CN115478430A - Bionic-structure core protection nanofiber aerogel and preparation method thereof - Google Patents
Bionic-structure core protection nanofiber aerogel and preparation method thereof Download PDFInfo
- Publication number
- CN115478430A CN115478430A CN202211030728.XA CN202211030728A CN115478430A CN 115478430 A CN115478430 A CN 115478430A CN 202211030728 A CN202211030728 A CN 202211030728A CN 115478430 A CN115478430 A CN 115478430A
- Authority
- CN
- China
- Prior art keywords
- nanofiber
- bismuth oxide
- polyurethane
- bionic
- aerogel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002121 nanofiber Substances 0.000 title claims abstract description 108
- 239000004964 aerogel Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000011664 nicotinic acid Substances 0.000 claims abstract description 31
- 239000012528 membrane Substances 0.000 claims description 87
- 239000007788 liquid Substances 0.000 claims description 72
- 239000004814 polyurethane Substances 0.000 claims description 56
- 239000000835 fiber Substances 0.000 claims description 55
- 229920002635 polyurethane Polymers 0.000 claims description 55
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 46
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 46
- 238000005470 impregnation Methods 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 46
- 239000002105 nanoparticle Substances 0.000 claims description 29
- 229940075613 gadolinium oxide Drugs 0.000 claims description 25
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims description 25
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 25
- 238000009987 spinning Methods 0.000 claims description 22
- 239000002135 nanosheet Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- 238000007710 freezing Methods 0.000 claims description 16
- 230000008014 freezing Effects 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 13
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical class [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 13
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 238000004108 freeze drying Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 9
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 8
- -1 fluoro-bis (propyl-2-yloxy) -mercaptophosphane Chemical class 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 8
- 238000000265 homogenisation Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000004132 cross linking Methods 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 7
- 238000010041 electrostatic spinning Methods 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 7
- 241000237852 Mollusca Species 0.000 claims description 6
- 239000011449 brick Substances 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 6
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- 239000003093 cationic surfactant Substances 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- SMTOKHQOVJRXLK-UHFFFAOYSA-N butane-1,4-dithiol Chemical compound SCCCCS SMTOKHQOVJRXLK-UHFFFAOYSA-N 0.000 claims description 3
- UPHWVVKYDQHTCF-UHFFFAOYSA-N octadecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCCCCCCCN UPHWVVKYDQHTCF-UHFFFAOYSA-N 0.000 claims description 3
- 229920000083 poly(allylamine) Polymers 0.000 claims description 3
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- ZHLKXBJTJHRTTE-UHFFFAOYSA-N Chlorobenside Chemical compound C1=CC(Cl)=CC=C1CSC1=CC=C(Cl)C=C1 ZHLKXBJTJHRTTE-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- HBRNMIYLJIXXEE-UHFFFAOYSA-N dodecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCN HBRNMIYLJIXXEE-UHFFFAOYSA-N 0.000 claims description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 2
- 238000009775 high-speed stirring Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000005057 refrigeration Methods 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 238000001523 electrospinning Methods 0.000 claims 1
- PZNOBXVHZYGUEX-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine;hydrochloride Chemical compound Cl.C=CCNCC=C PZNOBXVHZYGUEX-UHFFFAOYSA-N 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 20
- 230000001681 protective effect Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 230000005855 radiation Effects 0.000 description 11
- 230000003592 biomimetic effect Effects 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005865 ionizing radiation Effects 0.000 description 3
- 239000011454 mudbrick Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007123 defense Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002060 nanoflake Substances 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 208000031404 Chromosome Aberrations Diseases 0.000 description 1
- 206010067477 Cytogenetic abnormality Diseases 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 206010027439 Metal poisoning Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000000560 X-ray reflectometry Methods 0.000 description 1
- 206010000210 abortion Diseases 0.000 description 1
- 231100000176 abortion Toxicity 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000002710 gonadal effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000011132 hemopoiesis Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000036512 infertility Effects 0.000 description 1
- 208000000509 infertility Diseases 0.000 description 1
- 208000021267 infertility disease Diseases 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 208000008127 lead poisoning Diseases 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 210000004940 nucleus Anatomy 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 231100000915 pathological change Toxicity 0.000 description 1
- 230000036285 pathological change Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 210000001685 thyroid gland Anatomy 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000001291 vacuum drying Methods 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
- D06M11/32—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
- D06M11/45—Oxides or hydroxides of elements of Groups 3 or 13 of the Periodic Table; Aluminates
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
- D04H1/4358—Polyurethanes
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43825—Composite fibres
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/395—Isocyanates
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
- D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F1/00—Shielding characterised by the composition of the materials
- G21F1/02—Selection of uniform shielding materials
- G21F1/10—Organic substances; Dispersions in organic carriers
- G21F1/103—Dispersions in organic carriers
-
- 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
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/38—Polyurethanes
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to a bionic-structure core protection nanofiber aerogel and a preparation method thereof. Compared with the prior art, the core protection nanofiber aerogel with the bionic structure has the advantages that the shielding efficiency of X rays below 150keV can reach over 90 percent, the stretching performance is realized, the large-scale application can be realized, and the universality is better.
Description
Technical Field
The invention relates to the technical field of preparation of a nuclear protection nanofiber material, in particular to a nuclear protection nanofiber aerogel with a bionic structure and a preparation method thereof.
Background
With the continuous development of nuclear science and national defense industry, various radioactive rays are widely applied. The X-ray is used as a short-wave ionizing radiation source and is widely applied in the fields of national defense construction, industrial flaw detection, medical treatment and health and the like. However, the excessive X-ray radiation can affect the physiological function of the human body, cause chromosome abnormality, cause direct damage to the three major systems of human reproduction, nerve and immunity, are the main causes of cardiovascular diseases, diabetes and cancer mutation, and the inducing factors of abortion, sterility, teratogenesis and other pathological changes of pregnant women, and can directly affect the development of body tissues and bones of minors, so as to cause the reduction of vision, memory and liver hematopoiesis. Therefore, wearing protective clothing capable of shielding X-rays efficiently has become one of the important measures for reducing radiation hazard and protecting related people.
