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Enhanced high-temperature bonding performance of C/C composites joined by ZrW2O8 modified silicone resin adhesive with reduced thermal expansion coefficient

Yu Wang , Zhanming Hu , Maowei Su , Jingjing Li , Xiaoxia Hu , Tao Xu , Mingchao Wang , Wei Jing

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Extreme Materials ›› DOI: 10.1016/j.exm.2026.100058
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Enhanced high-temperature bonding performance of C/C composites joined by ZrW2O8 modified silicone resin adhesive with reduced thermal expansion coefficient
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Abstract

Silicone resin-based adhesive is a promising candidate for joining C/C composites. However, severe thermal-expansion mismatch with C/C substrates induces thermal-stress accumulation, interfacial crack growth and joint debonding under cyclic high-temperature conditions. To address this problem, negative-thermal-expansion ZrW2O8 filler was incorporated into MSABs adhesive. Three synergistic mechanisms are involved: volume compensation from ZrW2O8 decomposition products, NTE-driven CTE modulation, and boron-diffusion-enabled interfacial chemical anchoring. The effects of ZrW2O8 content (40-60 wt.%) and heat treatment temperature (500-900℃) on bonding performance were systematically investigated. At 700℃, the 50 wt.% ZrW2O8-modified MSABs exhibited optimal performance, achieving a room-temperature bonding strength (RTBS, shear strength measured at 25℃) of 12.48 MPa, a CTE of 3.13 × 10-6 K-1 well-matched to C/C substrate (0.94 × 10-6 K-1), and a strength retention rate of 70.51% after 50 thermal cycles from RT to 700℃. This work provides a feasible strategy for reliable C/C joining for hypersonic-vehicle thermal-protection systems.

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Keywords

ZrW2O8 / Silicone resin-based adhesive / C/C composites / Bonding performance / Low thermal expansion / Thermal cycling resistance

Highlight

· An interface-oriented thermal expansion regulation strategy is proposed to alleviate thermal mismatch stress in C/C joints.

· The adhesive achieves a low CTE of 3.13 × 10-6 K-1, approaching that of C/C composites after ZrW2O8 modification.

· ZrW2O8 decomposition products and softened SSP glass compensate pyrolysis shrinkage and heal interfacial defects.

· Oxide/glass phase evolution promotes adhesive-layer densification and enhances interfacial structural integrity.

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Yu Wang, Zhanming Hu, Maowei Su, Jingjing Li, Xiaoxia Hu, Tao Xu, Mingchao Wang, Wei Jing. Enhanced high-temperature bonding performance of C/C composites joined by ZrW2O8 modified silicone resin adhesive with reduced thermal expansion coefficient. Extreme Materials DOI:10.1016/j.exm.2026.100058

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1. Introduction

With the rapid advancement of hypersonic vehicles and reusable launch technologies, thermal structural materials are facing increasingly demanding service environments [1], [2]. C/C composites have become indispensable key materials in aerospace thermal structures due to their low density, excellent high-temperature mechanical properties, and good thermal shock resistance [3], [4]. However, the fabrication process of C/C composites is complex and time-consuming, making the direct fabrication of large and complex components difficult and expensive. To meet the processing requirements for components with special sizes and shapes, it is often necessary to assemble small and simple C/C composite components into integral structures through joining technologies [5]. Nevertheless, in practical applications, C/C composites, as high-temperature structural-functional integrated materials, are often subjected to repeated thermal shocks caused by severe temperature fluctuations [6], [7], [8], [9]. Typical applications include non-direct ablation areas of aircraft thermal protection structures such as noses and wings [10], as well as transition structures in engine hot-end components [11], [12]. Consequently, more stringent requirements are imposed on the thermal shock resistance of matching connecting components.
Current joining methods for C/C composites primarily include brazing, diffusion bonding, and in-situ reaction joining. For instance, Xiao et al. [13] designed a rare earth Ce-modified reduced graphene oxide-reinforced AgCuTi composite brazing filler, achieving high-strength joining of C/C composites and effectively alleviating the thermal expansion mismatch between the brazing seam and the C/C composites, with an average shear strength reaching up to 31.82 MPa. Wang et al. [14] employed spark plasma sintering (SPS) technology and used TiZrHfTa/Ni and ZrHfNbTa/Ni as composite interlayers for brazing C/C composites. By applying laser texture treatment to the C/C composite surface and holding at 1800 ℃ for 30 min, they in situ synthesized a high-entropy cermet joint structure, successfully achieving high-strength joining of C/C composites. The room-temperature bonding strength (RTBS) of the two types of joints reached 37.49 ± 1.44 MPa and 38.95 ± 1.26 MPa, respectively. However, methods such as brazing, diffusion bonding, and in-situ reaction joining are prone to causing fiber damage (high operating temperature) and stress concentration (thermal expansion mismatch). These methods are also struggling to meet the requirements for light weighting and high reliability [15]. In contrast, adhesive bonding, with its advantages such as non-destructive nature and uniform stress distribution, has emerged as the most promising alternative solution [16], [17].
Adhesives for high-temperature applications can be mainly categorized into organic resin-based and inorganic geopolymer-based types. Organic resin-based adhesives (such as epoxy resins, phenolic resins, and polyimides) [18], [19] offer the advantages of convenient room-temperature curing and high initial bonding strength. However, their carbon chain backbones are prone to thermal decomposition at elevated temperatures, leading to failure. Consequently, their heat resistance is generally limited, making it difficult to meet the requirements of extreme service conditions. Inorganic geopolymer-based adhesives (e.g., phosphates and silicates) [20], [21], [22] can withstand higher temperatures, but they suffer from issues such as high brittleness and poor wettability on adherends, which can easily result in interfacial debonding during thermal cycling. In recent years, researchers have attempted to adopt an organic-inorganic composite strategy by introducing heat-resistant fillers into polymer matrices to prepare high-temperature resistant composite adhesives, aiming to achieve high-strength bonding over a wide temperature range. Among these, systems based on silicone resins have attracted considerable attention [23], [24], [25]. The main chain of silicone resin is an inorganic Si-O-Si skeleton, with a bond energy as high as 443.7 kJ/mol [26]. Its organic side chains can pyrolyze and transform into a ceramic phase at high temperatures, endowing it with thermal stability far superior to that of traditional carbon-chain polymers [27], [28]. However, pristine silicone resin exhibits a large volume shrinkage during pyrolysis, which tends to introduce internal stress within the adhesive layer, thereby affecting the bonding strength and reliability of the joint [29], [30]. To address this issue, Wang et al. [31] introduced silicon powder, aluminum powder, boron carbide, and low-melting-point glass powder (SSP) as active heat-resistant fillers and volume compensators into a silicone resin matrix. By filling cracks and pores generated during matrix pyrolysis, effective volume compensation have been achieved, which significantly enhanced the densification and high-temperature resistance of the adhesive.
Although the introduction of active fillers can effectively compensate for the volume shrinkage of silicone resin during high-temperature pyrolysis and enhance the densification and high-temperature resistance of the adhesive, this strategy has not completely solved the reliability issues of the joint under service conditions [29]. The active fillers and the new ceramic phases generated by their in-situ reactions possess relatively high coefficients of thermal expansion (CTE), resulting in the overall CTE of the composite adhesive remaining significantly higher than that of the C/C composites [32]. During repeated thermal cycling, the CTE mismatch between the adhesive layer and the substrate (C/C composites) generates thermal stress at the interface, which gradually accumulates with an increasing number of cycles [33], [34], which can ultimately lead to the propagation of interfacial microcracks and even debonding failure. To tackle this problem, introducing a CTE-modulating phase into a composite adhesive system that already possesses volume compensation capability has emerged as a key strategy for enhancing its overall performance.
In recent years, the discovery of negative thermal expansion (NTE) materials has provided a novel approach for precisely tailoring the CTE of composites. These materials exhibit anomalous volume contraction upon heating, which enables an effective reduction of the matrix CTE over a wide temperature range through a positive-negative compensation mechanism [35], [36], [37], [38]. Among them, ZrW2O8 has attracted considerable attention as a functional NTE filler due to its unique crystal structure, which maintains isotropic NTE (CTE ≈ -9.1×10-6 K-1) over an exceptionally broad temperature range from 0.3 K to 1050 K [38], [39], [40]. Early studies have demonstrated that ZrW2O8 can be blended with glass braze components to effectively tailor the CTE of the resulting composites. Previously, Powancum et al. [41] fabricated near-zero thermal expansion porous ceramics via spark plasma sintering using soda lime glass as the bonding agent, and confirmed the feasibility of CTE regulation via ZrW2O8 in porous ceramics, providing an important reference for the present study. It should be noted, however, that most existing investigations on ZrW2O8-modified polymer-based adhesives mainly focus on low filler content (≤30 wt.%) for glass-related substrates, where the polymer matrix undergoes relatively mild thermal degradation [52]. For silicone-resin adhesives targeting C/C composite joining by contrast, the matrix suffers severe pyrolysis-induced volume shrinkage at high temperatures. Meanwhile, ZrW2O8 gradually decomposes within the 700-900℃ window, creating complex coupling between its retained negative-thermal-expansion function and volume-compensation originating from decomposition products. Furthermore, beyond simple CTE matching, the interfacial chemical interaction between the adhesive and chemically inert C/C substrates, as well as joint reliability under repeated thermal cycling have rarely been systematically evaluated in prior ZrW2O8-modified adhesive studies. Accordingly, these distinct challenges mean that the behavior of the C/C composite system cannot be directly extrapolated from glass-based or porous-ceramic systems. In particular, C/C composites differ fundamentally from glasses or ceramics in surface chemistry, interfacial reactivity, and thermal-matching requirements. The CTE-regulation behavior of ZrW2O8 in silicone-resin-based adhesives for C/C composites remains unexplored, necessitating systematic investigation.
To address these issues, this study introduced the NTE material ZrW2O8 into a modified silicone resin adhesive for C/C composites joining. The effect of ZrW2O8 content on the thermal expansion behavior, microstructural evolution, and bonding performance of the composite adhesive was systematically investigated, with an aim to uncover the coupled competing mechanism between ZrW2O8 decomposition, matrix pyrolysis shrinkage and interfacial bonding, and its thermal stress regulation mechanism was elucidated. This work aims to provide a novel design strategy and theoretical basis for achieving highly reliable joining of C/C composites by simultaneously addressing both pyrolysis shrinkage compensation and CTE matching. All thermal-cycling assessments in this work were performed under argon atmosphere to construct a simplified experimental model and focus on cyclic damage driven by thermal-expansion mismatch. Practical oxygen-rich service scenarios that require anti-oxidation protection will be explored in future studies.
From the perspective of filler design for C/C-based high-temperature composites, two representative modification strategies have been reported. Low-melting-point metallic fillers enable active thermal management via continuous conductive networks, yet suffer from melting- and-evaporation-induced limitations under long-term high-temperature exposure [42]. By comparison, refractory in-situ-grown ceramic nanowires can build three-dimensional conductive networks in C/C substrates to enhance electromagnetic-shielding and high-temperature oxidation resistance, avoiding thermal-stability risks from low-melting-phase constituents [43]. Inspired by these studies and considering filler thermal-stability limits in our adhesive system, we clarify the practical service-temperature range of the fabricated joints. This work targets adhesive joints for intermediate-to-high-temperature cyclic thermal environments, instead of sustained ultra-high-temperature operation, and focuses on cyclic damage driven by thermal-expansion mismatch rather than long-term degradation caused by filler melting.

2. Experimental

2.1. Materials

The silicone resin-based adhesive was composed of a silicone resin matrix and inorganic fillers. The silicone resin matrix was prepared by mixing commercially available polymethylsilsesquioxane (MK; Wacker-BelsilTM PMS, Wacker Chemie AG, Munich, Germany) with isopropanol (purity ≥ 99.7%; Tianjin Concord Technology Co., Ltd., China). The inorganic fillers consisted of silicon powder (Si; average diameter = 0.5 μm; Guangzhou Tuoyi Trading Co., Ltd., China), aluminum powder (Al; average diameter = 2-3 μm; Beijing Yijin New Material Technology Co., Ltd., China), boron carbide (B4C; average diameter = 2.5 μm; Jilin Zhenxing Abrasive Material Co., Ltd., China), low-melting-point glass powder (denoted as SSP, SnO·SiO2·P2O5 glass powder; average diameter = 3-4 μm; Guizhou Baibo New Material Technology Co., Ltd., China), and zirconium tungstate (ZrW2O8; purity 99.5%; Beijing Huawei Ruike Chemical Technology Co., Ltd., China). The bonded substrates, 0°/90° cross-ply laminated C/C composites reinforced by PAN-based carbon fibers and densified via chemical vapor deposition (CVD), with a bulk density of 1.72-1.78 g/cm3 and an in-plane CTE of 0.94 × 10-6 K-1, were purchased from Chengdu Fangda Carbon Composite Material Co., Ltd., China. The dimensions of C/C composite specimens were 10 mm × 10 mm × 20 mm.

2.2. Preparation of adhesive

Following the preparation procedure reported by Wang et al.[31], silicone resin (MK) powder was slowly added to a three-necked flask containing isopropanol under nitrogen protection. The mixture was then placed on a magnetic stirrer and stirred for 1 h until a uniform and transparent silicone resin matrix was formed. Subsequently, the functional fillers Al, Si, B4C, and SSP were added in sequence, and stirring was continued for 2 h under nitrogen protection to ensure homogeneous mixing, thereby obtaining a silicone resin-based adhesive, designated as MSABs. Finally, ZrW2O8 was incorporated into the MSABs adhesive at different mass ratios, and the mixture was ground for 1 h until uniform. Thus, silicone resin-based adhesives modified with varying concentrations of ZrW2O8 were successfully prepared.

2.3. Bonding joints and mechanical testing

To secure an excellent interfacial bonding state, the bonding surfaces of the C/C composites were first ground using a diamond grinding wheel, followed by sequential ultrasonic cleaning in anhydrous ethanol and drying at a constant temperature of 80℃ to remove surface contaminants, thereby obtaining clean and dry surfaces for bonding. Subsequently, the prepared adhesive was applied onto the bonding surfaces over an area of 10 mm × 20 mm, and the substrates were pressed together to form C/C joints. The thickness of the adhesive bonding layer was controlled at approximately 100 μm according to the optimized processing condition reported previously [31]. Finally, the C/C joints were placed in a forced convection drying oven at 200℃ and cured for 1 h. After curing, the C/C joints were transferred to a tube furnace under an argon atmosphere, heated to temperatures ranging from 500℃ to 900℃ at a heating rate of 5 ℃/min, and held at each target temperature for 1 h.
The RTBS of the MSABs adhesive for C/C composites after different heat treatment temperatures was characterized using a CSS-44001 electronic universal testing machine (Changchun Research Institute for Mechanical Science Co., Ltd., China). The cross-head loading speed was set to 0.2 mm/min [31]. Five valid parallel specimens were tested for each condition. Average values are adopted and data scatter is reflected by error bars in the figures. Additionally, thermal cycling tests were conducted in a tube furnace under an argon atmosphere. Three separate thermal-cycling tests were carried out for joints pre-calcined at 500℃, 700℃, and 900℃, respectively. Each complete thermal cycle included heating the C/C joints in a tube furnace under an argon atmosphere to the target peak temperature at a rate of 5 ℃/min, held for 1 h, followed by natural cooling down to room temperature under argon protection. The selected peak temperatures of 500℃, 700℃ and 900℃ represent typical service conditions of C/C joints for hypersonic-vehicle thermal-protection structures and aero-engine hot-end components. 500℃ simulates steady cruising environments [8], 700℃ corresponds to the steady-state temperature of non-ablation regions [2], [10], and 900℃ mimics extreme transient thermal loads during ascent, re-entry or aggressive maneuvering [10], [12]. A 1 h dwell at the peak temperature ensures through-thickness temperature homogeneity within the adhesive layer, allowing sufficient progression of phase evolution, interfacial reactions, and thermal-stress redistribution. This test targets cyclic damage induced by CTE mismatch rather than long-term creep or prolonged oxidation; long-duration static thermal exposure under oxidative environments will be explored in future work.
After completing multiple thermal cycles, the residual strength of the joints was measured and analyzed under the same conditions using the CSS-44001 electronic universal testing machine. Meanwhile, the heat-treated adhesive samples were ground into powder in an agate mortar, loaded into a mold with dimensions of 20 mm × 4 mm × 3 mm, and pressed into bulk specimens under a pressure of 10 MPa. These bulk specimens were then heat-treated again for 1 h at the same temperatures. Subsequently, the hardness and fracture toughness of the adhesive were determined using these bulk specimens. For hardness measurements, the bulk specimens were first polished to achieve a surface roughness of no more than 0.4 μm, and then hardness tests were performed using a Cratos W50 Vickers hardness tester (Opton, China) under a load of 0.3 kg (HV0.3). Fracture toughness tests were conducted on the bulk specimens using a CSS-44001 electronic universal testing machine in accordance with the national standard GB/T 23806-2009 [44]. Note that these repressed and reheated bulk specimens cannot fully reproduce the constrained microstructure of thin adhesive layers confined between rigid C/C substrates. Nevertheless, they adopt the same composition and argon-atmosphere heat-treatment schedule as joint adhesive layers and can represent the intrinsic CTE, hardness and fracture-toughness of the adhesive. Joint-level performances such as shear strength and thermal-cycling durability were characterized using real C/C bonded-joint samples to account for interfacial-constraint effects.

