Phenolic Resin Research Articles

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.

Experimental study on selected properties and microstructure of pine-based wood ceramics

Abstract Wood ceramics using biomass materials as templates possess the benefits of facile fabrication and versatile applicability. To investigate the physical properties, chemical properties and microstructure of wood ceramics prepared from biomass materials, the basic properties and potential applications of wood ceramics were expounded. In this paper, wood powder wood ceramics (WPWC) and wood fiber wood ceramics (WFWC) were prepared through the vacuum carbonization method, utilizing pine powder and pine fiber as raw materials. The impact of phenolic resin concentration and mixture filling mass on various properties of wood ceramics, including mass loss rate (MLR), volume shrinkage rate (VSR), apparent porosity (AP), and bending strength (BS) were investigated on this basis. The microtopography and pore structure of wood ceramics were also analyzed. The test results show that an increase in the concentration of phenolic resin led to a decrease in the MLR, VSR, and AP of WPWC and WFWC, while their BS exhibited an increase. When the concentration of phenolic resin was 60 %, the phenolic resin yielded a BS of 8.70 MPa and 9.20 MPa for WPWC and WFWC, respectively. Furthermore, the microstructures of both WPFC and WFWC reveal hierarchical porous structures. The difference is that WPFC has a dispersed three-dimensional network topology in its overall morphology, which is mainly formed by filamentous or long linear glass carbon in wood ceramics dominated by carbon. The natural and consistent pore structure of WFWC is comparable to a three-dimensional honeycomb structure, the primary mesoporous size was around 40.28 nm and the main macropore size was more than 10,000 nm. It elucidates the pore structure of WPWC and WFWC, characterized by “hierarchical porosity”, the differences and relationships between porous wood ceramics derived from powdery and fibrous biomass as raw materials were analyzed, which contributes to the advancement of the fundamental principles of wood ceramics and establishes a theoretical basis for the practical exploration and development of biomass materials.

Laser powder bed fusion sintering mechanism of phenolic resin investigated by ReaxFF molecular dynamics simulations

ABSTRACT This study presents an innovative approach utilising molecular dynamics simulations to elucidate the polymerisation and neck formation mechanisms of phenolic resin during laser powder bed fusion (L-PBF). By developing system and dual-particle models and employing infrared thermal imaging, we established a heat source model for phenolic resin under varying parameters. Our molecular dynamics simulations, using the ReaxFF reactive force field, indicate that high-power lasers significantly enhance cross-linking, achieving a peak polymerisation degree of 78.9% at 30W and 35W power levels. Conversely, increased scanning speed slows product degradation, reducing the polymerisation degree. The interplay of laser power and scanning speed influences polymerisation, with total input energy and heating rate impacting polymerisation and molecular size. Additionally, we investigated neck formation, revealing that small vortices evolve into larger ones during sintering, promoting neck formation. Optical microscopy confirmed diverse neck shapes under different conditions. Quantitative data showed that at a scanning speed of 1000 mm/s, the polymerisation degree reached 93%, with only 2 molecules remaining post-simulation. At 30W power, the largest individual molecule observed was C849H703O117. This research offers crucial insights for selective laser sintering processes, emphasising the importance of high energy input and optimal heating rates for well-formed necks.

Effect of Lignosulphonates on the Moisture Resistance of Phenol-Formaldehyde Resins for Exterior Plywood.

Phenol-formaldehyde (PF) resins remain the preferred adhesive for exterior plywood, as they confer these boards their extreme weather resistance. However, their high price and toxicity has made phenol alternatives, such as technical lignins, increasingly more attractive. While many works report the use of kraft lignin, the most commercially available form are lignosulphonates (LS). However, these lack industrial success and are associated with low moisture resistance. In the current study, lignosulphonate-phenol-formaldehyde (LPF) resoles were synthesized considering a phenol replacement of 30% (w/w). Two LS samples of softwood (SLS) and hardwood (HLS) origin were compared. These samples were previously methylolated to increase their reactivity. The effectiveness of the treatment was confirmed through the Automated Bonding Evaluation System. Plywood was manufactured and tested according to EN 314 class 3 for exterior conditions, which is seldom found in the literature. Although a 35% increase in shear strength is still necessary to comply with the standard, methylolated SLS was the most promising substitute, as it resulted in the highest board performance. Notably, when this sample was used without previous methylolation, the plywood boards suffered delamination during immersion in boiling water prior to shear testing. These results reinforce the need for the methylolation of LS to increase the weather resistance of plywood.

