Phenolic Resin Research Articles

Exploring boratrane's potential to enhance the thermal stability of phenol-formaldehyde resins by borate bridge as a crosslinker and the mechanistic formation of boron species in carbonaceous materials: A comprehensive study

In advanced material science, we explore the potential of boratrane, a promising agent for enhancing thermal stability. By combining rigorous Density Functional Theory (DFT) calculations with groundbreaking experimental analyses, we reveal the intricate interplay of radical intermediates and mechanisms underlying the thermal evolution of boratrane-infused materials. Our innovative approach illuminates dynamic structural transformations and elucidates boratrane's pivotal role in fortifying thermal resilience. The DFT calculations identify radical intermediates and mechanisms of thermal degradation, highlighting the role of borate bridges in delocalizing π-electrons in aromatic rings through Gibbs free energy (∆GRXN), Highest Occupied Molecular Orbital (HOMO), Lowest Unoccupied Molecular Orbital (LUMO), and electrostatic potential (ESP) analyses. Fukui function analysis provides insights into the reactivity of these structures towards free radical attacks. Our findings demonstrate that boratrane-modified resins exhibit a stable BO4- structure, which prevents self-condensation of boratrane to B2O3 and enhances the thermal stability of oxygenated resins. This improvement is due to the formation of intramolecular hydrogen bonds, contributing to helix-like structures that strengthen the resin. The mechanism by which the BO4- structure terminates radical agents and transforms into carbonaceous material is elucidated through thermodynamic values, revealing the plausible reactions and chemical structure of boron in the resulting material.

Effect of Si3N4 on the in-situ synthetized non-oxide reinforcements in Al-Al2O3 composites under N2 atmosphere

Al-Al2O3 composite is widely used in high-temperature industry due to its excellent properties obtained through in-situ synthesis of non-oxide reinforcing phases. The effect of nitrogen source on the non-oxide reinforcing phases synthesized in-situ in the Al-Al2O3 composites at 1500 °C was investigated. The results show that when N2-gas is the sole nitrogen source, Al4O4C is the major reinforcing phase formed in the composite due to insufficient nitrogen amount provided. Through the construction of an Al@AlN core-shell structure and spontaneous nitrogen introduction by solid Si3N4 and N2-gas, higher amount of AlN mesophase is generated, and the complete transformation of Al to (Al2OC)1-x(AlN)x solid solution is successfully achieved. However, when Si3N4 content is excessive (i.e. Si/C mole ratio ≥ 1, where Si comes from solid nitrogen source Si3N4, C comes from phenolic resin binder), the stability of (Al2OC)1-x(AlN)x solid solution decreases, and more stable AlN-SiC solid solutions and SiAl4O2N4 are generated as reinforcing phases in the composite. This work provides meaningful information for the phase control of Al-Al2O3 composite at high temperature application.

Hydrolytic Stability of Sengon-Oriented Strand Board Bonded with Hybrid Phenol-Formaldehyde/Polymeric Methylene Diphenyl Diisocyanate Adhesives

The hydrolytic stability of oriented strand board (OSB) is critical to guarantee good performance in humid conditions over the long term. The adhesive system impacts hydrolytic stability in addition to the wood strands. This study aims to investigate the hydrolytic stability of OSB bonded with a hybrid adhesive based on phenol-formaldehyde (PF) and polymeric methylene diphenyl diisocyanate (pMDI) modified with NaOH and CaCO3 catalyst. PF was mixed with each catalyst at approximately 1% of the PF solids content. The pMDI was added to the mixture at 2.5% and 5% of the PF solid content. The hybrid PF/pMDI adhesives were then used for OSB production. The hydrolytic stability of OSB samples was tested at 25°C and 100°C and compared with OSB using unmodified PF as a control. After hydrolysis, OSBs with hybrid PF/pMDI adhesives had lower weight loss than control adhesives at both temperatures. The pH indicates no significant polymer dissolution from the board into the hydrolysis solution. Hybrid PF/pMDI adhesives with a CaCO3 catalyst obtain significantly lower thickness swelling values. The findings of this study have significant implications for developing high-performance, environmentally-friendly OSB products. Keywords: eco-friendly composite, hydrolytic stability, oriented strand board, Paraserianthes falcataria, phenol-formaldehyde