The traditional radiation protection material such as lead rubber is a composite material prepared by taking lead or lead oxide as a main X-ray absorbent and natural rubber as a base material, has the X-ray shielding efficiency of over 90 percent, is used as a thyroid collar shield, a gonadal shield, a protection apron and a protection glove, and provides protection for doctors and examinees. However, in actual use, the lead clothes have the following three disadvantages: (1) Heavy, poor flexibility, air impermeability and extremely poor wearing comfort, and the weight of a lead apron with 0.5mmPb equivalent weight is 4.95kg; (2) Lead has an atomic number of 82, which has good absorption of ionizing radiation above 88keV and between 13keV and 40keV, but a weakly absorbing region for ionizing radiation between 40keV and 88 keV; (3) Lead-containing materials are biologically toxic and lead poisoning can result from wearing lead clothes for a long time. Therefore, the development of a leadless wearable radiation protection material is a key problem to be solved urgently in the field of current nuclear protection.
In order to overcome the above-mentioned drawbacks of lead-free garments, researchers have conducted a series of studies on lead-free wearable radiation protective garments in recent years. Patent CN101137285A discloses a composite shielding material for medical X-ray protection, which is prepared by adding barium, cadmium, tin and lanthanide into high polymer materials such as natural rubber and the like, and overcomes the defect of weak absorption area caused by using a single element. However, the high molecular material has low interface compatibility, the problem of gaps in the material, and the like, so that the material has poor dispersibility, low mechanical property and shielding holes; patent CN110341289a discloses a method for making a fabric resistant to X-rays, which is to coat a mixed liquid of tungsten metal and iron ore on a polyurethane film to obtain a protective garment capable of preventing X-rays, wherein the protective garment has good softness, but poor air permeability, and is difficult to meet the requirement of wearability; in addition, some researchers have prepared fibrous protective materials by adding X-ray absorbent into the spinning solution, which have good softness and air permeability, but have poor shielding efficiency against X-rays due to limited content and variety of added functional particles and low material thickness. In the latest research, patent CN111469506a discloses a novel nuclear radiation protective material and a preparation method thereof, wherein an outer layer, a shielding layer, a scattering layer and an inner layer of fiber fabric are bonded by thermal bonding to prepare the novel nuclear radiation protective material with high-efficiency nuclear protection performance and air permeability, but the high-efficiency shielding performance of the novel nuclear radiation protective material only depends on the absorption of a large amount of metal powder such as graphene, tungsten powder and bismuth powder on X-rays, so that the mechanical performance of the nuclear radiation protective clothing is reduced, the weight of the nuclear radiation protective clothing is increased, and the wearing comfort is reduced. Therefore, the development of a nuclear protection material which is light, breathable and capable of efficiently shielding the full-wave band X-ray and a preparation method thereof are needed.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a core protection nanofiber aerogel with a bionic structure and a preparation method thereof, so as to overcome the defects of poor mechanical property, heavy weight and low comfort of the existing core protection material, and the shielding efficiency of the prepared core protection nanofiber aerogel on X rays below 150keV can reach more than 90%.
The purpose of the invention can be realized by the following technical scheme:
the first purpose of the invention is to provide a preparation method of a bionic structure core protection nanofiber aerogel, which takes a polyurethane/bismuth oxide nanofiber membrane as a mud component and takes gadolinium oxide nanosheets as a brick component, and prepares the bionic structure core protection nanofiber aerogel by stacking layer by layer.
Further, the preparation method comprises the following steps:
the first step is as follows: performing surface hydrophobic modification on bismuth oxide nanoparticles by using a small molecular ligand to obtain modified bismuth oxide nanoparticles, and uniformly dispersing the modified bismuth oxide nanoparticles in a solvent by combining a micro-jet high-pressure homogenization method and mechanical stirring to obtain a dispersion liquid, wherein the content of the modified bismuth oxide nanoparticles is 1-15 wt%;
the second step is that: adding polyurethane polymer slices into the dispersion liquid obtained in the first step while performing ultrasonic stirring by using a gradient ultrasonic dispersion method to obtain a homogeneous and stable spinning solution, wherein the polyurethane content is 10-30 wt%;
the third step: spinning the spinning solution obtained in the second step by using a high-temperature electrostatic spinning process to obtain a polyurethane/bismuth oxide nanofiber membrane with uniform appearance;
the fourth step: soaking the polyurethane/bismuth oxide nanofiber membrane obtained in the third step into a cationic surfactant to endow the fiber membrane with positive charges, so as to obtain a positive charge polyurethane/bismuth oxide nanofiber membrane;
the fifth step: preparing gadolinium oxide nanosheets by utilizing a coprecipitation method of gadolinium oxide powder, dispersing the gadolinium oxide nanosheets and a water-based hexamethylene diisocyanate cross-linking agent in water, and stirring at a high speed for 2 hours to obtain a uniformly dispersed water-based impregnation liquid;
and a sixth step: shearing the positive charge polyurethane/bismuth oxide nanofiber membrane obtained in the fourth step, stacking layer by layer in the aqueous impregnation liquid obtained in the fifth step, and ultrasonically soaking to obtain a fiber membrane impregnation liquid;
the seventh step: pre-freezing the fiber membrane impregnation liquid obtained in the sixth step in a mould for 10-30 min, taking out the fiber membrane impregnation liquid from the mould after the fiber membrane impregnation liquid is completely frozen, and freeze-drying the fiber membrane impregnation liquid in refrigeration equipment at a low temperature for 10-24 h to obtain a long-range ordered lamellar and wavy blocky nanofiber assembly;
eighth step: and (3) heating the blocky nanofiber aggregate obtained in the seventh step to 140 ℃ in heating equipment, preserving heat, and establishing stable cross-linking points in the interlaminar fibers to obtain the core protection nanofiber aerogel with a bionic structure and good mechanical properties and X-ray shielding properties.
Further, in the first step, the solvent is DMF.
Preferably, in the first step, the average particle diameter of the bismuth oxide nanoparticles is 50nm.
