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Abstract

Improving the ablative resistance of carbon/phenolic (C/Ph) composites is an urgent need in the field of thermal protection of hypersonic vehicles. In this paper, novel C/Ph composites are fabricated by introducing different contents of ZrB₂ ceramic particles, and the anti-ablation properties of the composites are tested in plasma wind tunnel. Under mainstream conditions with enthalpy of 21.84 MJ/kg, heat flux of 1.6 MW/m², and pressure of 1.6 kPa, the effects of ZrB₂ ceramic content on the thermal stability, linear ablation rate and surface temperature of C/Ph composites are further analyzed. The maximum ablative surface temperature is positively correlated with the content of ZrB₂. As the ZrB₂ content increases, the back face temperature of the materials decreases gradually, while the linear ablation rate increases slightly after a significant decrease. When the ablation time is 50 s, The linear ablation rate of the sample with 7% ZrB₂ content is the lowest (0.0184 mm/s). These dates of the plasma wind tunnel test could provide a reference for applications of C/Ph composites. The oxidation of ZrB₂ in the materials contributes significantly to improving its anti-ablation properties in severe environments. Accordingly, optimizing the ZrB₂ content enables the development of high-performance C/Ph composites with enhanced thermal properties, and reduced ablation rates, making them well-suited for thermal protection applications.

Keywords

Thermal protection ceramic particles carbon/phenolic composite ablation resistance wind-tunnel test

Introduction

Thermal Protection System (TPS) is critical in hypersonic vehicles subjected to severe aerodynamic heating.^1,2 Low-density carbon/phenolic (C/Ph) composites have been extensively applied in the heatshield of hypersonic vehicles because of their excellent ablation resistance.³ The thermal protection mechanism is that C/Ph composites absorb heat mainly through phenolic pyrolysis and the thermal blocking effect generated by pyrolysis gas to prevent heat transfer to the back face.^4,5 However, the surface of the char is consumed through oxidation by the boundary-layer gases, causing the surface of traditional C/Ph composites to recede and affect the aerodynamic shape. It is still a rather complex and challenging issue to improve thermal and anti-ablation properties.

The modification of C/Ph composites by ceramic particles is one of the current research focuses. Many researchers have been committed to enhancing the performance of C/Ph composites in recent years.^6–10 Ceramic particles containing zirconium are particularly suitable for anti-ablation modification of materials due to the ultra-high melting point of the oxide.^11–13 Zhaoqi Niu et al.¹⁴ studied Zirconium chelated hybrid phenolic resin thermal insulation composites, and the results showed that the formation of ZrC and ZrO₂ thermal barrier ceramics is the main reason for enhanced thermal and anti-ablation properties. Masoud Salavati-Niasari et al.^15–21 studied nanoparticles in the catalysis application. In our previous study, the effects of ZrC content on C/Ph composites were investigated.²² The results showed that the thermal stability and anti-ablation resistance are improved with increasing ZrC content. ZrB₂ is a kind of ultra-high temperature ceramic, its melting point is very high in the absence of oxygen, and the volatilization of boron oxide (B₂O₃) produced at high temperatures may enhance the thermal blocking effect.^23,24 Amirsardari et al.²⁵ studied the thermal stability of GO/C/Phenolic Nanocomposite by introducing zirconium boride (ZrB₂) under oxyacetylene tests. They found that the ZrO₂ layer plays an essential role in improving anti-ablation properties, but did not conduct detailed research on the effect of ZrB₂ content. It is necessary to study further the effect of ZrB₂ content on the mechanical, thermal stability, and anti-ablation properties of C/Ph composites.

It is of great significance to investigate the thermal barrier effect under a severe environment with high heat flux, high enthalpy, high pressure, and even high-velocity erosion characteristics.^26–28 The widely used methods of ablation tests include oxyacetylene flame,²⁹ laser ablation,³⁰ plasma wind tunnel,³¹ arc-jet wind tunnel,³² and so on.^4,13 The first two methods can only simulate the high-temperature oxidizing atmosphere instead of the severe environment of high enthalpy, high velocity, and plasma non-equilibrium state,³³ and combustion products produced by oxyacetylene fuel will affect the ablative result of the materials. It is important to consider the interaction between the plasma environment and the materials. The dissociation and ionization of gas molecules in the shock layer of the hypersonic vehicle shouldn’t be ignored. The parameters of the two wind tunnel tests are more comprehensive. The plasma wind tunnel is superior to arc-jet in screening materials as it can provide pure environments rather than the copper contamination in arc-jet.³¹ The pure flow field formed by the plasma wind tunnel can simulate the service environment more realistically and consider the effects of gas composition, pressure, and thermochemical ablation comprehensively. The difference of gas medium has a great influence on material ablation. Compared with other methods of testing carbon phenolic materials, the plasma wind tunnel is more scientific and reasonable. It is very meaningful to study the effect of ZrB₂ content on the anti-ablation performance of C/Ph composites under the plasma wind tunnel condition, but there is limited research nowadays.

Based on this, we innovatively tested ZrB₂ modified C/Ph composites with plasma wind tunnel. Anti-ablation performance and microstructure of C/Ph composites with different ZrB₂ content were studied and the thermal protection mechanism was explored. We studied the effect of ZrB₂ contents on material microscopic properties, thermal stability, and the linear ablation rate. The best-modified particle content was obtained.

Experiment

Materials

Materials and reagents include absolute ethanol, boron modified phenolic resin, needle-punched carbon fiber felt, acetone, nitric acid, ZrB₂ particles, and hyperdispersant 7423. Phenolic resin THC-400 (Shanxi Taihang Impedefire Polymer Co., Ltd, China) is insoluble in water but soluble in ethanol. Needle-punched carbon felt as the preform (0.145 g/cm³, Tianniao High and New Technology Co., Ltd, Jiangsu, China) has 2.5 D-stitched fibrous architecture consisting of carbon fiber felt (T700SC-12,000-50C, Toray, Japan) in the thickness direction and needled fiber tows (3 K) in the through-thickness direction. The macrograph and microstructure of carbon fiber needle felt are shown in Figure 1. Particle size distributions of ZrB₂ (6.1 g/cm³, Ningbo Jinlei Nanomaterial Technology Co., Ltd) are 1∼2 μm. The chemical reagents used in the experiments are given in Table 1.

Figure 1.

Macrograph and microstructure of carbon fiber needle felt.

Table 1.

Chemical reagents used in the experiments.

Reagents	Chemical formula	Purity	Manufacturer
Anhydrous ethanol	C₂H₆O	≥99.7%	Sinopharm chemical reagent Co, Ltd, China
Acetone	CH₃COCH₃	≥99.5%	Beijing Chemical Works, Beijing, China
Concentrated nitric acid	HNO₃	65% ∼ 68%	Beijing Chemical Works, Beijing, China
Hyperdispersant 7423	(C₁₀H₈N₂O₂·C₆H₁₄O₃)_n	≥92%	Guangzhou Silok chemical Co, Ltd, China

Fabrication

The schematic illustrations of the preparation process of ZrB₂ modified C/Ph (ZrB₂-C/Ph) composites are presented in Figure 2. These composites were fabricated in turn by surface treatment, vacuum impregnation, drying, and curing. Firstly, surface treatment of the felt was conducted: it was treated with acetone for 24 h to desize carbon fibers; and then, the felt was dried in the oven after washing with distilled water; afterward, the felt was processed with concentrated nitric acid for 2 h, and dried in the oven. Secondly, the phenolic resin was dissolved in absolute ethanol to prepare the 25% phenolic ethanol solution; after that, ZrB₂ particles and hyperdispersant 7423 were added into the prepared solution. The addition amount of ZrB₂ was 3%, 5%, 7%, 9%, and 11%, respectively, and the hyperdispersant 7423 which was 7% of ZrB₂ in the phenolic ethanol solution, and used dispersion homogenizer (JFS 750S) to mechanically stir at 1500 r/min for 40 min until completely dissolved. The surface-treated fiber felt was impregnated in the mixed solution at room temperature in the vacuum oven. Thirdly, the impregnated carbon fiber felt was placed in the drying oven to dry thoroughly. Finally, ZrB₂-C/Ph composites were prepared after ZrB₂ curing by the double-stage method 35: the first was performed at 120°C for 1 h and the second was performed at 170°C for 2 h. The names of materials with their basic parameters are summarized in Table 2.

Figure 2.

Preparation process diagram of ZrB₂-C/Ph composites.

Table 2.

Parameters of the processed composites.

Sample	Ceramic content (%)	Phenolic resin (%)	Density (g/cm³)	Compressive stress (MPa)	Thermal conductivity (W/m·K)
Blank-C/Ph	0	25	0.322	56.97	0.129
3-C/Ph	3	25	0.341	27.68	0.136
5-C/Ph	5	25	0.376	22.84	0.143
7-C/Ph	7	25	0.395	17.71	0.147
9-C/Ph	9	25	0.436	15.86	0.150
11-C/Ph	11	25	0.443	12.43	0.154

Characterizations

In order to study the dispersion effect of hyperdispersant 7423 and determine the optimal addition amount, the stability of ZrB₂ particles in phenolic ethanol solution containing different amounts of dispersants is studied using the sedimentation test. Hyperdispersant 7423 was added to the solution containing 25% phenolic resin and 5% ZrB₂ particles, The dispersion state of ZrB₂ particles was observed, and the settling process of ZrB₂ was recorded within 180 min.

Compression strength and thermal conductivity of the samples were measured, respectively. Thermogravimetric (TG) analysis was conducted to estimate thermal stability. Anti-ablation performance was evaluated by the plasma wind tunnel. The test conditions were a surface pressure of 1.6 kPa, enthalpy of 21.84 MJ/kg, heat flux of 1.6 MW/m², and test time of 50 s. Before testing, the specimens were machined with a size of Φ30 mm × 25 mm, and held in a graphite mold on the water-cooled manipulator arm. The ablated surface was 50 mm from the nozzle outlet, perpendicular to the direction of the flame. The infrared pyrometer measured the temperature of the ablated surface, while a K-type thermocouple measured the temperature of the back face. Simultaneously, the shape change of samples during the test was recorded by the camera. The thickness of the ablated sample is measured after stripping the white ZrO₂ layer, and the linear ablation rate is calculated. The linear ablation rates of samples can be calculated by equation (1):

R_{L} = \frac{L_{0} - L_{a}}{t}

(1)

Where R_L is the linear ablation rate, L₀ is the thickness of samples before tests, L_a is the thickness of samples after tests; and t is ablation time. Micrographs of composite samples were obtained by the scanning electron microscope (SEM, Tescan Vega II, Tescan SRO Co., Czech Republic). The uniformity of the dispersion of the particles in the phenolic matrix was analyzed by energy dispersive spectrometer.

Results and discussions

Properties of carbon/phenolic composites with different ZrB₂ contents

The sedimentation process of ZrB₂ with different dispersant contents is shown in Figure 3. The addition amount of hyperdispersant 7423 from left to right are 0%, 3%, 5%, 7%, 9%, and 11% of the content of ZrB₂ in order. After hyperdispersant 7423 was dispersed in phenolic ethanol solution for 180 min, ZrB₂ particles with 7% dispersant content had the best uniform dispersion.

Figure 3.

Sedimentation experiment of ZrB₂ with different dispersants.

Figure 4 shows the microstructure and element mapping of C/Ph composites with 7% ZrB₂ content. It can be seen that the fibers are connected by phenolic resin, and the carbon fibers on the surface are disordered, and there is no obvious fiber orientation. The O, Zr, and B elements are well-distributed in the C/Ph composite. At the same time, there is no obvious agglomeration of ZrB₂ particles, which also proves that the dispersion of ZrB₂ particles in phenolic resin is uniform. A uniform ceramic protective layer is formed during ablation, which is beneficial to the ablative properties of the material.

Figure 4.

Element mapping of C/Ph composite with 7% ZrB₂ contents.

It can be seen from Table 2 that the density and thermal conductivity of the materials gradually increase as the ZrB₂ content increases. When the ceramic content is 0%, the density of C/Ph composites is the lowest (0.322 g/cm³), and when the ZrB₂ content is 11%, the C/Ph composites density is the highest (0.443 g/cm³). The introduction of ZrB₂ can form a local high thermal conductivity area inside the C/Ph material, and with the increase of ZrB₂ content, the high thermal conductivity area increases, resulting in an approximately linear increase in the thermal conductivity of C/Ph. The addition of ZrB₂ particles prevents the resin matrix from forming a continuous mesh structure, resulting in a decrease in the compressive stress of C/Ph composite.

TG curves of composite materials containing different contents of ZrB₂ tested in a nitrogen environment are shown in Figure 5. Below 700°C, the variation trend of composites is similar, and it can be observed that the main weight changes occur at this stage between 300°C and 700°C. But the temperature of the maximum degradation rate for the ZrB₂-modified materials is significantly higher than that of the blank-C/Ph composite (571°C). The weight loss of the blank-C/Ph composite (21.56%) at this stage is almost three times that of the 7-C/Ph composite (7.76%) and four times that of the 11-C/Ph composite (5.49%), indicating that the introduction of ZrB₂ particles significantly improves the thermal stability of phenolic. Because ZrB₂ can oxidize with oxidizing gases (such as CO, CO₂, and H₂O) generated from phenolic pyrolysis to increase the mass. Therefore, when the temperature exceeds 700°C, the mass loss of composites without ceramic particles increases. In contrast, the mass loss of several groups of materials modified by ZrB₂ particles is almost unchanged.

Figure 5.

TG curves of C/Ph composites with different contents of ZrB₂.

Morphological characterization

The states of blank-C/Ph and 7-C/Ph composites before, during, and after the ablation are shown in Figure 6. The two pre-test samples are displayed in Figure 6(a) and (d); there is no observable difference between the two pre-test samples. Figure 6(b) and (e) provide macrographs of samples during the plasma wind tunnel test. Figure 6(c) and (f) presents the post-test samples of the composites, respectively. It is clear to see that the white-colored layer on the ablated surface in Figure 6(f), significantly differs from blank-C/Ph composites. Similar phenomena and related mechanisms have been discussed in our previous work.²²

Figure 6.

Macrographs of the composites before, during, and after the ablation test, respectively: (a-c) C/Ph; (d-f) 7-C/Ph.

Linear ablation rates and microstructure characterization

Figure 7 shows the results of linear ablation rates of the materials after the test. The calculation of the ablation rate does not include the white layer. The addition of ZrB₂ decreases the linear ablation rate. The lowest linear ablation rate is obtained when the ZrB₂ content in the materials is 7%, which is 0.0184 mm/s. When the content of ZrB₂ exceeds 7%, the linear ablation rate increases slightly, but it is still lower than that of blank-C/Ph composites. The linear ablation rate of 11-C/Ph composites is 0.0236 mm/s, which is 0.0052 mm/s higher than that of 7-C/Ph composites, but 69% lower than that of blank-C/Ph composites. ZrB₂ particles strongly influence the reduction of the linear ablation rate. Compared with the oxy-acetylene ablation test results of Amirsardari et al,²⁵ line ablation rates of C/Ph composites are higher in plasma wind tunnel, the linear ablation rates of 7-C/Ph compared with blank-C/Ph decreased by 75% in plasma wind tunnel, but decreased by 90% under oxy-acetylene ablation. Because the thermal environment provided by the plasma wind tunnel is more realistic and severe. This could be considered that the mainstream in the plasma wind tunnel has higher recovery enthalpy and mechanical denudation than oxy-acetylene flame, which needs further comparative study in future work.

Figure 7.

Linear ablation rates of ZrB₂-C/Ph composites with different contents of ZrB₂.

After ablation, the surface ceramic coatings are removed, and the microstructure of the samples is observed in Figure 8. When the ZrB₂ content is less than 7%, the matrix on the ablated surface gradually increases as the content increases. However, When the ZrB₂ content in the material is greater than 7% (Figure 8 (e) and (f)), the matrix does not increase correspondingly, but the pore size increases slightly with the increase of ZrB₂ content. The matrix coated on the surface of carbon fiber can reduce the oxidation rate. There may be pyrolytic carbon, ZrO₂, ZrC, and unoxidized ZrB₂ in the matrix. In the wind tunnel test process, phenolic resins are pyrolyzed to generate pyrolytic carbon, and ZrB₂ is oxidized to generate ZrO₂ and B₂O₃, the production of B₂O₃ is less than the evaporation at the surface ablation temperature.³⁴

Figure 8.

SEM micrographs of the ablated surface of ZrB₂-C/Ph composites with different contents of ZrB₂: (a) blank; (b) 3%; (c) 5%; (d) 7%; (e) 9%; (f) 11%; (g)-(h) SEM micrographs of white colored layer on the ablated surface.

The presence of ceramic particles and their reaction products can improve the strength of the carbonization layer and reduce the effect of mechanical denudation, thus reducing the ablation rate of the composites.³⁵ When the content of ZrB₂ is low (less than 7%), the thermochemical ablation occupies the dominant position and the linear ablation rate decreases as the ZrB₂ content increases. When the ZrB₂ content in the material is excessive, the increase of the content of ZrB₂ would bring about the increase of the density of the matrix; the ZrO₂ coating would be so dense that the gases generated in the ablation process accumulate in the material, resulting in the peeling of the ZrO₂ layer. Therefore, when the content of ZrB₂ increases from 7% to 11%, the linear ablation rate is slightly increased by the combined action of mechanical denudation and thermochemical ablation. Figure 8(g)-(h) shows the micrographs of the white-colored layer on the ablated surface. Almost all of the carbon fiber is oxidized, and the pores formed by the fiber can be clearly seen.

The ablated surface temperatures

The temperature-time curve of the ablated surface of the sample measured by the infrared temperature measurement system during the plasma wind tunnel test is shown in Figure 9. The maximum ablated surface temperature is below 2200°C, and all curves show the same trend of rapid heating and constant surface temperature with the increase of ablation time. When the content of ZrB₂ varies from 0% to 7%, the content of ZrB₂ is positively correlated with the maximum ablated surface temperature; when the content is more than 7%, the maximum ablated surface temperature is almost constant. Such a result would confirm a limit to the effect of the ZrB₂ content on the ablated surface temperature. With the increase of the content of ZrB₂, the main factors affecting the maximum ablated surface temperature also change.

Figure 9.

Temperature of the ablated surface of ZrB₂-C/Ph composites with different content of ZrB₂.

For all the test samples, the external heating conditions are the same, and the presence and content of ZrB₂ mainly cause the difference in ablated surface temperatures. Due to the high ablated surface temperature, the radiative heat dissipation plays a dominant role more than the exothermic oxidation of ZrB₂, the heat absorption of B₂O₃ gasification and the heat dissipation from pyrolysis gas escape. ZrO₂ has a lower radiation coefficient compared with pyrolytic carbon and carbon fiber, which leads to the increase of ablated surface temperature by adding ZrB₂. As the content of ZrB₂ increases, the ZrO₂ produced on the ablated surface tends to densify. Hence, the ablated surface temperature remains unchanged when the ZrB₂ content is more than 7%.

The back face temperatures

Figure 10 shows the temperature-time curve of the back face measured by a thermocouple. The back face temperature decreases as ZrB₂ content increases. The 11-C/Ph composite has the lowest back face temperature, and is lower than Blank-C/Ph about 50% at 50 s. The back face temperature is controlled by multiple factors such as ablated surface temperature, thermal conductivity, thickness, and chemical reactions of ceramic particles. When the ZrB₂ content increases from 0 to 7%, the linear ablation rate of the composites decreases gradually, and the thickness increases, the ZrO₂ layer effectively prevents heat transfer from the material surface to the back, which is conducive to preventing the back face temperature from rising rapidly. When the content increases from 7% to 11%, the thermal conductivity of the material increases and thickness decreases, but the ablated surface temperature remains unchanged; the increase of ZrB₂ content leads to the increase of B₂O₃, volatilization and thermal blocking effect of B₂O₃ becomes the main reason to suppressed the heat transfer to the back face.

Figure 10.

Temperature of the back face of ZrB₂-C/Ph composites with different contents of ZrB₂.

Conclusions

In short, we successfully prepared ZrB₂-C/Ph with different ZrB₂ contents and investigated their ablative properties at a heat flux of 1.6 MW by plasma wind tunnel test. It is found that materials have excellent comprehensive performance when the content of ZrB₂ is 7%. Due to the oxidation of ZrB₂ to ZrO₂ ceramic protective layer, and the evaporation of B₂O₃ enhances the thermal blocking effect, the ablative resistance of ZrB₂-C/Ph is significantly improved. As the ZrB₂ content increases, the back face temperature of the materials decreases gradually, and the line ablation rate decreases first and then increases. The linear ablation rates of 7-C/Ph compared with blank-C/Ph decreased by 75%, this result is higher than that obtained under the condition of oxyacetylene ablation. The back face temperature of the sample with 11% ZrB₂ content rose the slowest, 50% lower than that of the composite without ZrB₂. ZrB₂ ceramic particles could be promising materials to improve the anti-ablation performance of carbon/phenolic composites. These results measured in the plasma wind tunnel can provide a reference for engineering applications. The effect of different proportions of multicomponent ceramic particles added to C/Ph composites on ablative properties could be investigated in the future.

Footnotes

Acknowledgments

The authors sincerely acknowledge the support from the National Natural Science Foundation of China (grant numbers 92271106).

Author contributions

Andi Lin contributed to the conceptualization, methodology, formal analysis, investigation, and writing the original draft. Haiming Huang and Shuang Wang contributed to supervision, experimental design, review, and editing. Ye Tian and Jie Huang contributed to experimental investigation and data analysis. Xinmeng Wang contributed to review and editing. All authors discussed the results and contributed to the final manuscript.

Declaration of conflicting interests

The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.

Funding

The author(s) disclosed receipt of the following financial support for the research, authorship, and/or publication of this article: This work was supported by the National Natural Science Foundation of China; (92271106).

ORCID iDs

Andi Lin

Shuang Wang

Data Availability Statement

The are available from the corresponding author on reasonable request.

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Anti-ablation properties of ZrB 2 modified carbon/phenolic composites in plasma wind tunnel

Abstract

Keywords

Introduction

Experiment

Materials

Fabrication

Characterizations

Results and discussions

Properties of carbon/phenolic composites with different ZrB2 contents

Morphological characterization

Linear ablation rates and microstructure characterization

The ablated surface temperatures

The back face temperatures

Conclusions

Footnotes

Acknowledgments

Author contributions

Declaration of conflicting interests

Funding

ORCID iDs

Data Availability Statement

References

Properties of carbon/phenolic composites with different ZrB₂ contents