CN114032675A - Conductive fiber and preparation method thereof - Google Patents
Conductive fiber and preparation method thereof Download PDFInfo
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- CN114032675A CN114032675A CN202111073485.3A CN202111073485A CN114032675A CN 114032675 A CN114032675 A CN 114032675A CN 202111073485 A CN202111073485 A CN 202111073485A CN 114032675 A CN114032675 A CN 114032675A
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- conductive fiber
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- 239000000835 fiber Substances 0.000 title claims abstract description 150
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 239000011159 matrix material Substances 0.000 claims abstract description 63
- 239000002923 metal particle Substances 0.000 claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 79
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 79
- 241001330002 Bambuseae Species 0.000 claims description 79
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 79
- 239000011425 bamboo Substances 0.000 claims description 79
- 229920003043 Cellulose fiber Polymers 0.000 claims description 52
- 229910021645 metal ion Inorganic materials 0.000 claims description 43
- 229910052751 metal Inorganic materials 0.000 claims description 41
- 239000002184 metal Substances 0.000 claims description 39
- 230000006911 nucleation Effects 0.000 claims description 38
- 238000010899 nucleation Methods 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 26
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 15
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 13
- 238000000151 deposition Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 239000002023 wood Substances 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 abstract description 32
- 239000002994 raw material Substances 0.000 abstract description 9
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 92
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 25
- 239000008103 glucose Substances 0.000 description 19
- 229920002678 cellulose Polymers 0.000 description 15
- 239000001913 cellulose Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 238000011065 in-situ storage Methods 0.000 description 14
- 230000007935 neutral effect Effects 0.000 description 12
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 11
- 239000001263 FEMA 3042 Substances 0.000 description 11
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 11
- 239000003638 chemical reducing agent Substances 0.000 description 11
- 229920002258 tannic acid Polymers 0.000 description 11
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 11
- 229940033123 tannic acid Drugs 0.000 description 11
- 235000015523 tannic acid Nutrition 0.000 description 11
- 229920002522 Wood fibre Polymers 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- 239000002025 wood fiber Substances 0.000 description 10
- 239000002082 metal nanoparticle Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 7
- 229960002218 sodium chlorite Drugs 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000004108 freeze drying Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- -1 silver ions Chemical class 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 229920002488 Hemicellulose Polymers 0.000 description 5
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229920005610 lignin Polymers 0.000 description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
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- 239000013078 crystal Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 241000219000 Populus Species 0.000 description 2
- 241000124033 Salix Species 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
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- 239000002798 polar solvent Substances 0.000 description 2
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- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 244000302661 Phyllostachys pubescens Species 0.000 description 1
- 235000003570 Phyllostachys pubescens Nutrition 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 239000011247 coating layer Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
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- 229960003638 dopamine Drugs 0.000 description 1
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- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 239000004744 fabric Substances 0.000 description 1
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- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002090 nanochannel Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
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- 238000004544 sputter deposition Methods 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
Images
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
- D06M11/83—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 metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
-
- 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
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic System
-
- 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
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
Abstract
The invention provides a conductive fiber and a preparation method thereof. The conductive fiber of the present invention comprises: a fiber matrix, and nano-metal particles attached to the surface and/or inside of the fiber matrix. The conductive fiber provided by the invention comprises a fiber matrix and nano metal particles, and the prepared conductive fiber is safe and environment-friendly and has excellent mechanical property, conductivity and washing resistance. Furthermore, the invention also provides a preparation method of the conductive fiber, and the preparation method has the advantages of safe and nontoxic raw materials, easy acquisition, simple and feasible preparation steps and suitability for mass production.
Description
Technical Field
The invention relates to a conductive fiber and a preparation method thereof, belonging to the field of wood processing materials.
Background
The metal nano particle coating fiber is widely applied to health care textiles or flexible electronic products, and higher requirements are put forward on the conductivity and the washability of the metal nano particle coating fiber. These conductive metal nanoparticle coated fibers, such as cellulose-based materials, show broad potential in the fields of flexible and portable electronics, smart wearable electronics, antibacterial and electromagnetic shielding.
Methods for preparing the metal nanoparticle coating layer include a sputtering method, a self-assembly method, an electroplating method, and a chemical plating method. Among them, the electroless plating method is considered to be the most promising method for preparing the metal nanoparticle-containing coated fabric due to its advantages of low cost, environmental friendliness, high efficiency, simple operation, etc. However, the surface of the fiber matrix is generally smooth and less reactive, and usually requires a pretreatment to activate the surface before preparation, thereby increasing the reduction rate of the metal ions.
In the case of electroless silver plating, the conventional pretreatment method is to pass cation, stannic chloride (SnCl), before preparation2) And palladium dichloride (PdCl)2) And carrying out coarsening, sensitizing and activating steps. While these necessary steps do improve the reduction of silver ions, the complex operations and use of noble metals such as palladium (Pd) can both increase cost and cause potential contamination.
To solve these problems, some alternatives, such as silver nitrate (AgNO)3) The prepared conductive simple pressure sensor aims at forming a catalytic center. In addition, in order to replace the conventional pretreatment methods, the surface is also modified by functionalization or grafting. For example, tetraethoxysilane is used to modify the glass fibers and act as a linking agent, thereby improving the adhesion of metallic silver to the glass fibers. However, these methods still do not guarantee a dense, continuous coating of metal nanoparticles in a convenient, green process step.
In recent years, natural and green materials are increasingly used for surface modification, such as dopamine and tannic acid, and the like. Tannic acid is a substance similar to water-soluble tannins, with five hydroxyl groups covalently linked to a glucose core. The abundant phenolic hydroxyl groups give tannic acid the ability to reduce and chelate metals, which makes it a competitive green reducing agent for metal ions. For example: which can form a functional surface by layer-by-layer self-assembly. In particular, tannic acid can be used to modify the surface of a substrate to enhance the in situ sequestration of Ag ions alone or with other metal ionsIn situ rate, e.g. of ferric (Fe)3+) And the like. However, the conductive fiber prepared by the method has poor conductivity and washing resistance.
Therefore, it is a technical problem to be solved urgently to research a conductive fiber with excellent conductivity and washing resistance, and the conductive fiber is applied to the field of flexible electronics or textiles.
Disclosure of Invention
Problems to be solved by the invention
In view of the technical problems in the prior art, the present invention provides a conductive fiber. The conductive fiber has excellent conductivity and washing resistance.
Furthermore, the invention also provides a preparation method of the conductive fiber, and the raw materials of the preparation method are safe, non-toxic and easy to obtain, and the preparation steps are simple and easy to implement, so that the preparation method is suitable for mass production.
Means for solving the problems
The present invention provides a conductive fiber, comprising:
a fibrous matrix, and
nano-metal particles attached to the surface and/or interior of the fiber matrix.
The conductive fiber of the present invention, wherein the average particle diameter of the nano metal particles is 10 to 500 nm; and/or
The content of the nano metal particles is 25-60% by mass of the total mass of the conductive fiber.
The conductive fiber at least comprises a carbon element, an oxygen element and a first metal element on the surface, wherein the first metal element is derived from nano metal particles; wherein the mass fraction of the carbon element is 20-40%, the mass fraction of the oxygen element is 20-40%, and the mass fraction of the first metal element is 5-60%.
The conductive fiber according to the present invention, wherein the fiber matrix is derived from bamboo cellulose fiber and/or wood cellulose fiber.
The conductive fiber of the invention, wherein the nano metal particles comprise one or two of nano silver particles, nano copper particles and nano nickel particles.
The invention also provides a preparation method of the conductive fiber, which comprises the following steps:
providing a surface and/or interior of a fiber matrix with metal ions to form nucleation sites, the metal ions comprising a second metal element;
depositing nano-metal particles on the surface and/or inside of the fiber matrix on which the nucleation sites are formed, and removing the metal ions, the nano-metal particles including a first metal element;
the second metal element is different from the first metal element.
The preparation method according to the present invention, wherein the fiber matrix is pretreated with a metal ion-containing solution, preferably by immersing the fiber matrix in the metal ion-containing solution, so that the metal ions are present on the surface and/or inside the fiber matrix to form nucleation sites.
The preparation method according to the present invention, wherein the metal ion-containing solution is a metal ion-containing alkali solution; preferably an alkali solution containing alkali metal ions.
The production method according to the present invention is a production method in which a fiber base body formed with nucleation sites is immersed in a solution containing a first metal element, and the first metal is deposited on the surface and/or inside of the fiber base body formed with nucleation sites to form nano-metal particles.
The preparation method according to the present invention, wherein the solution containing the first metal element includes one or a combination of two or more of a silver ion-containing solution, a copper ion-containing solution, and a nickel ion-containing solution; preferably comprises one or more of silver ammonia solution, copper sulfate solution and nickel sulfate solution.
ADVANTAGEOUS EFFECTS OF INVENTION
The conductive fiber provided by the invention comprises a fiber matrix and nano metal particles, and the prepared conductive fiber is safe and environment-friendly and has excellent mechanical property, conductivity and washing resistance.
Furthermore, the invention also provides a preparation method of the conductive fiber, and the preparation method has the advantages of safe and nontoxic raw materials, easy acquisition, simple and feasible preparation steps and suitability for mass production.
Drawings
Fig. 1 shows Scanning Electron Microscope (SEM) photographs of the conductive fiber of comparative example 1 at different magnifications and an elemental energy spectrum of the surface of the conductive fiber;
fig. 2 shows Scanning Electron Microscope (SEM) photographs of the conductive fiber of comparative example 2 at different magnifications and an elemental energy spectrum of the surface of the conductive fiber;
FIG. 3 shows Scanning Electron Microscope (SEM) photographs of the conductive fiber of example 1 of the present invention at different magnifications and an elemental energy spectrum of the surface of the conductive fiber;
FIG. 4 shows a schematic diagram of the preparation principle of the conductive fiber of the present invention;
FIG. 5 shows a graph comparing tensile strength, Young's modulus, and tensile stress for example 1 of the present invention and comparative examples 1-2;
FIG. 6 is a graph showing the results of conductivity tests on the bamboo cellulose fibers of the present invention, the conductive fibers prepared in example 1 and comparative examples 1-2;
FIG. 7 is a graph showing the results of a washing performance test comparing conductive fibers prepared in example 1 of the present invention and comparative examples 1 to 2.
Detailed Description
The present invention will be described in detail below. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:
in the present specification, the numerical range represented by "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, "plural" in "plural", and the like means a numerical value of 2 or more unless otherwise specified.
In this specification, the terms "substantially", "substantially" or "substantially" mean an error of less than 5%, or less than 3% or less than 1% as compared to the relevant perfect or theoretical standard.
In the present specification, "%" denotes mass% unless otherwise specified.
In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In this specification, "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
In the present specification, the temperature of "room temperature" or "normal temperature" is generally 10 to 40 ℃.
In the present specification, reference to "some particular/preferred embodiments," "other particular/preferred embodiments," "embodiments," and the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
First aspect
A first aspect of the present invention provides an electrically conductive fiber comprising:
a fibrous matrix, and
nano-metal particles attached to the surface and/or interior of the fiber matrix.
The conductive fiber provided by the invention comprises a fiber matrix and nano metal particles, and the prepared conductive fiber is safe and environment-friendly and has excellent mechanical property, conductivity and washing resistance.
< fibrous substrate >
The fibrous matrix of the present invention may be derived from wood cellulose fibers and/or bamboo cellulose fibers. Both the wood cellulose fiber and the bamboo cellulose fiber are natural fibers with rich resources, have the advantages of being renewable, biodegradable, safe, pollution-free and the like, and are widely applied to various fields.
Specifically, the present invention is not particularly limited with respect to the kind of the wood fiber, and various kinds of wood fibers commonly used in the art may be used. For example, the wood fiber may be one or a combination of two or more of poplar cellulose fiber, fir cellulose fiber and salix mongolica cellulose fiber. Similarly, the type of bamboo cellulose fiber is not particularly limited in the present invention, and various types of bamboo cellulose fibers commonly used in the art may be used. For example, the bamboo cellulose fiber may be a moso bamboo cellulose fiber, a tufted bamboo cellulose fiber, or the like.
< Metal nanoparticles >
The nano-metal particles of the present invention are attached to the surface and/or inside of the fiber matrix. The fiber matrix of the present invention has a dense layer of nano-metal particles formed on the surface and/or inside thereof, thereby enabling the cellulose fiber-based material to be applied as a flexible conductive fiber.
In some specific embodiments, the amount of the nano-metal particles is 25 to 60% by mass of the total mass of the conductive fiber, for example: 30%, 35%, 40%, 45%, 50%, 55%, etc.; and/or the average particle size of the nano-metal particles is 10-500nm, preferably 50-500nm, more preferably 80-250 nm; for example: 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, etc. The conductive fiber has higher content of nano metal particles and large particle size, so the obtained conductive fiber has more excellent mechanical property and conductivity.
In some embodiments, the nucleation sites comprising metal ions are formed on the surface of the fiber matrix, and the nano-metal particles are attached to the surface of the fiber matrix in situ based on the nucleation sites on the surface of the fiber matrix, followed by removal of the metal ions.
In other embodiments, the metal ions may be present in the fiber matrix due to the presence of a large number of irregular voids on the surface and/or inside the fiber matrix, and the nano-metal particles may be attached to the inside of the fiber matrix in situ based on the nucleation sites inside the fiber matrix, and then removed.
The nano metal particles comprise one or the combination of more than two of nano silver particles, nano copper particles and nano nickel particles.
In some specific embodiments, the surface of the conductive fiber comprises at least carbon element, oxygen element, and a first metal element, wherein the first metal element is derived from nano metal particles; wherein, the mass fraction of the carbon element is 40-85%, and the mass fraction of the carbon element can be 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% and the like; the mass fraction of the oxygen element is 10-40%, for example, the mass fraction of the oxygen element may be 15%, 20%, 25%, 30%, 35%, etc.; the mass fraction of the first metal element is 5-50%, for example: the mass fraction of the first metal element may be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or the like. When the contents of the carbon element, the oxygen element, and the first metal element are within the above ranges, the conductive property is excellent.
Second aspect of the invention
A second aspect of the present invention provides a method for preparing a conductive fiber according to the first aspect of the present invention by reducing and depositing nano metal particles in situ. The method specifically comprises the following steps:
providing a surface and/or interior of a fiber matrix with metal ions to form nucleation sites, the metal ions comprising a second metal element;
depositing nano-metal particles on the surface and/or inside of the fiber matrix on which the nucleation sites are formed, and removing the metal ions, the nano-metal particles including a first metal element;
the second metal element is different from the first metal element.
< preparation of fiber base >
In some specific embodiments, the fiber matrix is formed by at least one lignocellulose fiber and/or bamboo cellulose fiber, and the specific number of the lignocellulose fiber and/or the bamboo cellulose fiber is not particularly limited, and can be set according to needs, such as: 2, 5, 10, 20, 50, 100, etc., and may be wood cellulose fibers alone, bamboo cellulose fibers alone, or a mixture of wood cellulose fibers and bamboo cellulose fibers. In particular, the fibrous matrix may be obtained commercially or prepared using the methods of the present invention.
The preparation method of the wood fiber matrix comprises the following steps: after the wood fiber raw material is subjected to short-time high-temperature cooking, generally speaking, the cooking temperature is 150-180 ℃, the cooking time is 3-5min, and the wood fiber raw material can be cooked in water.
Further, the grinding of the wood fiber raw material by the grinding plate promotes the wood fiber raw material to be rapidly dissociated and converted into wood fiber. Wherein, the wood fiber raw material can be a fiber raw material containing one or more than two of poplar fiber, fir fiber and salix mongolica fiber.
In other specific embodiments, the method of making the bamboo fiber substrate may include the steps of: before the flexible electrode is prepared, the bamboo chips are firstly subjected to separation treatment.
Specifically, the separation treatment of the bamboo chips is to immerse the bamboo chips in a separation solution for separation. The separation solution may be some of the separation solutions commonly used in the present invention, for example: NaClO2At least one of a solution, a NaOH solution, and the like.
For the sodium chlorite solution, it can be obtained by dissolving sodium chlorite in a solvent, and the specific solvent is not particularly limited in the present invention, and may be a polar solvent commonly used in the art, for example: water, and the like. Specifically, the mass concentration of sodium chlorite in the separation solution is 0.05-5 wt.%, for example: 0.1 wt.%, 0.2 wt.%, 0.5 wt.%, 0.8 wt.%, 1.2 wt.%, 1.5 wt.%, 1.8 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, etc. In order to achieve the bamboo chip separation, glacial acetic acid is added to prepare a sodium chlorite solution, and the pH of the sodium chlorite solution is adjusted to be acidic, wherein the specific pH value can be 4 to 5, and preferably 4.4 to 4.6.
For the NaOH solution, it may be obtained by dissolving NaOH in a solvent, and the specific solvent is not particularly limited in the present invention, and may be a polar solvent commonly used in the art, for example: water, and the like. Specifically, the mass fraction of NaOH in the separation solution is 5-15%, for example: 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, etc.
In some specific embodiments, the bamboo chips are soaked by using a sodium chlorite solution at a water bath temperature of 40-80 ℃, and the sodium chlorite solution is replaced every 5-7 hours until the bamboo chips are whitened and then are washed to be neutral by using deionized water. And then soaking the bamboo chips in NaOH solution at the water bath temperature of 40-80 ℃, replacing the NaOH solution every 5-7h until the solution is transparent, and washing the bamboo chips to be neutral by using deionized water. And finally, carrying out freeze drying on the bamboo chips, and shaking the sample to realize the separation of the bamboo cellulose fibers and the parenchyma cells.
After the treatment, an interconnected porous structure is formed in the wood cellulose fiber and/or the bamboo cellulose fiber. The structure can be used as a physical anchoring site for subsequent nucleation and in-situ reduction, and the effective contact area between the nucleation site and a cellulose molecular chain is increased.
< formation of nucleation sites >
Further, the fiber matrix of the present invention is provided with metal ions on the surface and/or inside thereof to form nucleation sites, the metal ions containing a second metal element. The invention forms nucleation sites by using metal ions, so that nano metal particles can be reduced in situ and deposited on the surface and/or inside of a fiber matrix, thereby obtaining the conductive fiber.
Due to the existence of metal ions, the nano metal particles can be reduced in situ and deposited on nucleation sites, so that the nano metal particles can be well attached to the surface and/or the interior of a fiber matrix and are not easy to lose in the using process.
The invention is characterized in that the fiber matrix is pretreated by using a solution containing metal ions, such as: the fiber matrix may be immersed in a solution containing metal ions such that the metal ions are present at the surface and/or inside the fiber matrix to form nucleation sites. After the treatment of the solution containing the metal ions, the crystal structure of the fiber matrix is converted into an antiparallel chain structure in the solution containing the metal ions, so that the finally prepared conductive fiber has excellent toughness, namely excellent mechanical properties.
In some specific embodiments, the metal ion-containing solution is a metal ion-containing alkaline solution. The treatment with the alkali solution containing metal ions not only roughens the surface of the fibrous substrate but also converts the cellulose I to cellulose II crystals of the fibrous substrate. This allows the expansion of the cellulose molecular chains and the formation of a large number of sub-nano channels that can act as templates for the nano-metal particles, which are reduced and deposited in situ on the surface and/or inside the fiber matrix.
In some specific embodiments, the metal ions include one or a combination of two or more of alkali metal ions. The alkali metal ion may be one or a combination of two or more of lithium ion, sodium ion, potassium ion, and the like. Specifically, the alkali solution containing metal ions may be an alkali solution containing alkali metal ions. For example: NaOH, KOH, LiOH, and the like. For the mass concentration of the alkali solution of metal ions, the present invention preferably uses an alkali solution of metal ions at a high concentration, such as: an alkali solution with a mass concentration of 10% or more, preferably 10% to 30% by mass, for example: 15 wt%, 20 wt%, 25 wt%, etc. This is because when a high concentration of alkali solution of metal ions is used, it is possible to provide more nucleation sites on the surface and/or inside of the fiber matrix, facilitating the in-situ reduction and deposition of the nano-metal particles.
The time for the impregnation is not particularly limited in the present invention and may be selected as needed, and preferably, the time for the impregnation is not less than 0.5 hour, preferably 0.5 to 4 hours, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, etc.
After impregnation, the fiber matrix with the nucleation sites formed thereon is washed and/or dried to remove the alkaline solution present on the surface of the fiber matrix to facilitate the formation of the nano-metal particles.
< formation of Nano-Metal particles >
The invention obtains the conductive fiber by depositing nano metal particles on the surface and/or inside of the fiber matrix with the formed nucleation sites.
Specifically, a fiber base body formed with nucleation sites is immersed in a solution containing a first metal element, and the first metal is deposited on the surface and/or inside of the fiber base body formed with the nucleation sites to form nano-metal particles.
When the fiber matrix with the nucleation sites is immersed in the solution containing the first metal element, the fiber matrix with the nucleation sites is discolored, and in the case of silver ions, the fiber matrix with the nucleation sites can immediately change from white to golden yellow, then quickly change to dark brown, and finally change to silver gray. This indicates that the nano-metal particles have been formed.
Specifically, in the solution containing the first metal element, the fiber matrix formed with the nucleation sites acts as an alkali trigger, inducing the reduction of the nano-metal particles at the nucleation sites. After the nucleation of the elements, nano-metal particles with uniform size are grown and aggregated in situ in the fiber matrix where the nucleation sites are formed. Also, it was confirmed that the nano metal particles can be grown in situ in the porous structure of the fiber matrix.
Further, in the present invention, the solution containing the first metal element includes one or a combination of two or more of a silver element-containing solution, a copper element-containing solution, and a nickel element-containing solution; preferably comprises one or more of silver ammonia solution, copper sulfate solution and nickel sulfate solution.
In some specific embodiments, when the nano-metal particles are nano-silver particles, the solution containing the first metal element includes a silver ammonia solution and a reducing agent. When the nano-silver particles are formed, some reducing agent may be appropriately added to the silver ammonia solution so that the nano-silver particles may be reduced in situ and deposited at the nucleation sites. The invention uses silver ammonia solution to form nano silver particles.
The reducing agent is not particularly limited in the present invention, and may be selected as needed. Preferably, glucose is preferably used as the reducing agent in view of the loading of the nano silver particles. Specifically, a small amount of glucose solution may be added to the silver ammonia solution as a reducing agent, thereby obtaining a silver ammonia-glucose solution.
The content of glucose in the silver ammonia-glucose solution is not particularly limited in the present invention, and may be added as needed. Specifically, in the silver ammonia-glucose solution, the content of the glucose can be 3-30mg mL-1For example: 5mg mL-1、10mg mL-1、15mg mL-1、20mg mL-1、25mg mL-1、30mg mL-1Etc.; the silver ammonia content may be 3-50mg mL-1For example: 5mg mL-1、10mg mL-1、15mg mL-1、20mg mL-1、25mg mL-1、30mg mL-1、35mg mL-1、40mg mL-1、45mg mL-1And the like.
Further, after the fiber matrix with the nucleation sites is immersed in the silver ammonia-glucose solution, heating is carried out under the condition of water bath after the fiber matrix with the nucleation sites is turned into dark brown, thereby being beneficial to the formation of nano silver particles. The heating temperature and the time of the water bath are not particularly limited, and may be set as required.
Specifically, the temperature of heating may be 40 to 60 ℃, for example: 42 deg.C, 45 deg.C, 48 deg.C, 50 deg.C, 52 deg.C, 55 deg.C, 58 deg.C, etc.; the heating time may be 0.5-2 hours, for example: 0.7 hour, 0.9 hour, 1.1 hour, 1.2 hours, 1.4 hours, 1.6 hours, etc.
Finally, the metal ions can be removed by washing to obtain the desired conductive fibers. The washing method is not particularly limited in the present invention, and washing may be carried out by selecting an appropriate polar solution as needed, and washing with water is preferred. In addition, the obtained conductive fiber may be dried after washing to obtain a conductive fiber product.
The preparation method of the invention firstly enables metal ions to exist on the surface and/or inside the fiber matrix to form nucleation sites, thereby realizing the deposition and aggregation of nano metal particles on the surface and/or inside the fiber matrix. The nano-metal particles of the present invention can be not only loaded on the fiber surface, but also grown in the porous structure of the fiber matrix. The filling of the nano metal particles in the fiber matrix enables the conductive fiber to have excellent conductivity and tensile strength. In addition, the conductive fiber of the present invention maintains very high retention of nano metal particles after washing 50 times, and thus, washing resistance is also very excellent.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Comparative example 1
Removing lignin and hemicellulose, and extracting Bamboo Cellulose Fibers (BCFs) by a two-stage method. Firstly, acidified NaClO is used in water bath at 80 DEG C2The solution (1 wt.%, pH 4.5) treated the bamboo strands. The same dose of chemical solution was exchanged every 6 hours until the bamboo was completely whitened. And then washing the bamboo strips to be neutral by using deionized water to obtain delignified bamboo strips. The delignified bamboo strips were further treated with 8% by mass NaOH solution in a water bath at 80 ℃ with the solution exchanged every 6 hours until the bamboo strips were whitened again. And finally, washing the bamboo cellulose fiber to be neutral, and freeze-drying to obtain the bamboo cellulose fiber.
1g of bamboo cellulose fiber was immersed in 100mL of tannic acid solution (20mg mL) at room temperature-1PH8) for 24 hours. After washing the excess tannic acid on the surface of the bamboo cellulose fiber with deionized water, the sample was dried at room temperature. Subsequently, tannic acid/fiber infusion80mL 0.017g mL-1AgNO3And (4) the solution is kept for 24 hours to ensure that tannic acid in the cellulose is reduced in situ to obtain a reduction site.
By adding 32mg mL-1AgNO380mL of silver ammonia solution (Ag (NH) was prepared by adding 2 wt.% ammonia water dropwise thereto3)2OH). 80mL of 17mg mL was used-1Glucose solution as reducing agent and Ag (NH)3)2OH are mixed to obtain Ag (NH)3)2OH-glucose mixed solution. Then, the tannic acid-Ag/fiber was immersed in Ag (NH) at 50 deg.C3)2And (4) carrying out water bath for 1 hour in the OH-glucose mixed solution, and depositing the nano silver layer by layer. Finally, rinsing with deionized water and drying at room temperature to obtain tannin-Ag/Ag fiber, which can be recorded as Ag-AgNO3-TA-BCFs。
Comparative example 2
Removing lignin and hemicellulose, and extracting Bamboo Cellulose Fibers (BCFs) by a two-stage method. Firstly, acidified NaClO is used in water bath at 80 DEG C2The solution (1 wt.%, pH 4.5) treated the bamboo strands. The same dose of chemical solution was exchanged every 6 hours until the bamboo was completely whitened. And then washing the bamboo strips to be neutral by using deionized water to obtain delignified bamboo strips. Further treating the delignified bamboo strips with NaOH solution with the mass fraction of 8% in water bath at the temperature of 80 ℃. The solution was exchanged every 6 hours until the bamboo strands were whitened again. And finally, washing the bamboo cellulose fiber to be neutral, and freeze-drying to obtain the bamboo cellulose fiber.
1g of bamboo cellulose fiber was immersed in 100mL of tannic acid solution (20mg mL) at room temperature-1pH8) for 24 hours. After washing the excess tannic acid on the surface of the bamboo cellulose fiber with deionized water, the sample was dried at room temperature. The tannic acid/fiber was then immersed in 100mL FeCl3Solution (0.2mg mL)-1) And (5) neutralizing for 1 h. After the deposition process was completed, tannic acid-Fe/fiber was obtained by washing and drying again.
By adding 32mg mL-1AgNO380mL of silver ammonia solution (Ag (NH) was prepared by adding 2 wt.% ammonia water dropwise thereto3)2OH). 80mL of 16mg mL was used-1Glucose solution as reducing agent and Ag (NH)3)2OH are mixed to obtainAg(NH3)2OH-glucose mixed solution. Then, tannic acid-FeCl is added3Immersion of the fibres in 50 ℃ Ag (NH)3)2And (4) carrying out water bath for 1 hour in the OH-glucose mixed solution, and depositing the nano silver layer by layer. Finally, rinsed with deionized water and dried at room temperature to obtain tannin-Fe-Ag/fiber, denoted as Ag-FeCl3-TA-BCFs。
Example 1
Removing lignin and hemicellulose, and extracting Bamboo Cellulose Fibers (BCFs) by a two-stage method. Firstly, acidified NaClO is used in water bath at 80 DEG C2The solution (1 wt.%, pH 4.5) treated the bamboo strands. The same dose of chemical solution was exchanged every 6 hours until the bamboo was completely whitened. And then washing the bamboo strips to be neutral by using deionized water to obtain delignified bamboo strips. Further treating the delignified bamboo strips with NaOH solution with the mass fraction of 8% in water bath at the temperature of 80 ℃. The solution was exchanged every 6 hours until the bamboo strands were whitened again. And finally, washing the bamboo cellulose fiber to be neutral, and freeze-drying to obtain the bamboo cellulose fiber.
1g of bamboo cellulose fiber is soaked in 100mL of 20 wt.% NaOH solution for pretreatment for 2 h. Then, the treated cellulose was washed once with deionized water to remove an alkali solution on the surface, and dried at 40 ℃ to obtain NaOH-treated cellulose.
By adding 32mg mL-1AgNO of380mL of silver ammonia solution (Ag (NH) was prepared by adding 2 wt.% ammonia water dropwise thereto3)2OH). 80mL of 17mg mL was used-1Glucose solution as reducing agent and Ag (NH)3)2OH are mixed to obtain Ag (NH)3)2OH-glucose mixed solution.
Then, NaOH-treated cellulose-impregnated Ag (NH)3)2OH-glucose mixed solution. When the cellulose became dark brown within 10 seconds, the container was transferred to a water bath at 50 ℃ for 1 hour to completely deposit the nano silver particles, which were finally washed to neutrality and dried at room temperature to obtain a conductive fiber product, noted as: Ag-NaOH-BCFs.
Example 2
By removing lignin andand (3) extracting the hemicellulose by adopting a two-stage method to extract the Bamboo Cellulose Fibers (BCFs). Firstly, acidified NaClO is used in water bath at 80 DEG C2The solution (1 wt.%, pH 4.5) treated the bamboo strands. The same dose of chemical solution was exchanged every 6 hours until the bamboo was completely whitened. And then washing the bamboo strips to be neutral by using deionized water to obtain delignified bamboo strips. Further treating the delignified bamboo strips with NaOH solution with the mass fraction of 8% in water bath at the temperature of 80 ℃. The solution was exchanged every 6 hours until the bamboo strands were whitened again. And finally, washing the bamboo cellulose fiber to be neutral, and freeze-drying to obtain the bamboo cellulose fiber.
1g of bamboo cellulose fiber is soaked in 100mL of 20 wt.% NaOH solution for pretreatment for 2 h. Then, the treated cellulose was washed once with deionized water to remove an alkali solution on the surface, and dried at 40 ℃ to obtain NaOH-treated cellulose.
By adding 16mg mL-1AgNO of380mL of silver ammonia solution (Ag (NH) was prepared by adding 2 wt.% ammonia water dropwise thereto3)2OH). 10mL of 17mg mL was used-1Glucose solution as reducing agent and Ag (NH)3)2OH are mixed to obtain Ag (NH)3)2OH-glucose mixed solution.
Then, NaOH-treated cellulose-impregnated Ag (NH)3)2OH-glucose mixed solution. When the cellulose became dark brown within 10 seconds, the container was transferred to a water bath at 50 ℃ for 1 hour to completely deposit the nano silver particles, which was finally washed to neutrality and dried at room temperature to obtain a conductive fiber product, noted as: Ag-NaOH-BCFs.
Example 3
Removing lignin and hemicellulose, and extracting Bamboo Cellulose Fibers (BCFs) by a two-stage method. Firstly, acidified NaClO is used in water bath at 80 DEG C2The solution (1 wt.%, pH 4.5) treated the bamboo strands. The same dose of chemical solution was exchanged every 6 hours until the bamboo was completely whitened. And then washing the bamboo strips to be neutral by using deionized water to obtain delignified bamboo strips. Further treating the delignified bamboo strips with NaOH solution with the mass fraction of 8% in water bath at the temperature of 80 ℃. Exchange the solution every 6 hours untilThe bamboo strips are whitened again. And finally, washing the bamboo cellulose fiber to be neutral, and freeze-drying to obtain the bamboo cellulose fiber.
1g of bamboo cellulose fiber is soaked in 100mL of 20 wt.% NaOH solution for pretreatment for 2 h. Then, the treated cellulose was washed once with deionized water to remove an alkali solution on the surface, and dried at 40 ℃ to obtain NaOH-treated cellulose.
By adding 4mg mL-1AgNO of380mL of silver ammonia solution (Ag (NH) was prepared by adding 2 wt.% ammonia water dropwise thereto3)2OH). 40mL of 17mg mL was used-1Glucose solution as reducing agent and Ag (NH)3)2OH are mixed to obtain Ag (NH)3)2OH-glucose mixed solution.
Then, NaOH-treated cellulose-impregnated Ag (NH)3)2OH-glucose mixed solution. When the cellulose became dark brown within 10 seconds, the container was transferred to a water bath at 50 ℃ for 1 hour to completely deposit the nano silver particles. Finally, it is washed to neutrality and dried at room temperature to obtain the conductive fiber product, which is recorded as: Ag-NaOH-BCFs.
Performance testing
1. Element content
The elemental contents of each of the examples and comparative examples were obtained using an ESCALB 250Xi spectrometer manufactured by U.S. company (Thermo Fisher Scientific), and the results are shown in Table 1:
TABLE 1
As can be seen from Table 1, examples 1 to 3 of the present application have a high content of Ag element and do not contain other metal elements. In addition, the content of Ag element is high and other metal elements are not contained by example 1 as compared with comparative examples 1 to 2.
2. Content test of nano silver particles
The content (mass percentage) of the nano silver particles was obtained using an ICPMS7800 inductively coupled plasma mass spectrometer manufactured by american corporation (Agilent), and the results are shown in table 2:
TABLE 2
As can be seen from table 2, the nano silver particles of the present invention have high loading and no other metal impurities. In addition, by comparing example 1 with comparative examples 1-2, the nano silver particles of the present application are much higher than those of comparative examples 1-2 under the premise of using the same silver ammonia solution.
3. Mechanical Property test
The tensile strength, young's modulus and tensile strain of the individual fibers were obtained using a JSF08 high precision short fiber mechanical property tester manufactured by china corporation (shanghai, midmorning) and the results are shown in fig. 4.
As can be seen from FIG. 4, the Ag-NaOH-BCFs of example 1 according to the present invention has higher tensile strength, Young's modulus, and more excellent tensile strain than those of comparative example 1 and comparative example 2. Therefore, the Ag-NaOH-BCFs of example 1 of the present invention was excellent in mechanical properties. The excellent mechanical properties are derived from the crystal structure of the bamboo cellulose fiber and the enhancement of the nano silver particles in the cellulose fiber. In-situ reduction and aggregation of nanosilver particles within the bamboo cellulose fibers may fill the pores of the fibers and improve the mechanical properties of the microfiber network.
4. Conductivity test
The conductivity of the conductive fiber was obtained using an FM100GH powder resistivity tester manufactured by china (west ampere macro target), and the result is shown in fig. 6.
As can be seen from FIG. 6, the conductivities of the Ag-NaOH-BCFs of example 1 of the present invention were as high as 31800 S.m-1The single fiber can be used as a conductor to light a Light Emitting Diode (LED) as compared to Ag-AgNO of comparative example 13Conductivity of TA-BCFs and Ag-FeCl3-TA-BCF are respectively 110 S.m-1And 559 S.m-1. It can be seen that the conductive fibers of the present invention also have very strong conductive ability.
In addition, the Applicant has also observed changes in the Ag-NaOH-BCFs of example 3The conductivity is tested correspondingly, and the conductivity can still reach 17400S m-1. Thus, AgNO3The concentration of the Ag-NaOH-BCFs is reduced by 8 times, and the Ag-NaOH-BCFs still has excellent conductive capability.
5. Washing Performance test
The experiment was performed using example 1 and comparative examples 1 and 2, and the fiber mass was measured for different washing times (the washing control process was substantially identical) and calculated to obtain the retention of nano silver, and the result is shown in fig. 7.
As can be seen from fig. 7, the retention of silver after 10-50 cycles of washing is shown. Although with Ag-AgNO3-TA-BCFs and Ag-FeCl3The Ag-NaOH-BCFs of inventive example 1 had a larger Ag particle size than the TA-BCFs, but still retained over 96% of the silver nanoparticles.
It should be noted that, although the technical solutions of the present invention are described by specific examples, those skilled in the art can understand that the present invention should not be limited thereto.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen in order to best explain the principles of the embodiments, the practical application, or improvements made to the technology in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (10)
1. An electrically conductive fiber, comprising:
a fibrous matrix, and
nano-metal particles attached to the surface and/or interior of the fiber matrix.
2. The conductive fiber according to claim 1, wherein the nano-metal particles have an average particle diameter of 10 to 500nm, and/or
The content of the nano metal particles is 25-60% by mass of the total mass of the conductive fiber.
3. The conductive fiber according to claim 1 or 2, wherein the surface of the conductive fiber comprises at least carbon, oxygen and a first metal element, wherein the first metal element is derived from nano-metal particles; wherein the mass fraction of the carbon element is 40-85%, the mass fraction of the oxygen element is 10-40%, and the mass fraction of the first metal element is 5-50%.
4. The electrically conductive fiber according to any one of claims 1 to 3, wherein the fiber matrix is derived from bamboo cellulose fibers and/or wood cellulose fibers.
5. The conductive fiber according to any one of claims 1 to 4, wherein the nano metal particles comprise one or a combination of two or more of nano silver particles, nano copper particles and nano nickel particles.
6. A method for preparing the conductive fiber according to any one of claims 1 to 5, comprising the steps of:
providing a surface and/or interior of a fiber matrix with metal ions to form nucleation sites, the metal ions comprising a second metal element;
depositing nano-metal particles on the surface and/or inside of the fiber matrix on which the nucleation sites are formed, and removing the metal ions, the nano-metal particles including a first metal element;
the second metal element is different from the first metal element.
7. The method of claim 6, wherein the fiber matrix is pre-treated with a metal ion-containing solution, preferably the fiber matrix is immersed in the metal ion-containing solution, so that the metal ions are present on the surface and/or inside the fiber matrix to form nucleation sites.
8. The method according to claim 7, wherein the metal ion-containing solution is a metal ion-containing alkali solution; preferably an alkali solution containing alkali metal ions.
9. The production method according to claim 7 or 8, wherein the fiber base body formed with the nucleation sites is immersed in a solution containing a first metal element, and the first metal is deposited on the surface and/or inside of the fiber base body formed with the nucleation sites to form the nano-metal particles.
10. The method according to claim 9, wherein the solution containing the first metal element includes one or a combination of two or more of a silver ion-containing solution, a copper ion-containing solution, and a nickel ion-containing solution; preferably comprises one or more of silver ammonia solution, copper sulfate solution and nickel sulfate solution.
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