Exploring the potential of Gigantochloa levis and Gigantochloa scortechinii bamboo species for plybamboo production

Gigantochloa levis and G. scortechinii bamboo species were evaluated as material for plybamboo production. Plybamboo was composed of three layers with 12 mm thickness and used phenol formaldehyde (PF) as their binder. Representative samples were cut and tested for bonding, physical, mechanical, and finishing properties. Results indicated that G. levis plybamboo exhibited higher bending strength property compared to G. scortechinii plybamboo, as indicated by its higher modulus of rupture (121 N/mm2) and modulus of elasticity (16300 N/mm2). The G. levis plybamboo also displayed higher bond shear strength and was dimensionally stable compared to G. scortechinii plybamboo. The finishing properties revealed that all coatings performed well in the cross-cut tape and pull-off tests. Notably, plybamboo from both bamboo species showed excellent coating film adhesion. Based on minimum standard requirement, results revealed that both bamboo species were suitable to be used in plybamboo production for general use. The findings showed that those species are valuable renewable natural resources for plybamboo production and had potential to be utilized as a substitute for wood in board production.

Continuous flow-through electro-Fenton membrane reactor with Fe−N4-doped carbon membrane as cathode for efficient removal of dimethylacetamide

Fe − N4-doped conductive carbon membranes (FeCMs) were fabricated through high-temperature carbonization using chitosan and phenolic resin as the raw materials and ammonium ferrous sulfate (NH4Fe(SO4)2) as the dopant. The impact of the NH4Fe(SO4)2 doping rate (0 − 15 wt%) on the structure and performance of the FeCM was investigated. Moreover, a continuous flow-through electro-Fenton membrane reactor (EFMR) was constructed using an FeCM cathode and a Ti plate anode for the efficient removal of dimethylacetamide (DMAC). The resultant carbon membrane with 10 wt% NH4Fe(SO4)2 (M10) exhibited a smaller pore size (40.1 nm), a higher porosity (48.3 %), a larger specific surface area (531.6 m2/g), and a higher mechanical strength (6.7 M Pa) than the other membranes. The removal rate of DMAC by EFMR with M10 as the cathode at 2 V reached 42.1 %, which was much greater than that without NH4Fe(SO4)2 (3.6 %). The electrosynthesis ·OH concentration by EFMR with M10 as the cathode was approximately 89.1 mg/L, which was much greater than that of most carbon-based materials. The intermediates of DMAC degradation (such as N-methylacetamide, acetamide, acetaldehyde, and acetic acid) were determined by gas chromatography–mass spectrometry (GC–MS), and the removal of total organic carbon (TOC) was approximately 3.4 %. Density functional theory (DFT) calculations revealed that the Fe atom served as the active site for dissolved oxygen adsorption and electrogeneration of ·OH. After 5 days of continuous EFMR operation, the DMAC removal rate remained at 88.8 % of the initial value (42.1 %). This study presents a novel approach for designing and fabricating conductive carbon membranes to improve industrial wastewater treatment performance.

Bond line shear strength of structural wood adhesives at high temperatures up to wood carbonization – A classification approach

The European timber fire design code EN 1995-1-2 presently specifies that adhesives for timber construction products shall provide integrity throughout the intended fire exposure time, yet no test or requirement specifications are given. Contrary, in North America elevated temperature tests are mandatory and product standards for glued and cross laminated timber demand sufficient bond line shear strength up to 220 °C. This paper deals with block shear compression tests at ambient and elevated temperatures for development of a high temperature resistance classification system for structural wood adhesives. The investigations comprised 1200 specimens made from Norway spruce bonded with twelve brands from five adhesive families. Polycondensation (pcon) resins encompassed phenolic resorcinol formaldehyde, melamine urea formaldehyde and melamine formaldehyde adhesives. Polyaddition (padd) adhesives comprised five one-component polyurethanes and an emulsion polymer isocyanate. The focus was on the strength-temperature (fv-T) relationship of bonded and solid wood reference specimens at 180–270 °C. The pcon adhesives showed almost throughout a fv-T relationship close to solid wood up to 270 °C. Contrary, the padd adhesives revealed massive strength degradations vs. solid wood from 180 °C onwards. An adhesive test, evaluation and classification procedure with four classes T270 to T200 was derived. It is based on a comparison of the temperature-dependent shear strength decline in bonded samples vs. solid wood reference samples beyond 180 °C. Class T270 adhesives are proposed being suited for the linear charring model of EN 1995-1-2 as PRF adhesives without additional fire resistance testing of components deemed necessary today.

