COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
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2024
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IF 4.9
Ao Yang,Pan He,Guangzhao Li,Jiajia Ye,Yumin Huang,Rui Han,Shuai Zhang
Phthalonitrile (PN) resin is a thermosetting resin with excellent properties, but its poor processability hinders its wide application. Meanwhile, as a high-performance green fiber, basalt fiber (BF) shows good overall properties, but the chemical inertness and smooth surface limits its application as well. In this work, a highly reactive organic coating polydopamine (PDA) was used to promote the curing of PN resin and enhance the interfacial interaction between the polymer matrix and the fiber cloth. The successful coating of PDA was verified by SEM observation, FTIR and XPS spectra. It was found that PDA could not only increase the polarity of BF, aid the infiltration of PN resin into the fiber cloth, enhance the interfacial strength, but also promote the consumption of cyano groups and increase the chemical crosslinking density. Consequently, the overall performance of the composites was enhanced. Specifically, the laminate 0.4DABF/BAPh showed flexural strength of 447 MPa and flexural modulus of 23.3 GPa, which was 131 MPa and 4.5 GPa higher than those of BF/BAPh. The glass transition temperature of 0.4DABF/BAPh was also 77 °C higher than that of BF/BAPh.
研究领域:
材料科学
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化学工程
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DOI
高影响因子
JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY
·
2026
·
IF 16.8
Meina Li,Yuechao Zhao,Yiyang Wang,Benhao Xin,Wenlong Jiang,Ying Guo,Kun Zheng,Heng Zhou,Tong Zhao
Molecular rigidity and nanofiller hybridization regulate sol-gel kinetics and optimize nanoporous structure. • The aerogel shows ultralow thermal conductivity (0.036 W m - ¹ K - ¹) and high compressive strength (4.67 MPa). • The aerogel maintains dimensional stability at 300 °C for 3000 s with Td₅ % reaching 527.8 °C. • The material shows strong ablation resistance and self-extinguishing ability for aerospace thermal insulation. The development of high-performance polymers has facilitated the emergence of polymer aerogels, which integrate lightweight characteristics, mechanical strength, and excellent heat resistance. This advancement overcomes the brittleness of inorganic aerogels, fulfilling the requirements for high-temperature applications. Here, phthalonitrile (PN) aerogels are prepared via the sol-gel method. A systematic study is conducted on the fundamental process underlying PN aerogel formation. It was found that molecular rigidity and crosslinking density are the key factors that regulate the sol-gel process and affect the macroscopic performance. By introducing phenolic hydroxyl and amino fillers, the nucleation and growth of PN molecules are regulated, enabling the tailored design of hierarchical nanoporous structures. The hybrid PN aerogel exhibits ultralight characteristics (0.22 g cm −3 ), high specific surface area (575.57 m 2 g −1 ), low thermal conductivity (0.036 W m −1 K −1 ), excellent mechanical strength (4.67 MPa), and high-temperature resistance ( T d5% = 527.8°C). It also demonstrates exceptional thermal dimensional stability, maintaining almost unchanged dimensions up to 300°C for 3000 s. Moreover, it exhibits ablation resistance and self-extinguishing properties. This novel aerogel extends the limits of thermal resistance and thermal insulation compared with existing thermosetting aerogels. This work holds significant potential for extreme-environment applications such as thermal sealing for aerospace vehicles and thermal insulation for engine components. High-temperature-resistant phthalonitrile aerogels are developed via the sol-gel process, accompanied by rigid phenolic chain design and aminated silica nanoparticle hybridization. This cooperative regulation reduces the effective crosslinking sites and enhances the spatial hindrance, which ultimately refines pore sizes to the nanoscale and optimizes the hierarchical porosity. It results in ultralight aerogels (0.22 g cm -3 ) with high surface area (575.57 m² g -1 ), low thermal conductivity (0.036 W m -1 K -1 ), excellent mechanical strength (4.67 MPa), and superior thermal stability (T 5% = 527.8 °C, negligible shrinkage at 300 °C). Moreover, it also exhibits excellent ablation resistance and self-extinguishing properties. Download: Download high-res image (293KB) Download: Download full-size image
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DOI
高影响因子
ACS Applied Polymer Materials
·
2019
·
IF 0
Kan Zhang,Xinye Yu,Yuting Wang,Yuqi Liu