Preferably, the small molecule ligand is one or a combination of more of fluoro-bis (propyl-2-yloxy) -mercaptophosphane, dimethoxy- [ (2-methyl-1,3-oxathiolan-2-yl) methylthio ] -mercaptophosphane, dimethoxy- [ (2-methyl-1,3-oxathiolan-2-yl) methylthio ] -mercaptophosphane, dimethoxy- [ (2-methyl-1,3-oxathiolan-2-yl) methylthio ] -mercaptophosphane, 1-chloro-4- [ (4-chlorophenyl) mercaptomethyl ] benzene, thiophenol, 1,3-propanedithiol and 1,4-butanedithiol.
Further, in the first step, the micro-jet high-pressure homogenization method is to arrange a nano stirring source in the solution and generate a plurality of micro turbulent flow regions by using the nano stirring source.
Preferably, the number of the nano stirring sources is 3 to 5.
Further, in the second step, the gradient ultrasound method is that the ultrasound frequency gradient is increased during the process of adding the polyurethane polymer slice.
Preferably, the number of the gradients is 3, respectively before, during and after the addition of the polymer.
Further preferably, the gradient is 20HZ.
Further, in the third step, the high-temperature electrostatic spinning process is to arrange a real-time heating sheet in a jet flow drafting zone.
Preferably, the jet drafting zone temperature is 35 to 50 ℃.
Further, in the third step, the thickness of the polyurethane/bismuth oxide nanofiber membrane is 30-50 μm.
Further, in the third step, the diameter of the fiber of the polyurethane/bismuth oxide nanofiber membrane with the thickness of 30-50 μm is 200-300 nm.
Preferably, in the fourth step, the cationic surfactant is one or a combination of several of dodecylammonium acetate, octadecylammonium acetate, polyallylamine, sodium dodecylbenzene sulfonate, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, polydimethyldiallylammonium chloride and polyacrylamide.
Preferably, in the fourth step, the particle size of the gadolinium oxide powder is 50 to 500nm.
Preferably, in the fifth step, the addition amount of the aqueous hexamethylene diisocyanate crosslinking agent is 0.5wt% to 5wt%.
Preferably, in the fifth step, the rotation speed of the high-speed stirring is 200 to 2000rad/min.
Preferably, in the sixth step, the thickness of the positive charge polyurethane/bismuth oxide nanofiber membrane is 50 μm to 200 μm.
Preferably, in the sixth step, the cutting mode is automatic fixed-length cutting, and the fiber membrane is cut into the shape with the same size.
Preferably, in the sixth step, the ultrasonic soaking time is 30-90 min, and the bath ratio of the ultrasonic soaking is 1:50 to 1:200.
preferably, in the seventh step, the pre-freezing mode is one of liquid nitrogen, a refrigerator and a freeze dryer.
Preferably, in the seventh step, the freezing device is a vacuum freeze dryer.
Further preferably, the temperature of a cold plate of the vacuum freeze dryer is less than or equal to-20 ℃, the temperature of a cold trap is less than or equal to-50 ℃, and the vacuum degree is less than or equal to 100Pa.
Preferably, in the eighth step, the heating device is an oven.
Further preferably, the oven is a forced air oven or a vacuum oven.
Preferably, in the eighth step, the temperature increase rate is 5 ℃/mn to 20 ℃/min.
Preferably, in the eighth step, the heat preservation time is 0.5 to 2 hours.
The second purpose of the invention is to provide the core protection nano-fiber aerogel with a bionic structure prepared by the preparation method, wherein the core protection nano-fiber aerogel has a mollusk shell-imitated 'mud-brick' long-range ordered multilayer wave structure.
Compared with the prior art, the invention has the following beneficial effects:
1) The lowest density of the core protection nanofiber aerogel with the bionic structure can reach 1 g-cm -3 Far lower than the density of the lead plate of 11.34g cm -3 And the complementary Bi and Gd elements on the absorption edge of the K layer generate a synergistic shielding effect on X rays, so that the shielding efficiency of the core protection nanofiber aerogel with the bionic structure and the thickness of 2mm on the X rays below 150keV can reach more than 90%.
2) The core protection nanofiber aerogel with the bionic structure, provided by the invention, has the advantages that the tensile property is endowed to the material due to the excellent wave structure between nanofiber membrane layers and the excellent polyurethane, the elongation at break reaches 850%, and the plastic deformation is less than 20% after 500 times of stretching cycles.
3) The preparation method of the bionic-structure nuclear protection nanofiber aerogel provided by the invention is a continuous process, uniform distribution of nanoparticles in polyurethane is realized through micromolecule ligand modification, gradient ultrasound and spinning process control, and the problem of easy agglomeration in the traditional inorganic particle doping process is solved; the self-assembly of the gadolinium oxide nanosheet between polyurethane/bismuth oxide fiber membrane layers is realized by utilizing the electrostatic attraction effect, and the problem that inorganic matters are easy to fall off in the existing three-dimensional intercalation structure is solved; the long-range ordered wavy structure is constructed in the multilayer nanofiber membrane by the growth and extrusion of ice crystals and the nondestructive replacement of gas-liquid in the freeze drying process, and the method can be applied in scale and has better universality.
Drawings
Fig. 1 is a schematic diagram of an action mechanism of the core protection nanofiber aerogel with a biomimetic structure in the technical scheme.
Fig. 2 is an electron microscope image of a long-range ordered wave multilevel structure of the core-protective nanofiber aerogel with a biomimetic structure in example 1, wherein (a) is a structure display image, (b) is a partial enlarged view of (a), and (c) is a partial enlarged view of (b).
Fig. 3 is an XRD pattern of the core protective nanofiber aerogel of biomimetic structure in example 2.
Fig. 4 is a tensile fracture curve diagram of the core protective nanofiber aerogel of the biomimetic structure in example 3.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the concept of the invention. All falling within the scope of the present invention.
In the technical scheme, characteristics such as preparation means, materials, structures or composition ratios and the like which are not explicitly described are all regarded as common technical characteristics disclosed in the prior art.
The technical scheme fully realizes the defects of poor mechanical property, heavy weight, low comfort and poor shielding efficiency on X-rays in the existing nuclear protection material in the prior art in a conception process, and inspires the unique structure of mollusks, namely shells of mollusks have natural protection capability on nuclear radiation, the main component of the shell is mainly calcium carbonate and has unique adsorption efficacy on radioactive nuclides, and the shells have unique multi-scale and multi-level 'brick-mud' assembly structures, so that the shell has excellent characteristics of good toughness, good X-ray reflectivity and the like due to the multi-level layered structure, a polyurethane/bismuth oxide nanofiber membrane is innovatively used as a 'mud' component, and gadolinium oxide nanosheets are used as a 'brick' component to prepare the nuclear protection nanofiber aerogel with a bionic structure, wherein the nanofiber aerogel has a 'mud-brick' long-range ordered multilayer wave structure imitating shells of mollusks; wherein, the bismuth oxide and gadolinium oxide components have different K absorption edges, and can realize the full-wave-band absorption of X-rays below 150 keV; meanwhile, the multilayer fiber realizes multiple reflections of X-rays in the material, so that the excellent shielding effect of the X-rays is achieved, and the schematic action mechanism of the multilayer fiber is shown in figure 1.
The invention selects different organic micromolecular ligand pairs of bismuth oxide (Bi) 2 O 3 ) And (3) carrying out surface hydrophobic modification on the nano particles, dispersing the modified bismuth oxide nano particles in a solvent DMF (dimethyl formamide) by combining a micro-jet high-pressure homogenization method, slowly adding the Polyurethane (PU) polymer slices for multiple times, and further preparing the high-dispersity spinning solution by utilizing a gradient ultrasonic method. Wherein, the micromolecule ligand provides lone pair electrons for the bismuth oxide nano-particles, so that the nano-particles generate electrostatic repulsion in DMF, and the agglomeration of the nano-particles is avoided. Then, the high-temperature electrostatic spinning method is utilized to accelerate the phase separation rate of the electrostatic jet flow in the spinning process, promote the directional migration-fixation of the nano particles in the polymer jet flow, and prepare PU/Bi with uniform appearance, thickness of 30-50 mu m and fiber diameter of 200-300 nm 2 O 3 A nanofiber membrane. Then PU/Bi 2 O 3 The nanofiber membrane is immersed in an amine cationic surfactant, and amino groups with positive charges can be introduced to the surface of the fiber membrane. Preparation of gadolinium oxide (Gd) by coprecipitation method 2 O 3 ) The surface unsaturated oxygen of the nano-flake is adsorbed with hydroxyl group to coordinate so as to make the nano-flake negatively charged, and then Gd is added 2 O 3 Adding the nano-sheet and the aqueous hexamethylene diisocyanate cross-linking agent togetherAdding into water, stirring at high speed for 2 hr to obtain homogeneously dispersed soaking liquid; mixing PU/Bi 2 O 3 And cutting the nanofiber membrane into shapes with the same size, stacking the nanofiber membrane layer by layer in an impregnation liquid, and ultrasonically soaking the nanofiber membrane to enable the impregnation liquid to enter gaps of the nanofiber membrane. In this process, gd 2 O 3 Nano thin sheet and PU/Bi 2 O 3 The nanofiber membranes are stacked layer by layer due to electrostatic attraction to form a mud-brick structure similar to a mollusk shell. And then placing the fiber membrane impregnation liquid which is laid layer by layer in a prepared mould, pre-freezing the impregnation liquid in the mould at a low temperature for 10-30 min, taking the impregnation liquid out of the mould after the impregnation liquid is completely frozen, placing the impregnation liquid in a freezing device, and taking the impregnation liquid out after low-temperature freeze drying for 10-24 h to obtain the long-range ordered layered wavy nano-fiber aerogel. In the freezing and forming process, the temperature of the slurry in the mold is rapidly reduced, the solvent in the slurry is rapidly cooled and forms crystal nuclei and grows rapidly, and the nanofiber membrane deforms along the growth direction of the ice crystals due to the extrusion action of the ice crystals to form an arch-shaped wave structure. Carry out vacuum drying to the sample after the sample is thoroughly cooled off and solidifies, the freeze-drying process will make the solvent that freezes solidify not pass through liquid, directly converts into gaseous volatilization through sublimation and gets rid of, has kept the wave structure that solid-state solvent crystal formed to obtain the nuclear protection nanofiber aerogel that has long-range ordered multilayer wave structure, but do not have interact between the fibrous membrane of layer, the structure that obtains is unstable, consequently needs subsequent cross-linking solidification to handle.
Placing the block-shaped nanofiber aggregate which is subjected to freeze drying molding in heating equipment, heating to 140 ℃, preserving heat, and carrying out high-temperature heating treatment to enable diisocyanate between fiber layers and polyurethane components in the fibers to be subjected to in-situ polymerization and solidification, so that stable cross-linking points are established in the fibers between the layers, and finally the nuclear protection nanofiber aerogel with good mechanical properties and X-ray shielding properties is obtained. The reason why PU is not shrunk by high temperature in this process is that the inorganic component Bi 2 O 3 、Gd 2 O 3 So that the nanofiber aerogel has good thermal curing stability.
Example 1
The embodiment provides a preparation method of a core protection nanofiber aerogel with a bionic structure, which takes a polyurethane/bismuth oxide nanofiber membrane as a mud component and a gadolinium oxide nanosheet as a brick component, and prepares the core protection nanofiber aerogel with the bionic structure by stacking layer by layer, and comprises the following steps:
the first step is as follows: performing surface hydrophobic modification on bismuth oxide nanoparticles (with the average particle size of 50 nm) by utilizing 1,3-propanedithiol to obtain modified bismuth oxide nanoparticles, and dispersing the modified bismuth oxide nanoparticles in DMF by combining a micro-jet high-pressure homogenization method and mechanical stirring to obtain a dispersion liquid with uniformly dispersed nanoparticles, wherein the particle content in the dispersion liquid is 5wt%;
the second step: adding polyurethane polymer slices into the obtained dispersion liquid while ultrasonically stirring by using a gradient ultrasonic dispersion method (200 Hz, 220Hz and 240 Hz) to obtain a homogeneous and stable spinning liquid, wherein the polyurethane content in the spinning liquid is 15wt%;
the third step: spinning the homogeneous stable spinning solution by using a high-temperature electrostatic spinning process (the temperature of a drafting area is 35 ℃) to prepare a polyurethane/bismuth oxide nanofiber membrane with uniform appearance, wherein the thickness of the polyurethane/bismuth oxide nanofiber membrane is 50 microns;
the fourth step: immersing the polyurethane/bismuth oxide nanofiber membrane in a polyallylamine solution (2 wt%) to impart a positive charge to the fiber membrane;
the fifth step: using Gd 2 O 3 Preparing a gadolinium oxide nanosheet by a coprecipitation method of powder (50 nm), dispersing the gadolinium oxide nanosheet and a water-based hexamethylene diisocyanate cross-linking agent into deionized water together, wherein the addition amount of the cross-linking agent is 1wt%, and stirring at a high speed of 500rad/min for 2h to obtain a homogeneously dispersed water-based impregnation liquid;
and a sixth step: cutting a polyurethane/bismuth oxide nanofiber membrane with the thickness of 50 mu m into a shape with the same size, stacking the polyurethane/bismuth oxide nanofiber membrane in the impregnation liquid layer by layer for 50 layers, and ultrasonically soaking for 30 minutes (bath ratio 1;
the seventh step: placing the fiber membrane impregnation liquid which is layered layer by layer in a prepared mould, pre-freezing the fiber membrane impregnation liquid at a low temperature by using liquid nitrogen, taking the fiber membrane impregnation liquid out of the mould after the fiber membrane impregnation liquid is completely frozen, placing the fiber membrane impregnation liquid in a vacuum freezing dryer (the temperature of a cold plate is 25 ℃ below zero, the temperature of a cold trap is 55 ℃ below zero, and the vacuum degree is 50 Pa), and taking the fiber membrane impregnation liquid out after low-temperature freeze drying to obtain a long-range ordered lamellar wavy blocky nanofiber aggregate;
eighth step: and (3) placing the block-shaped nanofiber aggregate formed by freeze drying in a blast oven, heating to 140 ℃, preserving heat for 1h, and establishing a stable cross-linking point on the interlaminar fiber to finally obtain the core protection nanofiber aerogel with a bionic structure and good mechanical property and X-ray shielding property.
The long-range ordered layered wavy structure of the core protection nanofiber aerogel with the bionic structure in the embodiment is shown in fig. 2, and as can be seen from fig. 2, the fiber membrane layers are stacked to form a layered structure similar to a pearl layer; meanwhile, an arch-shaped wave structure is formed among the fiber membranes, and the fiber membranes have the characteristics of long-range order and short-range disorder; and gadolinium oxide nanosheets dispersed between the fibrous membranes.
Example 2
The embodiment provides a preparation method of a core protection nanofiber aerogel with a bionic structure, which takes a polyurethane/bismuth oxide nanofiber membrane as a mud component and a gadolinium oxide nanosheet as a brick component, and prepares the core protection nanofiber aerogel with the bionic structure by stacking layer by layer, and comprises the following steps:
the first step is as follows: performing surface hydrophobic modification on bismuth oxide nanoparticles (with the average particle size of 50 nm) by utilizing 1,4-butanedithiol to obtain modified bismuth oxide nanoparticles, and dispersing the modified bismuth oxide nanoparticles in DMF by combining a micro-jet high-pressure homogenization method and mechanical stirring to obtain a dispersion liquid with uniformly dispersed nanoparticles, wherein the particle content in the dispersion liquid is 10wt%;
the second step is that: adding polyurethane polymer slices into the obtained dispersion liquid while ultrasonically stirring by using a gradient ultrasonic dispersion method (300 Hz, 320Hz and 340 Hz) to obtain a homogeneous and stable spinning liquid, wherein the content of polyurethane in the spinning liquid is 20wt%;
the third step: spinning the homogeneous stable spinning solution by using a high-temperature electrostatic spinning process (the temperature of a drafting zone is 40 ℃) to prepare a polyurethane/bismuth oxide nanofiber membrane with uniform appearance, wherein the thickness of the polyurethane/bismuth oxide nanofiber membrane is 100 mu m;
the fourth step: immersing the polyurethane/bismuth oxide nanofiber membrane in a solution of octadecyl ammonium acetate (2 wt%) to impart a positive charge to the fiber membrane;
the fifth step: using Gd 2 O 3 Preparing a gadolinium oxide nanosheet by a coprecipitation method of powder (100 nm), dispersing the gadolinium oxide nanosheet and a water-based hexamethylene diisocyanate cross-linking agent into deionized water together, wherein the addition amount of the cross-linking agent is 1.5wt%, and stirring at a high speed of 1000rad/min for 2h to obtain a homogeneously dispersed water-based impregnation liquid;
and a sixth step: cutting a polyurethane/bismuth oxide nanofiber membrane with the thickness of 100 mu m into shapes with the same size, stacking the polyurethane/bismuth oxide nanofiber membrane layer by layer in the impregnation liquid for 40 layers, and ultrasonically soaking for 60 minutes (bath ratio 1;
the seventh step: placing the fiber membrane impregnation liquid which is layered in layers in a prepared mould, pre-freezing the fiber membrane impregnation liquid at a low temperature by using liquid nitrogen, taking the fiber membrane impregnation liquid out of the mould after the fiber membrane impregnation liquid is completely frozen, placing the fiber membrane impregnation liquid in a vacuum freezing dryer (the temperature of a cold plate is-22 ℃, the temperature of a cold trap is-54 ℃, and the vacuum degree is 100 Pa), and taking the fiber membrane impregnation liquid out after low-temperature freezing drying to obtain a long-range ordered lamellar wavy blocky nanofiber aggregate;
eighth step: and (3) placing the block nanofiber aggregate formed by freeze drying in a blast oven, heating to 140 ℃, preserving heat for 2 hours, and establishing stable cross-linking points on interlaminar fibers to finally obtain the core protection nanofiber aerogel with a bionic structure and good mechanical properties and X-ray shielding properties.
The XRD pattern of the core protection nanofiber aerogel of the biomimetic structure in this embodiment is shown in fig. 3, and it can be seen from fig. 3 that the surface of the biomimetic nanofiber aerogel has gadolinium oxide and bismuth oxide at the same time.
Example 3
The embodiment provides a preparation method of a core protection nanofiber aerogel with a bionic structure, which takes a polyurethane/bismuth oxide nanofiber membrane as a mud component and a gadolinium oxide nanosheet as a brick component, and prepares the core protection nanofiber aerogel with the bionic structure by stacking layer by layer, and comprises the following steps:
the first step is as follows: performing surface hydrophobic modification on bismuth oxide nanoparticles (with the average particle size of 50 nm) by using thiophenol to obtain modified bismuth oxide nanoparticles, and dispersing the modified bismuth oxide nanoparticles in DMF (dimethyl formamide) by combining a micro-jet high-pressure homogenization method and mechanical stirring to obtain a dispersion liquid with uniformly dispersed nanoparticles, wherein the particle content in the dispersion liquid is 15wt%;
the second step is that: adding polyurethane polymer slices into the obtained dispersion liquid while performing ultrasonic stirring by using a gradient ultrasonic dispersion method (400 Hz, 420Hz and 440 Hz) to obtain a homogeneous and stable spinning solution, wherein the polyurethane content in the spinning solution is 15wt%;
the third step: spinning the homogeneous stable spinning solution by using a high-temperature electrostatic spinning process (the temperature of a drafting area is 50 ℃) to prepare a polyurethane/bismuth oxide nanofiber membrane with uniform appearance, wherein the thickness of the polyurethane/bismuth oxide nanofiber membrane is 200 mu m;
the fourth step: immersing the polyurethane/bismuth oxide nanofiber membrane into a mixed solution (3 wt% of which the mass ratio of poly (dimethyldiallylammonium chloride) to polyacrylamide is 7:3) of poly (dimethyldiallylammonium chloride) and polyacrylamide to endow the fiber membrane with positive charges;
the fifth step: using Gd 2 O 3 Preparing a gadolinium oxide nanosheet by a coprecipitation method of powder (200 nm), dispersing the gadolinium oxide nanosheet and a water-based hexamethylene diisocyanate cross-linking agent into deionized water together, wherein the addition amount of the cross-linking agent is 2wt%, and stirring at a high speed of 1500rad/min for 2h to obtain a homogeneously dispersed water-based impregnation liquid;
and a sixth step: shearing a polyurethane/bismuth oxide nanofiber membrane with the thickness of 200 mu m into a shape with the same size, stacking the polyurethane/bismuth oxide nanofiber membrane in the impregnation liquid layer by layer for 20 layers, and ultrasonically soaking for 90 minutes (bath ratio 1;
the seventh step: placing the fiber membrane impregnation liquid which is layered layer by layer in a prepared mould, pre-freezing the fiber membrane impregnation liquid at a low temperature by using liquid nitrogen, taking the fiber membrane impregnation liquid out of the mould after the fiber membrane impregnation liquid is completely frozen, placing the fiber membrane impregnation liquid in a vacuum freezing dryer (the temperature of a cold plate is 20 ℃ below zero, the temperature of a cold trap is 50 ℃ below zero, and the vacuum degree is 10 Pa), and taking the fiber membrane impregnation liquid out after low-temperature freeze drying to obtain a long-range ordered lamellar wavy blocky nanofiber aggregate;
eighth step: and (3) placing the block-shaped nanofiber aggregate formed by freeze drying in a blast oven, heating to 140 ℃, preserving heat for 0.5h, and establishing stable cross-linking points on interlaminar fibers to finally obtain the core protection nanofiber aerogel with a bionic structure and good mechanical properties and X-ray shielding properties.
The tensile fracture curve of the core protection nanofiber aerogel with a biomimetic structure in the embodiment is shown in fig. 4, and it can be seen from fig. 4 that the tensile strength of the prepared core protection nanofiber aerogel with a biomimetic structure is 3.8MPa.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of a bionic-structure nuclear protection nanofiber aerogel is characterized in that a polyurethane/bismuth oxide nanofiber membrane is used as a mud component, gadolinium oxide nanosheets are used as a brick component, and the bionic-structure nuclear protection nanofiber aerogel is prepared by stacking layer by layer.
2. The preparation method of the bionic structure core-protection nanofiber aerogel according to claim 1, characterized by comprising the following steps:
the first step is as follows: performing surface hydrophobic modification on bismuth oxide nanoparticles by using a small molecular ligand to obtain modified bismuth oxide nanoparticles, and uniformly dispersing the modified bismuth oxide nanoparticles in a solvent by combining a micro-jet high-pressure homogenization method and mechanical stirring to obtain a dispersion liquid, wherein the content of the modified bismuth oxide nanoparticles is 1-15 wt%;
the second step is that: adding polyurethane polymer slices into the dispersion liquid obtained in the first step while ultrasonically stirring by using a gradient ultrasonic dispersion method to obtain a homogeneous and stable spinning solution, wherein the polyurethane content is 10-30 wt%;
the third step: spinning the spinning solution obtained in the second step by using a high-temperature electrostatic spinning process to obtain a polyurethane/bismuth oxide nanofiber membrane with uniform appearance;
the fourth step: soaking the polyurethane/bismuth oxide nanofiber membrane obtained in the third step into a cationic surfactant to endow the fiber membrane with positive charges, so as to obtain a positive charge polyurethane/bismuth oxide nanofiber membrane;
the fifth step: preparing gadolinium oxide nanosheets by utilizing a coprecipitation method of gadolinium oxide powder, dispersing the gadolinium oxide nanosheets and a water-based hexamethylene diisocyanate cross-linking agent in water, and stirring at a high speed for 2 hours to obtain a uniformly dispersed water-based impregnation liquid;
and a sixth step: shearing the positive charge polyurethane/bismuth oxide nanofiber membrane obtained in the fourth step, stacking layer by layer in the aqueous impregnation liquid obtained in the fifth step, and ultrasonically soaking to obtain a fiber membrane impregnation liquid;
the seventh step: pre-freezing the fiber membrane impregnation liquid obtained in the sixth step in a mould for 10-30 min, taking out the fiber membrane impregnation liquid from the mould after the fiber membrane impregnation liquid is completely frozen, and freeze-drying the fiber membrane impregnation liquid in a refrigeration device at a low temperature for 10-24 h to obtain a long-range ordered laminar wavy blocky nanofiber aggregate;
eighth step: and (3) heating the massive nanofiber aggregate obtained in the seventh step to 140 ℃ in heating equipment, preserving heat, and establishing stable cross-linking points in the interlaminar fibers to obtain the core protection nanofiber aerogel with a bionic structure and good mechanical properties and X-ray shielding properties.
3. The method for preparing the core-protective nanofiber aerogel with bionic structure as claimed in claim 2, wherein in the first step, the solvent is DMF;
the average particle size of the bismuth oxide nanoparticles is 50nm;
the small molecular ligand is one or a combination of more of fluoro-bis (propyl-2-yloxy) -mercaptophosphane, dimethoxy- [ (2-methyl-1,3-oxathiolan-2-yl) methylthio ] -mercaptophosphane, dimethoxy- [ (2-methyl-1,3-oxathiolan-2-yl) methylthio ] -mercaptophosphane, dimethoxy- [ (2-methyl-1,3-oxathiolan-2-yl) methylthio ] -mercaptophosphane, 1-chloro-4- [ (4-chlorophenyl) mercaptomethyl ] benzene, thiophenol, 1,3-propanedithiol and 1,4-butanedithiol;
the micro-jet high-pressure homogenization method is characterized in that a nano stirring source is arranged in a solution, and a plurality of micro turbulent flow areas are generated by using the nano stirring source; the number of the nano stirring sources is 3-5.
4. The method for preparing the core-protective nanofiber aerogel with a bionic structure as claimed in claim 2, wherein in the second step, the gradient ultrasonic method is that the ultrasonic frequency gradient is increased during the process of adding the polyurethane polymer slice; the number of the gradients is 3, and the gradient is 20HZ.
5. The method for preparing the core protection nanofiber aerogel with the bionic structure as claimed in claim 2, wherein in the third step, the high temperature electrospinning process is to arrange a real-time heating plate in a jet flow drafting area; the temperature of the jet flow drafting area is 35-50 ℃;
the thickness of the polyurethane/bismuth oxide nanofiber membrane is 30-50 mu m, and the fiber diameter is 200-300 nm.
6. The method for preparing the core-protective nanofiber aerogel with bionic structure as claimed in claim 2, wherein in the fourth step, the cationic surfactant is one or more of dodecyl ammonium acetate, octadecyl ammonium acetate, polyallylamine, sodium dodecyl benzene sulfonate, dodecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, polydimethyl diallyl ammonium chloride and polyacrylamide;
the particle size of the gadolinium oxide powder is 50-500 nm.
7. The preparation method of the core protection nanofiber aerogel with a bionic structure according to claim 2, wherein in the fifth step, the addition amount of the aqueous hexamethylene diisocyanate cross-linking agent is 0.5-5 wt%;
the high-speed stirring speed is 200-2000 rad/min.
8. The preparation method of the bionic structural nuclear protection nanofiber aerogel is characterized in that in the sixth step, the thickness of the positive charge polyurethane/bismuth oxide nanofiber membrane is 50-200 μm;
the cutting mode is automatic fixed-length cutting, and the fiber membrane is cut into the shape with the same size;
the ultrasonic soaking time is 30-90 min, and the bath ratio of the ultrasonic soaking is 1:50 to 1:200.
9. the method for preparing the core protection nanofiber aerogel with the bionic structure as claimed in claim 2, wherein in the seventh step, the pre-freezing mode is one of liquid nitrogen, a refrigerator and a freeze dryer;
in the seventh step, the freezing device is a vacuum freeze dryer; the temperature of a cold plate of the vacuum freeze dryer is less than or equal to minus 20 ℃, the temperature of a cold trap is less than or equal to minus 50 ℃, and the vacuum degree is less than or equal to 100Pa;
in the eighth step, the heating device is an oven, and the oven is a blast oven or a vacuum oven; the heating rate is 5 ℃/mn to 20 ℃/min;
in the eighth step, the heat preservation time is 0.5-2 h.
10. The core protection nanofiber aerogel with a bionic structure prepared by the preparation method of any one of claims 1 to 9, which is characterized by having a mollusk shell-imitated long-range ordered multilayer wave structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211030728.XA CN115478430B (en) | 2022-08-26 | 2022-08-26 | Nuclear protection nanofiber aerogel with bionic structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211030728.XA CN115478430B (en) | 2022-08-26 | 2022-08-26 | Nuclear protection nanofiber aerogel with bionic structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115478430A true CN115478430A (en) | 2022-12-16 |
| CN115478430B CN115478430B (en) | 2023-10-31 |
Family
ID=84423122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211030728.XA Active CN115478430B (en) | 2022-08-26 | 2022-08-26 | Nuclear protection nanofiber aerogel with bionic structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115478430B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090011110A (en) * | 2007-07-25 | 2009-02-02 | 지상협 | Fabric from radioactive ray shield |
| KR20110064988A (en) * | 2009-12-09 | 2011-06-15 | (주)버팔로 | Manufacturing method of fabric for shielding radiation, fabric for shielding radiation and the clothes including the same |
| KR20160029508A (en) * | 2014-09-05 | 2016-03-15 | 주식회사 빅스 | Eco-friendly high-solid polyurethane resin compositions for a radioactivity protective sheet and processing process thereof |
| US20160095265A1 (en) * | 2013-05-21 | 2016-03-31 | Korea Institute Of Industrial Technology | Electromagnetic wave shielding sheet comprising carbon composite fiber manufactured by electrospinning and method for manufacturing same |
| CN106350893A (en) * | 2016-08-29 | 2017-01-25 | 佛山市高明区尚润盈科技有限公司 | Antibacterial and radiation resistant composite fiber membrane preparing method |
| CN109094051A (en) * | 2018-08-20 | 2018-12-28 | 吉林省贞靓科技有限公司 | A kind of ultralight, ultra-thin, flexible, ventilative superfine fibre composite membrane and preparation method thereof with multiple spectra electromagnetic wave proof performance |
| CN109385069A (en) * | 2017-08-10 | 2019-02-26 | 北京化工大学 | A kind of high filling 3D printing polyurethane alpha ray shield composite material and preparation method |
| CN110438664A (en) * | 2019-07-10 | 2019-11-12 | 吉林大学 | A kind of high-energy ray protection bismuth tungstate/tungsten oxide/composite nano-polymers tunica fibrosa and preparation method thereof |
| CN112900110A (en) * | 2021-02-08 | 2021-06-04 | 南通大学 | Preparation method of core-shell structure tungsten/gadolinium oxide PU coating fabric for X, gamma ray protection |
| CN113276510A (en) * | 2021-05-20 | 2021-08-20 | 上海交通大学 | Janus flexible composite film for intelligent radiant heat control and preparation method thereof |
| CN113981670A (en) * | 2021-09-10 | 2022-01-28 | 西安交通大学 | Flexible and stretchable electromagnetic shielding fiber film and preparation method thereof |
-
2022
- 2022-08-26 CN CN202211030728.XA patent/CN115478430B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090011110A (en) * | 2007-07-25 | 2009-02-02 | 지상협 | Fabric from radioactive ray shield |
| KR20110064988A (en) * | 2009-12-09 | 2011-06-15 | (주)버팔로 | Manufacturing method of fabric for shielding radiation, fabric for shielding radiation and the clothes including the same |
| US20160095265A1 (en) * | 2013-05-21 | 2016-03-31 | Korea Institute Of Industrial Technology | Electromagnetic wave shielding sheet comprising carbon composite fiber manufactured by electrospinning and method for manufacturing same |
| KR20160029508A (en) * | 2014-09-05 | 2016-03-15 | 주식회사 빅스 | Eco-friendly high-solid polyurethane resin compositions for a radioactivity protective sheet and processing process thereof |
| CN106350893A (en) * | 2016-08-29 | 2017-01-25 | 佛山市高明区尚润盈科技有限公司 | Antibacterial and radiation resistant composite fiber membrane preparing method |
| CN109385069A (en) * | 2017-08-10 | 2019-02-26 | 北京化工大学 | A kind of high filling 3D printing polyurethane alpha ray shield composite material and preparation method |
| CN109094051A (en) * | 2018-08-20 | 2018-12-28 | 吉林省贞靓科技有限公司 | A kind of ultralight, ultra-thin, flexible, ventilative superfine fibre composite membrane and preparation method thereof with multiple spectra electromagnetic wave proof performance |
| CN110438664A (en) * | 2019-07-10 | 2019-11-12 | 吉林大学 | A kind of high-energy ray protection bismuth tungstate/tungsten oxide/composite nano-polymers tunica fibrosa and preparation method thereof |
| CN112900110A (en) * | 2021-02-08 | 2021-06-04 | 南通大学 | Preparation method of core-shell structure tungsten/gadolinium oxide PU coating fabric for X, gamma ray protection |
| CN113276510A (en) * | 2021-05-20 | 2021-08-20 | 上海交通大学 | Janus flexible composite film for intelligent radiant heat control and preparation method thereof |
| CN113981670A (en) * | 2021-09-10 | 2022-01-28 | 西安交通大学 | Flexible and stretchable electromagnetic shielding fiber film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115478430B (en) | 2023-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Asmatulu et al. | Synthesis and applications of electrospun nanofibers | |
| JP6743296B2 (en) | Graphene/nylon 6 fiber, woven fabric and manufacturing method | |
| DE102007044648B4 (en) | Bioresorbable gelatin non-woven fabric | |
| CN106757505A (en) | A kind of ice sense mosquito proof fiber and preparation method thereof and ice sense anti-mosquito fabric | |
| CN109355729B (en) | Manufacturing method of Taiji stone and polyester fiber composite material | |
| CN104975364B (en) | Fiber fabric and preparation method thereof | |
| CN103526329A (en) | Preparation method for radiation-proof fibers | |
| CN105624821B (en) | A kind of barium sulfate/polyvinyl alcohol composite fiber and preparation method thereof, non-woven cloth | |
| CN105231565A (en) | Stab-resistant protective fabric comprising ice-cold material | |
| WO2022048162A1 (en) | Preparation method for graphene heat dissipation fiber | |
| CN111087792A (en) | Electromagnetic shielding silicon rubber material for selective laser sintering 3D printing and preparation method thereof | |
| CN109551835A (en) | The ventilative cooling fabric of one kind and its application | |
| CN115478430B (en) | Nuclear protection nanofiber aerogel with bionic structure and preparation method thereof | |
| CN112659706A (en) | Nano radiation-proof fabric | |
| CN114687202B (en) | X-ray-proof shielding fabric and preparation method and application thereof | |
| CN110195266B (en) | Production method of functional fiber | |
| CN115467091A (en) | Composite material with alternately stacked bismuth oxide/gadolinium oxide nanofiber membranes and preparation method thereof | |
| CN110014705A (en) | A kind of preparation method of anti-stabbing lining | |
| CN112677606A (en) | Protective fabric and preparation method and application thereof | |
| CN113463270A (en) | Polypropylene melt-blown non-woven fabric based on composite antibacterial electret master batch and preparation method | |
| Meng et al. | Synergistic effects of polymaleic acid and di (dioctylpyrophosphato) ethylene titanate on B4C modification in highly filled polymer fibers for improved neutron protection safety and wear comfort of articles | |
| KR102080430B1 (en) | Sheath-core type composite yarn containing Inorganic antibiotics and manufacturing method thereof | |
| CN113699783A (en) | Sterilization fabric | |
| CN108310455B (en) | Nano hydroxyapatite and PGS-M composite bone repair material and preparation method thereof | |
| JP2005336635A (en) | Germanium component-attached staple fiber and fiber product using the staple fiber as material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |