CN117246004A - 一种添加微胶囊自修复层的纤维金属层板及其制备方法 - Google Patents
一种添加微胶囊自修复层的纤维金属层板及其制备方法 Download PDFInfo
- Publication number
- CN117246004A CN117246004A CN202311156992.2A CN202311156992A CN117246004A CN 117246004 A CN117246004 A CN 117246004A CN 202311156992 A CN202311156992 A CN 202311156992A CN 117246004 A CN117246004 A CN 117246004A
- Authority
- CN
- China
- Prior art keywords
- microcapsule
- layer
- fiber
- coating
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003094 microcapsule Substances 0.000 title claims abstract description 139
- 239000000835 fiber Substances 0.000 title claims abstract description 89
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 74
- 239000002184 metal Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000010410 layer Substances 0.000 claims abstract description 117
- 239000011248 coating agent Substances 0.000 claims abstract description 52
- 238000000576 coating method Methods 0.000 claims abstract description 52
- 239000011159 matrix material Substances 0.000 claims abstract description 41
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 16
- 230000000694 effects Effects 0.000 claims abstract description 10
- 239000003822 epoxy resin Substances 0.000 claims description 38
- 229920000647 polyepoxide Polymers 0.000 claims description 38
- 239000012948 isocyanate Substances 0.000 claims description 25
- 150000002513 isocyanates Chemical class 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 13
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 239000002966 varnish Substances 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 230000008439 repair process Effects 0.000 claims description 8
- 239000011257 shell material Substances 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 239000011162 core material Substances 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 244000137852 Petrea volubilis Species 0.000 claims description 6
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920001721 polyimide Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 238000005054 agglomeration Methods 0.000 claims description 5