Phthalonitrile polymers exhibit many attractive advantages including high thermal and mechanical properties, low water absorptivity, and excellent flame retardancy. However, the poor processability requiring high temperature polymerization for long duration seriously impedes their further applications. In this work, a benzoxazine monomer bearing both norbornene and phthalonitrile functionalities (oHPNI-apn) has been synthesized, and its chemical structure has been confirmed by NMR, FT-IR, and elemental analysis. In addition, the polymerization behavior of oHPNI-apn has been systematically studied using DSC, in situ FT-IR and solid-state 13C NMR analysis. The phthalonitrile in this developed thermosetting system can be thermally induced polymerized at a relatively lower temperature with no added catalysts, which indicates the existence of self-catalyzed effect during the terpolymerization of oHPNI-apn. Moreover, oHPNI-apn-based thermoset is found to possess excellent thermal stability and outstanding flame retardancy, with extremely high Tg temperature (419 °C), very high char yield value (68%, at 800 °C in N2), and extraordinarily low heat release capacity (25.1 J/(g K)) in the absence of any added antiflammable additives.
研究领域:
材料科学
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高分子化学
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产品关联
DOI
POLYMER
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2022
·
IF 4.432
Xiaoqian Xu,Mingzhen Xu,Dengxun Ren,Tian Liu,Bo Li,Yingfa Liu,Tianrui Li
Phthalonitrile resin is a kind of high-performance thermosetting resins . Decreasing the curing temperature and accelerating the curing reaction rate have become the focus of research on phthalonitrile modification. Based on the reactivity, thermal and mechanical properties of diamine-type benzoxazine , a monocyano-functionalized diamine-type benzoxazine (MD-cn) was synthesized and applied to modify bisphthalonitrile resin containing bisphenol-type benzoxazine/nitrile phenylenediamine (BA-ph/BAB). Curing reaction properties and curing mechanism of BA-ph/BAB/MD-cn were studied by gelation time, DSC, DRA and in-situ IR. Results showed that MD-cn could significantly boost the curing reaction rate and reduce its curing temperature of BA-ph/BAB. Meanwhile, glass fiber reinforced composites (BA-ph/BAB/MD-cn/GF) was prepared and their properties were studied. Results showed that MD-cn improved the crosslinking density and curing degree of BA-ph/BAB could make the BA-ph/BAB/MD-cn resin matrix possess higher stiffness. Therefore, BA-ph/BAB/MD-cn/GF composites exhibited higher flexural strength (494 MPa, increased 40%) and flexural modulus (26 GPa, increased 13%) as well as good dimensional stability. Compatibility between MD-cn and BA-ph/BAB was investigated by DMA and SEM. Moreover, with the increase of MD-cn content, the good thermal stabilities ( T 5% >404.5 °C, Y c, 800 °C >66%) of cured BA-ph/BAB/MD-cn were obtained. Besides, interfacial adhesion properties of BA-ph/BAB/MD-cn/GF composite laminates were also studied.
研究领域:
材料科学
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高分子化学
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复合材料工程
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DOI
高影响因子
Materials Today Communications
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2024
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IF 3.7
Zhaojun Chu,Leiqiong Zhao,Beitao Liu,Cijian Zhang,Jinyan Wang,Xigao Jian,Zhihuan Weng
Resin-based porous carbon materials are considered to be an important direction for CO 2 adsorption and supercapacitors due to their controllable chemical structure, large specific surface area, and stable physicochemical properties. But at present, the main source of resin-based porous carbon materials is petroleum-based polymer materials, which is incongruous with the tenets of green chemistry. Here, a bio-based phthalonitrile precursor containing s- triazine ring structure (TDPH) was synthesized from vanillin, then a nitrogen/oxygen co-doped hierarchical porous carbon with excellent properties, was prepared using TDPH via a two-step process, with urea/zinc chloride as hardener and potassium hydroxide as activator, respectively. The carbon material prepared under optimal conditions can achieve a maximum CO 2 adsorption capacity of 6.81 mmol g −1 at 273 K due to its high specific surface area (1607 m 2 g −1 ) and high N/O content (7.06 wt%/14.74 wt%). It is worth noting that the CO 2 adsorption capacity at 298 K can still reach 96.3 % of the initial adsorption after 7 cycles. In addition, the electrochemical properties of the resultant porous carbon were tested under a 1 M H 2 SO 4 three-electrode system, and the highest specific capacitance at a current density of 0.1 A g −1 was 473 F g −1 and the specific capacitance retention can still reach 87 % after 65,000 cycles. This work broadens the source of resin-based porous carbon materials and paves a new way for the functionalization of bio-based resins.
