Study on the synergistic effect of TPF phenolic curing agent and OMMT on the cured multifunctional epoxy grafted by SAP

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Here, multifunctional epoxy resin(AFG-90H) with high heat resistance and brittleness was chosen as matrix, and phenolic curing agent (TPF) based on diphenyl ether was prepared from p-tert-butylcatechol (TBC), formaldehyde and diphenyl ether. Due to the existence of diphenyl ether, the toughness of the cured AFG-90H epoxy resin can be improved. At the same time, bisaminopropyl polydimethylsiloxane modified by acid anhydride (SAP) and organic montmorillonite (OMMT) were introduced into AFG-90H epoxy resin to improve its comprehensive properties. The results show that the curing temperature of TPF and AFG-90H resin is below 100℃. When OMMT with mass fraction of 10 phr was added to AFG-90H grafted with SAP with mass fraction of 10 phr, the thermal degradation temperature (T d5% ) is up to 359℃, and the tensile strength, bending strength, impact strength and tensile shear strength is 73.29MPa, 75.00MPa, 11.31kJ/m 2 and 14.09MPa, respectively. The synergistic effect of TPF, OMMT and SAP can make the cured AFG-90H resin possess good comprehensive properties. phenolic resin mechanical properties thermal stability toughening polyorganosiloxane Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 1. INTRODUCTION Epoxy resin is widely used in construction engineering, transportation, aerospace and other fields because of its good mechanical properties, corrosion resistance and thermal stability. The cured of multifunctional epoxy resin can form a highly crosslinked network due to its more epoxy groups, thus partially replacing the traditional DGEBA [ 1 – 2 ] . However, multifunctional epoxy resin is brittle without the modification, which hinders its application fields. At present, there are some ways to toughen the epoxy resin, such as rigid particle reinforcement [ 3 – 4 ] , blending with thermoplastic polymer [ 5 – 6 ] and modification of molecular backbone by flexible chain [ 7 ] and so on. Among them, polydimethylsiloxane (PDMS) contains a large number of siloxane bonds with good flexibility and thermal stability, and is usually added to modify polymers [ 8 – 9 ] . Romo et al. [ 10 ] selected PDMS with 10% concentration of silyl ether as modifier of bisphenol a epoxy resin (DGEBA), and the fracture strain and toughness of the modified epoxy resin were increased by two times. Xie et al. [ 11 ] modified epoxy resin E-51 by the addition of hydroxyl-terminated polydimethylsiloxane (HTPDMS), and its elongation at break and impact strength were increased by about 50% and 114% respectively. At the same time, the decomposition of polydimethylsiloxane at high temperature will produce silicon dioxide to cover the residue and reduce the thermal degradation rate of the material [ 12 – 13 ] . As the adhesive of epoxy, the high adhesive strength is essential. The way to achieve high adhesion is to design the structure of adhesive. Catechol, which can establish hydrogen bond, π-π interaction and metal coordination bond with external surface [ 14 – 15 ] , is helpful for the epoxy adhesives to improve the adhesion. Many natural polymers contain this structure, such as polydopamine [ 16 ] , eugenol [ 17 ] and lignin. Poly(DHCA-co-4HCA) resin synthesized by Kaneko et al. [ 18 ] is characterized by high density catechol groups at the chain end, and its adhesion to steel substrate is about 9MPa. The adhesive prepared by Mei et al. [ 19 ] from bio-based renewable materials such as castor oil and levodopa can reach 14.6MPa at room temperature, and it can be reused. Gong et al. [ 20 ] discussed the development prospect of lignin-based phenolic adhesives by chemical modification and physical modification. However, the structure of biomass materials is complex and easy to degrade, and some synthesis mechanisms and modification processes are still unknown. Inorganic particles such as montmorillonite can improve the modulus and thermal stability of organic matter by intercalation or exfoliation [ 21 – 22 ] . Lim et al. [ 23 ] found that the addition of clay filler can enhance the adhesion between Napier fiber and epoxy resin matrix, and significantly improve the fracture morphology and toughness of composites. Vo et al. [ 24 ] synthesized binary nanocomposites (MMT-PGMA) by in-situ photoinduced polymerization of glyceryl methacrylate. The glass transition temperature and storage modulus (3℃) of MMT-PGMA is up to 112℃ and 3886MPa respectively. Li et al. [ 25 ] have chosen 4- p-tert-butylcatechol and diethylenetriamine as raw materials to prepare DETA-CMB curing agent, which is more helpful than the monophenol structure in enhancing the interfacial interaction between adhesive and metal. Here, the poxy adhesive with high adhesion and good heat-resistant is the focus. In order to achieve the goal, an individual path is not feasible, and the combination of serval modification methods is necessary. At first, based on the enhancement of the bonding strength from the role of diphenyl ether and catechol, a phenolic curing agent (TPF) is prepared from methoxydiphenyl ether, formaldehyde, methanol and 4- p-tert-butylcatechol, which is used as the curing agent of AFG-90H. Secondly, the bisaminopropyl polydimethylsiloxane (SAP) modified by acid anhydride was synthesized as the toughening modifier of AFG-90H epoxy resin. Finally, OMMT was introduced into the curing system of AFG-90H to obtain toughened epoxy composite adhesive. The synergistic effect of HPF, OMMT and SAP on the properties of the AFG-90H adhesive is worth exploring. 2. EXPERIMENTAL SECTION 2.1 Materials AFG-90H epoxy resin was from Greenlink Chemical Technology Co., Ltd. Jining, China. Resorcinol, methanol, formaldehyde (37%) and sulfuric acid (98%) were provided by Lingfeng Chemical Reagent Co., Ltd. Shanghai, China. p-Toluenesulfonic acid (PTSA) was purchased from Jiuding Chemical Co., Ltd. China. P-tert-butylcatechol (TBC) was purchased from Lanabai Pharmaceutical and Chemical Co., Ltd. Wuhan, China. Succinic anhydride was from Titan Technology Co., Ltd. Shanghai, China. Diaminopropyl polydimethylsiloxane (ATPDMS) was purchased from Xumei Chemical Technology Co., Ltd. Guangzhou, China. Ethanol (GR, 99.8%) and cetyltrimethylammonium bromide (CTAB) were purchased from Shanghai Bohr Chemical Reagent Co., Ltd., China. 2-ethyl-4- methylimidazole (2,4-EMI) was purchased from Hangzhou Gaosheng Biotechnology Co., Ltd., China. Montmorillonite (MMT) was purchased from Shandong Yousuo Chemical Technology Co., Ltd., China. Diphenyl ether are purchased from Titan Technology Co., Ltd. Shanghai. 2.2 Preparation process 2.2.1 Preparation of methoxy-terminated diphenyl ether resin (DETM) The preparation of DETM has been mentioned in previous literature [ 26 ] . According to a certain proportion, sulfuric acid (98%), formaldehyde (37%), methanol and diphenyl ether were first poured into a three-necked flask equipped with a condenser tube and a thermometer, and kept reacting at 80℃ for 6 h. Then, the crude product produced by the reaction was poured into a separatory funnel, and the excess sulfuric acid was removed by toluene extraction. The solvent in the reactant was removed by vacuum distillation, and finally a brown liquid was obtained named as DETM. 2.2.2 Preparation of p-tert-butylcatechol-terminated polyphenylene ether resin (TPF) In a three-neck flask, a proper amount of DETM and p-tert-butylcatechol were added in turn in proportion, and then a small amount of mixed solution of PTSA and ethanol was dropped as a catalyst, and nitrogen atmosphere was introduced to mix evenly at 100℃. Subsequently, the reactant was heated to 120℃ for 0.5h, then to 140℃ for 0.5h. Finally, the mixture was distilled under reduced pressure to remove excessive p-tert-butylcatechol and by-products to obtain the target product TPF (hydroxyl equivalent: 32.6 g/eq, according to GB/T 7383 − 2020). The specific synthesis process is shown in Fig. 1 . 2.2.3 Preparation of TASx Firstly, succinic anhydride (0.62g) and diaminopropyl polydimethylsiloxane (10g) were added into a beaker, and then an appropriate amount of tetrahydrofuran was added and stirred at room temperature until it was completely dissolved, thus obtaining the SAP toughening agent (Fig. 2 ). Add different proportions of SAP into a three-necked flask filled with AFG-90H, stir at 120℃ for 3h, and completely evaporate the solvent to obtain the product ASx. Then ASx, TPF and accelerator 2,4-EMI are evenly mixed in a blender, and degassed in a vacuum oven until there are no bubbles in the system. Finally, it is put into an oven for medium-temperature curing to obtain the product TASx. The dosage of SAP is 5 phr, 10 phr, 15 phr and 20 phr in turn (the proportion is based on the quality of ASx). 2.2.4 Preparation of TAS10My 25g MMT was dispersed in deionized water by ultrasonic treatment for 1h. 7.2 g of CTAB was poured into MMT and stirred at 80℃ for 3h. Wash and filter the mixing solution with deionized water for many times until no precipitate is generated with the addition of 1%AgNO 3 solution. Finally, it was dried in an oven at 80℃ until the mass is constant, then ground and sieved with a 600-mesh sieve to obtain OMMT. OMMT with different proportions was added into the uncured TAS10, stirred and mixed evenly at the speed of 1000 rpm/min. After degassing, it was put into an oven for medium-temperature curing to obtain the cured TAS10My. The dosage of OMMT is 5 phr, 10 phr and 15 phr (the proportion is based on the mass of ASx). The cured products were named as TAS10M5, TAS10M10 and TAS10M15. The scheme of mass ratio of raw material is shown in Table S1 . 2.3 Characterization. The chemical structure of SAP and the cured were detected by Fourier transform infrared (FTIR, Nicolet 6700, Thermo Fisher Scientific Shier Technology, Pittsburgh) spectra in the 4000-400cm − 1 wavelength range. The uncured sample was coated on a KBr sheet to form a thin layer. 