CN109183422A - 一种抗氧化涂层碳纤维的制备方法 - Google Patents
一种抗氧化涂层碳纤维的制备方法 Download PDFInfo
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 78
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 78
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000011248 coating agent Substances 0.000 title claims abstract description 31
- 238000000576 coating method Methods 0.000 title claims abstract description 31
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 25
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 24
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 22
- 235000006708 antioxidants Nutrition 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000005470 impregnation Methods 0.000 claims description 13
- 239000000395 magnesium oxide Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 235000012245 magnesium oxide Nutrition 0.000 claims description 11
- 235000013024 sodium fluoride Nutrition 0.000 claims description 11
- 239000011775 sodium fluoride Substances 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 10
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims description 10
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 10
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 10
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 9
- 235000019983 sodium metaphosphate Nutrition 0.000 claims description 9
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 239000000835 fiber Substances 0.000 abstract description 7
- 238000007598 dipping method Methods 0.000 abstract description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003026 anti-oxygenic effect Effects 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 2
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003064 anti-oxidating effect Effects 0.000 abstract description 2
- 239000000919 ceramic Substances 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000011226 reinforced ceramic Substances 0.000 description 3
- 229910019092 Mg-O Inorganic materials 0.000 description 2
- 229910019395 Mg—O Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 229910014472 Ca—O Inorganic materials 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000004792 oxidative damage Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- -1 therefore Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种抗氧化涂层碳纤维的制备方法，属于陶瓷技术领域。本发明以全氢聚硅氮烷为原料，采用浸渍热转化方法，在碳纤维表面成功包覆硅氧氮涂层，大量全氢聚硅氮烷填充在碳纤维表面孔隙中，既能够提高高孔隙率碳纤维复合材料的力学强度，又能在高温氧化过程中迅速吸收空气中的氧分子，在材料表面形成整体保护，阻碍氧气分子进入材料内部，保护碳纤维不被氧化，从而显著提高碳纤维的抗氧化性能，同时为后续抗氧化层提供更多活性位点，在P2O5中引入Na2O、CaO、MgO、NaF，从而加强分子间的结合力，起到了促进磷化成膜的作用，在碳纤维的表面及开口气孔内形成一层结构致密的玻璃状填充物，渗透到碳纤维的组织孔隙内，使材料的抗氧化性得到明显提高。
Description
技术领域
本发明涉及一种抗氧化涂层碳纤维的制备方法，属于陶瓷技术领域。
背景技术
碳纤维增强陶瓷基复合材料具有轻质、耐高温、低热导率等性能特点，且韧性比原有的航天飞机隔热瓦高，在经历室温到1700℃长时间的超高温环境，不会因烧蚀而引起形状变形，因此可以用于制备新型轨道机动飞行器关键组件——钝型头锥和翼前缘。但是由于增强相碳纤维的引入，当有氧环境下温度高于450℃时，碳纤维将发生氧化损伤进而引起复合材料的失效，这个缺陷使碳纤维增强陶瓷基复合材料在有氧环境下的使用受到了极大地限制，因此，高温条件下对复合材料进行氧气隔绝，提升碳纤维增强陶瓷基复合材料的抗氧化性能是迫切任务。纵观这几十年来国内外相关研究领域对碳纤维增强材料抗氧化性能的研究，在涂层材料的选择和涂层制备工艺上均取得了很大的进展，使原本受制于高温易氧化缺陷的碳纤维增强材料能够在复杂的有氧环境中广泛使用，特别是在航空航天领域更是得到了很宽的拓展。目前关于在1500℃长时间使用的涂层已经较为广泛地报道，单一涂层已经不能满足航空航天领域对材料性能不断提高的要求，复合涂层体系在更高温度和全温度范围抗氧化性能远优于单一涂层，因此，深入研究复合涂层体系，通过改变涂层体系的材料组分、优化制备工艺和优化涂层的结构设计等来进一步提高涂层的抗氧化、抗热震、耐腐蚀等综合性能显得尤为重要。
发明内容
本发明所要解决的技术问题：针对单层涂层制备虽然简单，但是其抗氧化效果只能针对一定范围的温度，难以从碳纤维开始氧化温度到目标温度全程范围进行抗氧化保护，且保护时间较短，很难满足优异的超高温材料抗氧化涂层要求的问题，提供了一种抗氧化涂层碳纤维的制备方法。
为解决上述技术问题，本发明采用的技术方案是：
（1）将碳纤维浸泡在丙酮中超声清洗，再水洗干燥后浸泡在质量分数为10%硝酸溶液中1～2h，水洗干燥得预处理碳纤维；
（2）将预处理碳纤维浸渍在质量分数为3～5%全氢聚硅氮烷正丁醚溶液中保温反应1～2h，冷却至室温得浸渍碳纤维；
（3）取偏磷酸钠、氧化镁、磷酸二氢钙、氧化镧、氟化钠加入磷酸中搅拌加热至沸腾，再加入浸渍碳纤维搅拌30～40min后取出并转入管式炉中煅烧1～2h，冷却至室温后得抗氧化涂层碳纤维。
步骤（1）所述超声清洗过程为以300W超声波超声清洗20～30min。
步骤（1）所述碳纤维与丙酮、硝酸溶液的质量比为1：6：6～1：20：20。
步骤（2）所述预处理碳纤维与全氢聚硅氮烷正丁醚溶液的质量比为1：5～1：20。
步骤（2）所述保温反应温度为100～120℃。
步骤（3）所述偏磷酸钠、氧化镁、磷酸二氢钙、氧化镧、氟化钠、磷酸、浸渍碳纤维的重量份为0.6～1.2份偏磷酸钠，0.05～0.10份氧化镁，0.12～0.24份磷酸二氢钙，0.01～0.02g氧化镧，0.01～0.02份氟化钠，10～20份磷酸，1～2份浸渍碳纤维。
步骤（3）所述煅烧过程为在氩气氛围下，以500～600℃煅烧1～2h。
本发明与其他方法相比，有益技术效果是：
本发明以全氢聚硅氮烷为原料，采用浸渍热转化方法，在碳纤维表面成功包覆硅氧氮涂层，大量全氢聚硅氮烷填充在碳纤维表面孔隙中，既能够提高高孔隙率碳纤维复合材料的力学强度，又能在高温氧化过程中迅速吸收空气中的氧分子，在材料表面形成整体保护，阻碍氧气分子进入材料内部，保护碳纤维不被氧化，从而显著提高碳纤维的抗氧化性能，同时为后续抗氧化层提供更多活性位点，在P2O5中引入Na2O，使P2O5结构中桥氧键断裂生成非桥氧键，使分子链变短，而位于P四面体楞角上的Na+则增强了磷氧分子间的结合力，使分子更加稳定，可以承受更高的温度，在P2O5中继续引入MgO，使P2O5结构中更多的桥氧键断裂生成非桥氧键，使分子链变短，生成了更加稳定的O—Mg—O键，在磷酸盐大分子中起到骨架的作用，引入CaO起到与MgO相似的作用，但Ca—O键长高于Mg—O，可以连接起更广范围的O，从而进一步提高大分子的稳定性，NaF浸渍样中F-的引入形成与磷酸盐中阳离子的静电作用，从而加强分子间的结合力，起到了促进磷化成膜的作用，在碳纤维的表面及开口气孔内形成一层结构致密的玻璃状填充物，渗透到碳纤维的组织孔隙内，使材料的抗氧化性得到明显提高。
具体实施方式
将3～5g碳纤维浸泡在30～60g丙酮中，以300W超声波超声清洗20～30min，再用去离子水洗涤碳纤维3～5次，在100～110℃烘箱中干燥1～2h后浸泡在30～60g质量分数为10%硝酸溶液中1～2h，用去离子水洗涤至清洗液清澈后转入100～110℃烘箱中干燥至恒重，得预处理碳纤维，将1～2g预处理碳纤维浸渍在10～20g质量分数为3～5%全氢聚硅氮烷正丁醚溶液中，在100～120℃下保温反应1～2h，冷却至室温得浸渍碳纤维，取0.6～1.2g偏磷酸钠，0.05～0.10g氧化镁，0.12～0.24g磷酸二氢钙，0.01～0.02g氧化镧，0.01～0.02g氟化钠，加入10～20g磷酸中，以300～400r/min搅拌加热至沸腾，再加入1～2g浸渍碳纤维，继续搅拌30～40min后取出并转入管式炉中，在氩气氛围下，以500～600℃煅烧1～2h，冷却至室温后得抗氧化涂层碳纤维。
实例1
将3g碳纤维浸泡在30g丙酮中，以300W超声波超声清洗20min，再用去离子水洗涤碳纤维3次，在100℃烘箱中干燥1h后浸泡在30g质量分数为10%硝酸溶液中1h，用去离子水洗涤至清洗液清澈后转入100℃烘箱中干燥至恒重，得预处理碳纤维，将1g预处理碳纤维浸渍在10g质量分数为3%全氢聚硅氮烷正丁醚溶液中，在100℃下保温反应1h，冷却至室温得浸渍碳纤维，取0.6g偏磷酸钠，0.05g氧化镁，0.12g磷酸二氢钙，0.01g氧化镧，0.01g氟化钠，加入10g磷酸中，以300r/min搅拌加热至沸腾，再加入1g浸渍碳纤维，继续搅拌30min后取出并转入管式炉中，在氩气氛围下，以500℃煅烧1h，冷却至室温后得抗氧化涂层碳纤维。
实例2
将4g碳纤维浸泡在40g丙酮中，以300W超声波超声清洗25min，再用去离子水洗涤碳纤维4次，在105℃烘箱中干燥1h后浸泡在40g质量分数为10%硝酸溶液中1h，用去离子水洗涤至清洗液清澈后转入100℃烘箱中干燥至恒重，得预处理碳纤维，将1g预处理碳纤维浸渍在15g质量分数为4%全氢聚硅氮烷正丁醚溶液中，在110℃下保温反应1h，冷却至室温得浸渍碳纤维，取1.0g偏磷酸钠，0.08g氧化镁，0.16g磷酸二氢钙，0.01g氧化镧，0.01g氟化钠，加入15g磷酸中，以300r/min搅拌加热至沸腾，再加入1g浸渍碳纤维，继续搅拌30min后取出并转入管式炉中，在氩气氛围下，以550℃煅烧1h，冷却至室温后得抗氧化涂层碳纤维。
实例3
将5g碳纤维浸泡在60g丙酮中，以300W超声波超声清洗30min，再用去离子水洗涤碳纤维5次，在110℃烘箱中干燥2h后浸泡在60g质量分数为10%硝酸溶液中2h，用去离子水洗涤至清洗液清澈后转入110℃烘箱中干燥至恒重，得预处理碳纤维，将2g预处理碳纤维浸渍在20g质量分数为5%全氢聚硅氮烷正丁醚溶液中，在120℃下保温反应2h，冷却至室温得浸渍碳纤维，取1.2g偏磷酸钠，0.10g氧化镁，0.24g磷酸二氢钙，0.02g氧化镧，0.02g氟化钠，加入20g磷酸中，以400r/min搅拌加热至沸腾，再加入2g浸渍碳纤维，继续搅拌40min后取出并转入管式炉中，在氩气氛围下，以600℃煅烧2h，冷却至室温后得抗氧化涂层碳纤维。
对照例：山西某公司生产的抗氧化涂层碳纤维。
将实例及对照例的抗氧化涂层碳纤维进行检测，具体检测结果如表1。
表1性能表征对比表
由表1可知，本发明制备的抗氧化涂层碳纤维抗氧化效果好。
Claims (7)
1.一种抗氧化涂层碳纤维的制备方法，其特征在于，具体制备步骤为：
（1）将碳纤维浸泡在丙酮中超声清洗，再水洗干燥后浸泡在质量分数为10%硝酸溶液中1～2h，水洗干燥得预处理碳纤维；
（2）将预处理碳纤维浸渍在质量分数为3～5%全氢聚硅氮烷正丁醚溶液中保温反应1～2h，冷却至室温得浸渍碳纤维；
（3）取偏磷酸钠、氧化镁、磷酸二氢钙、氧化镧、氟化钠加入磷酸中搅拌加热至沸腾，再加入浸渍碳纤维搅拌30～40min后取出并转入管式炉中煅烧1～2h，冷却至室温后得抗氧化涂层碳纤维。
2.如权利要求1所述的一种抗氧化涂层碳纤维的制备方法，其特征在于，步骤（1）所述超声清洗过程为以300W超声波超声清洗20～30min。
3.如权利要求1所述的一种抗氧化涂层碳纤维的制备方法，其特征在于，步骤（1）所述碳纤维与丙酮、硝酸溶液的质量比为1：6：6～1：20：20。
4.如权利要求1所述的一种抗氧化涂层碳纤维的制备方法，其特征在于，步骤（2）所述预处理碳纤维与全氢聚硅氮烷正丁醚溶液的质量比为1：5～1：20。
5.如权利要求1所述的一种抗氧化涂层碳纤维的制备方法，其特征在于，步骤（2）所述保温反应温度为100～120℃。
6.如权利要求1所述的一种抗氧化涂层碳纤维的制备方法，其特征在于，步骤（3）所述偏磷酸钠、氧化镁、磷酸二氢钙、氧化镧、氟化钠、磷酸、浸渍碳纤维的重量份为0.6～1.2份偏磷酸钠，0.05～0.10份氧化镁，0.12～0.24份磷酸二氢钙，0.01～0.02g氧化镧，0.01～0.02份氟化钠，10～20份磷酸，1～2份浸渍碳纤维。
7.如权利要求1所述的一种抗氧化涂层碳纤维的制备方法，其特征在于，步骤（3）所述煅烧过程为在氩气氛围下，以500～600℃煅烧1～2h。
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