- 230000002776 aggregation Effects 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000032798 delamination Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000838 Al alloy Inorganic materials 0.000 claims description 4
- 238000007259 addition reaction Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 4
- 239000003995 emulsifying agent Substances 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- 238000012695 Interfacial polymerization Methods 0.000 claims description 3
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 3
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 3
- 239000012790 adhesive layer Substances 0.000 claims description 3
- 239000004760 aramid Substances 0.000 claims description 3
- 229920006231 aramid fiber Polymers 0.000 claims description 3
- 239000002775 capsule Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000006355 external stress Effects 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 claims description 3
- 239000004530 micro-emulsion Substances 0.000 claims description 3
- 239000007764 o/w emulsion Substances 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 229920006254 polymer film Polymers 0.000 claims description 3
- 229920013657 polymer matrix composite Polymers 0.000 claims description 3
- 239000011160 polymer matrix composite Substances 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 230000000638 stimulation Effects 0.000 claims description 3
- 230000003746 surface roughness Effects 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005336 cracking Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 3
- 239000011229 interlayer Substances 0.000 abstract description 7
- 239000012466 permeate Substances 0.000 abstract description 2
- 230000002787 reinforcement Effects 0.000 abstract description 2
- 238000010008 shearing Methods 0.000 abstract description 2
- 230000006378 damage Effects 0.000 description 11
- 239000002131 composite material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical group NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- MDYWVERMLMSYEC-UHFFFAOYSA-N N=C=O.N=C=O Chemical compound N=C=O.N=C=O MDYWVERMLMSYEC-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000013003 healing agent Substances 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/05—5 or more layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/106—Carbon fibres, e.g. graphite fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/762—Self-repairing, self-healing
Landscapes
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Laminated Bodies (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
本发明为一种添加微胶囊自修复层的纤维金属层板及其制备方法,包括金属基体层、界面增强薄膜层和纤维预浸料层,所述纤维金属层板还包括微胶囊涂层,层板采用金属基体层/界面增强薄膜层/微胶囊涂层/纤维预浸料层/微胶囊涂层/界面增强薄膜层/金属基体层的结构进行交替铺层。提出关于纤维金属层板新的铺层结构,在界面增强层与纤维预浸料之间涂覆一层含有微胶囊的微胶囊涂层。所述微胶囊涂层中含有质量分数合适的微胶囊,其中微胶囊充分混匀在微胶囊涂层中,并不会渗透到相邻层之中,可以产生自愈合效应,实现自修复功能,提高纤维金属层板的抗剪切强度和层间粘结力。
Description
技术领域
本发明涉及纤维金属层板技术领域,特别是涉及一种添加微胶囊自修复层的纤维金属层板及其制备方法,增强纤维金属层板层间增韧效果,该纤维金属层板具有较高的韧性和疲劳寿命。
背景技术
航空航天材料目前正向着低密度、高比强度和更好的抗疲劳强度发展,而合金类材料的疲劳强度较差,复合材料由于铺层方式不同而具有各向异性,因此对于疲劳损伤不敏感但是耐冲击性能较差。纤维金属层板结合了金属材料与纤维复合材料的优点,抗冲击、耐疲劳性能优异。
由于纤维金属层板本质上是一种超混杂的复合材料,在界面粘结力不足或者外部剪切应力作用下,纤维金属层板可能会出现金属基体层和纤维层脱粘的情况,金属基体层与纤维预浸料层分离是纤维金属层板主要失效形式之一。
发明内容
针对现有技术的不足,本发明拟解决的技术问题是,提供一种添加微胶囊自修复层的纤维金属层板的制备方法,通过添加微胶囊来改善金属基体层与纤维层的层间粘结效果。
本发明解决所述技术问题采用的技术方案是,提供了一种添加微胶囊自修复层的纤维金属层板,包括金属基体层、界面增强薄膜层和纤维预浸料层,其特征在于,所述纤维金属层板还包括微胶囊涂层,层板采用金属基体层/界面增强薄膜层/微胶囊涂层/纤维预浸料层/微胶囊涂层/界面增强薄膜层/金属基体层的结构进行交替铺层。
纤维金属层板中纤维铺设角度为0°、90°、±45°;
所述金属基体层为铝合金、镁合金、钛合金中的至少一种,厚度不大于0.5毫米;
所述纤维预浸料层由纤维和树脂构成,所述纤维为玻璃纤维、碳纤维、芳纶纤维中的至少一种;所述树脂为热固性环氧树脂;
所述界面增强薄膜层采用可塑性材料,包括聚合物薄膜或者聚合物基复合材料;
所述微胶囊涂层3由喷涂或者涂覆方式均匀地覆盖在纤维预浸料层4的正反面上,所述微胶囊涂层由微米级微胶囊通过搅拌或超声分散在环氧树脂基清漆中再经过喷涂或涂覆形成;所述微米级微胶囊为球形,且为核壳结构。
所述微米级微胶囊的平均直径为2-5μm,微米级微胶囊在环氧树脂基清漆中无团聚现象,能够均匀分散在纤维预浸料层上。
所述微胶囊内封装化合物为异氰酸酯(IPDI),胶囊壳材质为聚氨酯,微米级微胶囊占环氧树脂基清漆的质量分数为1-5wt%,优选质量分数为1.5wt%;所述微胶囊涂层厚度为几十微米;当在外界应力作用下,界面层出现裂纹破坏时,微胶囊破裂,其内部自愈合物质—异氰酸酯(IPDI)被释放出来,异氰酸酯(IPDI)中的异氰基(NCO)与微胶囊涂层中的环氧树脂中的环氧基发生加成反应,形成尿素键或者尿酰基键;当异氰酸酯与环氧树脂接触时,异氰酸酯中的NCO基团与环氧树脂中的环氧基发生反应,产生化学键;反应后,异氰酸酯与环氧树脂发生化学结合,形成一个新的交联网络,从而达到修补环氧树脂基质的目的,同时破碎的微胶囊壳还能在结构弯曲时在纵向上促进嵌锁效应。
在层板受到剪切拉伸或者压缩载荷时,添加的微胶囊涂层会提供额外的粘结力保护,微胶囊通过机械刺激打开,其中封装的修复剂会释放到微胶囊涂层中或者相邻层的界面结合处,通过填补裂纹形成类榫卯结构来抑制裂纹传播并且通过在界面结合处形成新的粘结层,促进裂隙粘合来抵抗外部机械载荷破坏致使的分层脱粘情况。
本发明还保护一种添加微胶囊自修复层的纤维金属层板的制备方法,所述制备方法包括以下步骤:
1)金属基体的处理:对金属基体进行脱油处理,接着,使用细砂纸和粗砂纸进行打磨,提高金属基体的表面粗糙度,增大粘接面积;
2)纤维预浸料层的选择:选择环氧树脂基纤维预浸料,界面增强薄膜层选择具有良好热稳定性和化学稳定性的聚酰亚胺薄膜;
3)微胶囊的制备:采用微乳液体系结合界面聚合工艺制备聚氨酯微胶囊,包括:
预聚体制作:准备质量比例为1:6.5:0.2的对甲苯二异氰酸酯、环己酮、丁二醇,将对甲苯二异氰酸酯溶解于环己酮中,在缓慢倒入丁二醇的同时对溶液进行60-80℃的加热搅拌,待充分反应后,蒸馏得到预聚体;
将异佛尔酮二异氰酸酯(IPDI)作为芯材和预聚体按3.5:1的比例溶解在乙酸乙酯中,形成油相,并进行充分搅拌;
将去离子水和乳化剂混合并充分搅拌,形成乳液;
将油相以加入乳液中,形成水包油型(O/W)乳化体系;
然后缓慢加入丁二醇,将整个体系升温至60℃并以1500转/分钟搅拌1.5小时,得到微胶囊悬浮液;
经过洗涤、抽滤和真空干燥后,得到直径为2~5μm的微胶囊试样;
4)微胶囊涂层的制备:将微胶囊试样与环氧树脂基清漆混合,其中微胶囊试样所占的质量分数为1.5wt%,混合之后将其涂覆于纤维预浸料层上,并干燥;
5)成形与固化:将含有微胶囊涂层的纤维预浸料层与聚酰亚胺薄膜和金属基体放置于真空袋中,进行热压固化,直至形成所需的形状,获得添加微胶囊自修复层的纤维金属层板。
所述热压固化温度为130-140℃,所施加的压力不会造成微胶囊壳体破裂或IPDI芯材泄露。
与现有技术相比,本发明的有益效果是:
本发明创造性地提出了关于纤维金属层板新的铺层结构,在界面增强层与纤维预浸料之间涂覆一层含有微胶囊的微胶囊涂层。所述微胶囊涂层中含有质量分数合适(本实施例采用质量分数比为1.5%wt)的微胶囊,其中微胶囊充分混匀在微胶囊涂层中,并不会渗透到相邻层之中,可以产生自愈合效应,实现自修复功能,提高纤维金属层板的抗剪切强度和层间粘结力。
本发明提供了一种添加微胶囊自修复层的纤维金属层板的制备方法,通过在界面增强薄膜层与纤维预浸料层之间涂覆含有微胶囊的涂层,有效改善了金属基体层与纤维预浸料层的粘结性能,提高纤维金属层板的层间增韧效果。
本发明为一种全新的纤维金属层板结构,为开发更高性能的复合材料提供了思路和方法。本发明只用于修复纤维预浸料层和微胶囊涂层的层面结合的裂纹,提高层间结合力。
附图说明
图1为本发明纤维金属层板的铺层结构示意图。
图2为微胶囊自修复示意图。
图中,1—金属基体层;2—界面增强薄膜层;3—微胶囊涂层;4—纤维预浸料层。
具体实施方式
下面结合实施例及附图进一步解释本发明,但并不以此作为对本申请保护范围的限定。
本发明添加微胶囊自修复层的纤维金属层板(参见图1),包括金属基体层1、界面增强薄膜层2、微胶囊涂层3和纤维预浸料层4,层板采用金属基体层/界面增强薄膜层/微胶囊涂层3/纤维预浸料层4/微胶囊涂层3/界面增强薄膜层/金属基体层的结构进行交替铺层,纤维铺设角度为0°、90°、±45°等,具体铺层角度根据所制备层板零件及服役环境所承担载荷类型确定,铺层后通过加压热固化合为一体。
所述金属基体层:金属基体层可以为铝合金,镁合金,钛合金,厚度一般低于0.5毫米。
纤维预浸料层4:纤维预浸料由纤维和树脂构成,所述纤维可以为玻璃纤维、碳纤维、芳纶纤维等高性能纤维材料;所述树脂为热固性环氧树脂。
界面增强薄膜层2:纤维金属层板中夹杂的界面增强层采用可塑性材料,例如聚合物薄膜或者聚合物基复合材料,用以增强金属基体层与纤维预浸料层之间的粘结性能。
所述微胶囊涂层3由喷涂或者涂覆方式均匀地覆盖在纤维预浸料层4的正反面上,所述微胶囊涂层是由微米级微胶囊通过搅拌或超声分散在环氧树脂中再经过喷涂或涂覆形成;所述微米级微胶囊为球形,且为核壳结构,核壳结构的壳层质地均匀且相对无皱纹,微米级微胶囊的平均直径控制在2-5μm,粒径均匀。微米级微胶囊在环氧树脂基清漆中无团聚现象,能够均匀分散在纤维预浸料层上。
微胶囊涂层3的两侧分别与纤维预浸料层4和界面增强薄膜层2接触。本发明中微胶囊的尺寸在包覆足够修复剂的情况下,为避免占用过多树脂的空间,粒径越小越好,微胶囊的囊壁与芯材比例应根据基质选择最合适的,以达到最大的修复效果并减少微胶囊团聚现象。
本发明在应对剪切破坏等外部载荷施加时有更强的抵抗能力,在层板受到剪切拉伸或者压缩载荷时,添加的微胶囊涂层会提供额外的粘结力保护,微胶囊通过机械刺激打开,其中封装的修复剂会释放到微胶囊涂层中或者相邻层的界面结合处,通过填补裂纹形成类榫卯结构来抑制裂纹传播并且通过在界面结合处形成新的粘结层,促进裂隙粘合来抵抗外部机械载荷破坏致使的分层脱粘情况。
所述微胶囊内封装化合物为异氰酸酯(IPDI),因为它与OH基团等活性H高度反应,OH基团等活性H存在于环氧树脂基体之中,而微胶囊就包含在环氧树脂中。本发明中微胶囊的作用过程是:在CFRP(碳纤维增强复合材料)界面上提供额外的自修复界面层,从而提高金属与纤维预浸料之间的粘结力,减少脱粘及分层几率。当在外界应力作用下,界面层出现裂纹破坏时,微胶囊破裂,其内部自愈合物质—异氰酸酯(IPDI)被释放出来,异氰酸酯(IPDI)中的异氰基(NCO)与微胶囊涂层中的环氧树脂中的环氧基(Epoxide)发生加成反应,形成尿素键(Urea)或者尿酰基(Carbamate)键。这种反应在含有活性氢的化合物存在下进行,其中环氧树脂中的环氧基就是一种典型的活性氢来源。当异氰酸酯与环氧树脂接触时,异氰酸酯中的NCO基团与环氧树脂中的环氧基发生反应,产生化学键。反应后,异氰酸酯与环氧树脂发生化学结合,形成一个新的交联网络,从而达到修补环氧树脂基质的目的,同时破碎的微胶囊壳(胶囊壳材质为聚氨酯)还可以在结构弯曲时在纵向上促进嵌锁效应,这些自修复性能主要受影响于微胶囊的形态和尺寸以及添加量等。本发明中为微胶囊的添加量为1.0-5.0wt%,优选为1.5wt%,若添加量太大容易发生团聚,本发明的添加量范围在添加微胶囊时并不会过多压缩本来属于环氧树脂基质的空间,相反,适量尺寸的微胶囊会填补并减少其中的孔隙产生,能够实现对每一处裂纹的修复,实现全方位修复,提高整体的致密性。
本申请微胶囊破损修复过程类似榫卯结构而非类似于积木堆积形式,能够相互渗透,增强致密性,并有效防止裂纹扩大。
微胶囊封装:图中紧贴纤维预浸料层的微胶囊涂层,由含质量分数比占比1.5wt%微胶囊的环氧树脂组成,微胶囊涂层厚度约为几十微米,其中微胶囊均匀分布。
损伤发生:当层板遭受损伤时,如冲击等,层板中因为各层材料的各向异性,通常导致纤维预浸料层与金属层之间的剥离、脱粘等,这种损伤通常首先引起层间微小裂缝或缺陷。当层间产生裂缝时,处于两层之间并紧贴纤维预浸料层的微胶囊会破裂。
异氰酸酯释放:微胶囊破裂后,封装在其中的异氰酸酯修复剂会被释放到环氧树脂基体中。修复剂在毛细作用下涌入裂缝之中。
异氰酸酯与环氧树脂反应:异氰酸酯与环氧树脂的反应是自修复的关键步骤。异氰酸酯分子含有多个异氰酸官能团(NCO),而环氧树脂中含有多个羟基官能团(OH)。异氰酸酯中的异氰酸官能团(NCO)会与环氧树脂中的羟基官能团(OH)发生加成反应,形成新的化学键,这个反应称为异氰酸酯-异氰酸酯(NCO-OH)反应。这种反应会导致损伤部位的修复,因为它引入了新的交联点和化学键。
损伤修复:异氰酸酯与环氧树脂的反应会在损伤部位周围形成新的连接,填补裂缝或缺陷,从而修复了损伤。这种修复过程可以恢复层间的粘合强度和完整性,减少了损伤对材料性能的不利影响。
裂缝产生时,其内部认为是真空的,存在压差,在直接挤压或冲击作用下,同时利用压差导致微胶囊破裂进行修复,不会出现微胶囊由于承受过高温度而导致提前破裂发生。
本发明添加微胶囊自修复层的纤维金属层板的制备方法,具体包括以下步骤:
1)金属基体的处理:选择铝合金或钛等金属基体,首先进行脱油处理。将金属试样放置于丙酮溶液中,在60℃的水浴中处理20分钟,然后用清水清洗。接着,使用细砂纸和粗砂纸进行打磨,提高金属基体的表面粗糙度,增大粘接面积。
2)纤维预浸料层的选择:选择环氧树脂基碳纤维预浸料作为纤维预浸料。由于采用环氧树脂基体,因此界面增强薄膜层2无需采用耐高温的聚合物材料,可以选择具有良好热稳定性和化学稳定性的聚酰亚胺薄膜。
3)微胶囊的制备:为减少树脂中孔隙的含量,提高致密性,制备的微胶囊粒径需要足够小。采用微乳液体系结合界面聚合工艺制备聚氨酯微胶囊。预聚体制作:准备质量比例为1:6.5:0.2的对甲苯二异氰酸酯、环己酮、丁二醇,将对甲苯二异氰酸酯溶解于环己酮溶液中,在缓慢倒入丁二醇的同时对溶液进行70℃的加热搅拌,待充分反应后,蒸馏得到预聚体;
将异佛尔酮二异氰酸酯(IPDI)作为芯材和预聚体按3.5:1的比例溶解在乙酸乙酯中,形成油相,并进行充分搅拌;
将去离子水和乳化剂(天然乳化剂O/W)混合并充分搅拌,形成乳液;
将油相以适当速度加入乳液中,形成水包油型(O/W)乳化体系;
然后缓慢加入丁二醇,将整个体系升温至60℃并以1500转/分钟搅拌1.5小时,得到微胶囊悬浮液;
经过洗涤、抽滤和真空干燥后,得到符合要求的(直径为2到5微米的微胶囊)微胶囊试样。
4)微胶囊涂层的制备:将微胶囊试样与环氧树脂基清漆混合,其中微胶囊试样所占的质量分数为1.5wt%,混合之后将其涂覆于纤维预浸料层上,并待其干燥。
5)成形与固化:将含有微胶囊涂层的纤维预浸料层与聚酰亚胺薄膜和金属基体放置于真空袋中,进行热压固化(130-140℃),直至形成所需的形状,获得添加微胶囊自修复层的纤维金属层板。在该过程中,施加一定的压力,但不会造成微胶囊壳体破裂或IPDI芯材泄露。
本发明未述及之处适用于现有技术。
Claims (7)
1.一种添加微胶囊自修复层的纤维金属层板,包括金属基体层、界面增强薄膜层和纤维预浸料层,其特征在于,所述纤维金属层板还包括微胶囊涂层,层板采用金属基体层/界面增强薄膜层/微胶囊涂层/纤维预浸料层/微胶囊涂层/界面增强薄膜层/金属基体层的结构进行交替铺层。
2.根据权利要求1所述的纤维金属层板,其特征在于,纤维金属层板中纤维铺设角度为0°、90°、±45°;
所述金属基体层为铝合金、镁合金、钛合金中的至少一种,厚度不大于0.5毫米;
所述纤维预浸料层由纤维和树脂构成,所述纤维为玻璃纤维、碳纤维、芳纶纤维中的至少一种;所述树脂为热固性环氧树脂;
所述界面增强薄膜层采用可塑性材料,包括聚合物薄膜或者聚合物基复合材料;
所述微胶囊涂层由喷涂或者涂覆方式均匀地覆盖在纤维预浸料层的正反面上,所述微胶囊涂层由微米级微胶囊通过搅拌或超声分散在环氧树脂基清漆中再经过喷涂或涂覆形成;所述微米级微胶囊为球形,且为核壳结构。
3.根据权利要求1所述的纤维金属层板,其特征在于,所述微米级微胶囊的平均直径为2-5μm,微米级微胶囊在环氧树脂基清漆中无团聚现象,能够均匀分散在纤维预浸料层上。
4.根据权利要求1所述的纤维金属层板,其特征在于,所述微胶囊内封装化合物为异氰酸酯(IPDI),胶囊壳材质为聚氨酯,微米级微胶囊占环氧树脂基清漆的质量分数为1-5wt%,优选质量分数为1.5wt%;所述微胶囊涂层厚度为几十微米;当在外界应力作用下,界面层出现裂纹破坏时,微胶囊破裂,其内部自愈合物质—异氰酸酯(IPDI)被释放出来,异氰酸酯(IPDI)中的异氰基(NCO)与微胶囊涂层中的环氧树脂中的环氧基发生加成反应,形成尿素键或者尿酰基键;当异氰酸酯与环氧树脂接触时,异氰酸酯中的NCO基团与环氧树脂中的环氧基发生反应,产生化学键;反应后,异氰酸酯与环氧树脂发生化学结合,形成一个新的交联网络,从而达到修补环氧树脂基质的目的,同时破碎的微胶囊壳还能在结构弯曲时在纵向上促进嵌锁效应。
5.根据权利要求1所述的纤维金属层板,其特征在于,在层板受到剪切拉伸或者压缩载荷时,添加的微胶囊涂层会提供额外的粘结力保护,微胶囊通过机械刺激打开,其中封装的修复剂会释放到微胶囊涂层中或者相邻层的界面结合处,通过填补裂纹形成类榫卯结构来抑制裂纹传播并且通过在界面结合处形成新的粘结层,促进裂隙粘合来抵抗外部机械载荷破坏致使的分层脱粘情况。
6.一种添加微胶囊自修复层的纤维金属层板的制备方法,其特征在于,所述制备方法包括以下步骤:
1)金属基体的处理:对金属基体进行脱油处理,接着,使用细砂纸和粗砂纸进行打磨,提高金属基体的表面粗糙度,增大粘接面积;
2)纤维预浸料层的选择:选择环氧树脂基纤维预浸料,界面增强薄膜层选择具有良好热稳定性和化学稳定性的聚酰亚胺薄膜;
3)微胶囊的制备:采用微乳液体系结合界面聚合工艺制备聚氨酯微胶囊,包括:
预聚体制作:准备质量比例为1:6.5:0.2的对甲苯二异氰酸酯、环己酮、丁二醇,将对甲苯二异氰酸酯溶解于环己酮中,在缓慢倒入丁二醇的同时对溶液进行60-80℃的加热搅拌,待充分反应后,蒸馏得到预聚体;
将异佛尔酮二异氰酸酯(IPDI)作为芯材和预聚体按3.5:1的比例溶解在乙酸乙酯中,形成油相,并进行充分搅拌;
将去离子水和乳化剂混合并充分搅拌,形成乳液;
将油相以加入乳液中,形成水包油型(O/W)乳化体系;
然后缓慢加入丁二醇,将整个体系升温至60℃并以1500转/分钟搅拌1.5小时,得到微胶囊悬浮液;
经过洗涤、抽滤和真空干燥后,得到直径为2~5μm的微胶囊试样;
4)微胶囊涂层的制备:将微胶囊试样与环氧树脂基清漆混合,其中微胶囊试样所占的质量分数为1.5wt%,混合之后将其涂覆于纤维预浸料层上,并干燥;
5)成形与固化:将含有微胶囊涂层的纤维预浸料层与聚酰亚胺薄膜和金属基体放置于真空袋中,进行热压固化,直至形成所需的形状,获得添加微胶囊自修复层的纤维金属层板。
7.根据权利要求1所述的制备方法,其特征在于,所述热压固化温度为130-140℃,所施加的压力不会造成微胶囊壳体破裂或IPDI芯材泄露。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311156992.2A CN117246004A (zh) | 2023-09-08 | 2023-09-08 | 一种添加微胶囊自修复层的纤维金属层板及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311156992.2A CN117246004A (zh) | 2023-09-08 | 2023-09-08 | 一种添加微胶囊自修复层的纤维金属层板及其制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN117246004A true CN117246004A (zh) | 2023-12-19 |
Family
ID=89134153
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311156992.2A Pending CN117246004A (zh) | 2023-09-08 | 2023-09-08 | 一种添加微胶囊自修复层的纤维金属层板及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN117246004A (zh) |
-
2023
- 2023-09-08 CN CN202311156992.2A patent/CN117246004A/zh active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104842619B (zh) | 高韧性多层结构预浸料制造工艺 | |
US6045898A (en) | Resin compositions for fiber-reinforced composite materials and processes for producing the same, prepregs, fiber-reinforced composite materials, and honeycomb structures | |
Sanada et al. | Transverse tensile strength of unidirectional fibre-reinforced polymers and self-healing of interfacial debonding | |
JP4126978B2 (ja) | プリフォームおよびそれからなるfrpならびにfrpの製造方法 | |
CN103154129B (zh) | 环氧复合材料 | |
EP1408152A1 (en) | Carbon fiber reinforced base material, preform and composite material comprising the same | |
JP6239347B2 (ja) | 複合材接合システムおよび方法 | |
JPH04312237A (ja) | 積層型制振材料および該制振材料を内層に有する繊維 強化複合材料ならびにその作製方法 | |
Pittala et al. | Self-healing of matrix cracking and delamination damage assessment in microcapsules reinforced carbon fibre epoxy composite under flexural loading | |
EP2551093B1 (en) | Healable composite materials based on reversible binder systems | |
CN117246004A (zh) | 一种添加微胶囊自修复层的纤维金属层板及其制备方法 | |
JPH0625446A (ja) | クロスプリプレグおよびその製造法 | |
JPH0740491A (ja) | 自己修復性積層構造体及びその製造方法 | |
CN110819071B (zh) | 海洋开发装备用常温自修复型固体浮力材料及其制备方法 | |
CN116925325A (zh) | 一种胶囊型固化剂、固化自调控型纤维网格及其施工方法 | |
JPS6063229A (ja) | 改良した圧縮特性を有するインタ−リ−フした樹脂マトリツクス複合材料 | |
JP4609513B2 (ja) | プリフォームの製造方法 | |
Kumar et al. | Self‐Healing Materials in Aerospace Applications | |
Kumar et al. | Self-healing fiber-reinforced epoxy composites | |
Chen et al. | Interfacial toughening and bending performance of the CFRP/aluminum-honeycomb sandwich | |
Saeed et al. | Self-healing of low-velocity impact and mode-I delamination damage in polymer composites via microchannels | |
CN110951217B (zh) | 一种芳纶纤维增强碳纤维树脂预浸料及其制备方法 | |
US5021270A (en) | Method for improving moisture barrier protection and electrostatic discharge protection of a composite material cased rocket motor | |
Liu et al. | Bio-inspired helicoidal thin-ply carbon fiber reinforced epoxy laminates with nylon microparticles for improved toughness and healing | |
Shankar Rai et al. | Developments and Prospects of Self-Healing Design for Hierarchical Carbon Fiber Reinforced Polymer Composites |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |