CN105506962B - 用于纳米粒子改性碳纤维上浆剂的增容方法 - Google Patents
用于纳米粒子改性碳纤维上浆剂的增容方法 Download PDFInfo
- Publication number
- CN105506962B CN105506962B CN201510976902.3A CN201510976902A CN105506962B CN 105506962 B CN105506962 B CN 105506962B CN 201510976902 A CN201510976902 A CN 201510976902A CN 105506962 B CN105506962 B CN 105506962B
- Authority
- CN
- China
- Prior art keywords
- nano
- poss
- particle
- sizing agent
- carbon fiber
- 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.)
- Active
Links
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 64
- 238000004513 sizing Methods 0.000 title claims abstract description 58
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000002105 nanoparticle Substances 0.000 claims abstract description 44
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 20
- 239000003822 epoxy resin Substances 0.000 claims abstract description 19
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 239000000839 emulsion Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- -1 POSS Substances 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims 2
- 238000012545 processing Methods 0.000 abstract description 6
- 239000004067 bulking agent Substances 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000007822 coupling agent Substances 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 38
- 239000004917 carbon fiber Substances 0.000 description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 239000000835 fiber Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 238000009955 starching Methods 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000005543 nano-size silicon particle Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- APIBTMSFBUJAAC-UHFFFAOYSA-N 307531-92-6 Chemical group O1[Si](O)(CC(C)C)O[Si](O2)(CC(C)C)O[Si](O)(CC(C)C)O[Si]3(CC(C)C)O[Si](CC(C)C)(O)O[Si]1(CC(C)C)O[Si]2(CC(C)C)O3 APIBTMSFBUJAAC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
本发明公开了一种用于纳米粒子改性碳纤维上浆剂的增容方法,所述增容方法步骤如下:(1)将纳米粒子、POSS和催化剂共同溶于有机溶剂中,采用超声处理5~20min,得到纳米粒子分散液;(2)将步骤一中的纳米粒子分散液和环氧树脂、乳化剂混合均匀,经减压蒸馏除去其中的有机溶剂,采用相反转法制备得到相应的上浆剂乳液。本发明将POSS和纳米粒子同时引入到上浆剂中,能够综合二者的优点,可解决纳米粒子在上浆剂中相容性差,容易团聚和破乳的问题,同时相比传统的包覆改性和偶联剂改性,采用POSS作为增容剂处理方式简单,且拥有更加优异的耐热性能。
Description
技术领域
本发明涉及一种用于纳米粒子改性碳纤维上浆剂的增容方法。
背景技术
碳纤维凭借其优异的性能以及在国防军工方面的广阔应用前景,已经成为各国竞相研究开发的重要战略性物资。碳纤维中占95%以上的都是碳,但是由于其具有特殊的乱层石墨结构,其比强度和比模量甚至高于钢铁等传统金属材料,同时其还兼具耐腐蚀、抗老化等特点,因此碳纤维增强树脂基复合材料首先在对质量有严格要求的航空航天、武器装备等领域得到了应用。随着碳纤维生产技术的日益成熟,以及民用领域对材料性能要求的进一步提高,碳纤维的应用逐渐由航空航天向汽车制造、风力发电、医疗卫生、土木建筑以及高档体育用品等民用领域发展。目前碳纤维制品已经深入到我们日常生活的方方面面,比如自行车、羽毛球拍、汽车轮毂、风机叶片等等,但是相对来说碳纤维制品的成本依然居高不下,因此碳纤维制品要完全进入民用领域还有待进一步发展,不过即便如此,碳纤维在当今社会仍然具有无限广阔的发展前景,在未来必将得到更加广泛的应用。
碳纤维的工业生产加工过程十分复杂,主要包括PAN原丝的预氧化、低温碳化、高温碳化、石墨化、阳极氧化、上浆处理等过程。在工业生产线上,碳纤维都由导辊牵引,由于碳纤维脆性大,易与导辊摩擦而出现毛丝、劈丝或断丝等现象;另外阳极氧化处理后的碳纤维表面容易发生退化效应。这些方面会严重影响碳纤维丝束的性能,影响最终制品的质量。同时碳纤维断裂后漂浮在空气中,严重影响工作环境,更有可能导致电气设备短路而造成安全事故。因此必须要对碳纤维进行上浆处理。上浆剂的作用相当于在纤维表面形成了一层厚度约为几十到几百纳米的保护膜,使纤维在受机械摩擦的过程中减少毛丝及断丝的产生。上浆剂含量虽然只占碳纤维总重的1%左右,但是其作用却不可小觑。目前认为,碳纤维上浆剂具体有如下五个方面的作用:(1)提高碳纤维的集束性;(2)提高耐磨性,改善工艺;(3)改善界面,如在纤维表面引入活性基团,提高碳纤维与树脂基体间的浸润性;(4)提高耐环境性;(5)提高耐冲击性能和强度,如采用纳米SiO2补强。
传统的碳纤维上浆剂一般是将树脂分散在丙酮等有机溶剂中制备而成,按所用树脂的种类可以分为醋酸乙烯树脂型、环氧树脂型、聚氨酯型、酚醛树脂型、丙烯酸酯树脂型等。而随着社会环保意识的加强,传统的溶剂型碳纤维上浆剂逐渐被低VOC的乳液型碳纤维上浆剂所取代。乳液型碳纤维上浆剂是将主体树脂以乳液的形式分散在水中制备而成,目前主要以环氧树脂系列的乳液型碳纤维上浆剂为主,所使用的乳化剂一般分为阴离子乳化剂、阳离子乳化剂、非离子型乳化剂和两性乳化剂。相比于溶剂型上浆剂,乳液型上浆剂具有更加好的上浆效果和工艺性能,且不易燃烧,使用过程中没有溶剂挥发,但是由于乳液型碳纤维上浆剂在乳化的过程中要加入大量的乳化剂,其耐热性能往往会有所下降,因此如何提高乳液型碳纤维上浆剂的耐热性能,使其能够满足高温条件下使用的要求,对提高碳纤维增强树脂基复合材料的耐高温性能,拓展其在外太空等苛刻条件下的使用范围具有非常重要的科研价值和工业价值。
POSS(多面体低聚倍半硅氧烷)是国际上广泛关注的一类高聚物改性纳米材料,其由硅氧键连接的无机核和有机基团组成,POSS本身具有有机-无机杂化的笼形分子结构,其既和聚合物有很好的亲和性,又具有无机材料耐高温的特点,同时其还有类似于小分子的反应活性,因此很容易将其引入到聚合物体系中,用于改善聚合物的各种性能。根据POSS的结构特点,可以将POSS分为无规、梯形、桥型、笼型等,其中笼型POSS又有封闭型和开口型之分。开口型的POSS同时具有亲油的有机基团和亲水的硅羟基,因此具有一定的表面活性,利用亲水性的硅羟基对纳米粒子的吸附作用能够轻易的实现对纳米粒子的亲油改性。同时POSS的笼型结构能够有效限制分子链的运动,从而影响高分子的热性能。此外POSS在高温条件下发生热分解后,形成致密的二氧化硅包覆在高分子链上,可以起到阻燃和提高高聚物热分解温度的作用。
采用纳米粒子对碳纤维上浆剂进行改性是比较常见的改性方法。中国科学院山西煤炭化学研究所的杨禹等人采用纳米SiO2对乳液型碳纤维上浆剂进行改性,研究了纳米SiO2加入对上浆剂性能的影响,他们发现纳米SiO2的加入改善了上浆剂的上浆效果。研究表明,SiO2的加入能够明显提高碳纤维上浆后的表面能,增强了碳纤维和基体之间的锚定作用和化学粘接作用,使界面之间产生更加紧密的粘接,IFSS测试结果显示,SiO2改性上浆剂对纤维进行上浆后,纤维的IFSS提高了79%。同时他们还对上浆后的碳纤维的断裂行为进行了系统的研究,研究表明,和未加纳米SiO2的上浆剂相比,其上浆后的纤维的断裂过程表现为韧性断裂,且使纤维的强度明显提高。但是纳米二氧化硅的加入一方面会增加树脂的粘度,影响相反转乳化工艺;另一方面,亲水性的纳米二氧化硅和环氧树脂的相容性差,极易发生团聚,影响上浆剂的性能。采用硅烷偶联剂来处理纳米二氧化硅从而增加其和环氧树脂的亲和性是解决纳米二氧化硅团聚问题的有效方法,但是硅烷偶联剂本身耐热性差,会对上浆剂的耐热性能造成影响。
哈尔滨工业大学的赵峰博士系统地研究了POSS加入到溶剂型环氧树脂碳纤维上浆剂中对碳纤维上浆效果的影响。研究表明,当上浆剂中POSS的质量百分含量为0.5%时具有最好的上浆效果,POSS在碳纤维表面形成的晶粒大小均匀,不存在大量的团聚现象。由于POSS的存在能对材料中的裂纹起到诱导、偏转和阻碍的作用,当上浆剂中含有POSS时所制备的碳纤维复合材料的冲击强度和界面粘接强度最高。同时,实验还比较了阳极氧化和含POSS上浆剂处理对碳纤维表面性能的影响,研究发现单纯的含POSS上浆剂对碳纤维性能的改善效果并不如阳极氧化,但是将两种方法结合,能够获得最佳的改性效果。
发明内容
为了解决使用纳米粒子改性碳纤维上浆剂过程中,纳米粒子和树脂之间的相容性差、容易团聚的问题,本发明提供了一种用于纳米粒子改性碳纤维上浆剂的增容方法,该方法可在不影响上浆剂耐热性的前提下,实现纳米粒子的增容,能够应用于纳米粒子改性碳纤维上浆剂的过程中。
本发明的目的是通过以下技术方案实现的:
一种用于纳米粒子改性碳纤维上浆剂的增容方法,包括如下两种技术方案:
技术方案一、两步法:
(1)制备纳米粒子分散液
将纳米粒子、POSS和催化剂共同溶于有机溶剂中,控制纳米粒子和POSS的质量比为100:10~50,催化剂加入量为纳米粒子和POSS总质量的0~3%,采用超声处理5~20min,得到纳米粒子分散液;
(2)制备上浆剂
将步骤一中的纳米粒子分散液和环氧树脂、乳化剂混合均匀,控制纳米粒子和POSS的混合物与环氧树脂、乳化剂的质量比为1~20:100:20~50,经减压蒸馏除去其中的有机溶剂,采用相反转法制备得到相应的上浆剂乳液。
技术方案二、一步法:
将纳米粒子、POSS、环氧树脂和乳化剂共同溶解在有机溶剂中,控制纳米粒子和POSS的质量比为100:10~50,纳米粒子和POSS的混合物与环氧树脂、乳化剂的质量比为1~20:100:20~50。
本发明中,所述的纳米粒子为纳米SiO2、纳米TiO2或者纳米ZnO等。
本发明中,所述的POSS为开口型POSS,例如:TriSilanollsobutyl POSS(SO1450)、TriSilanollsooctyl POSS(SO1455)或TrisilanolPhenyl POSS(SO1458),其分子结构如图1所示。
本发明中,所述的有机溶剂为丙酮、丁酮、四氢呋喃或甲苯。
本发明中,所述催化剂为盐酸,加入量为纳米粒子和POSS总质量的0.5~3%。
开口型POSS的硅羟基对多种纳米粒子都具有较强的吸附特性,从而在纳米粒子表面实现定向排列,使纳米粒子具有亲油特性,且能够在纳米粒子表面形成稳定的隔离层,从而使纳米粒子能够稳定的存在于树脂基体之中而不发生团聚。本发明将POSS和纳米粒子同时引入到上浆剂中,能够综合二者的优点,制备得到稳定性和耐热性优异的碳纤维上浆剂。
相比于现有技术,本发明具有如下优点:
1、实施过程中不发生化学反应,操作方式简单;
2、可以实现对多种纳米粒子的增容,没有特定的选择性;
3、能够提高碳纤维上浆剂的耐热性能;
4、将POSS引入到上浆剂中能够改善碳纤维的界面性能;
5、可解决纳米粒子在上浆剂中相容性差,容易团聚和破乳的问题,同时相比传统的包覆改性和偶联剂改性,采用POSS作为增容剂处理方式简单,且拥有更加优异的耐热性能。
附图说明
图1为开口型POSS的分子结构;
图2为POSS在玻璃表面成膜后的接触角测量;
图3为纳米SiO2和POSS按质量比100:10的分散液在玻璃表面成膜后的接触角测量;
图4为纳米SiO2和POSS按质量比100:50的分散液在玻璃表面成膜后的接触角测量;
图5为纳米TiO2和POSS按质量比100:50的分散液在玻璃表面成膜后的接触角测量;
图6为纳米粒子改性碳纤维上浆剂的耐热性能。
具体实施方式
下面结合附图对本发明的技术方案作进一步的说明,但并不局限于此,凡是对本发明技术方案进行修改或者等同替换,而不脱离本发明技术方案的精神和范围,均应涵盖在本发明的保护范围中。
具体实施方式一:本实施方式提供的用于纳米粒子改性碳纤维上浆剂的增容方法分如下两步进行:
一、将100质量份纳米SiO2和10质量份SO1458 POSS共同溶于丙酮中,采用超声分散15分钟,得到纳米SiO2分散液,将该分散液铺展在玻璃片上进行接触角测试如图2-3所示。由图2可知,POSS在玻璃表面成膜,水的接触角为90°;由图3可知,分散液在玻璃表面成膜,水的接触角为130°。
二、将第一步中的分散液和环氧树脂、乳化剂混合均匀,控制纳米SiO2和SO1458POSS的混合物与环氧树脂、乳化剂的质量比为15:100:50,减压蒸馏除去其中的有机溶剂,采用相反转法制备得到相应的上浆剂乳液。
