CN100500979C - Metal-coated polymer fiber and preparing method - Google Patents
Metal-coated polymer fiber and preparing method Download PDFInfo
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- CN100500979C CN100500979C CNB2007100994727A CN200710099472A CN100500979C CN 100500979 C CN100500979 C CN 100500979C CN B2007100994727 A CNB2007100994727 A CN B2007100994727A CN 200710099472 A CN200710099472 A CN 200710099472A CN 100500979 C CN100500979 C CN 100500979C
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Abstract
One metal cover high macromolecule fiber and the preparation method. The metal cover high macromolecule fiber using at least one one of gathers phenylene benzene double wicked zuo fiber, the fragrant textile fiber, the superelevation molecular weight polyethylene fiber, the spider web in and so on as the substrate, and using at least one of nanometer titanium dioxide, nanometer silica, nanometer magnesia, nanometer zinc oxide, nanometer aluminum oxide, nanometer zirconium oxide, nanometer nickel oxide, nanometer cobalt blue and so on as modified material. Use soaks spreading method to cover the high macromolecule as the transitional layer in nanometer inorganic powder, then uses the chemical plating method in the nanometer inorganic powder body gable high polymer fibrous composite surface loading metal, the development metal gable high polymer fibrous composite. The advevtage, has a lighter quality compared to the traditional metal micro silk, a higher intensity and the durability as well as the better flexible metal cover high polymer fibrous composite.
Description
Technical field
The invention belongs to the advanced composite material technical field, particularly a kind of metal-coated polymer fiber and preparation method thereof.
Background technology
Metal fibril has that size is tiny, high strength, high temperature resistant, stability good, series of advantages such as in light weight, is widely used in every field such as Aero-Space, electronic information, communications and transportation, petrochemical industry, defence and military and daily life.But along with science and technology development, traditional metal fibril exposes problems such as density is higher, poor seismic behavior, intensity is still on the low side, is difficult to satisfy the diversity demand of civilian high-technology field and defence and military construction development.
Macromolecule fibers such as polyparaphenylene's benzo-dioxazole (PBO) fiber, aramid fiber, superhigh molecular weight polyethylene fibers, spider silk have high specific strength, specific modulus and a series of excellent properties such as high temperature resistant, national economy and defence and military every field of many uses [the PBO polymer fiber material of Wu state plum .21 century very-high performance. tec fiber and application, 2002,27 (3): 15-18].But above-mentioned macromolecular fibre smooth surface and active low is not suitable for it is directly prepared high-performance composite materials as wild phase, and macromolecular fibre do not have performances such as the good conduction of metal fibril, heat conduction, has influenced the extensive use of macromolecular fibre.Therefore, with high performance macromolecular fibre is matrix, realize the load of metal on the macromolecular fibre surface, develop performances such as the conduction that both has metal fibril, heat conduction, have the metal-coated polymer fiber composite of the good characteristic such as high specific strength, high ratio modulus of macromolecular fibre again, significant.
Up to now, around polymer surface clad nano inorganic particle and at the more existing reports of the research of nano inorganic powder area load metal.As people clad nano TiO on spider silk such as Junhui He
2Powder [Junhui He, Toyoki Kunitake.Preparation and thermalstability of gold nanoparticles in silk-templated porous filaments of titaniaand zirconia.Chemistry of Materials, 2004,16:2656-2661], people such as Baomei Wen are to monocrystalline phase nano-TiO
2Carried metal on the powder line [Baomei Wen, Chunyan Liu, Yun Liu.Depositional characteristics of metal coating on single-crystal TiO
2Nanowires.American Chemical Society, 2005,109 (12): 372-375].But because the binding ability between macromolecular fibre and the metal is very poor, open report is not seen in the research of at present relevant metal-coated polymer fiber Composite Preparation aspect as yet.
Summary of the invention
The object of the present invention is to provide a kind of metal-coated polymer fiber and preparation method thereof, utilize the characteristics such as high strength, high tenacity, low-density of the performance such as electricity, magnetic and heat conduction of clad metal and matrix macromolecular fibre, exploitation has lighter quality, higher intensity and durability and better flexible metal-coated polymer fiber composite than traditional metal fibril.
Metal-coated polymer fiber of the present invention is with polyparaphenylene's benzo-dioxazole (PBO) fiber, aramid fiber, superhigh molecular weight polyethylene fibers, at least a macromolecular fibre in the spider silk etc. is a matrix, with nano titanium oxide, nano silicon oxide, nano magnesia, nano zine oxide, nano aluminium oxide, nano zircite, nano-nickel oxide, at least a nano inorganic powder in the nanometer cobalt oxide etc. is as material modified, adopt the immersion coating method to coat one deck nano inorganic powder film as transition zone on the macromolecular fibre surface, adopt electroless plating method at nano inorganic powder coated high molecular fiber composite material surface carried metal then, development of metallic coated high molecular fiber composite.
Area load metal of the present invention is: at least a in metal such as copper, silver, nickel, aluminium, gold, iron and the alloy thereof.
The preparation technology of metal-coated polymer fiber of the present invention is as follows:
1, learnt from else's experience that to place volume be its absolute ethyl alcohol of 10～100 times for nano inorganic powder after the surface modification, the control temperature is 50～100 ℃, and ultrasonic dispersion 20～120min prepares homodisperse emulsion;
2, the macromolecular fibre that will adopt chemical method or physics method to carry out after the surface modification is dipped in the above-mentioned emulsion, drips the coupling agent that accounts for emulsion volume 0.1～10% in the emulsion simultaneously, continues sonic oscillation 60～600min;
3, the macromolecular fibre with surperficial clad nano inorganic particle takes out, and handles 60～180min in 100～300 ℃ of oven dry, makes the nano inorganic powder coated high molecular fiber composite;
4, slaine and the sodium potassium tartrate tetrahydrate with the equal-volume ratio is formulated as solution A, and the formaldehyde and the alkali of equal-volume ratio is formulated as solution B;
5, the nano inorganic powder coated high molecular fiber composite is immersed in the solution A, add solution B simultaneously, sonic oscillation 10～60min;
6, the nano inorganic powder coated high molecular fiber composite with surface clad takes out, and handles 60～180min in 50～200 ℃ of vacuum dryings, can make the metal-coated polymer fiber composite.
Nano inorganic powder of the present invention is at least a in nano titanium oxide, nano silicon oxide, nano magnesia, nano zine oxide, nano aluminium oxide, nano zircite, nano-nickel oxide, the nanometer cobalt oxide etc.; Described macromolecular fibre is at least a in pbo fiber, aramid fiber, superhigh molecular weight polyethylene fibers, the spider silk etc.; Described slaine is at least a in mantoquita, silver salt, nickel salt, aluminium salt, golden salt, the molysite etc.
The invention has the advantages that, utilize the characteristics such as high strength, high tenacity, low-density of the performance such as electricity, magnetic and heat conduction of clad metal and matrix macromolecular fibre, exploitation has lighter quality, higher intensity and durability and better flexible metal-coated polymer fiber composite than traditional metal fibril.
The specific embodiment
Below in conjunction with embodiment the present invention is specifically described; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the those of skill in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.。
Embodiment: pbo fiber is after ethanol, distilled water clean repeatedly, handle 1～60min in the modification liquid of immersion by polyphosphoric acids and absolute ethyl alcohol 1:1～3 preparations by volume, clean repeatedly with distilled water then, thoroughly remove residual polyphosphoric acids, handle 1～60min in 50～150 ℃ of oven dry, standby.
Get 1～3g nano-TiO
2Powder is dispersed in 50～500ml distilled water, adds 0.01～0.5g sodium polyphosphate simultaneously, and 0.01～0.3g neopelex is made dispersant, and regulating the pH value with ammoniacal liquor is 7～12, and sonic oscillation 20～120min prepares homodisperse nano-TiO
2The powder emulsion.With this nano-TiO
2The powder emulsion places water bath with thermostatic control, is warming up to 50～100 ℃ gradually.With salt acid for adjusting pH value to 2～6, drip 1～10ml silane coupler then, powerful mechanical agitation 20～120min.Leave standstill until nano-TiO
2Powder all precipitates, and isolates water, with nano-TiO
2Handle 20～60min in 50～100 ℃ of oven dry, standby.
Get the above-mentioned modified Nano TiO of 0.5～2.5g
2Powder places 100～300ml absolute ethyl alcohol, and the control temperature is 50～100 ℃, and ultrasonic dispersion 20～120min prepares homodisperse emulsion.Pbo fiber after the modification is dipped in the emulsion, drips 0.1～5ml silane coupler in the emulsion simultaneously, continue sonic oscillation 60～600min, take out the back and handle 60～180min, prepare nano-TiO in 100～300 ℃ of oven dry
2Powder coats the pbo fiber composite.
0.1～10gL with 50～100ml
-1CuSO
45H
20.1～10gL of O and 50～100ml
-1Sodium potassium tartrate tetrahydrate is formulated as 0.1～10mlL of solution 1,50～200ml
-10.1～10gL of formaldehyde and 50～200ml
-1NaOH is formulated as solution 2.
With nano-TiO
2Powder coats the pbo fiber composite and immerses in the solution 1, adds solution 2 simultaneously, and sonic oscillation 10～60min takes out the back in 50～200 ℃ of vacuum drying 60～180min, makes metallic copper and coats the pbo fiber composite.
Claims (4)
1, a kind of metal-coated polymer fiber, it is characterized in that, with polyparaphenylene's benzo-dioxazole fiber, aramid fiber, superhigh molecular weight polyethylene fibers, at least a macromolecular fibre in the spider silk is a matrix, with nano titanium oxide, nano silicon oxide, nano magnesia, nano zine oxide, nano aluminium oxide, nano zircite, nano-nickel oxide, at least a nano inorganic powder in the nanometer cobalt oxide is as material modified, coat one deck nano inorganic powder film as transition zone, then at nano inorganic powder coated high molecular fiber composite material surface carried metal on the macromolecular fibre surface.
According to the described metal-coated polymer fiber of claim 1, it is characterized in that 2, described area load metal is: at least a in copper, silver, nickel, aluminium, gold, ferrous metal and the alloy thereof.
3, a kind of method for preparing the described metal-coated polymer fiber of claim 1 is characterized in that, technology is:
(1) learnt from else's experience that to place volume be its absolute ethyl alcohol of 10～100 times for nano inorganic powder after the surface modification, the control temperature is 50～100 ℃, and ultrasonic dispersion 20～120min prepares homodisperse emulsion;
(2) macromolecular fibre that will adopt chemical method or physics method to carry out after the surface modification is dipped in the above-mentioned emulsion, drips the coupling agent that accounts for emulsion volume 0.1～10% in the emulsion simultaneously, continues sonic oscillation 60～600min;
(3) macromolecular fibre with surperficial clad nano inorganic particle takes out, and handles 60～180min in 100～300 ℃ of oven dry, makes the nano inorganic powder coated high molecular fiber composite;
(4) slaine and the sodium potassium tartrate tetrahydrate with the equal-volume ratio is formulated as solution A, and the formaldehyde and the alkali of equal-volume ratio is formulated as solution B;
(5) the nano inorganic powder coated high molecular fiber composite is immersed in the solution A, add solution B simultaneously, sonic oscillation 10～60min;
(6) the nano inorganic powder coated high molecular fiber composite with surface clad takes out, and handles 60～180min in 50～200 ℃ of vacuum dryings, can make the metal-coated polymer fiber composite.
4, in accordance with the method for claim 3, it is characterized in that described nano inorganic powder is at least a in nano titanium oxide, nano silicon oxide, nano magnesia, nano zine oxide, nano aluminium oxide, nano zircite, nano-nickel oxide, the nanometer cobalt oxide; Described macromolecular fibre is at least a in polyparaphenylene's benzo-dioxazole fiber, aramid fiber, superhigh molecular weight polyethylene fibers, the spider silk; Described slaine is at least a in mantoquita, silver salt, nickel salt, aluminium salt, golden salt, the molysite.
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| CN100500979C true CN100500979C (en) | 2009-06-17 |
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| CN101728007B (en) * | 2008-10-21 | 2013-02-27 | 财团法人工业技术研究院 | Transparent conductive film and manufacturing method thereof |
| CN101550546B (en) * | 2009-04-08 | 2010-08-18 | 北京科技大学 | A preparation method of surface metallized composite material through chemical plating under photocatalysis |
| TWI396788B (en) * | 2009-10-01 | 2013-05-21 | Taiwan Textile Res Inst | Color textile |
| CN102417205A (en) * | 2011-08-22 | 2012-04-18 | 南京理工大学 | Method for preparing zirconia heat insulation material from natural silk |
| CN104088138B (en) * | 2014-07-08 | 2016-03-02 | 山东建筑大学 | A kind of preparation method of aramid fiber surface copper zinc-iron ternary alloy three-partalloy chemistry coating |
| CN105040426B (en) * | 2015-07-07 | 2017-05-17 | 安徽理工大学 | Antibacterial warming anti-electromagnetic radiation textile fabric and preparation method thereof |
| CN104947411B (en) * | 2015-07-07 | 2016-09-28 | 安徽理工大学 | Multifunctional fabric slip compositions and preparation method thereof |
| CN105220461A (en) * | 2015-10-30 | 2016-01-06 | 无锡市长安曙光手套厂 | A kind of multifunctional fabric slip composition and method of making the same |
| CN108130722B (en) * | 2016-11-30 | 2020-03-31 | 比亚迪股份有限公司 | Metallized product and metallization method |
| CN109832621B (en) * | 2019-01-25 | 2022-05-17 | 芜湖航天特种电缆厂股份有限公司 | Light shock-resistant wave-proof sleeve and preparation method thereof |
| CN111188189B (en) * | 2020-01-13 | 2022-05-17 | 江苏大学 | Biomass membrane material with ultraviolet resistance and heat management functions and preparation method thereof |
| CN113430839B (en) * | 2021-07-13 | 2022-05-31 | 哈尔滨工业大学 | Method for preparing compact aramid fiber coring soft bag by using high-performance benzoxazole polymer |
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Non-Patent Citations (2)
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| 高性能纤维表面处理技术. 董卫国.山东纺织科技，第6期. 2001 |
| 高性能纤维表面处理技术. 董卫国.山东纺织科技，第6期. 2001 * |
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