Templating-induced graphitization of novolac using graphene oxide additives

Increasing graphite demand for energy storage applications creates the need to make graphite using precursors and processes that are affordable and friendly to the environment. Non-graphitizing precursors such as biomass or polymers are known for their low cost and sustainability; therefore, graphitizing them will be an accomplishment. In this work, a process of converting a non-graphitizing precursor, phenolic resin novolac (N), into a graphitic carbon is presented. This was achieved by the addition of five additives categorized as graphene oxide (GO) and its derivatives with varied oxygen concentrations. The hypothesis is that the additives act as templates that promote matrix aromatic alignment to their basal planes during carbonization (physical templating) in addition to forming radical sites that bond to the decomposing matrix (chemical templating). Results showed that the addition of reduced graphene oxide (RGO) additives of approximately 15.4 at.(%) oxygen content to the novolac matrix (RGO-N) show the best graphitic quality. In contrast, the addition of GO additive of twice or more oxygen content ≥ 30.8 at.(%) to the novolac matrix (GO-N) led to poor graphitic quality. This suggests that there is an optimum amount of oxygen content in GO additives needed to induce graphitization of the novolac matrix.

Synergistically improve the strength and porosity of carbon paper by using a novel phenol formaldehyde resin modified with cellulose nanofiber for proton exchange membrane fuel cells

To optimize the imbalance between the interfacial bonding and porosity properties of carbon paper (CP) caused by phenol formaldehyde resin (PF) impregnation, and therefore improve the performance of proton exchange membrane fuel cells (PEMFCs), a new approach through cellulose nanofibers grafted with methyl methacrylate (CNFM) as a modified reinforcement and pore-forming agent for PF is investigated. Through suppressing the methylene backbone fracture of CNFM-modified PF during its thermal depolymerization, the interfacial bonding between PF matrix carbon and carbon fibers is enhanced. Compared with unmodified CP, the in-plane resistivity of CNFM-modified CP is reduced by 35.78 %, while the connected porosity increases to 82.26 %, and more homogeneous pore size distribution (PSD) in the range of 20–40 μm is obtained for CNFM-modified CP. Besides, the tensile strength, flexural strength, and air permeability of CNFM-modified CP increase by 72.78 %, 298.4 %, and 103.97 %, respectively. In addition, CNFM-modified CP achieves the peak power density of PEMFCs to 701.81 mW·cm−2, exhibiting 10.98 % improvement compared with commercial CP (632.39 mW·cm−2), evidently achieving an integral promotion of CP and comprehensive performance.

Carbon whiskers reinforced porous glassy carbon composites by synchronous growth

A crystalline and non-crystalline composite of pure carbon was proposed, which is a carbon whiskers reinforced porous glassy carbon composite, where crystalline carbon whiskers support the microscopic pores of non-crystalline glassy carbon matrix. Two allotropes of carbon were produced simultaneously and compounded together in a single high temperature treatment of thermosetting phenolic resin, with aluminum oxide (Al2O3) as a catalyst. A synchronous growth theory was proposed to explain the growth mechanism. In the pyrolysis process of phenolic resin to generate porous glassy carbon, hydrocarbon gas was produced and trapped in the generated pores. By the same time, the hydrocarbon gas in pores was decomposed and grew carbon whiskers by catalysis of Al2O3. With linear thermal expansion coefficient from 2.0∙10−6 to 3.8∙10−6 K−1, thermal conductivity from 1.763 to 2.518 W∙m−1 K−1, specific heat capacity from 0.396 to 0.752 J∙g−1 K−1, thermal diffusivity from 6.115 to 4.598 mm2 s−1, between room temperature (RT) and 500 °C, the Vickers hardness is at 65 MPa, and the fracture toughness is at 0.329 Mpa∙m1/2 in RT. The carbon whiskers reinforced porous glassy carbon composite keeps a balance between thermophysical and mechanical properties, showing its application value in thermal insulation materials and high temperature structure materials.

Synthesis and characterization of biodegradable Kraft lignin-based hydrophilic phenol formaldehyde foams

Phenol formaldehyde foams, extensively utilized in wide range of applications face challenges due to depleting petroleum resources and adverse environmental concerns. This study explores a promising shift to biobased alternatives, specifically investigating the use of Kraft lignin (KL) by replacing about 10 to 50% phenol content to synthesize open-cell hydrophilic phenolic foams. The produced foams undergo comprehensive testing to evaluate wetting properties, porosity, mechanical strength, and biodegradation potential. Remarkably, foams with a high percentage of Kraft lignin exhibit outstanding physical and wetting characteristics. Notably, substituting 50% of phenol with KL gave rise to a foam with a density of 40 kg/m3, open cell porosity of about 100%, water absorption capacity of 2100%, and an average water uptake rate of 0.9 cm3/s. Furthermore, these lignin-substituted foams display enhanced biodegradability compared with their petroleum-based counterparts. The foam with the 40% phenol substitution exhibits the highest weight loss of approximately 68% in 15 days during the biodegradation test. The biodegradation was further confirmed using scanning electron microscopy and FT-IR analysis of the degraded samples.

The influence of sizing treatment on the mechanical and morphological properties of carbon fiber reinforced polyphenylene sulfide composites

AbstractCarbon fiber reinforced thermoplastics (CFRTPs) demonstrate promising applications in engineering sectors, and the interfacial interaction between CFs and the matrix plays a significant role in determining the properties of CFRPs. This work attempted to study the influence of sizing agent on the properties of polyphenylene sulfide/CF (PPS/CF) composites with an aim to fabricate PPS/CF composites with enhanced mechanical properties. The results showed that the use of 2 wt% boron phenolic resin as the sizing agent favored the formation of a uniform interfacial layer on the surface of CFs. Contact angle tests revealed that corresponding sized CFs exhibited the smallest contact angle and the highest surface energy among the studied systems. As a result, the sizing agents acted as a protective layer for CFs during melt processing process, which mitigated the damage to the CFs. The average length of CFs was longer after melt extrusion process which was vital for achieving high mechanical performance of PPS/CF composites.Highlights Coating sizing agent protected CFs from being fractured during melt processing. Applying 2 wt% BPR sizing agent yielded the best interfacial performance. The tensile strength and Yong's modulus of PPS/CFB2 reached as high as 155.9 and 7618.21 MPa. The tensile fracture mode between BPR‐treated CFs and PPS was cohesive damage.

Effect of Polycarbosilane (PCS) on the High-Temperature Properties of Phenolic Resin (Phen) Films and Quartz Fiber/Phen-PCS Composites

In this study phenolic resin (Phen)-loaded PCS (Phen-PCS) films were prepared and quartz fiber/Phen-PCS composites based on the resin films were also prepared. The quartz fiber/Phen-PCS composites were prepared by impregnating 2.5 Dimension (2.5D was an arrangement of fibers) quartz fibers using the resin film infusion (RFI) process. The properties of the composites were investigated. The study demonstrated that the density of the composites, after curing gradually increased with the increase in PCS. The flexural strength of the composites exhibited a trend of increasing and then decreasing after curing and pyrolysis at 1100 °C under an N2 atmosphere. The flexural strength of the composites reached 13.73 MPa when the addition of PCS was 30% of the phenolic resin, representing an increase of 74.23% compared to that of the composites without PCS. The porosity was found to be as low as 2.3% after curing and 2.1% after pyrolysis. X-ray diffraction (XRD) analysis and infrared spectroscopy tests demonstrated that ceramicization products, such as SiO2 and SiC, were produced after pyrolysis of the composites containing PCS. This transformation significantly enhanced the ablation resistance of the composites. Butane flame tests were performed, and the lowest line and mass ablation rates were 0.026 mm/s and 0.196 mg/s after curing. The results of the study revealed the potential of PCS as a precursor to improve the mechanical properties and heat resistance of composites, which offers promising material options for high-temperature applications.

Anode of Anthracite Hard Carbon Hybridized by Phenolic Epoxy Resin toward Enhanced Performance for Sodium-Ion Batteries

Anode of Anthracite Hard Carbon Hybridized by Phenolic Epoxy Resin toward Enhanced Performance for Sodium-Ion Batteries

Phase evolution of Al–Al2O3–ZrO2 refractories at 1300 °C under N2 flowing

In order to obtain Al–Al2O3–ZrO2 composite refractories with excellent oxidation resistance, erosion resistance and thermal shock stability, metallic aluminium and fused Al2O3–ZrO2 were used as the raw materials, while phenolic resin was used as the binding agent. The microstructure was characterised by means of X-ray diffraction and scanning electron microscopy tests. Based on the reaction between zirconia and metallic aluminium under N2 flowing at 1300 °C, the reaction mechanism of zirconia and metallic aluminium in-situ reaction at 1300 °C to generate (Al2OC) x(AlN)1− x solid solution, zirconium nitride, and aluminium–zirconium alloy was revealed, and a model for the evolution of the phases in the aluminium-added Al–Al2O3–ZrO2 specimen was constructed to realise the Al–Al2O3–ZrO2 composite refractories phase controlling. Based on the good corrosion resistance of ZrO2 to CaO and the excellent results of the in-situ reaction of metallic aluminium to generate a large number of non-oxide reinforcing phases capable of replacing elemental C, this work is of great significance for the study of refractory in erosion-heavy environments, such as calcium-treated steel.

The influence of binder type on the properties and performance of taphole clays for blast furnaces

Taphole clay (THC) is an unshaped refractory commonly used in blast furnaces to seal the taphole after the tapping process has been completed. THC is typically bonded with conventional coal tar pitch (CTP), but alternative binders have been developed due to the high toxicity of this material. This study investigated the performance of various binders commonly added to THCs, including CTP, phenolic novolac resin (PNR), low benzopyrene coal tar pitch (ECTP), and a petroleum-based binder (PBB). The properties of the prepared THCs were investigated, and the analytical hierarchy process was used to infer the behaviour of the prepared materials during blast furnace operation. The results obtained show that the best binder for a particular THC depends on its operational requirements. In cases where excellent injectability and hearth protection are mandatory, CTP or ECTP are highly recommended. Conversely, if a low-toxicity and easy-to-drill THC is required, PBB emerges as a promising binder. PNR is the recommended choice for blast furnaces where rapid cure and tapping stability are priorities.

Development of Mineral Fillers for Acid-Resistant Filling Composites

This article presents the results of research on the development of chemically resistant polymer–mineral casting composites based on industrial waste. The aim of this work is to develop a technological basis for obtaining effective inorganic fillers and highly filled composites for use in chlorine-containing environments. On the basis of theoretical data, mineral fillers and a polymer binder for filling composites were selected, optimal quantities of input hardeners and an appropriate thermal curing mode were determined, and the influence of the filling degree on the properties of composites was studied. The influence of various factors on the properties of the obtained composites was also studied, and the possibility of using local raw materials to obtain special-purpose composites was investigated. Ash from a thermal power plant (TPP) was used as an acid-resistant filler in composites. Two components were chosen as binders: phenol formaldehyde resin and mineral filler (TPP ash). As the third component, hydrolytically active fillers—anhydrite, phosphogypsum and phosphate slag—were used. The degree of filling has a significant influence on the properties of composites, including the compressive strength, chemical resistance and degree of curing, the values of which were elucidated across a wide range of composite variations based on the degree of filling. The conducted research allowed us to establish the limit of admissible anhydrite content, which should not exceed 15 mas.%. To optimize the chemical resistance and durability of the composites of the investigated substances, the method of mathematical planning was used. According to the results of this study, the optimal compositions of composites, in terms of anhydrite, phosphogypsum and phosphorus slag contents, were selected. At the maximum possible degree of filling, these composites exhibit high target characteristics.

Study of Plugging Compositions Based on Synthetic Resins for Repair and Insulation Work in Wells.

This research is aimed at analyzing existing plugging compositions and developing a new plugging composition based on phenol-formaldehyde resin. This paper presents the results of studies of a hardening composition based on phenol-formaldehyde resin for repair and insulation work in wells. The plugging composition consists of two parts: Component "A" (resin and additives) and Component "B" (hardener). A resol-type water-soluble phenol-formaldehyde resin was selected for testing. The resin was additionally modified with special additives to improve performance properties. A mixture of acids was chosen as a hardener. Concentrations of resin and hardener were selected to ensure optimal loss of fluidity of the composition for different temperatures. The main physicochemical properties of the plugging composition were determined. The elastic-strength characteristics of the developed composition after curing at various temperatures (Poisson's ratio, Young's modulus, and compressive strength) were assessed. It has been experimentally proven that samples based on phenol-formaldehyde resin do not collapse completely under load but undergo longitudinal and transverse deformations. As the amount of hardener in the system increases, the compressive strength decreases. The presence of the elastic-strength properties of cementing compositions based on synthetic resins distinguishes them favorably from hardening compositions based on cement and microcement.