具体实施方式二:本实施方式与具体实施方式一不同的是,步骤一中SO1458 POSS的用量为50质量份,其他内容与具体实施方式一相同。由图4可知,分散液在玻璃表面成膜,水的接触角为139°。
具体实施方式三:本实施方式与具体实施方式一不同的是,步骤一中SiO2的用量为50质量份,其他内容与具体实施方式一相同。由图6可知,对含不同比例的纳米SiO2和POSS的上浆剂的热失重分析可以看出,POSS的引入可以提高纳米SiO2改性碳纤维上浆剂的耐热性能。
具体实施方式四:本实施方式与具体实施方式一不同的是,步骤一中所使用的POSS的类型为SO1450,所使用的有机溶剂为四氢呋喃,其他内容与具体实施方式一相同。
具体实施方式五:本实施方式与具体实施方式二不同的是,步骤一中所使用的纳米粒子为纳米TiO2,其他内容与具体实施方式二相同。由图5可知,分散液在玻璃表面成膜,水的接触角为139°。
具体实施方式六:本实施方式与具体实施方式一不同的是,步骤一中先将10质量份的POSS溶解在丙酮中,然后向溶液中加入100质量份的纳米SiO2,其他内容与具体实施方式一相同。
具体实施方式七:本实施方式提供的用于纳米粒子改性碳纤维上浆剂的增容方法分如下两步进行:
一、将100质量份的纳米SiO2和10质量份的SO1458 POSS共同溶于丁酮中,采用超声分散15分钟,得到纳米SiO2分散液。将该分散液置于三口瓶中,并加入盐酸溶液作催化剂,其加入量为纳米SiO2和SO1458 POSS总质量的1%,在70℃的条件下搅拌反应6小时。
二、将第一步中反应后得到的分散液和环氧树脂、乳化剂混合均匀,控制纳米SiO2和SO1458 POSS的混合物与环氧树脂、乳化剂的质量比为15:100:50,减压蒸馏除去其中的有机溶剂,采用相反转法制备得到相应的上浆剂乳液。
具体实施方式八:本实施方式与具体实施方式七不同的是,不加入盐酸作为催化剂,其他内容与具体实施方式七相同。
具体实施方式九:本实施方式提供的用于纳米粒子改性碳纤维上浆剂的增容方法按一步进行:
将纳米SiO2、SO1458 POSS、环氧树脂和乳化剂共同溶解在丙酮中,控制纳米SiO2和SO1458 POSS的质量比为100:10,纳米粒子和POSS的混合物与环氧树脂、乳化剂的质量比为20:100:50,采用超声处理20min后经减压蒸馏除去丙酮,然后采用相反转法制备得到相应的上浆剂乳液。
Claims (6)
1.一种用于纳米粒子改性碳纤维上浆剂的增容方法,其特征在于所述增容方法步骤如下:
(1)制备纳米粒子分散液
将纳米粒子、POSS和催化剂共同溶于有机溶剂中,控制纳米粒子和POSS的质量比为100:10~50,催化剂加入量为纳米粒子和POSS总质量的0~3%,采用超声处理5~20min,得到纳米粒子分散液;所述纳米粒子为纳米SiO2、纳米TiO2或者纳米ZnO;所述POSS为开口型POSS;
(2)制备上浆剂
将步骤一中的纳米粒子分散液和环氧树脂、乳化剂混合均匀,控制纳米粒子和POSS的混合物与环氧树脂、乳化剂的质量比为1~20:100:20~50,经减压蒸馏除去其中的有机溶剂,采用相反转法制备得到相应的上浆剂乳液。
2.根据权利要求1所述的用于纳米粒子改性碳纤维上浆剂的增容方法,其特征在于所述有机溶剂为丙酮、丁酮、四氢呋喃或甲苯。
3.根据权利要求1所述的用于纳米粒子改性碳纤维上浆剂的增容方法,其特征在于所述催化剂为盐酸。
4.根据权利要求1或3所述的用于纳米粒子改性碳纤维上浆剂的增容方法,其特征在于所述催化剂的加入量为纳米粒子和POSS总质量的0.5~3%。
5.一种用于纳米粒子改性碳纤维上浆剂的增容方法,其特征在于所述增容方法步骤如下:
将纳米粒子、POSS、环氧树脂和乳化剂共同溶解在有机溶剂中,控制纳米粒子和POSS的质量比为100:10~50,纳米粒子和POSS的混合物与环氧树脂、乳化剂的质量比为1~20:100:20~50;所述纳米粒子为纳米SiO2、纳米TiO2或者纳米ZnO;所述POSS为开口型POSS。
6.根据权利要求5所述的用于纳米粒子改性碳纤维上浆剂的增容方法,其特征在于所述有机溶剂为丙酮、丁酮、四氢呋喃或甲苯。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510976902.3A CN105506962B (zh) | 2015-12-23 | 2015-12-23 | 用于纳米粒子改性碳纤维上浆剂的增容方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510976902.3A CN105506962B (zh) | 2015-12-23 | 2015-12-23 | 用于纳米粒子改性碳纤维上浆剂的增容方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105506962A CN105506962A (zh) | 2016-04-20 |
CN105506962B true CN105506962B (zh) | 2018-04-17 |
Family
ID=55715242
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510976902.3A Active CN105506962B (zh) | 2015-12-23 | 2015-12-23 | 用于纳米粒子改性碳纤维上浆剂的增容方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105506962B (zh) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107130433A (zh) * | 2017-04-21 | 2017-09-05 | 闫博文 | 一种耐高温碳纤维上浆剂的制备方法 |
CN107629224B (zh) * | 2017-10-31 | 2020-06-09 | 河北工业大学 | 双上浆剂改性碳纤维增强环氧树脂基复合材料的制备方法 |
CN109208320A (zh) * | 2018-07-12 | 2019-01-15 | 北京化工大学 | 一种干喷湿纺碳纤维的表面处理方法 |
CN108930190B (zh) * | 2018-08-08 | 2021-12-07 | 东莞市白天鹅纸业有限公司 | 一种无机纤维柔软剂及其制备方法 |
CN109505048B (zh) * | 2018-12-18 | 2020-04-03 | 上海兆妩品牌管理有限公司 | 基于超细桑蚕丝纤维/柞蚕丝纤维的真丝围巾面料 |
CN110079993B (zh) * | 2019-04-28 | 2021-09-17 | 陕西科技大学 | 一种二氧化锆/氧化石墨烯表面改性碳纤维的方法 |
CN115109471A (zh) * | 2022-07-05 | 2022-09-27 | 江西晨光新材料股份有限公司 | 一种改性二氧化硅气凝胶保温隔热涂料及其制备方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1271276C (zh) * | 2004-12-07 | 2006-08-23 | 中国科学院山西煤炭化学研究所 | 一种纳米SiO2改性碳纤维乳液上浆剂的制备方法 |
CN103451951A (zh) * | 2012-06-01 | 2013-12-18 | 中国石油天然气股份有限公司 | 一种碳纤维上浆剂的制备方法 |
CN103755898B (zh) * | 2014-02-11 | 2016-01-06 | 厦门大学 | 一种poss改性纳米粒子的制备方法 |
CN103991876B (zh) * | 2014-05-06 | 2016-11-02 | 上海大学 | 有机改性的二氧化硅溶胶及其制备方法 |
CN104389175A (zh) * | 2014-11-03 | 2015-03-04 | 哈尔滨工业大学 | 纳米SiO2改性乳液型碳纤维上浆剂及其制备方法 |
CN104389167A (zh) * | 2014-11-03 | 2015-03-04 | 哈尔滨工业大学 | 一种含有纳米粒子的涂层溶液及其应用 |
CN105064030A (zh) * | 2015-08-19 | 2015-11-18 | 国网智能电网研究院 | 一种碳纤维上浆剂及其制备方法 |
-
2015
- 2015-12-23 CN CN201510976902.3A patent/CN105506962B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
CN105506962A (zh) | 2016-04-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105506962B (zh) | 用于纳米粒子改性碳纤维上浆剂的增容方法 | |
CN105178025B (zh) | 一种耐高温型纳米poss改性环氧乳液碳纤维上浆剂的制备方法 | |
CN104151581B (zh) | 碳纤维/氧化石墨烯/有机硅树脂多维混杂复合材料的制备方法 | |
CN108035143B (zh) | 一种同时提高碳纤维环氧复合材料界面强度和韧性的方法 | |
CN105297448B (zh) | 一种碳纤维用界面增强型纳米二氧化硅改性环氧树脂上浆剂 | |
CN110172180B (zh) | 无机纤维/二氧化硅纳米材料及其制备方法和应用 | |
CN105064030A (zh) | 一种碳纤维上浆剂及其制备方法 | |
Zhang et al. | The effects of chemical grafting 1, 6-hexanediol diglycidyl ether on the interfacial adhesion between continuous basalt fibers and epoxy resin as well as the tensile strength of composites | |
CN102134394B (zh) | 一种芳纶浆粕分散体及其制备方法 | |
CN105153865B (zh) | 一种改性纳米SiO2/环氧‑丙烯酸酯复合材料的制备方法 | |
Li et al. | Improving the interfacial properties of carbon fiber–epoxy resin composites with a graphene‐modified sizing agent | |
Kerche et al. | Ionic liquid‐functionalized reinforcements in epoxy‐based composites: A systematic review | |
Yuan et al. | Nanoscale toughening of carbon fiber‐reinforced epoxy composites through different surface treatments | |
Zhou et al. | Synthesis and properties of fluorine–silicon modified polyacrylate hybrid latex particles with core–shell structure obtained via emulsifier‐free emulsion polymerization | |
Song et al. | Aramid fiber coated with aramid nanofiber coating to improve its interfacial properties with polycarbonate | |
Singh et al. | Effect of silanizion on mechanical and tribological properties of kenaf-carbon and kenaf-glass hybrid polymer composites | |
CN114015198B (zh) | 一种优化工艺的中温固化预浸料环氧树脂的制备方法 | |
Hu et al. | Layer-by-layer assembling MXene/poly (3-glycidyloxypropyldimethoxymethylsilane) hierarchical structure onto carbon fibers for high-performance carbon fiber/epoxy composites | |
CN108084677A (zh) | 一种耐热麻纤维增强聚乳酸复合材料的制备方法 | |
Liu et al. | Effect of sizing agent on properties of basalt fiber/blended resin matrix composites | |
Zhang et al. | Effect of graphene oxide on tensile and flexural properties of carbon/glass hybrid fiber‐reinforced polymer composite | |
Lu et al. | Improving interfacial strength of epoxy composites by constructing “palm‐tree”‐like structure on carbon fiber | |
Wang et al. | Mechanical performance of nanosilica filled quartz fiber/polyimide composites at room and elevated temperatures | |
CN109972397A (zh) | 原位合成纳米氧化物增强碳纤维上浆剂和玄武岩纤维浸润剂的制备及应用 | |
Liu et al. | Improvement of the interfacial shear strength of poly (p‐phenylene benzobisoxazole) fiber/epoxy resin composite via a novel surface coating agent |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |