CN114032675B - Conductive fiber and preparation method thereof - Google Patents
Conductive fiber and preparation method thereof Download PDFInfo
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- CN114032675B CN114032675B CN202111073485.3A CN202111073485A CN114032675B CN 114032675 B CN114032675 B CN 114032675B CN 202111073485 A CN202111073485 A CN 202111073485A CN 114032675 B CN114032675 B CN 114032675B
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- 239000000835 fiber Substances 0.000 title claims abstract description 123
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000011159 matrix material Substances 0.000 claims abstract description 69
- 239000002923 metal particle Substances 0.000 claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 80
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 80
- 241001330002 Bambuseae Species 0.000 claims description 80
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 80
- 239000011425 bamboo Substances 0.000 claims description 80
- 229920003043 Cellulose fiber Polymers 0.000 claims description 57
- 229910021645 metal ion Inorganic materials 0.000 claims description 51
- 229910052751 metal Inorganic materials 0.000 claims description 45
- 239000002184 metal Substances 0.000 claims description 44
- 230000006911 nucleation Effects 0.000 claims description 40
- 238000010899 nucleation Methods 0.000 claims description 40
- 239000002245 particle Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 20
- 239000003513 alkali Substances 0.000 claims description 18
- 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
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 239000002023 wood Substances 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 10
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 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
- 239000002585 base Substances 0.000 claims 2
- 238000005406 washing Methods 0.000 abstract description 33
- 239000002994 raw material Substances 0.000 abstract description 8
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 95
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 61
- 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 18
- 239000001913 cellulose Substances 0.000 description 18
- 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 13
- 239000003638 chemical reducing agent Substances 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 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 9
- 239000001263 FEMA 3042 Substances 0.000 description 9
- 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 9
- 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 9
- 229920002522 Wood fibre Polymers 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- 229920002258 tannic acid Polymers 0.000 description 9
- 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 9
- 229940033123 tannic acid Drugs 0.000 description 9
- 235000015523 tannic acid Nutrition 0.000 description 9
- 239000002025 wood fiber Substances 0.000 description 9
- 101710134784 Agnoprotein Proteins 0.000 description 8
- 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
- 239000000758 substrate Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004108 freeze drying Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920002488 Hemicellulose Polymers 0.000 description 5
- 229920005610 lignin Polymers 0.000 description 5
- 239000002082 metal nanoparticle Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- -1 silver ions Chemical class 0.000 description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 5
- 238000010411 cooking Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 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
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229920001864 tannin Polymers 0.000 description 3
- 239000001648 tannin Substances 0.000 description 3
- 235000018553 tannin Nutrition 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 241000219000 Populus Species 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 238000007772 electroless plating Methods 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000004753 textile Substances 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
- 241000605447 Anemarrhena Species 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 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
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 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
- 241000124033 Salix Species 0.000 description 1
- 241000112525 Salix psammophila Species 0.000 description 1
- 206010070834 Sensitisation Diseases 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
- 230000004913 activation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229930191283 anemarrhena Natural products 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application 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
- 238000005137 deposition process Methods 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 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 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 239000002090 nanochannel Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 230000009466 transformation Effects 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
- D06M11/83—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 Table
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention provides a conductive fiber and a preparation method thereof. The conductive fiber of the present invention comprises: a fibrous matrix, and nano-metal particles attached to the surface and/or the interior of the fibrous 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 raw materials of the preparation method are safe, nontoxic and easy to obtain, and the preparation method is simple and feasible in preparation steps and suitable 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 nanoparticle coating fiber is widely applied to health care textiles or flexible electronic products, and has higher requirements on conductivity and washing fastness. These conductive metal nanoparticle coated fibers, such as cellulose-based materials, show a broad potential in the fields of flexible and portable electronics, smart wearable electrical, antibacterial and electromagnetic shielding.
Methods for preparing the metal nanoparticle coating include sputtering, self-assembly, electroplating and electroless plating. Among them, electroless plating is considered as the most promising method for preparing metal nanoparticle-containing coated fabrics, in terms of its advantages of low cost, environmental friendliness, high efficiency, simplicity in operation, and the like. However, the surface of the fibrous matrix is generally smooth and less reactive, and it is often necessary to pre-treat the surface prior to preparation to activate the surface and increase the reduction rate of metal ions.
Taking chemical silver plating as an example, the traditional pretreatment method is to prepare the catalyst by cation and tin chloride (SnCl) 2 ) And palladium dichloride (PdCl) 2 ) Coarsening, sensitization and activation steps are performed. While these necessary steps do improve the reduction of silver ions, complex operations and the 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 method, the modification is also carried out by functionalization or grafting of the surface. For example, tetraethoxysilane is used to modify glass fibers and act as a connector to improve adhesion of metallic silver to glass fibers. However, these methods still do not guarantee that a dense, continuous coating of metal nanoparticles is obtained by a convenient, green operation.
In recent years, natural and green materials have been increasingly used for surface modification such as dopamine and tannic acid. Tannic acid is a substance similar to water-soluble tannins in that five hydroxyl groups are linked to the glucose core by covalent bonds. The rich phenolic hydroxyl groups impart tannins the ability to reduce and sequester metals, which makes it a competitive metal ion green reductant. For example: it can form a functional surface by layer-by-layer self-assembly. In particular, tannins can be used to modify the surface of a substrate to increase the in situ reduction rate of Ag ions alone or chelated with other metal ions, such as ferric iron (Fe) 3+ ) Etc. However, the conductive fiber prepared by the method has poor conductivity and washing resistance.
Therefore, research on a conductive fiber with excellent conductivity and washing resistance, and application of the conductive fiber in the field of flexible electronics or textiles, is a technical problem to be solved.
Disclosure of Invention
Problems to be solved by the invention
In view of the technical problems existing in the prior art, the present invention firstly provides a conductive fiber. The conductive fiber has excellent conductive performance 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, nontoxic and easy to obtain, and the preparation method is simple and feasible in preparation steps and suitable for mass production.
Solution for solving the problem
The present invention provides a conductive fiber comprising:
fibrous matrix
Nano-metal particles attached to the surface and/or the interior of the fibrous matrix.
The conductive fiber according to the present invention, wherein the average particle diameter of the nano metal particles is 10 to 500nm; and/or
The content of the nano metal particles is 25-60% based on the total mass of the conductive fiber.
The conductive fiber provided by the invention, wherein the surface of the conductive fiber at least comprises carbon element, oxygen element and first metal element, and 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 electrically conductive fiber according to the invention, wherein the fiber matrix is derived from bamboo cellulose fiber and/or wood cellulose fiber.
The conductive fiber of the present 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 the surface and/or interior of the fibrous 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 formed with nucleation sites, and removing the metal ions, the nano-metal particles comprising 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 solution containing metal ions, preferably the fiber matrix is immersed in the solution containing metal ions so that the metal ions are present on the surface and/or inside of the fiber matrix to form nucleation sites.
The preparation method according to the present invention, wherein the solution containing metal ions is an alkali solution containing metal ions; preferably an alkali solution containing alkali metal ions.
The production method according to the present invention, wherein a fiber substrate formed with nucleation sites is immersed in a solution containing a first metal element, and a first metal is deposited on the surface and/or inside of the fiber substrate formed with nucleation sites to form nano-metal particles.
The production 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 raw materials of the preparation method are safe, nontoxic and easy to obtain, and the preparation method is simple and feasible in preparation steps and suitable for mass production.
Drawings
FIG. 1 shows a Scanning Electron Microscope (SEM) photograph of the conductive fibers of comparative example 1 at different magnifications and an elemental energy spectrum of the surface of the conductive fibers;
FIG. 2 shows a Scanning Electron Microscope (SEM) photograph of the conductive fibers of comparative example 2 at different magnification and an elemental energy spectrum of the surface of the conductive fibers;
FIG. 3 shows a Scanning Electron Microscope (SEM) photograph of the conductive fibers of example 1 of the present invention at various magnifications and an elemental energy spectrum of the surface of the conductive fibers;
fig. 4 shows a schematic representation of the preparation principle of the conductive fiber of the present invention;
FIG. 5 shows a comparative graph of 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 comparison of the results of conductivity tests of the conductive fibers prepared in the inventive bamboo cellulose fibers, example 1 and comparative examples 1-2;
fig. 7 is a graph showing comparison of the results of the washing performance test of the conductive fibers prepared in example 1 of the present invention and comparative examples 1-2.
Detailed Description
The following describes the present invention in detail. The following description of the technical features is based on the representative 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 indicated by the term "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, unless specifically stated otherwise, "a plurality" of "a plurality of" etc. means a numerical value of 2 or more.
In this specification, the terms "substantially", "substantially" or "substantially" mean that the error is less than 5%, or less than 3% or less than 1% compared to the relevant perfect or theoretical standard.
In the present specification, "%" means mass% unless otherwise specified.
In the present specification, the meaning of "can" 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 "room temperature" or "normal temperature" is generally 10 to 40 ℃.
Reference throughout this specification to "some specific/preferred embodiments," "other specific/preferred embodiments," "an embodiment," and so forth, 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 elements may be combined in any suitable manner in the various embodiments.
First aspect
A first aspect of the present invention provides a conductive fiber comprising:
fibrous matrix
Nano-metal particles attached to the surface and/or the interior of the fibrous 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 matrix >
The fibrous matrix of the present invention may be derived from wood cellulose fibers and/or bamboo cellulose fibers. 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 have wide application in various fields.
Specifically, the present invention is not particularly limited as to the kind of wood fiber, and various kinds of wood fibers commonly used in the art may be used. For example, the wood fibers may be one or a combination of two or more of poplar cellulose fibers, fir cellulose fibers, salix cellulose fibers. Similarly, the type of the bamboo cellulose fiber is not particularly limited, and various types of bamboo cellulose fibers commonly used in the art may be used. For example, the bamboo cellulose fibers may be moso bamboo cellulose fibers, tufted bamboo cellulose fibers, and the like.
< nano-metal particles >
The nano-metal particles of the present invention are attached to the surface and/or the interior of the fibrous matrix. The surface and/or the interior of the fiber matrix of the present invention is formed with a dense nano-metal particle layer, thereby enabling the application of cellulose fiber-based materials as flexible conductive fibers.
In some specific embodiments, the nano-metal particles are present in an amount of 25-60% based on the total mass of the conductive fibers, for example: 30%, 35%, 40%, 45%, 50%, 55%, etc.; and/or the average particle diameter of the nano-metal particles is 10 to 500nm, preferably 50 to 500nm, more preferably 80 to 250nm; 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 that the obtained conductive fiber has more excellent mechanical property and conductivity.
In some embodiments, nucleation sites containing metal ions are formed on the surface of the fibrous substrate, and the nano-metal particles are attached to the surface of the fibrous substrate in situ based on the nucleation sites on the surface of the fibrous substrate, after which the metal ions are removed.
In other embodiments, the metal ions may be present in the interior of the fibrous matrix due to the presence of a plurality of irregular voids on the surface and/or within the fibrous matrix, and the nano-metal particles may be attached in situ to the interior of the fibrous matrix based on nucleation sites within the fibrous matrix, after which the metal ions are removed.
The nano metal particles comprise one or 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 a carbon element, an oxygen element, and a first metal element, the first metal element being 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, excellent conductivity is exhibited.
Second aspect
A second aspect of the invention provides a method of preparing a conductive fiber according to the first aspect of the invention by in situ reduction and deposition of nano-metal particles. The method specifically comprises the following steps:
providing the surface and/or interior of the fibrous 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 formed with nucleation sites, and removing the metal ions, the nano-metal particles comprising a first metal element;
the second metal element is different from the first metal element.
< preparation of fiber matrix >
In some specific embodiments, the fibrous matrix is formed from at least one wood cellulose fiber and/or bamboo cellulose fiber, and the present invention is not particularly limited with respect to the specific number of wood cellulose fibers and/or bamboo cellulose fibers, and may be set as desired, for example: the number of the wood cellulose fibers can be 2, 5, 10, 20, 50, 100, etc., and the wood cellulose fibers can be singly used, the bamboo cellulose fibers can be singly used, and the wood cellulose fibers and the bamboo cellulose fibers can be mixed for use. In particular, the fibrous matrix may be obtained commercially or may be prepared using the method of the present invention.
The preparation method of the wood fiber matrix can comprise the following steps: after the wood fiber raw material is subjected to short-time high-temperature cooking, in general, the cooking temperature is 150-180 ℃, the cooking time is 3-5min, and the cooking can be performed in water.
Further, the grinding of the wood fiber raw material by the grinding disc promotes the wood fiber raw material to be rapidly dissociated and converted into the wood fiber. Wherein the wood fiber raw material can be one or more fiber raw materials of poplar fiber, fir fiber and salix psammophila fiber.
In other specific embodiments, the method of making a bamboo fiber matrix may include the steps of: before the flexible electrode is prepared, bamboo chips are separated.
Specifically, the bamboo chips are separated by immersing the bamboo chips in a separating solution. The separation solution may be some separation solution commonly used in the present invention, for example: naClO 2 At least one of a solution, a NaOH solution, and the like.
For the sodium chlorite solution, which may be obtained by dissolving sodium chlorite in a solvent, 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. In particular, the mass concentration of sodium chlorite in the separation solution is 0.05-5wt.%, for example: 0.1wt.%, 0.2wt.%, 0.5wt.%, 0.8wt.%, 1.2wt.%, 1.5wt.%, 1.8wt.%, 2wt.%, 3wt.%, 4wt.%, etc. In addition, in order to better realize the separation of bamboo chips, glacial acetic acid is required to be added to adjust the pH of the sodium chlorite solution to be acidic when preparing the sodium chlorite solution, and the specific pH value can be 4-5, preferably 4.4-4.6.
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 method comprises the steps of firstly soaking the bamboo chips by using sodium chlorite solution at the water bath temperature of 40-80 ℃, and replacing the sodium chlorite solution every 5-7 hours until the bamboo chips are whitened, and then washing the bamboo chips to be neutral by using deionized water. Then using NaOH solution to soak the bamboo chips at the water bath temperature of 40-80 ℃ and replacing the NaOH solution every 5-7 hours until the solution is transparent, and using deionized water to wash the bamboo chips to be neutral. Finally, the bamboo chips are subjected to freeze drying and then the sample is shaken, so that the separation of the bamboo cellulose fibers and the parenchyma cells is realized.
After the above treatment, an interconnected porous structure is formed in the wood cellulose fibers and/or the bamboo cellulose fibers. This structure can act as a physical anchor site for subsequent nucleation in situ reduction and increase the effective contact area between the nucleation site and the cellulose molecular chain.
< formation of nucleation site >
Further, the surface and/or the inside of the fiber matrix of the present invention is provided with metal ions comprising a second metal element to form nucleation sites. 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 inside of a fiber matrix, and are not easy to run off in the use process.
The present invention pretreats a fibrous substrate by using a solution containing metal ions, for example: the fibrous matrix may be immersed in a solution containing metal ions such that the metal ions are present on the surface and/or inside the fibrous matrix to form nucleation sites. After the treatment of the solution containing metal ions, the crystal structure of the fiber matrix is converted into an antiparallel chain structure in the solution containing 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. Treatment with an alkali solution containing metal ions not only roughens the surface of the fibrous matrix but also causes the crystalline transformation of cellulose I to cellulose II of the fibrous matrix. This allows for 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, allowing the nano-metal particles to be reduced in situ and deposited on the surface and/or inside the fibrous matrix.
In some specific embodiments, the metal ion comprises 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, etc. For the mass concentration of the alkali solution of metal ions, the present invention preferably uses an alkali solution of metal ions of high concentration, for example: 10% or more of alkali solution, preferably 10% -30% of alkali solution, for example: 15wt%, 20wt%, 25wt%, etc. This is because when using an alkali solution with a high concentration of metal ions, it is possible to have more nucleation sites on the surface and/or inside of the fiber matrix, facilitating in situ reduction and deposition of the nano-metal particles.
The time of the impregnation is not particularly limited and may be selected as required, and it is preferable that the time of the impregnation is not less than 0.5 hours, 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 fibrous matrix with nucleation sites formed is washed and/or dried to remove the alkali solution present on the surface of the fibrous matrix to facilitate the formation of nano-metal particles.
< formation of nano-metal particles >
The invention obtains the conductive fiber by depositing nano metal particles on the surface and/or the inside of the fiber matrix with nucleation sites.
Specifically, a fiber matrix formed with nucleation sites is immersed in a solution containing a first metal element, and a first metal is deposited on the surface and/or inside of the fiber matrix formed with nucleation sites to form nano-metal particles.
When the fiber matrix with nucleation sites formed therein is immersed in a solution containing a first metal element, the fiber matrix with nucleation sites formed therein may be discolored, and as an example, the fiber matrix with nucleation sites formed therein may be immediately changed from white to golden yellow, then rapidly changed to dark brown, and finally changed to silver gray. This indicates that the nano-metal particles have formed.
Specifically, in a solution containing a first metal element, a fiber matrix formed with nucleation sites serves as an alkali trigger, inducing reduction of nano-metal particles at the nucleation sites. After element nucleation, nano-metal particles of uniform size grow and aggregate in situ within the fibrous matrix formed with nucleation sites. And, it was confirmed that nano-metal particles can grow in situ in the porous structure of the fibrous matrix.
Further, the solution containing the first metal element in the present invention 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 forming the nano silver particles, some reducing agent may be added to the silver ammonia solution appropriately so that the nano silver particles may be reduced in situ and deposited at nucleation sites. The use of silver ammonia solution in the present invention is more advantageous for the formation of nano silver particles.
The reducing agent is not particularly limited, and may be selected as required. Preferably, glucose is preferably used as the reducing agent in consideration of the loading condition 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, and may be added as needed. Specifically, the content of glucose in the silver ammonia-glucose solution can be 3-30mg mL -1 For example: 5mg mL -1 、10mg mL -1 、15mg mL -1 、20mg mL -1 、25mg mL -1 、30mg mL -1 Etc.; the silver ammonia content can be 3-50mg mL -1 For 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 -1 Etc.
Further, after the fiber matrix with nucleation sites formed is immersed in the silver ammonia-glucose solution, heating is performed under the water bath condition after the fiber matrix with nucleation sites formed becomes dark brown, thereby facilitating 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 needed.
Specifically, the temperature of heating may be 40-60 ℃, for example: 42 ℃, 45 ℃, 48 ℃, 50 ℃, 52 ℃, 55 ℃, 58 ℃ and the like; the heating time may be 0.5-2 hours, for example: 0.7 hours, 0.9 hours, 1.1 hours, 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 mode of washing is not particularly limited, and washing may be performed by selecting an appropriate polar solution as needed, preferably washing with water. 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 the inside of the fiber matrix to form nucleation sites, thereby realizing the deposition and aggregation of nano metal particles on the surface and/or the inside of the fiber matrix. The nano-metal particles of the present invention can be supported not only on the surface of the fiber, but also can grow within the porous structure of the fiber matrix. Filling 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 a very high retention rate of nano metal particles after washing 50 times, and thus, the washing resistance is also very excellent.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Comparative example 1
Bamboo Cellulose Fibers (BCFs) are extracted by a two-stage process by removing lignin and hemicellulose. First, acidifying NaClO in a water bath at 80 DEG C 2 The solution (1 wt.%, pH 4.5) treated the bamboo splints. 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 deionized water to obtain delignified bamboo strips. The delignified bamboo strands were further treated with 8% by mass NaOH solution in a 80 ℃ water bath, exchanging the solution every 6 hours until the strands again turned white. 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 (20 mg mL) at room temperature -1 pH 8) for 24 hours. After washing the surface of the bamboo cellulose fiber with deionized water for excess tannic acid, the sample was dried at room temperature. Subsequently, tannic acid/fiber was immersed in 80mL of 0.017g mL -1 AgNO 3 And (3) in the solution for 24 hours to ensure that tannic acid in the cellulose is reduced in situ to obtain a reduction site.
By directing at 32mg mL -1 AgNO 3 To prepare 80mL of silver ammonia solution (Ag (NH) 3 ) 2 OH). 80mL 17mg mL was used -1 Glucose solution asReducing agent and Ag (NH) 3 ) 2 OH mixing to obtain Ag (NH) 3 ) 2 OH-glucose mixed solution. Then, the tannic acid-Ag/fiber was immersed in Ag (NH) at 50 ℃ 3 ) 2 And (3) carrying out water bath for 1 hour in the OH-glucose mixed solution, and depositing nano silver layer by layer. Finally, rinsing with deionized water and drying at room temperature to obtain tannic acid-Ag/Ag fiber, which can be called Ag-AgNO 3 -TA-BCFs。
Comparative example 2
Bamboo Cellulose Fibers (BCFs) are extracted by a two-stage process by removing lignin and hemicellulose. First, acidifying NaClO in a water bath at 80 DEG C 2 The solution (1 wt.%, pH 4.5) treated the bamboo splints. 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 deionized water to obtain delignified bamboo strips. The delignified bamboo strands were further treated with 8% by mass NaOH solution in a 80 ℃ water bath. The solution was exchanged every 6 hours until the bamboo strands again whitened. 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 (20 mg mL) at room temperature -1 pH 8) for 24 hours. After washing the surface of the bamboo cellulose fiber with deionized water for excess tannic acid, the sample was dried at room temperature. Tannic acid/fiber was then immersed in 100mL FeCl 3 Solution (0.2 mg mL) -1 ) 1h in (2). After the deposition process is completed, tannic acid-Fe/fiber is obtained by washing and drying again.
By directing at 32mg mL -1 AgNO 3 To prepare 80mL of silver ammonia solution (Ag (NH) 3 ) 2 OH). 80mL 16mg mL was used -1 Glucose solution is used as reducing agent and is combined with Ag (NH) 3 ) 2 OH mixing to obtain Ag (NH) 3 ) 2 OH-glucose mixed solution. Then, tannic acid-FeCl 3 Immersion of the fibers in Ag (NH) at 50 DEG C 3 ) 2 And (3) carrying out water bath for 1 hour in the OH-glucose mixed solution, and depositing nano silver layer by layer. Finally, rinsing with deionized water and drying at room temperature to obtain tannic acid-Fe-Ag/fiber, designated as Ag-FeCl 3 -TA-BCFs。
Example 1
Bamboo Cellulose Fibers (BCFs) are extracted by a two-stage process by removing lignin and hemicellulose. First, acidifying NaClO in a water bath at 80 DEG C 2 The solution (1 wt.%, pH 4.5) treated the bamboo splints. 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 deionized water to obtain delignified bamboo strips. The delignified bamboo strands were further treated with 8% by mass NaOH solution in a 80 ℃ water bath. The solution was exchanged every 6 hours until the bamboo strands again whitened. Finally, washing the bamboo cellulose fiber to be neutral, and freeze-drying to obtain the bamboo cellulose fiber.
1g of bamboo cellulose fiber was pretreated by impregnating with 100mL of 20wt.% NaOH solution for 2h. Then, the treated cellulose was washed once with deionized water, the alkali solution on the surface was removed, and dried at 40 ℃ to obtain NaOH-treated cellulose.
By directing at 32mg mL -1 AgNO of (A) 3 To prepare 80mL of silver ammonia solution (Ag (NH) 3 ) 2 OH). 80mL 17mg mL was used -1 Glucose solution is used as reducing agent and is combined with Ag (NH) 3 ) 2 OH mixing to obtain Ag (NH) 3 ) 2 OH-glucose mixed solution.
Then, cellulose treated with NaOH impregnates Ag (NH) 3 ) 2 And (3) adding the mixture into the OH-glucose mixed solution. When the cellulose turns dark brown in 10 seconds, the vessel is transferred to a 50 ℃ water bath and held for 1 hour to completely deposit the nano silver particles, which are finally washed to neutrality, dried at room temperature to give a conductive fiber product, designated as: ag-NaOH-BCFs.
Example 2
Bamboo Cellulose Fibers (BCFs) are extracted by a two-stage process by removing lignin and hemicellulose. First, acidifying NaClO in a water bath at 80 DEG C 2 The solution (1 wt.%, pH 4.5) treated the bamboo splints. 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 deionized water to obtain delignified bamboo strips. In water bath at 80deg.CThe delignified bamboo strips were further treated with 8% NaOH solution. The solution was exchanged every 6 hours until the bamboo strands again whitened. Finally, washing the bamboo cellulose fiber to be neutral, and freeze-drying to obtain the bamboo cellulose fiber.
1g of bamboo cellulose fiber was pretreated by impregnating with 100mL of 20wt.% NaOH solution for 2h. Then, the treated cellulose was washed once with deionized water, the alkali solution on the surface was removed, and dried at 40 ℃ to obtain NaOH-treated cellulose.
By directing at 16mg mL -1 AgNO of (A) 3 To prepare 80mL of silver ammonia solution (Ag (NH) 3 ) 2 OH). 10mL 17mg mL was used -1 Glucose solution is used as reducing agent and is combined with Ag (NH) 3 ) 2 OH mixing to obtain Ag (NH) 3 ) 2 OH-glucose mixed solution.
Then, cellulose treated with NaOH impregnates Ag (NH) 3 ) 2 And (3) adding the mixture into the OH-glucose mixed solution. When the cellulose turns dark brown in 10 seconds, the vessel is transferred to a 50 ℃ water bath and held for 1 hour to completely deposit the nano silver particles, which is finally washed to neutrality and dried at room temperature to give a conductive fiber product, designated as: ag-NaOH-BCFs.
Example 3
Bamboo Cellulose Fibers (BCFs) are extracted by a two-stage process by removing lignin and hemicellulose. First, acidifying NaClO in a water bath at 80 DEG C 2 The solution (1 wt.%, pH 4.5) treated the bamboo splints. 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 deionized water to obtain delignified bamboo strips. The delignified bamboo strands were further treated with 8% by mass NaOH solution in a 80 ℃ water bath. The solution was exchanged every 6 hours until the bamboo strands again whitened. Finally, washing the bamboo cellulose fiber to be neutral, and freeze-drying to obtain the bamboo cellulose fiber.
1g of bamboo cellulose fiber was pretreated by impregnating with 100mL of 20wt.% NaOH solution for 2h. Then, the treated cellulose was washed once with deionized water, the alkali solution on the surface was removed, and dried at 40 ℃ to obtain NaOH-treated cellulose.
By adding to 4mg mL -1 AgNO of (A) 3 To prepare 80mL of silver ammonia solution (Ag (NH) 3 ) 2 OH). 40mL 17mg mL was used -1 Glucose solution is used as reducing agent and is combined with Ag (NH) 3 ) 2 OH mixing to obtain Ag (NH) 3 ) 2 OH-glucose mixed solution.
Then, cellulose treated with NaOH impregnates Ag (NH) 3 ) 2 And (3) adding the mixture into the OH-glucose mixed solution. When the cellulose turns dark brown in 10 seconds, the container is transferred to a 50 ℃ water bath and held for 1 hour to completely deposit the nano silver particles. Finally, washing the fiber to be neutral, and drying the fiber at room temperature to obtain a conductive fiber product, which is marked as: ag-NaOH-BCFs.
Performance testing
1. Elemental content
The elemental content of each example and comparative example was obtained using an esclab 250Xi spectrometer manufactured by american company (Thermo Fisher Scientific), and the results are shown in table 1:
TABLE 1
As can be seen from Table 1, the Ag element content in examples 1-3 of the present application is high, and no other metal element is contained. In addition, the content of Ag element was high and other metal elements were not contained by example 1 as compared with comparative examples 1-2.
2. Nano silver particle content test
The silver nanoparticle content (mass%) was obtained using an ICPMS7800 inductively coupled plasma mass spectrometer manufactured by american company (Agilent) and the results are shown in table 2:
TABLE 2
It can be seen from table 2 that the nano silver particles of the present invention are highly loaded and have no other metal impurities. In addition, by comparing example 1 with comparative example 1-2, the nano-silver particles of the present application are much higher than comparative example 1-2 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 by using a JSF08 high-precision short fiber mechanical property tester produced by China company (Shanghai, mianchen), and the results are shown in FIG. 4.
As can be seen from FIG. 4, the Ag-NaOH-BCFs of example 1 of the present invention have higher tensile strength, young's modulus and more excellent tensile strain than those of comparative examples 1 and 2. Therefore, the Ag-NaOH-BCFs of example 1 of the present invention were excellent in mechanical properties. The excellent mechanical properties are derived from the crystal structure of the bamboo cellulose fibers and the reinforcement of the nano silver particles in the cellulose fibers. In-situ reduction and aggregation of nano silver particles in the bamboo cellulose fibers can 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 (western Anemarrhena macro-target) company, and the result is shown in FIG. 6.
As can be seen from FIG. 6, the Ag-NaOH-BCFs of example 1 of the present invention have a conductivity as high as 31800 S.m -1 The individual fibers can be used as conductors to illuminate a Light Emitting Diode (LED), while the Ag-AgNO of comparative example 1 3 Conductivity of TA-BCFs and Ag-FeCl 3 TA-BCF of 110 S.m respectively -1 And 559 S.m -1 . It can be seen that the conductive fibers of the present invention also have very strong conductivity.
In addition, the applicant also conducted a correlation test on the conductivity of the Ag-NaOH-BCFs of example 3, which conductivity still reached 17400S m -1 . Thus, agNO is to be 3 The concentration of the Ag-NaOH-BCFs prepared by 8 times is reduced, and the Ag-NaOH-BCFs still have excellent conductivity.
5. Wash performance test
Experiments were performed using example 1 and comparative examples 1 and 2, and the fiber mass at different times of washing (the process of controlling washing is substantially identical) was weighed and calculated to obtain retention of nano silver, and the results are shown in fig. 7.
As can be seen from fig. 7, the retention of silver after 10 to 50 cycles of washing is shown. Although with Ag-AgNO 3 -TA-BCFs and Ag-FeCl 3 The Ag-NaOH-BCFs of example 1 of the present invention had a larger Ag particle size than the TA-BCFs, but still retained more than 96% of the silver nanoparticles.
It should be noted that, although the technical solution of the present invention is described in specific examples, those skilled in the art can understand that the present invention should not be limited thereto.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or 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 various embodiments described. The terminology used herein was chosen in order to best explain the principles of the embodiments, the practical application, or the technical improvements in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (8)
1. A conductive fiber, comprising:
fibrous matrix
Nano-metal particles attached to the surface and/or the interior of the fibrous matrix;
the content of the nano metal particles is 25-60% based on the total mass of the conductive fibers;
the surface of the conductive fiber at least comprises a carbon element, an 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%, the mass fraction of the oxygen element is 10-40%, and the mass fraction of the first metal element is 5-50%;
the fiber matrix is derived from bamboo cellulose fibers and/or wood cellulose fibers, and the wood cellulose fibers and/or the bamboo cellulose fibers have an interconnected porous structure therein;
the nano metal particles comprise one or more than two of nano silver particles, nano copper particles and nano nickel particles;
the preparation method of the conductive fiber comprises the following steps:
pretreating the fiber matrix with a solution containing metal ions, wherein the solution containing metal ions is an alkali solution containing metal ions;
providing the surface and/or interior of the fibrous 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 formed with nucleation sites, and removing the metal ions, the nano-metal particles comprising a first metal element;
the second metal element is different from the first metal element.
2. The conductive fiber of claim 1, wherein said nano-metal particles have an average particle size of 10 to 500 nm.
3. A method of producing the conductive fiber according to claim 1 or 2, comprising the steps of:
pretreating the fiber matrix with a solution containing metal ions, wherein the solution containing metal ions is an alkali solution containing metal ions;
providing the surface and/or interior of the fibrous 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 formed with nucleation sites, and removing the metal ions, the nano-metal particles comprising a first metal element;
the second metal element is different from the first metal element.
4. A method of preparing according to claim 3, wherein the fibrous matrix is immersed in a solution containing metal ions such that the metal ions are present on the surface and/or inside the fibrous matrix to form nucleation sites.
5. The method according to claim 3 or 4, wherein the solution containing metal ions is an alkali solution containing alkali metal ions.
6. The production method according to claim 3 or 4, 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 nano-metal particles.
7. The production method according to claim 6, 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.
8. The production method according to claim 7, wherein the solution containing the first metal element includes one or a combination of two or more of a silver ammonia solution, a copper sulfate solution, and a nickel sulfate solution.
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