微热压增材制造轻质、高强度、低导热碳化硅/石墨复合材料

吴海华; 贺俊超; 钟磊; 叶永盛; 黄才华

doi:10.13801/j.cnki.fhclxb.20210905.002

微热压增材制造轻质、高强度、低导热碳化硅/石墨复合材料

doi: 10.13801/j.cnki.fhclxb.20210905.002

三峡大学　机械与动力学院，宜昌 443002

详细信息

通讯作者:
吴海华，博士，教授，博士生导师，研究方向为石墨3D打印技术　 E-mail：wuhaihua@ctgu.edu.cn

中图分类号: TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2021-06-25
- 修回日期: 2021-07-30
- 录用日期: 2021-08-25
- 网络出版日期: 2021-09-06
- 刊出日期: 2022-07-30

Micro-thermocompression molded light weight, high-strength, low thermal conductivity silicon carbide/graphite composites

School of Machinery and Power, The China Three Gorges University, Yichang 443002, China

摘要

摘要: 轻质隔热材料已在飞行器动力装置热防护系统中获得广泛应用，但现有的工艺技术难以实现高承载、轻质、隔热等多个技术目标的协同。基于微热压增材制造成形技术原理快速制备了一种轻质、高强度、低导热碳化硅/石墨复合材料。研究了不同成形密度下复合材料的抗压强度和导热系数变化规律，通过改变材料配方组成(包括热固性酚醛树脂粉末、高纯硅粉和可膨胀石墨质量分数)实现了复合材料的抗压强度和导热系数正反向调节，揭示了其内在机制。研究发现当酚醛树脂粉末、高纯硅粉、可膨胀石墨质量分数分别为30wt%、30wt%、2wt%时，所制备的碳化硅/石墨隔热复合材料兼具低密度(＜1.2 g/cm³)、高抗压(＞15 MPa)和低导热(＜1 W/(m·K))性能，该复合材料在航空航天具有良好的应用前景。
- 碳化硅/石墨隔热材料 /
- 微热压增材制造 /
- 导热系数 /
- 抗压强度 /
- 调控
Abstract: Light weight thermal insulation materials have been widely used in the thermal protection system of aircraft power plant, but the existing technology is difficult to achieve the synergy of many technical goals such as high load, light weight and thermal insulation. In this paper, a kind of lightweight, high strength and low thermal conductivity silicon carbide/graphite composite was rapidly prepared based on the principle of micro-hot pressing additive manufacturing and forming technology. The variation law of compressive strength and thermal conductivity of composite materials under different forming densities was studied. By changing the material formula composition (including thermosetting phenolic resin powder, high purity silicon powder and expandable graphite, etc.), the compressive strength and thermal conductivity of composite materials were adjusted forward and backward, and its internal mechanism was revealed. This research finds that when the mass fraction of phenolic resin powder, high purity silicon powder and expandable graphite is 30wt%, 30wt% and 2wt%, respectively, the silicon carbide/graphite thermal insulation composite has the properties of low density (<1.2 g/cm³), high compressive strength (>15 MPa) and low thermal conductivity (< 1 W/(m·K)), which has a good application prospect in aerospace.
- silicon carbide/graphite thermal insulation material /
- micro-hot pressing additive manufacturing /
- coefficient of thermal conductivity /
- compressive strength /
- regulation

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图 1 各石墨件微热压增材制造成形工艺原理

Figure 1. Forming process principle of micro hot pressing of graphite parts

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图 2 酚醛树脂/石墨件成形密度对抗压强度与导热系数的影响：(a)抗压强度；(b)导热系数

Figure 2. Effects of forming density of phenolic resin/graphite parts on compressive strength and thermal conductivity: (a) Compressive strength; (b) Thermal conductivity

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图 3 传统热压成形与微热压成形酚醛树脂/石墨件试样

Figure 3. Traditional hot pressing and micro hot pressing phenolic resin/graphite parts samples

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图 4 热固性酚醛树脂粉末质量分数对酚醛树脂/石墨件抗压强度、导热系数的影响

Figure 4. Effect of mass fraction of thermosetting phenolic resin powder on compressive strength and thermal conductivity of phenolic resin/graphite parts

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图 5 碳化后酚醛树脂/石墨件微观形貌图(热固性酚醛树脂粉末质量分数分别为：(a) 5wt%；(b) 10wt%；(c) 20wt%；(d) 25wt%；(e) 30wt%)

Figure 5. Micro morphology of phenolic resin/graphite parts after carbonization (The mass fraction of thermosetting phenolic resin powder: (a) 5wt%; (b) 10wt%; (c) 20wt%; (d) 25wt%; (e) 30wt%)

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图 6 不同的热固性酚醛树脂粉末质量分数对酚醛树脂/石墨件气孔率和开气孔率的影响

Figure 6. Effect of different mass fractions of thermosetting phenolic resin powder on porosity and open porosity of phenolic resin/graphite parts

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图 7 高纯硅粉质量分数对高温烧结后硅粉-酚醛树脂/石墨件抗压强度和导热系数的影响

Figure 7. Effect of mass fraction of high purity silicon powder on compressive strength and thermal conductivity of silicon powder-phenolic resin/graphite after high temperature sintering

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图 8 高温烧结后硅粉-酚醛树脂/石墨件内部微形貌图(高纯硅粉质量分数：(a) 15wt%；(b) 20wt%；(c) 25wt%；(d) 30wt%；(e) 35wt%)

Figure 8. Internal micro morphology of silicon powder-phenolic resin/graphite after high temperature sintering (Mass fraction of high purity silicon powder: (a) 15wt%; (b) 20wt%; (c) 25wt%; (d) 30wt%; (e) 35wt%)

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图 9 不同硅粉含量的硅粉-酚醛树脂/石墨件XRD图谱

Figure 9. XRD patterns of samples with different silicon powder contents of silicon powder-phenolic resin/graphite

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图 10 高纯硅粉质量分数对硅粉-酚醛树脂/石墨件气孔率和开气孔率的影响

Figure 10. Effect of mass fraction of high purity silicon powder on porosity and open porosity of silicon powder-phenolic resin/graphite parts

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图 11 可膨胀石墨质量分数对可膨胀石墨-硅粉-酚醛树脂/石墨件抗压强度和导热系数的影响

Figure 11. Effect of mass fraction of expandable graphite on compressive strength and thermal conductivity of expandable graphite-silica fume-phenolic resin/graphite parts

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图 13 可膨胀石墨质量分数对可膨胀石墨-硅粉-酚醛树脂/石墨件气孔率、开气孔率和成形密度的影响

Figure 13. Effect of mass fraction of expandable graphite on porosity, open porosity and forming density of expandable graphite-silica fume-phenolic resin/graphite parts

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图 12 包覆两次后可膨胀石墨微观形貌图：(a)未包覆；(b)包覆两次

Figure 12. Micromorphology of expandable graphite powder after twice coating: (a) Uncoated; (b) Twice coated

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图 14 不同可膨胀石墨含量制备的可膨胀石墨-硅粉-酚醛树脂/石墨件内部微形貌图：(a) 0wt%；(b) 0.5wt%；(c) 1.0wt%；(d) 1.5wt%；(e) 2.0wt%

Figure 14. Internal micro morphology of expandable graphite-silica fume-phenolic resin/graphite prepared with different expandable graphite contents: (a) 0wt%; (b) 0.5wt%; (c) 1.0wt%; (d) 1.5wt%; (e) 2.0wt%

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图 15 石墨件有效导热系数的计算值与实测值：(a)酚醛树脂/石墨件；(b)硅粉-酚醛树脂/石墨件

Figure 15. Calculated and measured values of effective thermal conductivity of graphite parts: (a) Phenolic resin/graphite parts; (b) Silicon powder-phenolic resin/graphite parts

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图 16 比例系数与孔隙率关系的拟合曲线图

Figure 16. Fitting curve of the relationship between proportional coefficient and porosity

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表 1 不同热固性酚醛树脂和天然鳞片石墨粉末的质量分数制备的酚醛树脂/石墨件

Table 1. Phenolic resin/graphite parts prepared by different mass fractions of thermosetting phenolic resin and natural flake graphite powder

Materials	Mass fraction/wt%
Graphite	90	85	80	75	70
Phenolic resin	10	15	20	25	30

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表 2 不同天然鳞片石墨粉末与高纯硅粉的质量分数制备的硅粉-酚醛树脂/石墨件

Table 2. Silicon powder-phenolic resin/graphite parts prepared by different mass fractions of natural flake graphite powder and high-purity silicon powder

Materials	Mass fraction/wt%
Graphite	55	50	45	40	35
Phenolic resin	30	30	30	30	30
Si	15	20	25	30	35

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表 3 不同可膨胀石墨粉末的质量分数制备的可膨胀石墨-硅粉-酚醛树脂/石墨件

Table 3. Expandable graphite-silica fume-phenolic resin/graphite parts prepared with different mass fractions of expandable graphite powder

Materials	Mass fraction/wt%
Graphite	39.75	39.5	39.25	39.00	39.75
Phenolic resin	30	30	30	30	30
Si	30	30	30	30	30
Expandable graphite	0.25	0.50	0.75	1.00	1.25

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表 4 与各种轻质隔热材料综合性能对比

Table 4. Comprehensive performance comparison with various lightweight thermal insulation materials

Material composition	Forming methods	Density/ (g·cm⁻³)	Thermal conductivity/ (W·(m·K)⁻¹)	Compressive strength/MPa	Ref.
Expandable graphite, alumina fiber, aluminium silicate	Press forming	—	0.10	0.74	[25]
Hollow balls, Al₂O₃-SiO₂	Gel-casting	1.09	0.13	15.0	[26]
Carbon fiber, graphite fiber	High temperature graphitization treatment	0.16	0.14	2.0	[27]
Graphite felt core, graphite paper, carbon fiber	Chemical vapor deposition	0.31	0.40	—	[28]
Graphite, phenolic resin, silicon, expandable graphite	Micro-thermal press additive manufacturing	1.00	0.85	18.37	This work

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