Highly stable carbon-coated nZVI composite Fe0@RF-C for efficient degradation of emerging contaminants

Nanoscale zerovalent iron (nZVI) has garnered significant attention as an efficient advanced oxidation activator, but its practical application is hindered by aggregation and oxidation. Coating nZVI with carbon can effectively addresses these issues. A simple and scalable production method for carbon-coated nZVI composite is highly desirable. The anti-oxidation and catalytic performance of carbon-coated nZVI composite merit in-depth research. In this study, a highly stable carbon-coated core-shell nZVI composite (Fe0@RF-C) was successfully prepared using a simple method combining phenolic resin embedding and carbothermal reduction. Fe0@RF-C was employed as a heterogeneous persulfate (PS) activator for degrading 2,4-dihydroxybenzophenone (BP-1), an emerging contaminant. Compared to commercial nZVI, Fe0@RF-C exhibited superior PS activation performance and oxidation resistance. Nearly 95% of BP-1 was removed within 10 min in the Fe0@RF-C/PS system. The carbon layer promotes the enrichment of BP-1 and accelerates its degradation through singlet oxygen oxidation and direct electron transfer processes. This study provides a straightforward approach for designing highly stable carbon-coated nZVI composite and elucidates the enhanced catalytic performance mechanism by carbon layers.

Heterogeneous carbon coated resin-based hard carbon anode material for high-performance sodium ion batteries

Resin-based hard carbons are promising anode materials for sodium ion batteries (SIBs) due to their high storage capacity and purity. However, the low initial coulombic efficiency (ICE) still hinders their practical application. Crosslinking and high-temperature pyrolysis strategies have been demonstrated to improve ICE effectively, but the complex process and high energy consumption hinder their industrialization. This paper proposes a facile synthesis of resin-based hard carbon with a soft carbon coating strategy to improve ICE. By carbonizing commercial phenolic resin at 1150℃, hard carbon with a reversible capacity of 291.6 mAh g−1 and 82.6 % ICE was obtained. After asphalt-based soft carbon coating, the optimized sample (CHC-1150) with a heterogeneous carbon coating layer of about 8.5 nm displays a high reversible capacity and ICE of 309.8 mAh g−1 and 88.2 %. Moreover, when combined with NaFe1/3Ni1/3Mn1/3O2 cathode, the assembled 18650 cylindrical-type batteries deliver a high ICE of 84.3 %, excellent low-temperature capability and cycling stability. Additionally, the disassembly results after cycling indicate that the soft carbon layer can inhibit the decomposition of electrolytes and avoid sodium plating. These encouraging results suggest that heterogeneous carbon coating should be a promising strategy to promote the electrochemical performance of resin-based hard carbon anode materials for SIBs.

A latent curing agent for rapid curing of phenolic epoxy resin at low temperature

AbstractDeveloping effective latent curing agent for rapid curing of epoxy resins at low temperatures remains challenging. This study reports a latent curing agent, ortho‐cresol phenolic epoxy resin‐bisphenol A (EOCN‐BPA), prepared through the addition reaction of o‐methyl phenolic epoxy resin with BPA. When blended with dicyandiamide (DICY) in a 1:3 molar ratio, EOCN‐BPA/DICY is used to cure a linear epoxy phenolic novolac (EPN) resin (epoxy equivalent: 550 g eq−1, softening point: approximately 82°C), at an onset curing temperature of 90°C, which is considerably lower than the onset curing temperature of DICY with EPN (160°C). However, EOCN‐BPA does not react with EPN without a catalyst. Therefore, this latent curing system is successfully applied in powder coatings, rapid curing at 120°C within 3 min without an additional catalyst, outperforming the EPN/EOCN‐BPA system using cocatalyst 2‐methylimidazole. Consequently, DICY catalyzes the curing reaction between the phenol hydroxyl group and epoxy resin and participates in it. The prepared powder coating exhibits excellent storage stability, maintaining its properties for over 3 months at room temperature. These findings demonstrate the excellent latent properties of EOCN‐BPA/DICY, highlighting its potential as a highly effective latent curing agent.