研究领域:
材料科学
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绿色化学
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能源存储与转换
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DOI
高影响因子
HIGH PERFORMANCE POLYMERS
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2024
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IF 1.8
Abdelwahed Berrouane,Mehdi Derradji,Karim Khiari,Oussama Mehelli,Slimane Abdous,Abdelmalek Habes,Wenbin Liu,Azzedine Khadraoui
Quercetin (Q), one of the most abundant molecules in nature, remains relatively unexplored in the realm of bio-based thermosets. In line with the pursuit of sustainability, we report the successful synthesis of a novel bio-based phthalonitrile (PN) monomer (Q-Ph) using Q. The synthesis involved a nitro displacement reaction with 4-nitrophthalonitrile (4-NPN). Confirmation of the monomer’s structure utilized hydrogen and carbon nuclear magnetic resonances (1H and 13C NMR), Fourier transform infrared spectra (FTIR), and elemental analysis. Curing characteristics were examined by differential scanning calorimetry (DSC), and polymerization was analyzed using FTIR. The resulting monomers showed a wide processing window and low melt viscosity via rheological analysis. Thermal and thermomechanical properties were assessed using dynamic mechanical analyzer (DMA) and thermogravimetric analysis (TGA), revealing lower curing and polymerization temperatures compared to petroleum-based counterparts. The synthesized resin achieved a high Tg exceeding 400°C, a char yield of 79% at 1000°C, and T5% and T10% values of 564 and 660°C, respectively. The Q-Ph polymer demonstrated superior performance, with evidence of an autocatalytic curing mechanism. These results highlight quercetin as a promising petrochemical replacement for the preparation of self-curable PN thermosets, especially for high-performance applications.
研究领域:
材料科学
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有机化学
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DOI
高影响因子
POLYMER
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2024
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IF 4.1
Zichun Ding,Siying Wang,Runze Liu,Yuhang Wang,Jianing Guo,Xuedong Wu,Jiaming Wang,Xigao Jian,Lishuai Zong,Jinyan Wang
Phthalonitrile (PN) resin is renowned for its absence of small molecule release during curing, high processing stability, and exceptional thermal stability, positioning it favorably in the realm of high-temperature resin applications. However, its narrow processing window and high melting point present challenges to its development and practical use. To address these limitations, this work synthesized PN prepolymers 4,4′-bis (sulfonylbiphenyl) thiophtalonitrile (BSPS) and 4,4′-bis(carbonylbiphenyl) thiophtalonitrile (BSPC) by introducing thioether bonds as a substitute for ether bonds, aiming to expand the prepolymers' processing window. Meanwhile, building upon the oxidation process of thioether to sulfone observed in pharmaceutical production, the potential for in-situ oxidation of thioether bonds during the curing of phthalonitrile prepolymers was investigated. A comprehensive analysis of the curing behavior, viscosity changes, and thermal stability was conducted using differential scanning calorimetry (DSC), rheological analysis, and thermogravimetric analysis (TGA). The DSC and rheological test results reveal that the experimental group prepolymers BSPS and BSPC exhibit lower melting points (BSPS 179 °C; BSPC 180 °C) and broader processing windows (BSPS 52 °C; BSPC 79 °C) than blank. Additionally, the thermal performance of resins show improvement over the blank, with BSPS achieving a decomposition temperature of up to 530 °C ( T d5% ). XPS analysis of the curing process confirmed that the enhanced thermal stability is attributable to the partial oxidation of thioether bonds into stable sulfone groups. This innovative structural approach allows for satisfactory processing performance in the initial stage, followed by a spontaneous transformation into a more robust and thermo-resistant structure post-shaping. This finding carries significant implications for the development of a balanced phthalonitrile system that harmonizes processing ease with superior thermal endurance.
研究领域:
材料科学
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化学工程
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DOI
高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
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2022
·Vol. 139
·期 34
·e52804
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IF 3.057
Hassan Alshahrani,Abdul Qadeer Dayo,Wen-Bin Liu
The randomly-oriented glass fibers (GF) reinforced composites with Bisphenol A–amine based benzoxazine (BA-a) and bio-based eugenol-based phthalonitrile (EPN) copolymer were developed by an isothermal compression molding technique. The silane coupling agent-treated GF (TGF) reinforced composites showed much better impact strength as compared to as-received GF reinforced composites. A rise of 95.2 MPa, 5.5GPa, 69.1 MPa, and 2.5GPa in flexural strength, flexural modulus, tensile strength, and Young's modulus were observed, respectively. The DMA results confirmed that the storage modulus ( E' ) and glass transition temperature ( T g ) were gradually increased and the damping factor decreased as the TGF reinforcement was raised from 0 to 40 wt%. E' and T g values were 3.09 GPa and 27°C, respectively, higher than the recorded values for the neat copolymer. The 40 wt% TGF reinforced poly(BA-a/EPN) composite showed the maximum thermal stability values of 475.4, 507.3°C, and 75.43% for T 5 , T 10 , and Y c , respectively. The LOI values confirm that the TGF/copolymer composites have self-extinguishing properties.
研究领域:
材料科学
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化学工程
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DOI
高影响因子
JOURNAL OF MOLECULAR STRUCTURE
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2023
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IF 3.8
Xian He,Menghao Chen,Jiangbo Lv,Hang Xiao,Hao Wu,Rongtao Zhou,Jianghuai Hu,Ke Zeng,Gang Yang
Aromatic nitriles play an important role in the preparation of high-performance polymers. In order to guide the rational design of new molecules, it is necessary to carry out systematic theoretical research on molecular structures. This article takes a new type of aromatic nitriles, pyrazine-2,3-dicarbonitrile (PQ) and its control group 1,4-dicyanobenzene (PN) as examples to conduct systematic theoretical research on their chemical environments using DFT calculation with experimental verification. Results show that the electronic effect of pyrazine withdraws the electron form cyano to pyrazine, which makes the cyano carbon more exposed and prone to nucleophilic reaction. This electronic deffect also causes the π-electron delocalization from cyano nitrogen to pyrazine, and results in a lower polarity of the cyano and an anomalous law for the 13 C NMR shift of cyano carbon. In addition, pyrazine changes the stacking mechanism of PQ to be dominated by electrostatic force rather than commonly observed dispersion force-dominant π-π stacking in PN. This research method provides important guidance for the design of new crosslinkable aromatic nitrile and help to deepen our understanding of their structure-property relationship.
研究领域:
化学
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材料科学
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DOI
高影响因子
PROGRESS IN ORGANIC COATINGS
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2015
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IF 2.358
Mehdi Derradji,Noureddine Ramdani,Tong Zhang,Jun Wang,Lin-dan Gong,Xiao-dong Xu,Zai-wen Lin,Abdelkhalek Henniche,H.K.S. Rahoma,Wen-bin Liu
A new type of nanocomposites was prepared by reinforcing a high performance bisphenol-A phthalonitrile resin with different amounts of silane surface modified titania nanoparticles. The effect of the nanofillers amount on the thermal, mechanical, and corrosion protective properties was investigated. Thermogravimetric analysis shows that the starting decomposition temperatures and the residual weight at 800 °C were highly improved upon adding the nanofillers. At 6% nanoloading, the glass transition temperature and the storage modulus were considerably enhanced reaching 364.4 °C and 3.2 GPa, respectively. The tensile strength and modulus as well as the microhardness values increased with the increasing of the nanoparticles amount. The tensile modulus calculations were investigated using Series, Halpin–Tsai, and Kerner models. Haplin–Tsai model was found to reproduce the experimental data with the best accuracy. Finally, results from electrochemical impedance spectroscopy revealed that the neat resin and its related nanocomposites offer excellent corrosion protective properties.
