-ray photoelectron spectroscopy revealed that the cycled LiCoO2 electrode was covered with approximately 10-nanometer-thick decomposition products when a conventional poly(vinylidene fluoride) binder was used. The electrodes with SAR-based binders with low cross-linkage formed a stable passivation surface during the initial cycle, and further continuous electrolyte decomposition was successfully suppressed. This passivation improved the cycle stability of LiCoO2 electrode up to 4.5 V, i.e., 87.1 % capacity retention, even after 100 cycles and suppressed self-discharge performance at 45 °C.

Innovative role of polyvinylpyrrolidone in tailoring polyamide layer for high-performance nanofiltration membranes

While being the preferred choice in the desalination industry, polyamide (PA) nanofiltration (NF) membranes still suffer from the permeability-selectivity trade-off challenge. This study successfully fabricated a high-performing PA NF membrane by regulating the role of polyvinylpyrrolidone (PVP) in the PA layer, which is contrary to the traditional view of PVP as a simple pore-forming agent. The study demonstrated that PVP can partially persist in the polyethersulfone (PES) substrate and impact the interfacial polymerization (IP) process, resulting in a thinner PA layer with a higher cross-linking degree and a more uniform pore structure compared to a PA layer formed on a control substrate without PVP. Molecular dynamic simulations revealed that the van der Waals force between PVP and piperazine (PIP) slowed down the diffusion of PIP at the PVP-PES substrate surface, facilitating the formation of a PA layer with a uniform pore size distribution and reduced thickness. By adjusting the concentrations of PVP in the dope solution and PIP during interfacial polymerization, a PA membrane with pure water permeability of 30.2 ± 0.9 L·m−2·h−1·bar−1 and a Na2SO4 rejection rate of 97.7 ± 0.1 % was obtained. This study provides new insights and presents a novel approach to tailoring the PA layer structure of NF membranes.

Visible light-induced crosslinking enables highly permeable and chlorine-resistant polyamide membranes for water purification

Nanofiltration (NF) based purification technology plays a growing role in water softening, wastewater reuse, and drinking water production, whose core component is the thin-film composite (TFC) polyamide (PA) surface separating layer with high water permeation and significant antifouling and chemical resistance. Strengthening water transport with simultaneously improving chemical tolerance and fouling resistance accords with the demands for sustainable water treatment. In this work, a photo-assisted crosslinked NF membrane with a regulated interlaced stripe surface morphology was fabricated through grafting 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) into the PA network during visible light irradiation. Surface structures and chemical features were characterized, and the NF performance, antifouling and chlorine resistance were systematically evaluated. The optimal membrane with AMPS molecules carrying sulfonyl groups crosslinked in the PA network was rendered electronegative charge, uniformly narrowed pore size, improved hydrophilicity, and higher crosslinking degree. The water permeation was augmented to 30.5 L m−2 h−1·bar−1 for the optimal membrane, four times more advanced than the pristine membrane with a water permeability of 5.9 L m−2 h−1·bar−1, and the divalent salt retention was improved to 99.7%. In addition, the optimal membrane also exhibited outstanding chlorine tolerance, fouling removal, and antifouling capacity. The flux recovery ratio (FRR) of the best membrane outperformed that of the pristine membrane and the flux declined more slowly in the whole fouling cycle testing. This work provides a novel avenue for fabricating high-efficiency TFC membranes with great water permeation and fouling resistance.

Effect of 3D Food Printing Processing on Polyphenol System of Loaded Aronia melanocarpa and Post-Processing Evaluation of 3D Printing Products.

Aronia melanocarpa polyphenols (AMP) have good nutritional values and functions. This study aimed to explore the printability and storage properties of AM gels in 3D food printing (3DFP). Therefore, 3DFP was performed on a loaded AMP gel system to determine its textural properties, rheological properties, microstructure, swelling degree and storage performance. The results revealed that the best loading AMP gel system to meet the printability requirements of 3DFP processing was AM fruit pulp:methylcellulose:pea albumin: hyaluronic acid = 100:14:1:1. Compared with other ratios and before 3DFP processing, the best loading AMP gel system processed by 3DFP exhibited the lowest deviation of 4.19%, the highest hardness, the highest elasticity, the least adhesion, a compact structure, uniform porosity, difficulty in collapsing, good support, a high degree of crosslinking, and good water retention. Additionally, they could be stored for 14 d at 4 °C. After post-processing, the AMP gel had a favorable AMP release rate and good sustained release effect in gastrointestinal digestion, which conformed to the Ritger-Peppas equation model. The results revealed that the gel system had good printability and applicability for 3D printing; as well, 3DFP products had good storage properties. These conclusions provide a theoretical basis for the application of 3D printing using fruit pulp as a raw material.

Phosphonium based anion exchange resin for enrichment of phenolic acids

The aim of this work is to investigate the efficiency of a phosphonium-based strong anion exchange sorbent for the extraction of some selected phenolic acids. The material was synthesized through chloromethylation of a porous poly(styrene-divinylbenzene) substrate with high degree of crosslinking, followed by quaternarization with tributyl phosphine. The parameters affecting the solid phase extraction of five phenolic acids, namely chlorogenic acid, caffeic acid, dihydroxybenzoic acid, ferulic acid and rosmarinic acid were optimized. The sample pH and the type, volume and concentration of the eluting solutions were investigated. The analysis of the phenolic acids after extraction was performed using HPLC with diode array detection. Limit of detection, limit of quantitation, linear range, correlation coefficient and reproducibility for the determination of the phenolic acids were estimated. The retention of the phenolic acids on the developed phase was studied using breakthrough analysis. The experimental breakthrough curves were fitted by Boltzmann's function, and the regression parameters were utilized for the determination of the breakthrough parameters. The results obtained using the developed phase were compared with those obtained by the commercially available Oasis MAX sorbent. The proposed approach was successfully applied for the extraction and pre-concentration of rosmarinic acid from rosemary leaf (Rosmarini folium) alcoholic extract.

Characterization of chitosan-gelatin cryogel templates developed by chemical crosslinking and oxidation resistance of camellia oil cryogel-templated oleogels

In this study, chitosan-gelatin conjugates were prepared by chemical crosslinking of tannic acid. The cryogel templates were developed through freeze-drying and immersed in camellia oil to construct cryogel-templated oleogels. Chemical crosslinking resulted in apparent colour changes and improved emulsion-related/rheological properties on conjugates. The cryogel templates with different formulas exhibited different microstructures with high porosities (over 96 %), and crosslinked samples might have higher hydrogen bonding strength. Tannic acid crosslinking also led to enhanced thermal stabilities and mechanical properties. Cryogel templates could reach a considerable oil absorption capacity of up to 29.26 g/g and prevent oil from leaking effectively. The obtained oleogels with high tannic acid content possessed outstanding antioxidant abilities. After 8 days of rapid oxidation at 40 °C, Oleogels with a high degree of crosslinking owned the lowest POV and TBARS values (39.74 nmol/kg, and 24.40 μg/g, respectively). This study indicates that the involvement of chemical crosslinking would favor the preparation and the application potential of cryogel-templated oleogels, and the tannic acid in the composite biopolymer systems could act as both the crosslinking agent and the antioxidant.

Reactive force-field MD simulation on the pyrolysis process of phenolic with various cross-linked and branched structures

Based on the reactive force-field (ReaxFF) molecular dynamics, the thermostability of cross-linked and non-cross-linked phenolic was compared to study the effect of cross-linked and branched structures on the pyrolysis mechanism. The results show that during the pyrolysis process, phenolic tends to break into low-boiling molecules with less than 4 carbon atoms and polymerizes into macromolecules with more than 1500 carbon atoms. The results of residual carbon rate and products distribution confirm that carbon skeleton of phenolic resin with high degree of crosslinking and branching is better preserved and has better thermostability. The reaction kinetics path of phenolic pyrolysis was reasonably summarized, revealing the generation mechanism of low-boiling molecules with less than 4 carbon atoms and large carbon clusters, which is in good agreement with the experimental results of activation energy and chemical bond energy. The reaction kinetics data obtained in this work provide a reliable basis for multi-scale reaction simulation.

Hydrogel Preparation from Shrimp Shell-Based Chitosan: The Degree of Crosslinking and Swelling Study

Chitosan is a natural polymer derived from different starting materials such as fish scales, crab and shrimp shells. Due to the advantages like biocompatibility and biodegradability, chitosan has been widely used in hydrogel development. This current study aims to make chitosan from shrimp shells, synthesize hydrogel from chitosan, and observe the effect of various chitosan preparation treatments on the properties of the hydrogel. The preparation of chitosan was carried out through demineralization, deproteinization, and deacetylation process. HCl concentration during demineralization and NaOH concentration during deproteinization were varied (1; 1,5; 2) M and (1; 1,5; 2) M, respectively. Chitin deacetylation was conducted using 60% (w/v) of NaOH at the temperature of 90oC for 120 min, and chitosan was resulted. Chitosan based hydrogel was then synthesized with the addition of alginate and glutaraldehyde. The effect of HCl and NaOH concentrations during demineralization and deproteinization on the deacetylation degree of chitosan was observed. The effect of deacetylation degree of chitosan on the degree of crosslinking and swelling property of the hydrogel were also evaluated. Chitosan resulted from this study has the optimum degree of deacetylation at 57.28 %, resulting from demineralization by using HCl 2M and deproteinization with NaOH2 M. Higher deacetilation degree of chitosan causing the increase of the degree of cross-linking and decrease of the swelling capacity of the hydrogel. The highest degree of cross-linking is 78.85 %, and the swelling capacity is 47 %.

Facile preparation of epoxidized soybean oil-hexanediamine resin for fabrication of pressure-sensitive adhesives

Due to the massive consumption of petroleum-derived resources, it is imperative to develop biomass adhesives to replace traditional petroleum-derived materials. The current work deals with the possibility to undergo crosslinking of epoxidized soybean oil (ESO) using hexanediamine (HDA) via one-pot method to produce a pressure-sensitive adhesive, poly(epoxidized soybean oil)-hexanediamine (PESH). The chain growth reaction between ESO and HAD involved the ester group in ESO be destroyed via aminolysis, as evidenced by Fourier Transform Infrared Spectroscopy (FTIR) and 1H Nuclear Magnetic Resonance (1H NMR). The bonding properties of PESH pressure-sensitive adhesive were studied by rolling ball method, shear strength and 180° peeling. The results revealed that the initial viscosity, adhesion persistence and peeling were significantly improved when the molar ratio of ESO to HDA was 1:3. At the same time, the PESH adhesive exhibited good bonding performance under water, especially with PVC substrates, in which the underwater bonding strength can reach 1043 KPa. In addition, PESH adhesive with high crosslinking degree presented excellent resistivity at high voltage. It can be implied that the addition of HDA can acquire the PSA antifungal action. All the results support that at a molar ratio of ESO to HDA of 1:3, it is easier to produce robust crosslinked network structure with overall upgraded properties. Conclusively, the developed PESH adhesive can provide a good application prospect in packaging and insulating fields.

Effect of hindered phenolic antioxidants on crosslinking characteristics of low-density polyethylene initiated by peroxide

Hindered phenolic antioxidants are the most prevalent antioxidants used in crosslinked polyethylene (XLPE) insulating materials of high-voltage (HV) cables. Doping antioxidants is conducive to delaying the low-temperature pre-crosslinking, but decreases final crosslinking degree. In order to comprehensively reveal the effect of hindered phenolic antioxidants on the crosslinking characteristics of XLPE insulating materials, four kinds of insulating materials doped with different hindered phenolic antioxidants are studied by experiment and simulation methods. The results demonstrate that antioxidant 300 is better for delaying low-temperature pre-crosslinking of insulating materials, but negative for maintaining high crosslinking efficiency and degree. Although insulating materials with antioxidant 1010 have higher crosslinking degree, it is poor to delay the low-temperature pre-crosslinking. Notably, antioxidant 245 with phenolic hydroxyl of lower bond dissociation energies can delay the low-temperature pre-crosslinking to some extent, meanwhile, crosslinking efficiency and degree of XLPE are still higher. Notably, the crosslinking characteristics of XLPE insulating materials are closely related to molecular structure of antioxidants, including functional group and ortho-substituents. Comprehensively considering the demands of delaying low-temperature pre-crosslinking and maintaining high crosslinking degree of insulating materials, antioxidant 245 is the better choice. This study provides a theoretical guidance for the choice of hindered phenolic antioxidants used for HV cable insulating materials.

An efficient co-solvent tailoring interfacial polymerization for nanofiltration: enhanced selectivity and mechanism

The interfacial polymerization (IP) plays a fundamental role in the fabrication of polyamide (PA) nanofiltration (NF) membranes with high ion selectivity and water permeability, which has enormous value for the increasing permeate quality and production in desalination. Herein, this study adopted a weak-polar organic solvent of ethyl formate (EF) to effectively regulate the IP process between piperazine (PIP) and trimesoyl chloride (TMC). The engineered PA separate layer conferred a uniform and ultrafine pore size (∼0.195 nm), exhibited a precise solute separation, and maintained a desirable permeability (18.4 ± 0.9 L m−2 h−1 bar−1). Molecular dynamics (MD) simulation indicated that EF involvement would significantly reduce the interfacial tension to motivate a fast and abundant diffusion of amine monomers from the aqueous phase into organic phase during the IP reaction, contributing to engineering a PA film with higher crosslinking degree. The optimized PA NF membranes conferred a more efficient rejection for divalent anions and cations (e.g., 99.5% for Na2SO4 and 98.8% for MgCl2). Remarkably, the membrane endowed a fairly high mono/divalent ion selectivity at sub-angstrom size, such as 145 for Cl−/SO42− and 61 for Na+/Mg2+. The outstanding NF performance successfully broke the "trade-off" bound of perm-selectivity and was superior to the most "state-of-the-art" NF membranes. Overall, the co-solvent based IP strategy was beneficial to developing high-performance NF membranes without any significant changes to the existing fabrication process, and its facile and cost-effective merits were full of significance to the membrane manufacture.

Structure and properties of citric acid cross-linked chitosan/poly(vinyl alcohol) composite films for food packaging applications

In this study, the composite films of poly(vinyl alcohol) and citric acid cross-linked chitosan were prepared, and the effect of mass ratio on their structure and properties was investigated in detail. Chitosan was cross-linked by citric acid via an amidation reaction at an elevated temperature, which was confirmed by infrared spectra and X-ray photoelectron spectra. Chitosan is miscible with PVA due to the formation of strong hydrogen bonds between them. Among these composite films, 1:1 CS/PVA film showed excellent mechanical properties, good creep resistance, and shape recovery ability, attributing to its high crosslinking degree. In addition, this film possessed hydrophobicity, excellent self-adhesion property, and the lowest WVP, and it was successfully used as a packaging material for cherry. These observations indicate that the cooperative effects of crosslinking and hydrogen bonds control the structure and properties of chitosan/PVA composite film, which is a very potential material for food packaging and preservation.

Development of hesperetin methacrylates and their high performance thermosets

AbstractHesperetin based monomers substituted to varying degrees of methacrylate functionality were synthesized namely trimethacrylate, dimethacrylate and monomethacrylated hesperetin monomers, HTM, HDM and HMM respectively. Resins employing reactive diluents 4‐acryloylmorpholine (4AM) and styrene (Sty) were formulated. Resin formulations were determined to be Newtonian fluids with viscosities below 800 cP. Thermosets of hesperetin monomers were produced with glass transition temperature (Tg) values up to 225°C. Ultimate strength up to 20 MPa and tensile modulus of 5.0 GPa were also observed. Additionally, thermosets with char yield near 30% were measured. Char yield, ultimate strength and tensile modulus of hesperetin based thermosets were superior to those derived from the petrochemical bisphenol A dimethacrylate (BPAM). However, thermosets that employed hesperetin derived monomers displayed properties that were less than expected compared to Bicerano model predictions. Also, select HTM:Sty thermosets displayed a noticeable holographic type morphology. Reactivity ratios, spectroscopy, microscopy and structure property relationships indicated that poor copolymerization behavior during cure and high degrees of crosslinking during postcure were responsible for the microcrack formation in the material. This also caused the observed morphology and resulted in reduced properties relative to Bicerano predictions.

3D Printing Thermally Stable High‐Performance Polymers Based on a Dual Curing Mechanism

AbstractHigh‐performance polymers are an important class of materials that are used in challenging conditions, such as in aerospace applications. Until now, 3D printing based on stereolithography processes can not be performed due to a lack of suitable materials. There is report on new materials and printing compositions that enable 3D printing of objects having extremely high thermal resistance, with Tg of 283 °C and excellent mechanical properties. The printing is performed by a low‐cost Digital Light Processing printer, and the formulation is based on a dual‐cure mechanism, photo, and thermal process. The main components are a molecule that has both epoxy and acrylate groups, alkylated melamine that enables a high degree of crosslinking, and a soluble precursor of silica. The resulting objects are made of hybrid materials, in which the silicon is present in the polymeric backbone and partly as silica enforcement particles.