Sulfonated lignin-based phenol–formaldehyde resin: stability and structure changes during aggregation

Sulfonated lignin-based phenol–formaldehyde resin: stability and structure changes during aggregation

In-situ formation of surface “self-protective” graphitic layer on phenolic resin-based thermal protection composites

Phenolic resin (PR) composites are widely utilized as thermal protection materials for high-speed aircraft, where their protection mechanisms have been investigated in earlier studies. However, it remained indistinct about the evolution behavior of the outermost surface and its subsequent effects on the ablation performance. Herein, this work re-investigated the morphological transformation and chemical conversion on the outermost surface of a silica fiber-reinforced PR board after ablation by means of combined experimental characterizations at micro- and nanoscale (SEM, TEM, Raman spectroscopy, XRD, XPS) and computational study (ReaxFF-based molecular dynamic simulation). For the first time, our study revealed that its outermost ablated surface demonstrated a distinct evolution behavior in terms of both the in-situ formation of “self-protective” graphitic layer and the radial redistribution of surface carbonaceous substances with different degrees of graphitization, leading to varied ablation resistance along the radial direction of the PR board. In addition, the computational study investigates the ablation-induced graphitization and its influence on the ablative resistance of PR surface. It indicated that, at equivalent energy flux density, PR with graphitized structures exhibited improved thermal protection performance, which can be attributed to decreased thermal conductivity and increased density, leading to a reduced ablation recession rate. Such revelation provides an alternative route in the design of PR-based ablative materials with enhanced ablation resistance.

Preparation and Magnetic Properties of Low-Loss Soft Magnetic Composites Using MgO-Phenolic Resin Coating.

Optimizing the interface between a magnetic powder matrix and an oxide-insulating layer is an effective method to improve the permeability and lower eddy current loss of iron-based soft magnetic composites. In this study, in order to improve the bonding strength of the substrate and insulation layer, soft magnetic composites were prepared by pressing and heat treating with reduced iron powder as a magnetic matrix, high-temperature MgO nanoparticles as insulating coating, and phenolic resin as an adhesive. The effects of MgO content on the microstructure and magnetic properties of the composites were investigated. The results of a scanning electron microscopy and an energy-dispersive spectrometer analysis corroborate that the results obtained regarding the frequency characteristics and the resistivity of the iron powder agree with the scanning electron microscope (SEM) and energy dispersive spectrometer (EDS) analysis and confirm their improvement by the presence of an insulating layer of MgO. The resistivity of the sample coated with 4 wt.% MgO is nearly 45 times higher than that of the uncoated sample under the same conditions. The MgO-insulating film formed on the surface of iron powder makes the coated sample have low effective grain size, high resistivity, and low magnetic loss at a high frequency. At 1 kHz, the magnetic loss of the 4 wt.% MgO-coated sample is reduced by 77.3%, and the magnetic loss is only 5.8% compared with the uncoated sample at 50 kHz. This magnetic loss separation study shows that the addition of MgO insulation material can effectively reduce the eddy current loss of the magnetic powder core. The 4 wt.% MgO-coated sample has the lowest hysteresis loss factor and relatively low eddy current loss factor, so it can be determined that the addition of 4 wt.% MgO is the optimum content to attain a low magnetic loss.

Wear-resistant phenolic composites reinforced with attapulgite and short carbon fibers for applications subjected to both dry and oil-lubricated sliding

Attapulgite (AT) nanofibers were integrated into phenol-formaldehyde resin (PF) and PF composites reinforced with short carbon fibers (CF). Inclusion of AT significantly enhances the wear resistance of PF under both dry and oil-lubrication conditions. The hybrid nanocomposites, reinforced with both AT and CF, exhibit a high mechanical strength. Interestingly, AT and CF lower synergistically the friction coefficient of PF subjected to harsh dry sliding conditions. The hybrid nanocomposites exhibit excellent tribological performance under both dry and oil-lubrication conditions. Tribofilms’ nanostructures were comprehensively analyzed for disclosing dominant tribological mechanisms. Outcome of this work provides new ideas for developing tribo-materials of a high adaptability to various dry/oil-lubrication conditions.

Highly graphitized carbon foam to construct phase change materials composites for multiple solar−thermal energy conversion

Nowadays, converting and storing solar energy is crucial in contemporary society. Thermal energy storages (TESs) can be vital in harnessing solar energy effectively. Phase change materials (PCMs) are favorable candidates for TESs owing to the smoothing outcome and, thus, increasing reliability. However, these materials suffer from limited thermal conductivity, inadequate light absorption, and high leakage during phase transition. In the present study, a facile and scalable graphitized carbon foam/Ni nanoparticles composite with exciting properties such as excellent light adsorption and high thermal conductivity was prepared as a platform to overcome the PCMs challenges. To obtain this composite, the coated commercial melamine foams (CMF) with an ethanolic solution containing the phenolic resin and NiCl2.6H2O were pyrolyzed at 900 °C. The composite foam (CNiF) was utilized as a framework for paraffin (PA), which was soaked in melted PA at 75 °C under the vacuum drying oven for 50 min (CNiF/PA). The prepared black and magnetic composites exhibited high photo-to-thermal energy efficiency of 66, 80, and 92 % under light intensities of 900, 1000, and 1100 W/m2, respectively. In addition, the composite controls voltage fluctuations and prevents voltage drops in thermoelectric generators (TEGs) in solar thermal systems. The output voltages were 0.51, 0.63, and 0.81 V under light intensities of 1500, 1800, and 2100 W/m2, respectively. Moreover, the magnetically moving magnetic carbon foam solar absorber within the molten PA along the solar illumination path dramatically enhances the speed of solar-thermal energy storage. The set-up was subjected to light with an intensity of 1500 W/m2, which revealed a decrease in melting time, with the PA melting in 86 min. The PA melting time decreased by 37 % under solar irradiation.

Synthesis of phenolic resins with cyclotriphosphazene for enhancement of ablation and char yields

A novel phenolic resin with combined hydroxymethyl-substituted phosphazene unit as a part of cured network was prepared which exhibited excellent thermal properties and ablation resistance. The novel phenolic resin was synthesized via copolymerizing from hexa (4-hydroxymethylphenoxy) cyclotriphosphazene (CHPP), phenol and paraformaldehyde. The CHPP contains abundant –CH2OH groups, which can be a part of phenolic resin network through condensation reactions between the –CH2OH groups and active hydrogens on benzene rings of phenolic resins. The optimal curing temperature for the modified phenolic resins was determined using the non-isothermal DSC method. The ablation resistance was investigated using the oxyacetylene flame method. The char yield and linear ablation rate of the modified phenolic resins are 71.3 % and 0.0020 mm/s, respectively. The ablation resistance of the novel resin is significantly improved, compared with other phenolic resin composites. The modification method for the phenolic resin provides a novel pathway to improve the application prospects of phenolic resins in the field of thermal protective materials.

Experimental Analysis of Bonding in Steel Glued into Pine Timber.

Combining steel with wood has been practised for many years. The issue is related to two main areas, i.e., bonding steel elements with wood so that they serve as connectors facilitating the assembly of wood elements and bonding steel elements to wood beams to improve their load-bearing capacity. In the first case, the adhesives used may be relatively expensive and more difficult to apply, whereas in the second one, especially when steel elements are glued inside the glulam (GL) beams, it is better if the adhesives used are more accessible to apply and cheaper. As it seems rational to reinforce wood with high-modulus ties, research has been carried out to compare the connection quality of commercially available adhesives that can be used for this purpose. Moreover, thermosetting adhesives have been applied as an alternative and cheaper solution. Thermostat adhesives also have a high pH of the bond, which prevents the steel from rusting. The research shows that the load-bearing capacity of the bond depends on whether the bars are ribbed or sheet metal. Moreover, among thermosetting adhesives, the most favourable load-bearing values were obtained using a mixture of PF/pMDI (phenol formaldehyde resin/polymeric diphenylmethane diisocyanate) and powder from recycled tyres. The shear strength of these joints was 1.63 N/mm2 and 3.14 N/mm2 for flat specimens and specimens with ribbed bars, respectively.

Anti-oxidative quartz/carbon-braided fiber reinforced ceramizable composites modified with B4C and AlB2: Mechanical robustness, phase evolution and anti-oxidation mechanism

Carbon fiber reinforced ceramizable phenolic resin matrix composites (Cf/CPR) have been widely used in the field of thermal protection materials. However, the industrial application of the Cf/CPR is restricted by its easy oxidation failure under high temperature condition. In this work, a novel antioxidative ceramizable composites modified with AlB2 and B4C (Cf-Qf/CPR) were prepared by using quartz fiber-coated carbon fiber (Cf-Qf) as reinforcements via co-weaving technique. The thermal stability, mechanical properties, interfacial phase evolution and anti-oxidation mechanism of the composites were investigated. The residue yield and the flexural strength of the composites after treatment at 1200°C for 15 min were 93.4 % and 62.4 MPa, increased by 5.4 % and 67.3 % compared with those of Cf/CPR. Quartz fiber and ceramic protective layer showed synergistic effect to improve the oxidation resistance of carbon fiber and PyC, confirming good high temperature mechanical properties and oxidation resistance of as-received composites.

N-doped nano-casted carbon monolith for Pb (II) removal and photocatalytic degradation of thiamethoxam from aqueous solution.

Single rock-like N-doped carbon monolith (ND-PFCM) was successfully constructed via nanocasting method. Phenol formaldehyde resin was taken as carbon source and nitrogen was incorporated in monoliths through NaNH2 activation. The synthesized monoliths were used for the removal of Pb (II) from aqueous solution. Various characterization techniques, namely Brunauer-Emmett-Teller (BET), Raman spectroscopy, UV-visible diffuse reflectance spectra (DRS) UV-DRS, zeta potential, scanning electron microscopy (SEM), TEM (transmission electron microscopy), TGA (thermogravimetric analysis), and XPS (X-ray photoelectron spectroscopy), were utilized to characterize synthesized monolithic samples. The different parameters such as pH, adsorbent dosage, and time were enquired on the removal efficiency of monoliths toward Pb(II). ND-PFCM exhibited the highest adsorption capacity of 330.03mgg-1 in 180min at pH 6. This is attributed to the fact that the better texture properties and presence of nitrogen functional groups enhance the uptake of Pb (II) ions on the monolith surface. In the kinetic studies, pseudo-second-order model fitted best with the experimental data. Furthermore, the removal of thiamethoxam (TM) from aqueous solution was done by using different weight ratios of ND-PFCM under the visible light. The maximum removal efficiency of 97.35% with rate constant of 0.02085min-1was obtained in 160min. Moreover, monoliths exhibited good reusability for five consecutive cycles. The findings suggest that the synthesized monoliths exhibit characteristics suitable and eco-friendly for sustainable use in water treatment applications.

Morphological Control and Mechanical Properties of Porous Phenolic Resins Derived from Poly(4‐Vinylphenol): Effects of Molecular Weight and Polydispersity of Prepolymer

Improvement of mechanical stability for porous polymer monoliths is one of the prime concerns as represented by the long‐standing research efforts on resorcinol‐formaldehyde (RF) aerogels. To this end, it is imperative not only to tailor mechanically robust porous morphology but also to design macromolecular structure of polymer scaffolds. Previously, we have developed porous RF gels showing a unique mechanical feature combining high mechanical strength and outstanding flexibility against uniaxial compression. Comparison of mechanical properties between the porous gels with varied morphologies has elucidated the influence of porous structure, whereas effects of macromolecular structure still remain elusive. Herein, we have fabricated a series of macroporous phenolic resins from three types of linear prepolymers with phenol pendant groups, poly(4‐vinylphenol) or poly(4‐hydroxystyrene), which differ in molecular‐weight properties, by the sol–gel process in conjunction with spinodal decomposition. The difference in gelation and phase separation behaviors observed for the discrete systems indicates the dissimilar cross‐linked networks developed in the respective gels, which consequently influence the mechanical strength and flexibility against uniaxial compression. This study also demonstrates the improvement of mechanical features by thermal treatment for the porous monoliths derived from the high‐molecular‐weight prepolymer with a view to the application in mechanical energy absorption.

Phenolic resin-based nanoflower porous carbon synthesized by self-assembly of MgO hydrolysis for boosting supercapacitor performance

Although electrode materials with flower-like structures have showing promising achievement for battery energy storage for stable structure and rich specific surface area, there are still some challenges in precisely controlling their microstructure. Inspired by the hydrolysis and self-assembly of MgO into petal-like magnesium hydroxide crystals under alkaline critical micelle conditions, we have proposed to synthesize a unique phenolic resin with a 3D flower-like structure as a carbon precursor. After a series of treatments, the optimal sample consists of nanosheets (thickness ≈27 nm) extending in all directions from the core, with a porous structure, significant specific surface area of 2028 m2/g and pore volume of 1.79 m3/g. Electrochemical experiments confirmed that the sample exhibits satisfactory electrochemical performance as the electrode of supercapacitor. It shows an amazing unique capacitance of 320.1 F/g, and the charge–discharge capacity retention rate exceeds 94.6 % after 5000 cycles. Moreover, a high energy density of 9.44 Wh/kg at 126 W/kg is shown for the symmetrical supercapacitors. We believe that the 3D flower-like morphology formed by the unique lamellar structure can provide more active sites, promote ion transports and increase the stability of structure. These findings suggest a new strategy to control the morphology of phenolic resin-based carbon materials.

Study on the physico-mechanical properties and mechanisms of poplar wood co-modified by anoxic high-temperature heat treatment and impregnation with silica sol/phenolic resin

Addressing the challenges of fast-growing poplar wood in construction, decoration, and furniture, including low density, insufficient strength, poor toughness, and suboptimal dimensional stability, this study introduces an innovative organic/inorganic impregnation-heat treatment technique. This method significantly enhances the physico-mechanical properties of poplar wood and overcomes issues associated with thermosetting resin modification, such as reduced impact toughness, uneven resin penetration, and wood swelling. Utilizing in situ polymerization with silica sol and phenolic resin, specifically with particle sizes between 8 and 15 nm, the process markedly improves wood permeability and overall properties through vacuum pressure impregnation and heat treatment. The findings indicate a 54.42 % increase in the wood's density. Optimized heat treatment at 180 °C for 1 h significantly enhances dimensional stability and reduces water absorption, with the ASE value reaching up to 69.3 %. Furthermore, the impregnation-heat treated wood exhibits a 50.19 % increase in bending strength to 81.6 MPa, a 103.93 % increase in modulus of elasticity to 16.5 GPa, and a 29.42 % increase in impact toughness to 92.5 kJ/m2, demonstrating substantial improvements over the raw material. FT-IR analysis reveals the presence of Si-O-Si vibration peaks, indicating the effective penetration of silica sol. TGA analysis displays the treated material's superior thermal stability compared to the raw material. XRD analysis confirms that the impregnation and heat treatment processes have not adversely affected the wood's crystalline regions but have instead reduced hygroscopicity and enhanced stability. SEM analysis showed that the composite impregnation liquid effectively penetrated and distributed within the wood cells. These results open new theoretical and technical pathways for enhancing the physico-mechanical properties of fast-growing poplar wood.

Preparation Conditions and Property Characterizations of Semi-coking Wastewater based Phenolic Resin

Preparation Conditions and Property Characterizations of Semi-coking Wastewater based Phenolic Resin

Improving the Oxidation Resistance of Phenolic Resin Pyrolytic Carbons by In Situ Catalytic Formation of Carbon Nanofibers via Copper Nitrate.

Phenolic resin pyrolytic carbons were obtained by catalytic pyrolysis of phenolic resin at 500 °C, 600 °C, 700 °C, and 800 °C for 3 h in an argon atmosphere using copper nitrate as a catalyst precursor. The effects of copper salts on the pyrolysis process of phenolic resin as well as the structural evolution and oxidation resistance of phenolic resin pyrolytic carbons were studied. The results showed that copper oxide (CuO) generated from the thermal decomposition of copper nitrate was reduced to copper (Cu) by the gas generated from the thermal decomposition of the phenolic resin. Carbon nanofibers with tapered structures were synthesized by Cu catalysis of pyrolysis gas at 500-800 °C. The catalytic pyrolysis of phenolic resin with Cu increased the graphitization degree and reduced the pore volume of the phenolic resin pyrolytic carbons. The combined action improved the oxidation resistance of phenolic resin pyrolytic carbons.