研究领域:
材料科学
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化学工程
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腐蚀科学
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产品关联
DOI
高影响因子
COMPOSITES PART A-APPLIED SCIENCE AND MANUFACTURING
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2025
·
IF 8.9
Haizhou Fan,Benhao Xin,Yuechao Zhao,Ying Guo,Kun Zheng,Min Li,Heng Zhou,Tong Zhao
To further improve the comprehensive performance of phthalonitrile (PN), a novel compound SiBPN-Ce was prepared using 2-benzimidazolinone (2-BI), diphenyldichlorosilane (DPDCS), 4-aminophthalonitrile (4-APN), and cerium chloride. The addition of SiBPN-Ce decreased the viscosity of PN exponentially and reduced the peak curing temperature by 29.4 °C. Through copolymerization modification, a highly efficient physical–chemical hybrid reinforcement mechanism was introduced into PN by SiBPN-Ce. The results indicated that SiBPN can effectively increase the temperature of 5 % mass loss (T 5% ) and char yield of PN by 29 °C and 7.2 %, respectively. In the aging test at 350 °C, the formation of a SiO 2 -Ce protective layer derived from SiBPN-Ce delayed the occurrence of microcracks on the PN matrix surface by 60 h. Meanwhile, PN modified with SiBPN-Ce (SiBPN15-Ce) retained most of its surface morphology after aging for 100 h. For the SiBPN-Ce composite, its flexural strength (FS) and interlaminar shear strength (ILSS) increased by 449.1 MPa and 17.2 MPa respectively compared to pure PN composite. Based on all the results, this physical–chemical hybrid reinforcement mechanism in SiBPN15-Ce was carefully analyzed.
研究领域:
高分子材料科学
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复合材料工程
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功能材料化学
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热固性树脂
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耐高温材料
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2024
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IF 13.3
Yabin Zhang,Wenguang Zhang,Houxiang Yin,Yanlin Wang,Bingbing Wang,Lishuai Zong,Jinyan Wang,Xigao Jian
The robust human–machine interaction systems of the aerospace industry necessitate the development of thermal resistant wave-transparent composites, with a pivotal focus on organic resin matrix. However, enhancing the heat resistance of such materials while preserving other critical attributes has been a formidable challenge. In this study, a novel designed strategy of a dual-curing functional phosphorus-based phthalonitrile monomer (P-ALK-PN) has been proposed. The optimized curing temperatures for intra- or intermolecular Diels-Alder reactions of alkynyl groups and polyaddition reaction of cyano groups resulted in a homogeneous and highly crosslinked N-enriched phthalonitrile system. After curing at 450 °C, the resin, namely P-ALK-PN-450 °C, demonstrated exceptional thermal stability ( T 5% = 644 °C), thermo-oxidative stability ( T 5% = 554 °C), and char yield at 800 °C (90.7 % in N 2 and 67.5 % in air). Their quartz fiber reinforced composites (P-ALK-PN/QFs) were subsequently fabricated by the hot-pressing process. Upon post-curing at 420 °C, P-ALK-PN-420 °C/QF displayed elevated glass transition temperature (550 °C), flexural strength (319 MPa), and relatively low dielectric properties with a dielectric constant (D k ) of approximately 4.2 and a dissipation factor (D f ) less than 0.02 across a wide temperature ranging from 25 °C to 600 °C. Especially, it exhibited excellent flame retardancy (only a 6.7 % weight loss at ambient temperatures exceeding 1300 °C for 200 s) as well, stemming from release of eco-friendly inert gases (NH 3 ) and formation of a graphitized protective layer during pyrolysis. These promising results highlight the potential applications of P-ALK-PN resins in aerospace and high-performance engineering fields.
研究领域:
材料科学
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航空航天工程
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）