1 H NMR spectroscopy was performed on a superconducting Fourier nuclear magnetic resonance spectrometer (AVANCE III 400 MHz, Brook, Switzerland) via using deuterated acetone as solvent and tetramethylsilane (TMS) as internal standard. Differential scanning calorimetry (DSC) was performed on a differential scanning calorimeter (DSC8500, PerkinElmer, Germany) at a heating rate of 10℃/min from 50 to 100℃ in nitrogen atmosphere (20 mL/min). Thermogravimetric analysis (TGA) was executed with a TGA8000 (PerkinElmer, USA) to analyze the heat resistance of the composites at a heating rate of 10℃/min under a nitrogen atmosphere. The test of time-of-flight mass spectrometry was carried out on the XEVO-G2-TOF instrument. The morphology of impact fracture surface of the cured resins was observed by a field emission scanning electron microscope (ZEISS GeminiSEM 300, Germany) at an acceleration voltage of 3 kV. Transmission electron microscope (TEM, JEOL JEM-F200, Japan) was performed at an acceleration voltage of 200 kV. The dynamic mechanics of composites was studied on a dynamic mechanical thermal analyzer (DMA Q800, USA). The samples with the size of 55×12×4mm 3 were measured from 30℃ to 180℃ at the heating rate of 3℃/min and 1Hz in the mode of double cantilever beam. According to GB/T 2567 − 2021, the tensile strength and bending strength of spline were tested on a universal testing machine (CMT 4204, Sans, Shenzhen, China). The impact strength was tested by a cantilever impact tester (CEAST 9050, Italy) with a range of 5.5J. The sample is a spline with a size of 80×10×4mm 3 and no notch. The results of all mechanical tests were averaged by three samples. According to GB/T 7124 − 2008, the tensile shear strength of aluminum-aluminum alloy bonding joint with epoxy adhesive was carried out. LY12-CZ aluminum alloy (100×25×2mm 3 ) was polished with coarse sandpaper and assembled into lap joint. The lap length is 12.5mm and the test rate is 5mm/min. Three samples were measured in each group and the average value was taken. The cured product was soaked in 25%NaOH and 98%H 2 SO 4 solution respectively, and after standing for 7 days, the corrosion resistance of epoxy resin was evaluated by testing the quality and hardness of the spline and observing the change of the solution. 3. RESULTS AND DISSCUSSION 3.1 TPF. Figure 3 a is the FT-IR spectra of DETM (A) and TPF (B). As shown in Fig. 3 a, the stretching vibration absorption peaks of -CH 2 and -CH groups in the molecule are at 3073-2821cm − 1 ; the vibration absorption peak at 1602cm − 1 corresponds to benzene ring skeleton C = C; the peak at 1498cm − 1 is the deformation vibration absorption peak of methylene bridge connected ortho to benzene ring. Tensile vibration absorption peaks and bending vibration absorption peaks of phenolic hydroxyl groups is at 3421cm − 1 and 1331cm − 1 ; the stretching vibration peak of phenolic hydroxyl C-O group is at 1238cm − 1 . The characteristic absorption peak of ether bond (-COC-) is at 1165 cm − 1 , and the C-H out-of-plane bending vibration absorption peaks of disubstituted benzene and tetrasubstituted benzene are at 870cm − 1 and 752cm − 1[ 27 ] . Comparing the curve A and B, it is found that the characteristic peak of methoxy group (-OCH 3 ) at 1046cm − 1 in the infrared spectrum of DETM, disappears in the infrared spectrum of TPF, indicating the complete reaction of DETM with p-tert-butylcatechol. From above, it reveals that the phenolic resin TPF has been successfully prepared. Figure 3 b shows the 1 H NMR spectrum of TPF. In Fig. 3 b, the positions of hydrogen atoms in different chemical environments in TPF are marked with 1 ~ 7 respectively. Peak 1 (5.35 ppm) corresponds to the hydrogen on the phenolic hydroxyl. Peak 2(1.35 ppm) belongs to the hydrogen of three methyl groups attached to the same tertiary carbon. The chemical shifts at peaks 3 and 4 are 6.98 ppm and 7.03 ppm, which represent the unsubstituted hydrogen on the phenol ring, respectively. Peak 6(6.75 ppm) and Peak 7(7.21 ppm) belong to the hydrogen on the benzene ring in the phenyl ether. Peak 5(3.99 ppm) corresponds to methylene (-CH 2 -) connecting phenol ring and benzene ring. It is reasonable to infer that the reaction product from methoxydiphenyl ether and p-tert-butylcatechol is in line with the expected structure, indicating that TPF has been successfully prepared. TPF was further analyzed by time-of-flight mass spectrometry (Fig. 3 c). It was shown that the molar mass of curing agent is 386g/mol and 408g/mol by subtracting H + (1g/mol), indicating that TPF is an oligomer. 3.2 TASx composite Figure 4 is the infrared spectrum of succinic anhydride, diaminopropyl polydimethylsiloxane (ATPDMS) and toughening agent (SAP). In Fig. 4 , 1862cm − 1 and 1783cm − 1 belong to typical symmetrical and antisymmetric vibration absorption peaks in succinic anhydride. In the FT-IR spectrum of ATPDMS, due to the low ammonia value, only a weak aliphatic primary amine double peak is at 3300–3500 cm − 1 . In the FT-IR spectrum of SAP, the weak double peaks of aliphatic primary amine turn into a single characteristic absorption peak of secondary amine. The peaks at 2905cm − 1 and 2962cm − 1 correspond to the stretching vibration of saturated methylene (-CH 2 -) and methyl (-CH 3 -) respectively. The characteristic absorption peak at 1412cm − 1 corresponds to Si-O-C; the characteristic absorption peaks of Si-(CH 3 ) 2 are at 1260 cm − 1 , 864cm − 1 and 798cm − 1[ 28 ] ; the stretching vibration peaks of Si-O are at 1089cm − 1 and 1021cm − 1 . In the infrared spectrum of SAP, the characteristic peaks of siloxane are unchanged, but the obvious carboxyl (-COOH) absorption peak at 1720cm − 1 and a new secondary amide (-O = C-NR) stretching vibration peak at 1641cm − 1 appear. From the above FT-IR spectra, the ring-opening reaction between anhydride and primary amino group occurs, and polydimethylsiloxane with amide and carboxylic acid group have been generated. Figure 5 a is the DSC curing curve of TASx (TPF as the curing agent). As shown in Fig. 5 a, with the increase of the content of the toughening agent SAP, the exothermic peak slightly shifts to low temperature (the exothermic peak temperature of TAS0 is 94.6℃). For TASx, the more siloxane segments are introduced, the easier the curing reaction is. At the same time, the curing peak gradually widens. This is because long polysiloxane chains in SAP increase the flexibility, and can make the crosslinking reaction between epoxy group and phenolic curing agent occur at lower temperature. Therefore, the curing process of TASx (TPF as the curing agent) is set as below: 80℃/1h + 90℃/1h + 100℃/2h. As shown in Fig. 5 b ( the FT-IR of the cured TASx), 1743cm − 1 is recognized as the characteristic absorption peak of ester group (-C-OOR), because carboxyl groups at both ends of SAP molecule can open epoxy groups [ 29 – 30 ] , the characteristic absorption peak of epoxy group at 910cm − 1 disappears, indicating that the AFG-90H epoxy resin modified by SAP has been completely cured. Figure 6 shows mechanical properties of the cured TASx with different contents of SAP. With the increase of SAP content, the tensile strength of TASx is first large and then decreases. The tensile strength and elongation at break of the cured TAS0 without toughening agent are 47.41MPa and 1.52%, respectively. When SAP is grafted, the longer siloxane chain can further form an interpenetrating network structure with epoxy resin. When the dosage of SAP is less than 10 phr, the interaction between AFG-90 resin and SAP network can improve the tensile strength (62.17MPa) and elongation at break (2.99%) of the cured. On the further increase of the content of SAP, the strength is lowered. The cause is that the long siloxane chain can entangle, hindering the movement of molecular chains, resulting in low curing density per unit volume and the overall composition uniformity. As shown in Fig. 6 b, the bending strength of the cured TASx is from 44.69MPa to 58.31MPa, and then down to 46.87MPa. As the bond length and bond angle of Si-O-Si are larger than the C-O-C bond of epoxy resin, the flexibility of the curd of the modified epoxy is superior to the cured of AFG-90H (TAS0). The cured TAS10 shows high impact strength ( 7.19 kJ/m 2 ) (Fig. 6 c), but on further increase of the content of the toughening agent, the impact strength is reduced. The catechol segment in TPF is easy to form coordination bonds with metal atoms, leading to good adhesion to metal substrates. The maximum shear strength of TASx is up to 9.41MPa (see Fig. 6 d). From the peeled metal surface (Fig. 6 e), resin is tightly adhered to the shear sections of TAS0 ~ TAS20, which is the proof of good adhesion between the aluminum sheet and the modified epoxy adhesive. Figure 7 is SEM images of the impact fracture cross section of the cured TASx. TAS0 shows a relatively uniform and flat surface (Fig. 7 a). In Fig. 7 b, due to the low content of SAP, the cross section presents cracks extending uniformly, and some sparse and tiny holes are generated. It can be seen from Fig. 7 c that holes with the pore size ranging from 2 to 10 µm appear on the cross section of TAS10, which is also commonly called "island structure". This "island structure" acts as the nail anchor like rubber particles, which can restrain the further expansion or extension of closed microcracks. However, with the further increase of SAP content, the number and volume of "island structures" are on the increase correspondingly (see Fig. 7 d), but the strength of the cured is lowered. Figure 8 shows thermogravimetric curves (TG) and thermal decomposition rate (DTG) of the cured TASx. As shown in Fig. 8 and Table 1 , the cured TAS0 begins to decompose at 360℃, and its corresponding T max is 403℃, and the carbon residue is 28.1%. When the ratio of epoxy resin toughening agent SAP is large, T d5% the cured TASx is down to 345 ℃(TAS20). This can be explained by the fact that Si-O bonds with high bond energy replace some C-O bonds with low bond energy, and more heat needs to be absorbed in the thermal decomposition process to break the bonds, while the formation of holes can weaken the thermal stability of the cured. For the cured TAS5- TAS20, the thermal decomposition rate is almost unchangeable, and the stability at high temperature is obviously enhanced, especially above 500℃. Compared with pure TAS0, the carbon residue of TAS20 at 700℃ increased by 36%, up to 38.2%, which is due to the formation of more SiO 2 during thermal degradation. The toughening agent SAP plays an important role of delaying the thermal decomposition of the cured AFG-90H epoxy resin, and of enhancing the carbon residue of the cured. To sum up, TASx has the best heat resistance and mechanical properties when the content of SAP is 10 phr, so TAS10 was chosen as the basic formula for the next exploration. 3.3 TAS10My composites Figure 9 shows the mechanical properties of cured TAS10My composites. In Fig. 9 a, the tensile strength of cured TAS10My filled with 10 phr OMMT is the highest, up to 73.29MPa, and the elongation at break is 4.62%. It can be seen from Fig. 9 b that the bending strength and modulus of TAS10M10 are the highest, which are 75.00 MPa and 7616.12 MPa, respectively. When the content of OMMT exceeds 10 phr, the agglomeration of OMMT occurs, resulting in the formation of intercalation structure in the cured composites. According to Fig. 9 c, the impact strength of TAS10My composites can be increased from 7.19 kJ/m 2 to 11.31 kJ/m 2 by the addition of OMMT, which is 187.8% higher than that of TAS0. In Fig. 9 d, the maximum tensile shear strength (TAS10M10) is 14.09MPa at room temperature, and it begins to decrease with the further increase of OMMT content. From Fig. 9 (e), there are the cured on the peeling cross sections of two aluminum sheets for TAS10M5- TAS10M15, indicating the good adhesion between the aluminum sheet and the composite adhesives (TAS10M5- TAS10M15) (see Fig. 9 e). From above, the addition of OMMT is helpful to enhance the shear strength of the system based on the improvement of cohesive strength, so the failure is internal aggregation failure, supplemented by adhesion failure. SEM images of the impact fracture section of TAS10My are shown in Figure S1 . In Figure S1 (a-b), OMMT in the cured TAS10M5 and TAS10M10 is uniformly distributed in epoxy resin. The existence of OMMT can also induce micro-cracks in holes to absorb external energy. However, it can be clearly seen that due to the poor dispersibility of OMMT, aggregation and agglomeration occur between particles, making the particle size close to micron scale (Figure S1 c). At the same time, under the doping of excessive OMMT, the space of island holes is squeezed, thus splitting into more holes, which greatly reduces the crosslinking density of epoxy resin. Figure 10 shows thermogravimetric curves (TG) and thermal decomposition rate (DTG) curves of the cured TAS10My. As shown in Fig. 10 and Table 1 , the degradation processes of the cured composites are similar, and with the increase of OMMT proportion, the degradation rate of the systems slow down. Among them, the T d5% of the cured TAS10M5, TAS10M10 and TAS10M15 were 356℃, 359℃ and 363℃, respectively, showing a gradual upward trend, and the carbon residue of these systems also increases (from 32.1% to 35.5%). Thermal stability depends on the dispersion degree of OMMT in resin matrix. On one hand, Al 2 O 3 and MgO in OMMT are high thermal conductors with excellent thermal conductivity, which can reduce the thermal stress inside the matrix; On the other hand, the treated OMMT can be uniformly dispersed in the substrate [ 31 ] . The network structure of the system becomes more compact and the interaction between the filler and the substrate is enhanced, limiting the thermal movement of the molecular chain of epoxy resin. Most of the residues left after high-temperature degradation are silicon carbon containing magnesium and aluminum metals. Therefore, the cured composite has good heat resistance. Table 1 Mechanical and thermal parameters of composite materials Systems T g /℃ ρ/mol·dm − 3 T d5% /℃ Char yield/% TAS0 132.8 4.88 360 28.1 TAS5 128.0 4.23 357 29.9 TAS10 124.1 3.98 353 31.4 TAS15 120.9 3.18 348 34.7 TAS20 115.8 2.59 345 38.2 TAS10M5 127.2 4.15 356 32.1 TAS10M10 130.7 4.41 359 33.8 TAS10M15 128.9 4.07 363 35.5 Tg: Glass transition temperature; E’: Storage modulus; ρ: Crosslinking density Figure 11 shows the storage modulus (E') and loss tangent (tanδ) of the cured TASx and TAS10My composites versus temperature. In Fig. 11 , after SAP was added, the E' of the cured TASx in the glass zone slightly increases. The temperature corresponding to the peak value of tanδ represents the glass transition temperature (Tg) of the cured. As indicated in Table 1 , the Tg of cured TASx shows a decreasing trend, because SAP is flexible. After OMMT is added, Tg and ρ of the cured epoxy resin system increases slightly. The interfacial interaction between epoxy resin matrix and OMMT lamellae will lead to the decrease of chain mobility. However, when the OMMT content exceeds 10 phr, agglomeration occurs, so the dynamic thermodynamic properties of the system become worse. Table 2 Corrosion resistance and hardness change of composites Systems Chemical mediator Quality change (%) Shore hardness/HA Before soaking After soaking TAS0 98%H 2 SO 4 + 0.72 97 97 25%NaOH + 0.54 97 96 TAS5 98%H 2 SO 4 + 0.69 94 94 25%NaOH + 0.70 93 93 TAS10 98%H 2 SO 4 + 0.88 93 93 25%NaOH + 0.47 93 92 TAS15 98%H 2 SO 4 -0.83 95 95 25%NaOH + 1.02 96 95 TAS20 98%H 2 SO 4 -0.96 91 90 25%NaOH -0.75 92 91 TAS10M5 98%H 2 SO 4 -1.44 92 92 25%NaOH + 0.95 92 92 TAS10M10 98%H 2 SO 4 -1.35 93 93 25%NaOH + 0.15 94 94 TAS10M15 98%H 2 SO 4 -1.65 97 95 25%NaOH -0.48 97 96 Figure S2 shows the spline and solution changes of the composites after soaking in acid or alkali for 7 d, respectively. Table 2 shows the mass and hardness changes of the composite. From Figure S2, it can be seen that after soaking in 25%NaOH solution for 7 d, all splines and solutions remain unchanged, indicating that the composite system has good alkali resistance. However, after soaking in 98%H 2 SO 4 , the color of the spline and solution of TAS20 composites changes slightly at the 7th day, while the spline of TAS10M15 composites begins to change color at the 5th day, meanwhile the solution becomes reddish, and the color deepens at the 7th day. This may be due to excessive OMMT agglomerating on the spline surface, leading to the reaction between metal oxide and acid slowly. In addition, there is no obvious change in other groups. The above phenomenon can also be verified by the change of hardness and quality. It proves that the introduction of proper amount of SAP and OMMT will not affect the acid and alkali resistance of the system. 4. CONCLUSION In this work, a phenolic curing agent (TPF) based on diphenyl ether was prepared from p-tert-butylcatechol, formaldehyde and diphenyl ether. At the same time, toughening agent (SAP) and organic montmorillonite (OMMT) were introduced into AFG-90H epoxy resin. The results showed that TASx can be cured and crosslinked at 100℃. When the OMMT content is 10phr, the T d5% of AFG-90H grafted by 10 phr SAP cured by HPF is 359℃; the tensile strength, impact strength and the tensile shear strength is 73.29MPa, 11.31 kJ/m 2 and 14.09MPa, respectively. It revealed that the introduction of silicon-oxygen bond and OMMT plays an important role in improving the thermal stability and mechanical properties of the system. The curing system with good heat resistance, toughness and adhesive strength has application potential in aerospace, civil construction and other industrial fields. Declarations Authorship contribution statement Zhuhuan Chen: Methodology, Formal analysis, Writing – original draft. Shijie Zhang: Methodology, Formal analysis. Ruobing Yu: Conceptualization, Resources, Writing – review & editing, Funding acquisition. 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European Polymer Journal. 2004, 40 (8): 1743–1748. Additional Declarations No competing interests reported. Supplementary Files Supportinginformation0723.docx Cite Share Download PDF Status: Published Journal Publication published 09 Apr, 2026 Read the published version in Mechanics of Time-Dependent Materials → Version 1 posted Editorial decision: Revision requested 03 Feb, 2026 Reviews received at journal 03 Feb, 2026 Reviewers agreed at journal 22 Jan, 2026 Reviews received at journal 22 Jan, 2026 Reviewers agreed at journal 21 Jan, 2026 Reviews received at journal 20 Jan, 2026 Reviews received at journal 30 Dec, 2025 Reviewers agreed at journal 24 Dec, 2025 Reviewers agreed at journal 02 Dec, 2025 Reviewers invited by journal 01 Dec, 2025 Editor assigned by journal 01 Dec, 2025 Submission checks completed at journal 28 Nov, 2025 First submitted to journal 27 Nov, 2025 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. 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08:43:33","extension":"html","order_by":27,"title":"","display":"","copyAsset":false,"role":"acdc-reference","size":96656,"visible":true,"origin":"","legend":"","description":"","filename":"earlyproof.html","url":"https://assets-eu.researchsquare.com/files/rs-8225846/v1/869684ec8e071b0df34d182d.html"},{"id":97326857,"identity":"4a3d3e1b-1283-46e0-9f58-3d7c239cc23c","added_by":"auto","created_at":"2025-12-03 08:43:32","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":262760,"visible":true,"origin":"","legend":"\u003cp\u003eSynthesis of TPF\u003c/p\u003e","description":"","filename":"image1.png","url":"https://assets-eu.researchsquare.com/files/rs-8225846/v1/550fc01d031dce55950a095c.png"},{"id":97326859,"identity":"9cdee898-1b86-4ef1-bb07-b49ac5b2359a","added_by":"auto","created_at":"2025-12-03 08:43:33","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":101731,"visible":true,"origin":"","legend":"\u003cp\u003eThe synthesis process of SAP\u003c/p\u003e","description":"","filename":"image2.png","url":"https://assets-eu.researchsquare.com/files/rs-8225846/v1/27698d6486c41db006abaa62.png"},{"id":97326862,"identity":"42dd6ce7-5c8e-4a6a-b68d-9da56402e75b","added_by":"auto","created_at":"2025-12-03 08:43:33","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":424723,"visible":true,"origin":"","legend":"\u003cp\u003e(a) The FT-IR spectra of DETM(A) and HPF(B), (b) \u003csup\u003e1\u003c/sup\u003eH NMR spectrum and (c) Time-of-flight mass spectrometry analysis of TPF\u003c/p\u003e","description":"","filename":"image3.png","url":"https://assets-eu.researchsquare.com/files/rs-8225846/v1/0725a440b3e5d34a02cadba8.png"},{"id":97326860,"identity":"f246ca68-6409-430b-8ca7-686950640a1e","added_by":"auto","created_at":"2025-12-03 08:43:33","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":1752137,"visible":true,"origin":"","legend":"\u003cp\u003eThe infrared spectrum of succinic anhydride, diaminopropyl polydimethylsiloxane (ATPDMS) and SAP\u003c/p\u003e","description":"","filename":"image4.png","url":"https://assets-eu.researchsquare.com/files/rs-8225846/v1/88c8b1a273855713929b8349.png"},{"id":97326864,"identity":"18e74a4f-7ce5-4d99-9269-87cecd8bdaff","added_by":"auto","created_at":"2025-12-03 08:43:33","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":1837483,"visible":true,"origin":"","legend":"\u003cp\u003e(a) DSC curing curves of TASx mixtures and (b) The FTIR spectrum of the cured TASx\u003c/p\u003e","description":"","filename":"image5.png","url":"https://assets-eu.researchsquare.com/files/rs-8225846/v1/68c6aaeb02579153bb6f2e11.png"},{"id":97326869,"identity":"6cecb2e6-9fac-4084-b36d-83e683ab1b9f","added_by":"auto","created_at":"2025-12-03 08:43:33","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":2615589,"visible":true,"origin":"","legend":"\u003cp\u003eEffect of SAP addition on (a) tensile strength and elongation at break, (b) flexural strength and flexural modulus, (c) impact strength, (d) tensile shear strength of the cured TASx composites and (e) metal section of broken tensile shear specimen\u003c/p\u003e","description":"","filename":"image6.png","url":"https://assets-eu.researchsquare.com/files/rs-8225846/v1/6717e2fb9095c4471808ebfa.png"},{"id":97369146,"identity":"e86ca632-b082-4fd5-97f0-6e3be5b8dbe8","added_by":"auto","created_at":"2025-12-03 16:23:46","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":137764,"visible":true,"origin":"","legend":"\u003cp\u003eSEM image of impact fracture surface of the cured (a) TAS0, (b) TAS5, (c) TAS10, (d) TAS15 and (e) TAS20\u003c/p\u003e","description":"","filename":"image7.png","url":"https://assets-eu.researchsquare.com/files/rs-8225846/v1/87d3c8e2c2d3c713a4568d11.png"},{"id":97369620,"identity":"b0801711-2a10-435c-a6b4-951367c4cb39","added_by":"auto","created_at":"2025-12-03 16:25:19","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":731717,"visible":true,"origin":"","legend":"\u003cp\u003e(a)TG and (b)DTG curves of the cured TASx composites\u003c/p\u003e","description":"","filename":"image8.png","url":"https://assets-eu.researchsquare.com/files/rs-8225846/v1/25f7d60bc2c91ce41ac523de.png"},{"id":97370389,"identity":"f4f6d187-3dee-47b2-9062-185061cb351e","added_by":"auto","created_at":"2025-12-03 16:27:14","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":2918647,"visible":true,"origin":"","legend":"\u003cp\u003eEffect of OMMT addition on (a) tensile strength and elongation at break, (b) flexural strength and flexural modulus, (c) impact strength, (d) tensile shear strength of the cured TAS10My composites and (e) metal section of broken tensile shear specimen\u003c/p\u003e","description":"","filename":"image9.png","url":"https://assets-eu.researchsquare.com/files/rs-8225846/v1/c267ff4522b3e8ff423b0ad1.png"},{"id":97371094,"identity":"d2dbae90-a68e-43c2-98cb-1a39bdaaa7c6","added_by":"auto","created_at":"2025-12-03 16:28:24","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":722594,"visible":true,"origin":"","legend":"\u003cp\u003e(a)TG and (b)DTG curves of the cured TAS10My composites\u003c/p\u003e","description":"","filename":"image10.png","url":"https://assets-eu.researchsquare.com/files/rs-8225846/v1/e9ac88995e040e3bde590a0e.png"},{"id":97326875,"identity":"e5ff9ea1-be66-402e-9c67-9a33a06a07d1","added_by":"auto","created_at":"2025-12-03 08:43:33","extension":"png","order_by":11,"title":"Figure 11","display":"","copyAsset":false,"role":"figure","size":1000358,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Storage modulus and (b) tan δ vs. temperature of the cured TASx and TAS10My composites\u003c/p\u003e","description":"","filename":"image11.png","url":"https://assets-eu.researchsquare.com/files/rs-8225846/v1/2efef421c9f559af88d25b62.png"},{"id":106809337,"identity":"62e6aacb-ad72-4a4a-9802-15aaa2b92108","added_by":"auto","created_at":"2026-04-13 16:09:40","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":13002702,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8225846/v1/ed806dc2-1871-4977-a98b-d20a4d9ed427.pdf"},{"id":97369144,"identity":"89cea951-c99b-4f30-8d47-1c30f1447d54","added_by":"auto","created_at":"2025-12-03 16:23:46","extension":"docx","order_by":0,"title":"","display":"","copyAsset":false,"role":"supplement","size":326735,"visible":true,"origin":"","legend":"","description":"","filename":"Supportinginformation0723.docx","url":"https://assets-eu.researchsquare.com/files/rs-8225846/v1/b14b7c3c48192e7f903232b8.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Study on the synergistic effect of TPF phenolic curing agent and OMMT on the cured multifunctional epoxy grafted by SAP","fulltext":[{"header":"1. INTRODUCTION","content":"\u003cp\u003eEpoxy resin is widely used in construction engineering, transportation, aerospace and other fields because of its good mechanical properties, corrosion resistance and thermal stability. The cured of multifunctional epoxy resin can form a highly crosslinked network due to its more epoxy groups, thus partially replacing the traditional DGEBA\u003csup\u003e[\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]\u003c/sup\u003e. However, multifunctional epoxy resin is brittle without the modification, which hinders its application fields.\u003c/p\u003e\u003cp\u003eAt present, there are some ways to toughen the epoxy resin, such as rigid particle reinforcement\u003csup\u003e[\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e]\u003c/sup\u003e, blending with thermoplastic polymer\u003csup\u003e[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]\u003c/sup\u003e and modification of molecular backbone by flexible chain\u003csup\u003e[\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e]\u003c/sup\u003e and so on. Among them, polydimethylsiloxane (PDMS) contains a large number of siloxane bonds with good flexibility and thermal stability, and is usually added to modify polymers\u003csup\u003e[\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e]\u003c/sup\u003e. Romo et al.\u003csup\u003e[\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e]\u003c/sup\u003e selected PDMS with 10% concentration of silyl ether as modifier of bisphenol a epoxy resin (DGEBA), and the fracture strain and toughness of the modified epoxy resin were increased by two times. Xie et al.\u003csup\u003e[\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e]\u003c/sup\u003e modified epoxy resin E-51 by the addition of hydroxyl-terminated polydimethylsiloxane (HTPDMS), and its elongation at break and impact strength were increased by about 50% and 114% respectively. At the same time, the decomposition of polydimethylsiloxane at high temperature will produce silicon dioxide to cover the residue and reduce the thermal degradation rate of the material\u003csup\u003e[\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e]\u003c/sup\u003e.\u003c/p\u003e\u003cp\u003eAs the adhesive of epoxy, the high adhesive strength is essential. The way to achieve high adhesion is to design the structure of adhesive. Catechol, which can establish hydrogen bond, π-π interaction and metal coordination bond with external surface\u003csup\u003e[\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e]\u003c/sup\u003e, is helpful for the epoxy adhesives to improve the adhesion. Many natural polymers contain this structure, such as polydopamine\u003csup\u003e[\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e]\u003c/sup\u003e, eugenol\u003csup\u003e[\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]\u003c/sup\u003e and lignin. Poly(DHCA-co-4HCA) resin synthesized by Kaneko et al.\u003csup\u003e[\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]\u003c/sup\u003e is characterized by high density catechol groups at the chain end, and its adhesion to steel substrate is about 9MPa. The adhesive prepared by Mei et al.\u003csup\u003e[\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]\u003c/sup\u003e from bio-based renewable materials such as castor oil and levodopa can reach 14.6MPa at room temperature, and it can be reused. Gong et al.\u003csup\u003e[\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]\u003c/sup\u003e discussed the development prospect of lignin-based phenolic adhesives by chemical modification and physical modification. However, the structure of biomass materials is complex and easy to degrade, and some synthesis mechanisms and modification processes are still unknown.\u003c/p\u003e\u003cp\u003eInorganic particles such as montmorillonite can improve the modulus and thermal stability of organic matter by intercalation or exfoliation\u003csup\u003e[\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]\u003c/sup\u003e. Lim et al.\u003csup\u003e[\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e]\u003c/sup\u003e found that the addition of clay filler can enhance the adhesion between Napier fiber and epoxy resin matrix, and significantly improve the fracture morphology and toughness of composites. Vo et al.\u003csup\u003e[\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]\u003c/sup\u003e synthesized binary nanocomposites (MMT-PGMA) by in-situ photoinduced polymerization of glyceryl methacrylate. The glass transition temperature and storage modulus (3℃) of MMT-PGMA is up to 112℃ and 3886MPa respectively.\u003c/p\u003e\u003cp\u003eLi et al.\u003csup\u003e[\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]\u003c/sup\u003e have chosen 4- p-tert-butylcatechol and diethylenetriamine as raw materials to prepare DETA-CMB curing agent, which is more helpful than the monophenol structure in enhancing the interfacial interaction between adhesive and metal. Here, the poxy adhesive with high adhesion and good heat-resistant is the focus. In order to achieve the goal, an individual path is not feasible, and the combination of serval modification methods is necessary. At first, based on the enhancement of the bonding strength from the role of diphenyl ether and catechol, a phenolic curing agent (TPF) is prepared from methoxydiphenyl ether, formaldehyde, methanol and 4- p-tert-butylcatechol, which is used as the curing agent of AFG-90H. Secondly, the bisaminopropyl polydimethylsiloxane (SAP) modified by acid anhydride was synthesized as the toughening modifier of AFG-90H epoxy resin. Finally, OMMT was introduced into the curing system of AFG-90H to obtain toughened epoxy composite adhesive. The synergistic effect of HPF, OMMT and SAP on the properties of the AFG-90H adhesive is worth exploring.\u003c/p\u003e"},{"header":"2. EXPERIMENTAL SECTION","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e\u003ch2\u003e2.1 Materials\u003c/h2\u003e\u003cp\u003eAFG-90H epoxy resin was from Greenlink Chemical Technology Co., Ltd. Jining, China. Resorcinol, methanol, formaldehyde (37%) and sulfuric acid (98%) were provided by Lingfeng Chemical Reagent Co., Ltd. Shanghai, China. p-Toluenesulfonic acid (PTSA) was purchased from Jiuding Chemical Co., Ltd. China. P-tert-butylcatechol (TBC) was purchased from Lanabai Pharmaceutical and Chemical Co., Ltd. Wuhan, China. Succinic anhydride was from Titan Technology Co., Ltd. Shanghai, China. Diaminopropyl polydimethylsiloxane (ATPDMS) was purchased from Xumei Chemical Technology Co., Ltd. Guangzhou, China. Ethanol (GR, 99.8%) and cetyltrimethylammonium bromide (CTAB) were purchased from Shanghai Bohr Chemical Reagent Co., Ltd., China. 2-ethyl-4- methylimidazole (2,4-EMI) was purchased from Hangzhou Gaosheng Biotechnology Co., Ltd., China. Montmorillonite (MMT) was purchased from Shandong Yousuo Chemical Technology Co., Ltd., China. Diphenyl ether are purchased from Titan Technology Co., Ltd. Shanghai.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec4\" class=\"Section2\"\u003e\u003ch2\u003e2.2 Preparation process\u003c/h2\u003e\u003cdiv id=\"Sec5\" class=\"Section3\"\u003e\u003ch2\u003e2.2.1 Preparation of methoxy-terminated diphenyl ether resin (DETM)\u003c/h2\u003e\u003cp\u003eThe preparation of DETM has been mentioned in previous literature\u003csup\u003e[\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e]\u003c/sup\u003e. According to a certain proportion, sulfuric acid (98%), formaldehyde (37%), methanol and diphenyl ether were first poured into a three-necked flask equipped with a condenser tube and a thermometer, and kept reacting at 80℃ for 6 h. Then, the crude product produced by the reaction was poured into a separatory funnel, and the excess sulfuric acid was removed by toluene extraction. The solvent in the reactant was removed by vacuum distillation, and finally a brown liquid was obtained named as DETM.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec6\" class=\"Section3\"\u003e\u003ch2\u003e2.2.2 Preparation of p-tert-butylcatechol-terminated polyphenylene ether resin (TPF)\u003c/h2\u003e\u003cp\u003eIn a three-neck flask, a proper amount of DETM and p-tert-butylcatechol were added in turn in proportion, and then a small amount of mixed solution of PTSA and ethanol was dropped as a catalyst, and nitrogen atmosphere was introduced to mix evenly at 100℃. Subsequently, the reactant was heated to 120℃ for 0.5h, then to 140℃ for 0.5h. Finally, the mixture was distilled under reduced pressure to remove excessive p-tert-butylcatechol and by-products to obtain the target product TPF (hydroxyl equivalent: 32.6 g/eq, according to GB/T 7383\u0026thinsp;\u0026minus;\u0026thinsp;2020). The specific synthesis process is shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec7\" class=\"Section3\"\u003e\u003ch2\u003e2.2.3 Preparation of TASx\u003c/h2\u003e\u003cp\u003eFirstly, succinic anhydride (0.62g) and diaminopropyl polydimethylsiloxane (10g) were added into a beaker, and then an appropriate amount of tetrahydrofuran was added and stirred at room temperature until it was completely dissolved, thus obtaining the SAP toughening agent (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e). Add different proportions of SAP into a three-necked flask filled with AFG-90H, stir at 120℃ for 3h, and completely evaporate the solvent to obtain the product ASx. Then ASx, TPF and accelerator 2,4-EMI are evenly mixed in a blender, and degassed in a vacuum oven until there are no bubbles in the system. Finally, it is put into an oven for medium-temperature curing to obtain the product TASx. The dosage of SAP is 5 phr, 10 phr, 15 phr and 20 phr in turn (the proportion is based on the quality of ASx).\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec8\" class=\"Section3\"\u003e\u003ch2\u003e2.2.4 Preparation of TAS10My\u003c/h2\u003e\u003cp\u003e25g MMT was dispersed in deionized water by ultrasonic treatment for 1h. 7.2 g of CTAB was poured into MMT and stirred at 80℃ for 3h. Wash and filter the mixing solution with deionized water for many times until no precipitate is generated with the addition of 1%AgNO\u003csub\u003e3\u003c/sub\u003e solution. Finally, it was dried in an oven at 80℃ until the mass is constant, then ground and sieved with a 600-mesh sieve to obtain OMMT.\u003c/p\u003e\u003cp\u003eOMMT with different proportions was added into the uncured TAS10, stirred and mixed evenly at the speed of 1000 rpm/min. After degassing, it was put into an oven for medium-temperature curing to obtain the cured TAS10My. The dosage of OMMT is 5 phr, 10 phr and 15 phr (the proportion is based on the mass of ASx). The cured products were named as TAS10M5, TAS10M10 and TAS10M15. The scheme of mass ratio of raw material is shown in Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e.\u003c/p\u003e\u003c/div\u003e\u003c/div\u003e\u003cdiv id=\"Sec9\" class=\"Section2\"\u003e\u003ch2\u003e2.3 Characterization.\u003c/h2\u003e\u003cp\u003eThe chemical structure of SAP and the cured were detected by Fourier transform infrared (FTIR, Nicolet 6700, Thermo Fisher Scientific Shier Technology, Pittsburgh) spectra in the 4000-400cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e wavelength range. The uncured sample was coated on a KBr sheet to form a thin layer. \u003csup\u003e1\u003c/sup\u003eH NMR spectroscopy was performed on a superconducting Fourier nuclear magnetic resonance spectrometer (AVANCE III 400 MHz, Brook, Switzerland) via using deuterated acetone as solvent and tetramethylsilane (TMS) as internal standard. Differential scanning calorimetry (DSC) was performed on a differential scanning calorimeter (DSC8500, PerkinElmer, Germany) at a heating rate of 10℃/min from 50 to 100℃ in nitrogen atmosphere (20 mL/min). Thermogravimetric analysis (TGA) was executed with a TGA8000 (PerkinElmer, USA) to analyze the heat resistance of the composites at a heating rate of 10℃/min under a nitrogen atmosphere. The test of time-of-flight mass spectrometry was carried out on the XEVO-G2-TOF instrument.\u003c/p\u003e\u003cp\u003eThe morphology of impact fracture surface of the cured resins was observed by a field emission scanning electron microscope (ZEISS GeminiSEM 300, Germany) at an acceleration voltage of 3 kV. Transmission electron microscope (TEM, JEOL JEM-F200, Japan) was performed at an acceleration voltage of 200 kV.\u003c/p\u003e\u003cp\u003eThe dynamic mechanics of composites was studied on a dynamic mechanical thermal analyzer (DMA Q800, USA). The samples with the size of 55\u0026times;12\u0026times;4mm\u003csup\u003e3\u003c/sup\u003e were measured from 30℃ to 180℃ at the heating rate of 3℃/min and 1Hz in the mode of double cantilever beam. According to GB/T 2567\u0026thinsp;\u0026minus;\u0026thinsp;2021, the tensile strength and bending strength of spline were tested on a universal testing machine (CMT 4204, Sans, Shenzhen, China). The impact strength was tested by a cantilever impact tester (CEAST 9050, Italy) with a range of 5.5J. The sample is a spline with a size of 80\u0026times;10\u0026times;4mm\u003csup\u003e3\u003c/sup\u003e and no notch. The results of all mechanical tests were averaged by three samples.\u003c/p\u003e\u003cp\u003eAccording to GB/T 7124\u0026thinsp;\u0026minus;\u0026thinsp;2008, the tensile shear strength of aluminum-aluminum alloy bonding joint with epoxy adhesive was carried out. LY12-CZ aluminum alloy (100\u0026times;25\u0026times;2mm\u003csup\u003e3\u003c/sup\u003e) was polished with coarse sandpaper and assembled into lap joint. The lap length is 12.5mm and the test rate is 5mm/min. Three samples were measured in each group and the average value was taken.\u003c/p\u003e\u003cp\u003eThe cured product was soaked in 25%NaOH and 98%H\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e solution respectively, and after standing for 7 days, the corrosion resistance of epoxy resin was evaluated by testing the quality and hardness of the spline and observing the change of the solution.\u003c/p\u003e\u003c/div\u003e"},{"header":"3. RESULTS AND DISSCUSSION","content":"\u003cdiv id=\"Sec11\" class=\"Section2\"\u003e\u003ch2\u003e3.1 TPF.\u003c/h2\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eFigure \u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea is the FT-IR spectra of DETM (A) and TPF (B). As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea, the stretching vibration absorption peaks of -CH\u003csub\u003e2\u003c/sub\u003e and -CH groups in the molecule are at 3073-2821cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e; the vibration absorption peak at 1602cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e corresponds to benzene ring skeleton C\u0026thinsp;=\u0026thinsp;C; the peak at 1498cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e is the deformation vibration absorption peak of methylene bridge connected ortho to benzene ring. Tensile vibration absorption peaks and bending vibration absorption peaks of phenolic hydroxyl groups is at 3421cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1331cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e; the stretching vibration peak of phenolic hydroxyl C-O group is at 1238cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. The characteristic absorption peak of ether bond (-COC-) is at 1165 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and the C-H out-of-plane bending vibration absorption peaks of disubstituted benzene and tetrasubstituted benzene are at 870cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 752cm\u003csup\u003e\u0026minus;\u0026thinsp;1[\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e]\u003c/sup\u003e. Comparing the curve A and B, it is found that the characteristic peak of methoxy group (-OCH\u003csub\u003e3\u003c/sub\u003e) at 1046cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e in the infrared spectrum of DETM, disappears in the infrared spectrum of TPF, indicating the complete reaction of DETM with p-tert-butylcatechol. From above, it reveals that the phenolic resin TPF has been successfully prepared.\u003c/p\u003e\u003cp\u003eFigure \u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb shows the \u003csup\u003e1\u003c/sup\u003eH NMR spectrum of TPF. In Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb, the positions of hydrogen atoms in different chemical environments in TPF are marked with 1\u0026thinsp;~\u0026thinsp;7 respectively. Peak 1 (5.35 ppm) corresponds to the hydrogen on the phenolic hydroxyl. Peak 2(1.35 ppm) belongs to the hydrogen of three methyl groups attached to the same tertiary carbon. The chemical shifts at peaks 3 and 4 are 6.98 ppm and 7.03 ppm, which represent the unsubstituted hydrogen on the phenol ring, respectively. Peak 6(6.75 ppm) and Peak 7(7.21 ppm) belong to the hydrogen on the benzene ring in the phenyl ether. Peak 5(3.99 ppm) corresponds to methylene (-CH\u003csub\u003e2\u003c/sub\u003e-) connecting phenol ring and benzene ring. It is reasonable to infer that the reaction product from methoxydiphenyl ether and p-tert-butylcatechol is in line with the expected structure, indicating that TPF has been successfully prepared. TPF was further analyzed by time-of-flight mass spectrometry (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec). It was shown that the molar mass of curing agent is 386g/mol and 408g/mol by subtracting H\u003csup\u003e+\u003c/sup\u003e(1g/mol), indicating that TPF is an oligomer.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec12\" class=\"Section2\"\u003e\u003ch2\u003e3.2 TASx composite\u003c/h2\u003e\u003cp\u003eFigure \u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e is the infrared spectrum of succinic anhydride, diaminopropyl polydimethylsiloxane (ATPDMS) and toughening agent (SAP). In Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e, 1862cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1783cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e belong to typical symmetrical and antisymmetric vibration absorption peaks in succinic anhydride. In the FT-IR spectrum of ATPDMS, due to the low ammonia value, only a weak aliphatic primary amine double peak is at 3300\u0026ndash;3500 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. In the FT-IR spectrum of SAP, the weak double peaks of aliphatic primary amine turn into a single characteristic absorption peak of secondary amine. The peaks at 2905cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 2962cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e correspond to the stretching vibration of saturated methylene (-CH\u003csub\u003e2\u003c/sub\u003e-) and methyl (-CH\u003csub\u003e3\u003c/sub\u003e-) respectively. The characteristic absorption peak at 1412cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e corresponds to Si-O-C; the characteristic absorption peaks of Si-(CH\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e are at 1260 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, 864cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 798cm\u003csup\u003e\u0026minus;\u0026thinsp;1[\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e]\u003c/sup\u003e; the stretching vibration peaks of Si-O are at 1089cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1021cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. In the infrared spectrum of SAP, the characteristic peaks of siloxane are unchanged, but the obvious carboxyl (-COOH) absorption peak at 1720cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and a new secondary amide (-O\u0026thinsp;=\u0026thinsp;C-NR) stretching vibration peak at 1641cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003eappear. From the above FT-IR spectra, the ring-opening reaction between anhydride and primary amino group occurs, and polydimethylsiloxane with amide and carboxylic acid group have been generated.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ea is the DSC curing curve of TASx (TPF as the curing agent). As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ea, with the increase of the content of the toughening agent SAP, the exothermic peak slightly shifts to low temperature (the exothermic peak temperature of TAS0 is 94.6℃). For TASx, the more siloxane segments are introduced, the easier the curing reaction is. At the same time, the curing peak gradually widens. This is because long polysiloxane chains in SAP increase the flexibility, and can make the crosslinking reaction between epoxy group and phenolic curing agent occur at lower temperature. Therefore, the curing process of TASx (TPF as the curing agent) is set as below: 80℃/1h\u0026thinsp;+\u0026thinsp;90℃/1h\u0026thinsp;+\u0026thinsp;100℃/2h. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eb ( the FT-IR of the cured TASx), 1743cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e is recognized as the characteristic absorption peak of ester group (-C-OOR), because carboxyl groups at both ends of SAP molecule can open epoxy groups\u003csup\u003e[\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e]\u003c/sup\u003e, the characteristic absorption peak of epoxy group at 910cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e disappears, indicating that the AFG-90H epoxy resin modified by SAP has been completely cured.\u003c/p\u003e\u003cp\u003eFigure \u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e shows mechanical properties of the cured TASx with different contents of SAP. With the increase of SAP content, the tensile strength of TASx is first large and then decreases. The tensile strength and elongation at break of the cured TAS0 without toughening agent are 47.41MPa and 1.52%, respectively. When SAP is grafted, the longer siloxane chain can further form an interpenetrating network structure with epoxy resin. When the dosage of SAP is less than 10 phr, the interaction between AFG-90 resin and SAP network can improve the tensile strength (62.17MPa) and elongation at break (2.99%) of the cured. On the further increase of the content of SAP, the strength is lowered. The cause is that the long siloxane chain can entangle, hindering the movement of molecular chains, resulting in low curing density per unit volume and the overall composition uniformity. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eb, the bending strength of the cured TASx is from 44.69MPa to 58.31MPa, and then down to 46.87MPa. As the bond length and bond angle of Si-O-Si are larger than the C-O-C bond of epoxy resin, the flexibility of the curd of the modified epoxy is superior to the cured of AFG-90H (TAS0). The cured TAS10 shows high impact strength ( 7.19 kJ/m\u003csup\u003e2\u003c/sup\u003e) (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ec), but on further increase of the content of the toughening agent, the impact strength is reduced. The catechol segment in TPF is easy to form coordination bonds with metal atoms, leading to good adhesion to metal substrates. The maximum shear strength of TASx is up to 9.41MPa (see Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ed). From the peeled metal surface (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ee), resin is tightly adhered to the shear sections of TAS0\u0026thinsp;~\u0026thinsp;TAS20, which is the proof of good adhesion between the aluminum sheet and the modified epoxy adhesive.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eFigure \u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e is SEM images of the impact fracture cross section of the cured TASx. TAS0 shows a relatively uniform and flat surface (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ea). In Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003eb, due to the low content of SAP, the cross section presents cracks extending uniformly, and some sparse and tiny holes are generated. It can be seen from Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ec that holes with the pore size ranging from 2 to 10 \u0026micro;m appear on the cross section of TAS10, which is also commonly called \"island structure\". This \"island structure\" acts as the nail anchor like rubber particles, which can restrain the further expansion or extension of closed microcracks. However, with the further increase of SAP content, the number and volume of \"island structures\" are on the increase correspondingly (see Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ed), but the strength of the cured is lowered.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eFigure \u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e shows thermogravimetric curves (TG) and thermal decomposition rate (DTG) of the cured TASx. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e and Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, the cured TAS0 begins to decompose at 360℃, and its corresponding T\u003csub\u003emax\u003c/sub\u003e is 403℃, and the carbon residue is 28.1%. When the ratio of epoxy resin toughening agent SAP is large, T\u003csub\u003ed5%\u003c/sub\u003e the cured TASx is down to 345 ℃(TAS20). This can be explained by the fact that Si-O bonds with high bond energy replace some C-O bonds with low bond energy, and more heat needs to be absorbed in the thermal decomposition process to break the bonds, while the formation of holes can weaken the thermal stability of the cured. For the cured TAS5- TAS20, the thermal decomposition rate is almost unchangeable, and the stability at high temperature is obviously enhanced, especially above 500℃. Compared with pure TAS0, the carbon residue of TAS20 at 700℃ increased by 36%, up to 38.2%, which is due to the formation of more SiO\u003csub\u003e2\u003c/sub\u003e during thermal degradation. The toughening agent SAP plays an important role of delaying the thermal decomposition of the cured AFG-90H epoxy resin, and of enhancing the carbon residue of the cured.\u003c/p\u003e\u003cp\u003eTo sum up, TASx has the best heat resistance and mechanical properties when the content of SAP is 10 phr, so TAS10 was chosen as the basic formula for the next exploration.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec13\" class=\"Section2\"\u003e\u003ch2\u003e3.3 TAS10My composites\u003c/h2\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eFigure \u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e shows the mechanical properties of cured TAS10My composites. In Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003ea, the tensile strength of cured TAS10My filled with 10 phr OMMT is the highest, up to 73.29MPa, and the elongation at break is 4.62%. It can be seen from Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003eb that the bending strength and modulus of TAS10M10 are the highest, which are 75.00 MPa and 7616.12 MPa, respectively. When the content of OMMT exceeds 10 phr, the agglomeration of OMMT occurs, resulting in the formation of intercalation structure in the cured composites. According to Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003ec, the impact strength of TAS10My composites can be increased from 7.19 kJ/m\u003csup\u003e2\u003c/sup\u003e to 11.31 kJ/m\u003csup\u003e2\u003c/sup\u003e by the addition of OMMT, which is 187.8% higher than that of TAS0. In Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003ed, the maximum tensile shear strength (TAS10M10) is 14.09MPa at room temperature, and it begins to decrease with the further increase of OMMT content. From Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e(e), there are the cured on the peeling cross sections of two aluminum sheets for TAS10M5- TAS10M15, indicating the good adhesion between the aluminum sheet and the composite adhesives (TAS10M5- TAS10M15) (see Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003ee). From above, the addition of OMMT is helpful to enhance the shear strength of the system based on the improvement of cohesive strength, so the failure is internal aggregation failure, supplemented by adhesion failure.\u003c/p\u003e\u003cp\u003eSEM images of the impact fracture section of TAS10My are shown in Figure \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e. In Figure \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e(a-b), OMMT in the cured TAS10M5 and TAS10M10 is uniformly distributed in epoxy resin. The existence of OMMT can also induce micro-cracks in holes to absorb external energy. However, it can be clearly seen that due to the poor dispersibility of OMMT, aggregation and agglomeration occur between particles, making the particle size close to micron scale (Figure \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003ec). At the same time, under the doping of excessive OMMT, the space of island holes is squeezed, thus splitting into more holes, which greatly reduces the crosslinking density of epoxy resin.\u003c/p\u003e\u003cp\u003eFigure \u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003e shows thermogravimetric curves (TG) and thermal decomposition rate (DTG) curves of the cured TAS10My. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003e and Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, the degradation processes of the cured composites are similar, and with the increase of OMMT proportion, the degradation rate of the systems slow down. Among them, the T\u003csub\u003ed5%\u003c/sub\u003e of the cured TAS10M5, TAS10M10 and TAS10M15 were 356℃, 359℃ and 363℃, respectively, showing a gradual upward trend, and the carbon residue of these systems also increases (from 32.1% to 35.5%). Thermal stability depends on the\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003edispersion degree of OMMT in resin matrix. On one hand, Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and MgO in OMMT are high thermal conductors with excellent thermal conductivity, which can reduce the thermal stress inside the matrix; On the other hand, the treated OMMT can be uniformly dispersed in the substrate\u003csup\u003e[\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e]\u003c/sup\u003e. The network structure of the system becomes more compact and the interaction between the filler and the substrate is enhanced, limiting the thermal movement of the molecular chain of epoxy resin. Most of the residues left after high-temperature degradation are silicon carbon containing magnesium and aluminum metals. Therefore, the cured composite has good heat resistance.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003e\u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e\u003cdiv class=\"CaptionContent\"\u003e\u003cp\u003eMechanical and thermal parameters of composite materials\u003c/p\u003e\u003c/div\u003e\u003c/caption\u003e\u003ccolgroup cols=\"5\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\"\u003e\u003cp\u003eSystems\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c2\"\u003e\u003cp\u003eT\u003csub\u003eg\u003c/sub\u003e/℃\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c3\"\u003e\u003cp\u003eρ/mol\u0026middot;dm\u003csup\u003e\u0026minus;\u0026thinsp;3\u003c/sup\u003e\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c4\"\u003e\u003cp\u003eT\u003csub\u003ed5%\u003c/sub\u003e/℃\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c5\"\u003e\u003cp\u003eChar yield/%\u003c/p\u003e\u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eTAS0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e132.8\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e4.88\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e360\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e28.1\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eTAS5\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e128.0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e4.23\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e357\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e29.9\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eTAS10\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e124.1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e3.98\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e353\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e31.4\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eTAS15\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e120.9\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e3.18\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e348\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e34.7\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eTAS20\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e115.8\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e2.59\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e345\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e38.2\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eTAS10M5\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e127.2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e4.15\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e356\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e32.1\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eTAS10M10\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e130.7\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e4.41\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e359\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e33.8\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eTAS10M15\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e128.9\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e4.07\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e363\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e35.5\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/colgroup\u003e\u003ctfoot\u003e\u003ctr\u003e\u003ctd colspan=\"5\"\u003eTg: Glass transition temperature; E\u0026rsquo;: Storage modulus; ρ: Crosslinking density\u003c/td\u003e\u003c/tr\u003e\u003c/tfoot\u003e\u003c/table\u003e\u003c/div\u003e\u003c/p\u003e\u003cp\u003eFigure \u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e11\u003c/span\u003e shows the storage modulus (E') and loss tangent (tanδ) of the cured TASx and TAS10My composites versus temperature. In Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e11\u003c/span\u003e, after SAP was added, the E' of the cured TASx in the glass zone slightly increases. The temperature corresponding to the peak value of tanδ represents the glass transition temperature (Tg) of the cured. As indicated in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, the Tg of cured TASx shows a decreasing trend, because SAP is flexible.\u003c/p\u003e\u003cp\u003eAfter OMMT is added, Tg and ρ of the cured epoxy resin system increases slightly. The interfacial interaction between epoxy resin matrix and OMMT lamellae will lead to the decrease of chain mobility. However, when the OMMT content exceeds 10 phr, agglomeration occurs, so the dynamic thermodynamic properties of the system become worse.\u003c/p\u003e\u003cp\u003e\u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e\u003cdiv class=\"CaptionContent\"\u003e\u003cp\u003eCorrosion resistance and hardness change of composites\u003c/p\u003e\u003c/div\u003e\u003c/caption\u003e\u003ccolgroup cols=\"5\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003eSystems\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003eChemical mediator\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003eQuality change (%)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e\u003cp\u003eShore hardness/HA\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003eBefore soaking\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003eAfter soaking\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003e\u003cb\u003eTAS0\u003c/b\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e98%H\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e+\u0026thinsp;0.72\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e97\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e97\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e25%NaOH\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e+\u0026thinsp;0.54\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e97\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e96\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003e\u003cb\u003eTAS5\u003c/b\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e98%H\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e+\u0026thinsp;0.69\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e94\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e94\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e25%NaOH\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e+\u0026thinsp;0.70\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e93\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e93\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003e\u003cb\u003eTAS10\u003c/b\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e98%H\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e+\u0026thinsp;0.88\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e93\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e93\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e25%NaOH\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e+\u0026thinsp;0.47\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e93\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e92\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003e\u003cb\u003eTAS15\u003c/b\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e98%H\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e-0.83\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e95\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e95\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e25%NaOH\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e+\u0026thinsp;1.02\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e96\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e95\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003e\u003cb\u003eTAS20\u003c/b\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e98%H\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e-0.96\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e91\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e90\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e25%NaOH\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e-0.75\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e92\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e91\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003e\u003cb\u003eTAS10M5\u003c/b\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e98%H\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e-1.44\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e92\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e92\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e25%NaOH\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e+\u0026thinsp;0.95\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e92\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e92\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003e\u003cb\u003eTAS10M10\u003c/b\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e98%H\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e-1.35\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e93\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e93\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e25%NaOH\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e+\u0026thinsp;0.15\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e94\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e94\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003e\u003cb\u003eTAS10M15\u003c/b\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e98%H\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e-1.65\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e97\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e95\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e25%NaOH\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e-0.48\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e97\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e96\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/colgroup\u003e\u003c/table\u003e\u003c/div\u003e\u003c/p\u003e\u003cp\u003eFigure S2 shows the spline and solution changes of the composites after soaking in acid or alkali for 7 d, respectively. Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e shows the mass and hardness changes of the composite. From Figure S2, it can be seen that after soaking in 25%NaOH solution for 7 d, all splines and solutions remain unchanged, indicating that the composite system has good alkali resistance. However, after soaking in 98%H\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e, the color of the spline and solution of TAS20 composites changes slightly at the 7th day, while the spline of TAS10M15 composites begins to change color at the 5th day, meanwhile the solution becomes reddish, and the color deepens at the 7th day. This may be due to excessive OMMT agglomerating on the spline surface, leading to the reaction between metal oxide and acid slowly. In addition, there is no obvious change in other groups. The above phenomenon can also be verified by the change of hardness and quality. It proves that the introduction of proper amount of SAP and OMMT will not affect the acid and alkali resistance of the system.\u003c/p\u003e\u003c/div\u003e"},{"header":"4. CONCLUSION","content":"\u003cp\u003eIn this work, a phenolic curing agent (TPF) based on diphenyl ether was prepared from p-tert-butylcatechol, formaldehyde and diphenyl ether. At the same time, toughening agent (SAP) and organic montmorillonite (OMMT) were introduced into AFG-90H epoxy resin. The results showed that TASx can be cured and crosslinked at 100℃. When the OMMT content is 10phr, the T\u003csub\u003ed5%\u003c/sub\u003e of AFG-90H grafted by 10 phr SAP cured by HPF is 359℃; the tensile strength, impact strength and the tensile shear strength is 73.29MPa, 11.31 kJ/m\u003csup\u003e2\u003c/sup\u003e and 14.09MPa, respectively. It revealed that the introduction of silicon-oxygen bond and OMMT plays an important role in improving the thermal stability and mechanical properties of the system. The curing system with good heat resistance, toughness and adhesive strength has application potential in aerospace, civil construction and other industrial fields.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAuthorship contribution statement\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eZhuhuan Chen:\u0026nbsp;\u003c/strong\u003eMethodology, Formal analysis, Writing \u0026ndash; original draft.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eShijie Zhang:\u003c/strong\u003e Methodology, Formal analysis.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eRuobing Yu:\u0026nbsp;\u003c/strong\u003eConceptualization, Resources, Writing \u0026ndash; review \u0026amp; editing, Funding acquisition.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDeclaration of Competing Interest\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgements:\u0026nbsp;\u003c/strong\u003eThe authors acknowledge the financial support from East China University of Science and Technology.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData availability:\u0026nbsp;\u003c/strong\u003eData will be made available on request.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eOZTURKMEN, M. 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F., et al. Effect of PDMS content on waterproofing and mechanical properties of geopolymer composites [J]. Ceramics International. 2022, 48 (18): 26248\u0026ndash;26257.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eYIN, X., XIE, Z., LIU, Q., et al. Synergistic toughening of epoxy resin by CTBN and CM-β-CD [J]. Journal of Applied Polymer Science. 2021, 138 (42).\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eFEI, X., WEI, W., TANG, Y., et al. Simultaneous enhancements in toughness, tensile strength, and thermal properties of epoxy-anhydride thermosets with a carboxyl-terminated hyperbranched polyester [J]. European Polymer Journal. 2017, 90: 431\u0026ndash;441.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eGUO, B. C., HA, D. M., CAI, C. G. Effects of organo-montmorillonite dispersion on thermal stability of epoxy resin nanocomposites [J]. European Polymer Journal. 2004, 40 (8): 1743\u0026ndash;1748.\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"mechanics-of-time-dependent-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"mtdm","sideBox":"Learn more about [Mechanics of Time-Dependent Materials](http://link.springer.com/journal/11043)","snPcode":"11043","submissionUrl":"https://submission.nature.com/new-submission/11043/3","title":"Mechanics of Time-Dependent Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"phenolic resin, mechanical properties, thermal stability, toughening, polyorganosiloxane","lastPublishedDoi":"10.21203/rs.3.rs-8225846/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8225846/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eEpoxy adhesive with excellent comprehensive properties is in demand. Here, multifunctional epoxy resin(AFG-90H) with high heat resistance and brittleness was chosen as matrix, and phenolic curing agent (TPF) based on diphenyl ether was prepared from p-tert-butylcatechol (TBC), formaldehyde and diphenyl ether. Due to the existence of diphenyl ether, the toughness of the cured AFG-90H epoxy resin can be improved. At the same time, bisaminopropyl polydimethylsiloxane modified by acid anhydride (SAP) and organic montmorillonite (OMMT) were introduced into AFG-90H epoxy resin to improve its comprehensive properties. The results show that the curing temperature of TPF and AFG-90H resin is below 100℃. When OMMT with mass fraction of 10 phr was added to AFG-90H grafted with SAP with mass fraction of 10 phr, the thermal degradation temperature (T\u003csub\u003ed5%\u003c/sub\u003e) is up to 359℃, and the tensile strength, bending strength, impact strength and tensile shear strength is 73.29MPa, 75.00MPa, 11.31kJ/m\u003csup\u003e2\u003c/sup\u003e and 14.09MPa, respectively. The synergistic effect of TPF, OMMT and SAP can make the cured AFG-90H resin possess good comprehensive properties.\u003c/p\u003e","manuscriptTitle":"Study on the synergistic effect of TPF phenolic curing agent and OMMT on the cured multifunctional epoxy grafted by SAP","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-12-03 08:43:28","doi":"10.21203/rs.3.rs-8225846/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2026-02-03T16:53:52+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-02-03T07:39:05+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"324847601346745901750638291958580617958","date":"2026-01-23T02:35:11+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-01-22T09:56:41+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"196570893294426350031444898559901956108","date":"2026-01-21T15:56:26+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-01-21T03:15:46+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-12-30T12:13:53+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"156185177778330537097018837028844471079","date":"2025-12-24T17:37:28+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"102182148952576825129912557906263518880","date":"2025-12-02T15:29:39+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-12-02T03:05:38+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-12-02T03:04:36+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-11-28T10:27:03+00:00","index":"","fulltext":""},{"type":"submitted","content":"Mechanics of Time-Dependent Materials","date":"2025-11-28T02:29:55+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"mechanics-of-time-dependent-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"mtdm","sideBox":"Learn more about [Mechanics of Time-Dependent Materials](http://link.springer.com/journal/11043)","snPcode":"11043","submissionUrl":"https://submission.nature.com/new-submission/11043/3","title":"Mechanics of Time-Dependent Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"3299156a-323d-4591-81ee-2abe0f7731d7","owner":[],"postedDate":"December 3rd, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2026-04-13T16:05:40+00:00","versionOfRecord":{"articleIdentity":"rs-8225846","link":"https://doi.org/10.1007/s11043-026-09872-6","journal":{"identity":"mechanics-of-time-dependent-materials","isVorOnly":false,"title":"Mechanics of Time-Dependent Materials"},"publishedOn":"2026-04-09 15:59:02","publishedOnDateReadable":"April 9th, 2026"},"versionCreatedAt":"2025-12-03 08:43:28","video":"","vorDoi":"10.1007/s11043-026-09872-6","vorDoiUrl":"https://doi.org/10.1007/s11043-026-09872-6","workflowStages":[]},"version":"v1","identity":"rs-8225846","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8225846","identity":"rs-8225846","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}