2.4. Characterizations

The CTE of the adhesive was measured using the prepared bulk specimens with a STA-449 C thermo-mechanical analyzer (NETZSCH-Gerätebau GmbH, Berkenbusch 3, 95100 Selb, Germany). Subsequently, the composition evolution of the adhesive samples calcined at different temperatures was investigated by X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectroscopy. XRD analysis was performed using a Rigaku MiniFlex 600 X-ray diffractometer (Rigaku Corporation, Tokyo, Japan), with a scanning range of 15-65° and a scanning speed of 5 °/min, for calcined-adhesive powder specimens. FT-IR analysis was conducted using a Nicolet iS10 FT-IR spectrometer (Thermo Fisher Scientific, Madison, WI, USA), for both calcined-adhesive powder specimens and scraped interface mixed-phase powders. Thereafter, to determine the decomposition behavior and the endothermic/exothermic events associated with phase changes of the various components in the adhesive, thermogravimetric and differential scanning calorimetry (TG/DSC) analyses were carried out on different adhesive samples using a TA Instruments TGA-Q600SDT thermal analyzer (TA Instruments, New Castle, DE, USA). The bonding interfaces and fracture surfaces were imaged and analyzed for composition using field-emission scanning electron microscopy (FESEM, Hitachi S-4800, Japan) equipped with an energy-dispersive X-ray spectroscopy (EDS) detector. Raman spectroscopic measurements were performed on the scraped interface mixed-phase powders using a DXR Raman Microscope (Thermo Fisher Scientific, Madison, WI, USA).

3. Results and discussion

3.1. Effects of ZrW2O8 contents and heat treatment temperature on the bonding properties of adhesives

According to Fig. S1, ZrW2O8 decomposes above 700℃, and the degree of ceramization of the silicone resin matrix increases with rising heat treatment temperature [29], [45]. Therefore, 700℃ was selected as the priority factor for investigation. Fig. 1 (a) presents the RTBS of MSABs adhesives with different ZrW2O8 modification amounts after calcination at 700℃. Compared with the pristine MSABs adhesive, the introduction of ZrW2O8 significantly modulates the RTBS, which exhibits a non-linear variation, first increasing and then decreasing with increasing ZrW2O8 content. The maximum RTBS values achieved at ZrW2O8 modification levels of 40 wt.%, 50 wt.%, and 60 wt.% are 11.7 MPa, 12.48 MPa, and 11.4 MPa, respectively, which are significantly higher than the 7.54 MPa of the pristine MSABs adhesive.
To further clarify the synergistic effect of ZrW2O8 modification concentration and pretreatment temperature on the bonding performance of the adhesive, adhesives with three ZrW2O8 modification ratios (40 wt.%, 50 wt.%, and 60 wt.%) were selected to investigate the variation in their RTBS after calcination at different temperatures, as shown in Fig. 1 (b). When the calcination temperature is below 700℃ (e.g. at 600℃), the adhesive modified with 60 wt.% ZrW2O8 exhibits the best bonding performance, with the RTBS of 9.77 MPa. When the calcination temperature is 700℃ or higher (e.g. at 700℃), the adhesive modified with 50 wt.% ZrW2O8 demonstrates the best bonding performance, and the RTBS peaks at 12.48 MPa. Consequently, 50 wt.% is determined to be the optimal modification concentration.
To investigate the effect of heat treatment temperature on the bonding performance of the adhesive, The 50 wt.% ZrW2O8 modification concentration was chosen as the representative proportion of modified MSABs, and its RTBS after calcination at different temperatures was tested, and with results shown in Fig. 1 (c). The RTBS of this modified adhesive exhibits significant variations with calcination temperature. After calcination at 700 and 800℃, the RTBS is significantly higher than that at other temperatures, reaching a peak at 12.48 MPa at 700℃ and maintaining a high level of 11.49 MPa at 800℃. With further increasing the calcination temperature to 900℃ and 1000℃, the RTBS gradually decreases to 9.78 MPa and 9.1 MPa, respectively.
Fig. 1 (d)-(f) display the residual bonding strength of C/C joints bonded with MSABs adhesives modified with different ZrW2O8 contents after calcination at 500℃, 700℃, and 900℃, followed by thermal cycling from 25℃ to the corresponding calcination temperatures, respectively. Fig. 1 (d) shows that joints calcined at 500℃ possess low initial strength and undergo rapid degradation with cycling. After 50 cycles, the strength degradation rate for ZrW2O8-modified MSABs with modification contents of 40 wt.%, 50 wt.%, and 60 wt.% is 91.83%, 82.80%, and 86.86%, respectively, revealing overall poor thermal cycling stability under this condition. Fig. 1 (e) and (f) indicate that calcination at 700℃ and 900℃ significantly improves initial strength and cycling stability. After 50 cycles, the strength degradation rate for ZrW2O8-modified MSABs with contents of 40 wt.%, 50 wt.%, and 60 wt.% is 63.48%, 29.49%, and 53.82% at 700 ℃, and 86.7%, 68.45%, and 89.76% at 900 ℃, respectively. The 50 wt.% ZrW2O8 joint calcined at 700℃ exhibits the optimal performance, as its strength degradation rate is merely 29.49%.
In summary, the bonding performance of ZrW2O8-modified MSABs adhesives is governed by the synergistic effect of ZrW2O8 modification concentration and calcination temperature. The optimal formulation and processing conditions are determined to be 50 wt.% ZrW2O8 for the modification content and 700℃ for the calcination temperature, which deliver the highest peak RTBS of 12.48 MPa, as well as the most superior long-term thermal cycling stability. Under this optimal condition, the adhesive exhibits the lowest strength degradation rate of only 29.49% after 50 thermal cycles between 25℃ and 700℃, far outperforming the other tested formulations and processing temperatures.

3.2. Effects of heat treatment temperature on the composition and thermal behavior of 50 wt.% ZrW2O8-modified adhesive

Fig. 2 shows the phase composition of the optimal 50 wt.% ZrW2O8-modified MSABs adhesive at different heat treatment temperatures, as characterized by XRD. As shown in the pattern, after calcination at 500℃ and 600℃, the adhesive is mainly composed of unreacted Si, Al, B4C and undecomposed ZrW2O8, along with minor WO3 and ZrO2 phases. During this period, the amorphous silicon resin decomposes gradually, as reported by Wang et al.[31]. When the temperature increases to 700℃, the diffraction peak of B4C at 2θ = 37.22° disappears, indicating the oxidation of B4C at this temperature. Simultaneously, ZrW2O8 begins to decompose, with the formation of WO2 at 2θ = 25.82°, 36.66°, 53.06°, and 59.92°, although a substantial amount of undecomposed ZrW2O8 still remains. At 800℃, ZrW2O8 is almost fully decomposed into ZrO2, WO2 and WO3; meanwhile, SSP glass reacts with Al to form Al(PO3)3, SnO and Sn, leading to a sharp rise in CTE. At 900 ℃, Al(PO3)3 at 2θ equal to 20.32° transforms into hexagonal AlPO4, and SnO is oxidized to SnO2. The WO2 diffraction peaks at 2θ values of 25.76°, 36.98°, 53.14° and 60.08° weaken, as WO2 reacts with Sn to form SnxWO3 and Al2(WO4)3. As an NTE material [46], [47], Al2(WO4)3 helps reduce the CTE at 900 ℃. Fig. S2(a) and (b) indicate that ZrW2O8 content does not alter the phase evolution route but affects product content: diffraction peaks of ZrO2, WO3 and WO2 strengthen with increasing ZrW2O8 from 40 to 60 wt.%, and 50 wt.% ZrW2O8 achieves the optimal modification effect.
Fig. 3 (a) presents the FT-IR spectra of the 50 wt.% ZrW2O8-modified MSABs adhesive at different calcination temperatures. The W-O-Zr characteristic peak at 885 cm−1 remains from 500℃ to 700℃, verifying the incomplete decomposition of ZrW2O8, which is in good agreement with the XRD results in Fig. 2.
At 800℃, the W-O-Zr peak disappears, accompanied by the appearance of the W=O peak corresponding to the formation of WO2 and WO3 derived from the decomposition of ZrW2O8. The gradually weakened Si-O-Si peak indicates the disintegration of the silicone resin structure. The B-O peak at 1367 cm−1 is insignificant at 500℃ and 600℃, becomes prominent at 700℃, and remains clearly observable up to 900℃, reflecting the oxidation of B4C to boron oxides. The Si-O peak at 448 cm−1 shows low intensity at 500℃, increases obviously from 600℃ and keeps stable until 800℃, then fades remarkably at 900℃, verifying the densification of silica-based ceramic network. As shown in Fig. S3 (a)-(b) and 2 (b), the chemical bond evolution of the three adhesives is basically consistent. At 900℃, only the 50 wt.% ZrW2O8-modified MSABs shows a characteristic Sn-O-W peak at 610 cm−1 corresponding to SnxWO3 formation, while this peak is absent in the 40 wt.% and 60 wt.% ZrW2O8-modified MSABs. The low filler content of the 40 wt.% ZrW2O8-modified MSABs generates insufficient SnxWO3 for FTIR detection, whereas excessive ZrW2O8 in the 60 wt.% ZrW2O8-modified MSABs produces abundant WO2 and WO3. These excess tungsten oxides form massive internal W-O-W bridging bonds with strong characteristic absorption, which in turn overwhelms the weak Sn-O-W peak.
As shown in the TG curves in Fig. 3 (b), for the 50 wt.% ZrW2O8-modified MSABs adhesive, an initial mass loss of 2.39% appears from room temperature to 150℃, which is mainly attributed to the volatilization of free water. The main pyrolysis stage occurs between 150℃ and 400℃, with a cumulative mass loss of 5.60%, corresponding to the thermal decomposition of organic side chains in the silicone resin and the disintegration of its amorphous network structure. From 400℃ to 700℃, the mass decreases slowly, and the total mass loss reaches 7.61% at 700℃, which is ascribed to the deep ceramization of silicone resin and the release of residual small-molecule gases. After 700℃, the mass remains nearly stable, indicating basically complete ceramization and effectively suppressed volume shrinkage. The DSC curve in Fig. 3 (b) further indicates that the 50 wt.% ZrW2O8-modified MSABs adhesive exhibits a single exothermic peak at 666℃.
For the 50 wt.% ZrW2O8-modified MSABs adhesive pre-calcined at 700℃, the TG curve in Fig. 3 (b) shows an initial mass loss of 0.59% from room temperature to 150℃, which is ascribed to the removal of residual moisture. From 150℃ to 500℃, the adhesive exhibits a cumulative mass loss of 4.25%, which is mainly attributed to the further release of trace adsorbed species and small-molecule gases trapped in the ceramic network during pre-calcination. Above 500℃, the TG curve displays a slight mass increase, owing to the mild oxidation of residual Si particles within the adhesive to form SiO2, thereby compensating for the minor mass loss. The DSC curve of this adhesive in Fig. 3 (b) only presents a weak endothermic peak at around 130℃ corresponding to moisture evaporation, and no obvious high-temperature exothermic peak can be observed, indicating that the adhesive has completed ceramization during the pre-calcination process.
As shown in Fig. S4 and 3 (b), within 400-800℃, the mass loss of the 40 wt.% ZrW2O8-modified MSABs adhesive continuously increases to 8.25%, while those of the 50 wt.% and 60 wt.% ZrW2O8-modified MSABs remain stable from 700℃ up to 800℃, reaching 7.61% and 6.60%, respectively. Meanwhile, the 40 wt.% ZrW2O8-modified MSABs shows multiple exothermic peaks, whereas the 50 wt.% and 60 wt.% ZrW2O8-modified MSABs exhibit a single exothermic peak. Higher ZrW2O8 content effectively compensates for mass loss and restrains the exothermic oxidation of the resin, which is unavailable in the 40 wt.% ZrW2O8-modified MSABs due to insufficient doping. Notably, the 50 wt.% ZrW2O8-modified MSABs achieves the best balance between mass loss control and thermal stability, enabling sufficient volume compensation and a dense interfacial structure, further confirming it as the optimal doping ratio.
Overall, combined XRD, FT-IR and TG-DSC results suggest the temperature-dependent phase transformation, chemical bond evolution and thermal degradation behavior of ZrW2O8-modified MSABs adhesives. The ZrW2O8 modification dosage hardly alters the thermal evolution pathway but regulates the composition of reaction products and thermal stability. The 50 wt.% ZrW2O8-modified MSABs achieves the optimal comprehensive performance in phase composition, structural evolution and thermal stability.

3.3. Effects of ZrW2O8 contents f and heat treatment temperature on the physical properties of adhesives

Fig. 4 (a) presents the CTE of MSABs adhesives with different ZrW2O8 contents calcined at 700℃. The CTE first decreases and then increases as the ZrW2O8 content rises. The 50 wt.% ZrW2O8-modified MSABs adhesive exhibits the lowest CTE value of 3.13×10-6 K-1, which achieves the best matching with the C/C substrate (0.94 × 10-6 K-1). The 60 wt.% ZrW2O8-modified MSABs has the highest CTE, as excessive ZrW2O8 decomposition produces high-expansion WO3, WO2, and ZrO2 that offset the NTE effect.
Fig. 4 (b) depicts the CTE evolution of the 50 wt.% ZrW2O8-modified adhesive calcined at different temperatures. At 500℃ and 600℃, the adhesive shows a relatively high CTE because silicone resin ceramization is insufficient and dominates the thermal expansion behavior. The CTE reaches its minimum at 700℃, where the partial decomposition of ZrW2O8 brings its NTE effect into synergy with resin ceramization for optimal CTE regulation. At 800℃, the CTE rises sharply to a peak, as extensive ZrW2O8 decomposition eliminates the NTE effect and produces high-expansion phases including Sn and ZrO2. When heated to 900 ℃, the CTE decreases again due to the full ceramization of the resin matrix and the formation of NTE-type Al2(WO4)3 that provides secondary CTE modulation.
To more clearly demonstrate the performance advantages of the ZrW2O8-modified MSABs adhesive developed in this work, Table 1 compares its CTE and RTBS with those of other reported typical joining materials for C/C composites, such as brazing and solid-state reaction diffusion.
As illustrated in Fig. 5 (a), the hardness of all ZrW2O8-modified MSABs adhesives rises continuously with increasing calcination temperature from 500℃ to 900℃. At identical temperatures, the 50 wt.% ZrW2O8-modified MSABs possesses the highest hardness, followed by the 40 wt.% ZrW2O8-modified MSABs, while the 60 wt.% ZrW2O8-modified MSABs shows the lowest value due to particle agglomeration and reduced densification. For the 40 wt.%, 50 wt.% and 60 wt.% ZrW2O8-modified MSABs, the hardness values of specimens calcined at 900℃ reach 5.11 GPa, 5.25 GPa and 4.00 GPa, respectively.
As shown in Fig. 5 (b), the fracture toughness of all adhesives increases with temperature from 500 to 900℃, consistent with the hardness trend. The 50 wt.% ZrW2O8-modified MSABs exhibits the highest fracture toughness, indicating that ZrW2O8 acts as an effective toughening phase. The 40 wt.% ZrW2O8-modified MSABs shows limited toughening due to insufficient filler content, while the 60 wt.% ZrW2O8-modified MSABs presents the lowest value because of particle agglomeration and stress concentration. The corresponding values at 900℃ are 2.56, 3.65, and 1.51 MPa·m1/2, respectively.

3.4. Effects of ZrW2O8 contents and heat treatment temperature on the structural evolution and interface reaction of adhesives

Fig. 6 displays the SEM morphologies of MSABs joints with various ZrW2O8 contents after heat treatment at 700℃. All samples show continuous, uniform adhesive layers with tight interfaces and no macroscopic cracks or delamination. The 40 wt.% and 50 wt.% ZrW2O8-modified MSABs exhibit relatively dense microstructures, while the 60 wt.% ZrW2O8-modified MSABs shows severe agglomeration and the loosest structure. The 50 wt.% ZrW2O8-modified MSABs presents the optimal microstructure with a dense, pore-free adhesive layer.
Fig. 7 shows the SEM morphologies of 50 wt.% ZrW2O8-modified MSABs joints treated at various temperatures. Fig. 7 (a1)-(a3) reveal a loose and porous adhesive layer at 500℃, while Fig. 7 (b1)-(b3) illustrate that the layer remains loose at 600℃ owing to resin decomposition. Fig. 7 (c1)-(c3) indicate that complete resin pyrolysis and partial ZrW2O8 decomposition at 700℃ fill pores and construct a compact interface. At 800℃, corresponding to Fig. 7 (d1)-(d3), excessive ZrW2O8 decomposition lowers densification and reintroduces micropores. At 900℃, as shown in Fig. 7 (e1)-(e3), the adhesive is fully ceramized, forming a brittle ceramic matrix that develops obvious microcracks due to thermal stress and volume shrinkage.
Fig. 8 shows the fracture morphologies of MSABs joints with different ZrW2O8 contents after heat treatment at 700℃. As observed in Fig. 8 (a)-(c), the 40 wt.% ZrW2O8-modified MSABs displays mixed failure with little adhesive residue, numerous pores and cracks, which is attributed to the large CTE mismatch confirmed in Fig. 4 (a) and insufficient NTE effect. As presented in Fig. 8 (d)-(f), the 50 wt.% ZrW2O8-modified MSABs exhibits typical cohesive failure with sufficient adhesive retention and few defects. This favorable performance stems from the optimal CTE matching shown in Fig. 4 (a), as well as the effective volume compensation offered by ZrW2O8 decomposition products displayed in Fig. 2. As shown in Fig. 8 (g)-(i), the 60 wt.% ZrW2O8-modified MSABs suffers severe structural damage with interfacial peeling and dense microcracks, caused by excessive high-expansion decomposition products that increase the CTE and aggravate thermal stress.
Fig. 9 shows the fracture morphologies of 50 wt.% ZrW2O8-modified MSABs joints at different temperatures. Fig. 9 (a1)-(b3) indicate that joints heated at 500-600℃ present typical mixed failure, with loose structure, severe fiber exposure, interfacial debonding, and abundant internal microdefects resulting from continuous resin pyrolysis. As shown in Fig. 9 (c1)-(c3), the adhesive treated at 700℃ achieves typical cohesive failure, featuring a dense interface and optimal bonding due to the best CTE matching. Fig. 9 (d1)-(e3) demonstrate that joints heated at 800-900℃ return to mixed failure with larger cracks, reflecting aggravated thermal stress and deteriorated bonding performance.
Fig. 10 presents element mapping and line scan analyses of 50 wt.% ZrW2O8-modified MSABs adhesives at different temperatures. As shown in Fig. 10 (a), Al, Si, Sn, and W are uniformly distributed in the adhesive after calcination at 500℃, with a clear interface and no obvious elemental diffusion, indicating physical mixing without significant interfacial chemical reactions. Based on the line scan results in Fig. 10 (b) and (c), the distribution of Al, Sn, and P becomes more uniform at 700 and 900℃ owing to the in-situ reactions and component diffusion during ceramization; P remains in the adhesive layer for ceramic reactions without aggregation, while Si, W, and Zr show no obvious distribution changes. Meanwhile, element mapping reveals that B diffusion into the C/C substrate is enhanced with rising temperature. During heating, the boron oxides generated from B4C oxidation serve a dual role: on one hand, they decompose to release active boron atoms that are incorporated into the sp2 carbon network of the C/C substrate [50], forming stable C-O-B covalent bonds to establish strong chemical anchoring at the interface; on the other hand, the residual molten B2O3 glass phase exhibits favorable wettability on the carbon surface and penetrates microcracks, providing mechanical interlocking and self-healing effects that further improve the interfacial bonding strength [51].
Fig. 11 (a) shows the FT-IR spectra of interface powders scraped from the fracture surfaces of C/C composites after heat-treatment at different temperatures. The broad absorption band at 3660 cm-1 corresponds to O-H stretching vibrations originating from adsorbed water and surface hydroxyl groups, whose intensity gradually decreases with increasing temperature due to high-temperature dehydration and dehydroxylation of the samples [26]. Two weak absorption bands at 2977 cm-1 and 2902 cm-1 are assigned to combination bands of O-H stretching and B-O bending vibrations of hydrogen-bonded boric acid (H3BO3), which forms upon hydration of B2O3 generated by B4C oxidation. The progressive rise in peak intensity indicates an aggravated oxidation degree of B4C at elevated temperatures [51]. These -OH species are introduced as an artifact of secondary sample preparation: during the procedure of scraping and grinding the interfacial region into powder, the specimen readily reacts with atmospheric moisture to produce hydroxyl groups. The absorption peaks at 2097 cm-1 and 1988 cm-1 are attributed to overtones of asymmetric and symmetric Si-O-Si stretching vibrations, respectively. Their increasing intensity demonstrates advancing ceramization of silicone resin and the continuous densification of the Si-O-Si inorganic network [29].
As the heat-treatment temperature increases from 500℃ to 900℃, the prominent absorption band at 1396 cm-1, assigned to asymmetric B-O stretching vibrations of three-coordinated BO3 units in boron oxides, grows considerably, further confirming that high temperature accelerates B4C oxidation and the enrichment of boron-containing oxides at the interface [51]. Moreover, a shoulder peak at 1250 cm-1 gradually emerges with rising temperature, which is ascribed to the asymmetric stretching vibration of interfacial C-O-B bonds. This provides direct spectroscopic evidence that diffused active boron atoms react with oxygen-containing groups on the C/C surface to form stable borate-type bridging bonds for interfacial chemical anchoring. The strong absorption band centered at 1056 cm-1 mainly arises from asymmetric Si-O-Si stretching of the ceramized silicone-resin matrix, with overlapping contributions from symmetric C-O-B stretching vibrations, stretching modes of four-coordinated BO4 units, and residual B-C vibrations of unreacted B4C [29], [31]. The absorption band at 880 cm-1 is assigned to B-O stretching vibrations of four-coordinated BO4 structures, further verifying the formation of continuous boron-oxide glassy phases at high temperatures [51].
Table 2 summarizes the characteristic FT-IR absorption bands and vibrational assignments of the interface powders. It should be noted that the strong band at 1056 cm-1 consists of overlapping contributions from Si-O-Si, C-O-B, B-O and residual B-C vibrations.
Fig. 11 (b) shows the Raman spectra of mixed powders scraped from the interface between 50 wt.% ZrW2O8-modified MSABs and C/C composites after heat treatment at different temperatures. The G band at 1580 cm-1 and D band at 1350 cm-1 are intrinsic characteristic bands of sp2 carbon in the C/C substrate, corresponding to the in-plane stretching vibration of graphitic carbon and structural vibration of defective carbon, respectively. The theoretical vibration range of C-O-B bridging bonds is 1300-1380 cm-1; however, the region above 1350 cm-1 is fully covered by the intense main D band. Therefore, the shoulder region of 1300-1350 cm-1 on the low-wavenumber side of the D band was selected to evaluate the characteristic signal of potential C-O-B bonding in this work. With increasing heat-treatment temperature, the signal intensity of this shoulder region gradually rises and the spectral profile broadens, exhibiting obvious temperature-dependent evolution. This trend is consistent with the enhanced diffusion of B toward the C/C substrate revealed by EDS line scanning, as shown in Fig. 10, demonstrating the gradually strengthened interaction between boron oxides and the carbon matrix surface at the interface. This observation supports the formation of interfacial C-O-B bonding and provides complementary verification together with the FT-IR results.

3.5. Bonding mechanism

Based on the analyses of XRD, FTIR, TG-DSC, CTE, SEM, and EDS results, the bonding mechanisms of the ZrW2O8-modified MSABs adhesive can be summarized into the following three aspects, with the corresponding schematic diagram shown in Fig. 12.
1. Volume compensation and interfacial densification.
As shown in Fig. 7 (a1)-(a3), from room temperature to 500℃, the cleavage of organic side chains and preliminary ceramization of the silicone resin give rise to abundant microvoids within the adhesive layer, rendering the interfacial structure loose and porous. With increasing temperature from 500 to 700℃, as shown in Fig. 7 (a)-(c), the resin undergoes thorough ceramization accompanied by pronounced microstructural densification. Within this temperature range, the system achieves efficient volume compensation through three complementary effects: in-situ oxidation of Si and B4C produces oxide phases that fill the microdefects derived from matrix pyrolysis; partial decomposition of ZrW2O8 generates WO2, WO3 and ZrO2 to further occupy the shrinkage voids; melting of the low-melting-point SSP glass forms a liquid phase that wets, infiltrates and heals microcracks and pores. These synergistic effects are proposed to collectively counteract the volume shrinkage caused by pyrolysis of the silicone resin, and significantly improve the densification and structural stability of the adhesive layer.
2. Thermal expansion matching.
As shown in Fig. 4 (b), at 700℃, ZrW2O8 remains partially decomposed and continuously exerts its negative thermal expansion (NTE) effect. This synergizes with the volume shrinkage during silicone resin ceramization, which could enable precise regulation of the overall CTE of the adhesive via positive-negative thermal expansion compensation. As a result, the CTE of the 50 wt.% ZrW2O8-modified MSABs decreases to 3.13 × 10-6 K-1 at 700 ℃, achieving optimal matching with the C/C substrate (0.94 × 10-6 K-1).
3. Interfacial element diffusion and strengthening.
As shown in Fig. 10, with increasing heat treatment temperature, the diffusion of B element into the C/C substrate is significantly enhanced. The boron oxides derived from B4C oxidation play a dual role: on one hand, they decompose to release active B atoms that insert into the sp2 carbon network of the C/C substrate and form stable C-O-B covalent bonds (Fig. 11), realizing strong interfacial chemical anchoring; on the other hand, the residual molten B2O3 glass phase shows excellent wettability on the carbon surface and penetrates into microcracks to provide mechanical interlocking and self-healing effects, which synergistically improve the interfacial bonding strength.

4. Conclusions

This study aimed to address the critical issues of thermal expansion mismatch and thermal stress accumulation in C/C composite joints by introducing the NTE material ZrW2O8 into a silicone resin-based adhesive (MSABs) modified with Al, Si, B4C, and SSP glass powder. Beyond empirical formulation screening, this work seeks to clarify the coupled competing mechanism between filler decomposition and matrix pyrolysis, as well as its influence on joint reliability. The effects of ZrW2O8 content (40-60 wt.%) and heat treatment temperature (500-900℃) on bonding performance, thermal expansion behavior, microstructure evolution, and failure mechanism were systematically investigated. The results demonstrated that the 50 wt.% ZrW2O8-modified MSABs heat-treated at 700℃ exhibited the optimal overall performance, achieving a RTBS of 12.48 MPa, a CTE of 3.13 × 10-6 K-1 well-matched to C/C substrate (0.94 × 10-6 K-1), and a strength retention rate of 70.51% after 50 thermal cycles from room temperature to 700℃. Several important findings emerged from this study. First, the introduction of ZrW2O8 exerted a dual modulation effect on the thermal behavior of the adhesive: its partial decomposition products (WO2, WO3, ZrO2) together with the molten SSP glass provided effective volume compensation, filling the pores generated by resin pyrolysis and achieving interfacial densification; meanwhile, the retained NTE effect of ZrW2O8 synergized with the ceramization shrinkage of the silicone resin to realize optimal CTE matching, and its endothermic decomposition counteracted the exothermic oxidation of the resin, reducing thermal stress accumulation. Second, the failure mechanism evolved from mixed failure of joints after calcination at 500-600℃ to cohesive failure of joints after calcination at 700℃, and then reverted to mixed failure of joints after calcination at 800-900℃, correlating closely with the CTE matching state. Third, the 50 wt.% ZrW2O8-modified MSABs exhibited the highest hardness and fracture toughness among the three doping levels, indicating that ZrW2O8 also served as a toughening phase at moderate concentrations.
Compared with the work of Zhang et al.[52], who investigated ZrW2O8-modified silicone resin adhesives for joining microcrystalline glass with ZrW2O8 contents of 0-30 wt.%, the present study extended the concentration range to 40-60 wt.% and focused on C/C composites as the bonding substrate. Both studies confirmed the effectiveness of ZrW2O8 in reducing the CTE of silicone resin-based adhesives. However, significant differences were observed. Zhang et al. reported that ZrW2O8 decomposed at 700℃ and reacted with the matrix to form Al2(WO3)4, with optimal bonding performance achieved at 900℃. In contrast, the present study found that at 700℃, partial decomposition of ZrW2O8 was beneficial for retaining its NTE effect, whereas complete decomposition at 800℃ led to an increase in CTE and performance degradation. The optimal bonding temperature for the C/C system was 700℃, which was lower than the 900℃ reported for microcrystalline glass, highlighting the influence of substrate material on the thermal evolution of the adhesive. Furthermore, the present study placed greater emphasis on thermal cycling stability in the intermediate temperature range (RT-700℃), which is critical for C/C composite applications but was not addressed in Zhang et al.’s work. Building on these comparative observations, while ZrW2O8 has been well-established as a negative-thermal-expansion filler for composite CTE regulation, this work reveals the unique coupled relationship among matrix pyrolysis shrinkage, temperature-dependent ZrW2O8 decomposition, boron-mediated interfacial anchoring, and thermal-cycling performance within pre-ceramic silicone-resin adhesives for C/C composite joints. By jointly realizing pyrolysis-shrinkage compensation and CTE matching, this study provides a novel strategy for the reliable joining of C/C composites under thermal cycling conditions. The successful application of ZrW2O8 as a functional filler in preceramic polymer adhesives demonstrates the potential of NTE materials for high-temperature adhesive applications, offering valuable insights for the design of next-generation adhesives for advanced thermal protection systems and hot-end components in hypersonic and reusable launch vehicles.

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