CN115478430B - Nuclear protection nanofiber aerogel with bionic structure and preparation method thereof - Google Patents
Nuclear protection nanofiber aerogel with bionic structure and preparation method thereof Download PDFInfo
- Publication number
- CN115478430B CN115478430B CN202211030728.XA CN202211030728A CN115478430B CN 115478430 B CN115478430 B CN 115478430B CN 202211030728 A CN202211030728 A CN 202211030728A CN 115478430 B CN115478430 B CN 115478430B
- Authority
- CN
- China
- Prior art keywords
- nanofiber
- bismuth oxide
- polyurethane
- aerogel
- bionic structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002121 nanofiber Substances 0.000 title claims abstract description 106
- 239000004964 aerogel Substances 0.000 title claims abstract description 53
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000012528 membrane Substances 0.000 claims abstract description 73
- 239000004814 polyurethane Substances 0.000 claims abstract description 51
- 229920002635 polyurethane Polymers 0.000 claims abstract description 50
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 41
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229940075613 gadolinium oxide Drugs 0.000 claims abstract description 26
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims abstract description 26
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002135 nanosheet Substances 0.000 claims abstract description 14
- 239000011449 brick Substances 0.000 claims abstract description 7
- 239000000835 fiber Substances 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 51
- 239000010410 layer Substances 0.000 claims description 50
- 239000007788 liquid Substances 0.000 claims description 29
- 239000002105 nanoparticle Substances 0.000 claims description 29
- 238000009987 spinning Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 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 13
- 239000006185 dispersion Substances 0.000 claims description 13
- 238000007710 freezing Methods 0.000 claims description 13
- 230000008014 freezing Effects 0.000 claims description 13
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical class [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 claims description 13
- 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
- 238000002791 soaking Methods 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
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 238000010041 electrostatic spinning Methods 0.000 claims description 8
- 238000004108 freeze drying Methods 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
- 239000003446 ligand Substances 0.000 claims description 7
- 238000000975 co-precipitation Methods 0.000 claims description 6
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- 239000011229 interlayer Substances 0.000 claims description 6
- 239000003093 cationic surfactant Substances 0.000 claims description 5
- 238000005520 cutting process Methods 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
- 230000003592 biomimetic effect Effects 0.000 claims description 4
- -1 fluoro-di (propan-2-yloxy) -sulfhydryl phosphine alkane Chemical class 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 238000010008 shearing Methods 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
- 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
- 150000003384 small molecules Chemical class 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 238000005057 refrigeration Methods 0.000 claims 1
- 241000237852 Mollusca Species 0.000 abstract description 6
- 239000011454 mudbrick Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 48
- 239000000463 material Substances 0.000 description 21
- 230000005855 radiation Effects 0.000 description 9
- 239000002060 nanoflake Substances 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 5
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000005865 ionizing radiation Effects 0.000 description 3
- PZNOBXVHZYGUEX-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine;hydrochloride Chemical compound Cl.C=CCNCC=C PZNOBXVHZYGUEX-UHFFFAOYSA-N 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
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000009471 action 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
- 230000007123 defense Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000411 inducer 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
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 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
- 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 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
- 238000010586 diagram Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000008717 functional decline Effects 0.000 description 1
- 210000002149 gonad Anatomy 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000003394 haemopoietic effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000013007 heat curing Methods 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
- 208000000509 infertility Diseases 0.000 description 1
- 230000036512 infertility Effects 0.000 description 1
- 208000021267 infertility disease Diseases 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000003993 interaction Effects 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
- 230000003902 lesion Effects 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000008897 memory decline Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 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
- 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
- 229920006264 polyurethane film Polymers 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000004223 radioprotective effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 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
- 208000001608 teratocarcinoma Diseases 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
- 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
- 238000009423 ventilation Methods 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
- D06M11/32—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 System; 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
Abstract
The invention relates to a nuclear protection nanofiber aerogel with a bionic structure and a preparation method thereof, wherein a polyurethane/bismuth oxide nanofiber membrane is used as a mud component, gadolinium oxide nanosheets are used as a brick component, the nuclear protection nanofiber aerogel with the bionic structure is prepared by stacking layers by layers, and the prepared nuclear protection nanofiber aerogel with the bionic structure has a mud-brick long-range ordered multilayer wave structure imitating mollusc shells. Compared with the prior art, the nuclear protection nanofiber aerogel with the bionic structure has the advantages that the X-ray shielding efficiency of the nuclear protection nanofiber aerogel with the bionic structure below 150keV can reach more than 90%, the nuclear protection nanofiber aerogel has the tensile property, can be applied in a large scale, and has good universality.
Description
Technical Field
The invention relates to the technical field of preparation of nuclear protection nanofiber materials, 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 used. The X-ray is used as a short-wave ionizing radiation source and is widely applied to the fields of national defense construction, industrial flaw detection, medical treatment and health and the like. However, the X-ray radiation with overdose can influence the physiological functions of human bodies, cause chromosome abnormality, cause direct injury to three systems of reproduction, nerves and immunity of human bodies, are main inducers of cardiovascular diseases, diabetes and cancer mutation and inducers of lesions such as abortion, sterility and teratocarcinoma of pregnant women, can directly influence the development of body tissues and bones of minors, and cause vision, memory decline and liver hematopoietic function decline. Therefore, wearing protective clothing that can effectively shield X-rays has become one of the important measures to reduce radiation hazards and protect the relevant population.
The traditional radiation protection materials such as lead rubber are composite materials prepared by taking lead or lead oxide as a main X-ray absorber and natural rubber as a base material, the X-ray shielding efficiency of the composite materials exceeds 90 percent, and the composite materials are used as thyroid collar shields, gonad shields, protective aprons and protective gloves, thereby providing protection for doctors and testees. However, in practical use, lead clothing suffers from three disadvantages: (1) The lead apron is heavy, poor in flexibility, airtight and extremely poor in wearing comfort, and the weight of one lead apron with the lead equivalent of 0.5mmPb is 4.95kg; (2) Lead has an atomic number of 82, which has a good absorption capacity for ionizing radiation having an energy higher than 88keV and between 13keV and 40keV, but has a weak absorption region for ionizing radiation between 40keV and 88 keV; (3) Lead-containing materials are biotoxic and lead poisoning can result from long-term wear of lead clothing. Therefore, the development of lead-free wearable radioprotective materials is a critical problem to be solved in the current nuclear protection field.
In order to overcome the above-mentioned drawbacks of lead clothing, in recent years, researchers have made a series of researches on lead-free wearable radiation protection clothing. Patent CN101137285a discloses a composite shielding material for medical X-ray protection, which is prepared by adding barium, cadmium, tin and lanthanide into polymer materials such as natural rubber, and overcomes the defect of weak absorption area caused by using single element. However, the high polymer material has low interfacial compatibility, the problem of gaps of the material and the like, so that the material has poor dispersibility, low mechanical property and shielding loopholes; patent CN110341289a discloses a method for making fabric resistant to X-rays, which is to coat a polyurethane film with a mixed liquid of tungsten metal and iron ore to obtain an X-ray-resistant protective garment, wherein the protective garment has good softness but poor air permeability, and is difficult to meet the requirement of wearability; in addition, researchers have prepared fibrous protective materials by adding an X-ray absorber to the spinning solution, which have better 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 researches, patent CN111469506a discloses a novel nuclear radiation protection material and a preparation method thereof, wherein an outer layer, a shielding layer, a scattering layer and an inner layer fiber fabric are bonded through thermal bonding, so that the novel nuclear radiation protection material with high-efficiency nuclear protection performance and ventilation is prepared, however, the high-efficiency shielding performance only depends on the absorption effect of a large amount of metal powder such as graphene, tungsten powder, bismuth powder and the like on X rays, so that the mechanical performance of the nuclear radiation protection garment is reduced, the weight of the nuclear radiation protection garment is increased, and the wearing comfort is reduced. Therefore, there is a need to develop a nuclear protection material which is lightweight, breathable, and can efficiently shield all-band X-rays, and a method for preparing the same.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the nuclear protection nanofiber aerogel with the bionic structure and the preparation method thereof, so as to solve the defects of poor mechanical property, heavy weight and low comfort of the existing nuclear protection material, and the prepared nuclear protection nanofiber aerogel has the X-ray shielding efficiency of more than 90 percent for less than 150 keV.
The aim of the invention can be achieved by the following technical scheme:
the first object of the invention is to provide a preparation method of a nuclear protection nanofiber aerogel with a bionic structure, which takes polyurethane/bismuth oxide nanofiber membrane as a mud component and gadolinium oxide nanosheets as a brick component, and prepares the nuclear protection nanofiber aerogel with the bionic structure by stacking layer by layer.
Further, the preparation method comprises the following steps:
the first step: carrying out 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%;
and a second step of: adding polyurethane polymer slices into the dispersion liquid obtained in the first step by utilizing a gradient ultrasonic dispersion method while ultrasonic stirring to obtain a homogeneous and stable spinning liquid, wherein the polyurethane content is 10-30wt%;
and a third step of: 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 morphology;
fourth step: immersing the polyurethane/bismuth oxide nanofiber membrane obtained in the third step into a cationic surfactant to endow the nanofiber membrane with positive charges to obtain a positively charged polyurethane/bismuth oxide nanofiber membrane;
fifth step: preparing gadolinium oxide nano-sheets by using a coprecipitation method of gadolinium oxide powder, dispersing the obtained gadolinium oxide nano-sheets and a water-based hexamethylene diisocyanate cross-linking agent in water, and stirring at a high speed for 2 hours to obtain a homogeneously dispersed water-based impregnating solution;
sixth step: shearing the positively charged polyurethane/bismuth oxide nanofiber membrane obtained in the fourth step, stacking layer by layer in the aqueous impregnating solution obtained in the fifth step, and carrying out ultrasonic soaking to obtain a fiber membrane impregnating solution;
seventh step: pre-freezing the fiber membrane impregnating solution obtained in the sixth step in a mold for 10-30 min, taking out the fiber membrane impregnating solution from the mold after the fiber membrane impregnating solution is completely frozen, and performing low-temperature freeze drying in freezing equipment for 10-24 h to obtain a long-range ordered lamellar wavy blocky nanofiber aggregate;
eighth step: heating the blocky nanofiber aggregate obtained in the seventh step to 140 ℃ in heating equipment, preserving heat, and establishing stable crosslinking points on interlayer fibers to obtain the nuclear 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 several of fluoro-bis (propan-2-yloxy) -mercaptophosphine alkane, dimethoxy- [ (2-methyl-1, 3-oxathiolan-2-yl) methylthio ] -mercaptophosphine alkane, 1-chloro-4- [ (4-chlorophenyl) mercaptomethyl ] benzene, thiophenol, 1, 3-propanedithiol, 1, 4-butanedithiol.
Further, in the first step, the microfluidic high-pressure homogenization method is to set a nano stirring source in the solution, and generate a plurality of micro turbulent flow areas by using the nano stirring source.
Preferably, the number of the nano stirring sources is 3-5.
Further, in the second step, the gradient ultrasound method is that ultrasound frequency gradient increases during the process of adding the polyurethane polymer slice.
Preferably, the number of the gradients is 3, namely before, during and after adding 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 plate in a jet drawing area.
Preferably, the jet drawing zone temperature is between 35 and 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 polyurethane/bismuth oxide nanofiber membrane has a fiber diameter of 200 to 300nm, wherein the fiber diameter is 30 to 50 μm.
Preferably, in the fourth step, the cationic surfactant is one or a combination of several 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.
Preferably, in the fourth step, the particle size of the gadolinium oxide powder is 50 to 500nm.
Preferably, in the fifth step, the aqueous hexamethylene diisocyanate cross-linking agent is added in an amount of 0.5wt% to 5wt%.
Preferably, in the fifth step, the rotation speed of the high-speed stirring is 200-2000 rad/min.
Preferably, in the sixth step, the positively charged polyurethane/bismuth oxide nanofiber membrane has a thickness of 50 μm to 200 μm.
Preferably, in the sixth step, the shearing mode is automatic fixed-length cutting, and the fiber film is cut into the shape with the same size.
Preferably, in the sixth step, the time of ultrasonic soaking is 30-90 min, and the bath ratio of ultrasonic soaking is 1: 50-1: 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 apparatus is a vacuum freeze dryer.
Further preferably, 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.
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 heating rate is 5 ℃/mn to 20 ℃/min.
Preferably, in the eighth step, the time of heat preservation is 0.5-2 h.
The second object of the present invention is to provide a core-protecting nanofiber aerogel of a bionic structure prepared by the above preparation method, which has a mud-brick long-range ordered multilayer wave structure imitating mollusk shells.
Compared with the prior art, the invention has the following beneficial effects:
1) The minimum density of the nuclear protection nanofiber aerogel with the bionic structure provided by the invention can reach 1g cm -3 Far lower than the density of the lead plate 11.34g cm -3 The Bi and Gd elements with complementary absorption edges of the K layers generate a synergistic shielding effect on X rays, so that the shielding efficiency of the nuclear protection nanofiber aerogel with the thickness of 2mm and a bionic structure on the X rays below 150keV can reach more than 90%.
2) The nuclear protection nanofiber aerogel with the bionic structure provided by the invention has the advantages that the wavy structure between nanofiber membrane layers and polyurethane are excellent, the tensile property of the material is endowed, the elongation at break reaches 850%, and the plastic deformation is less than 20% after 500 stretching cycles.
3) The preparation method of the nuclear protection nanofiber aerogel with the bionic structure provided by the invention is a continuous process, and uniform distribution of nanoparticles in polyurethane is realized through modification of small molecular ligands, gradient ultrasound and control of spinning process, so that the problem of easy agglomeration in the traditional inorganic particle doping process is solved; the self-assembly of the gadolinium oxide nano sheet between polyurethane/bismuth oxide fiber membrane layers is realized by utilizing the electrostatic attraction effect, so that the problem that inorganic matters are easy to fall off in the existing three-dimensional intercalation structure is solved; the long-range ordered wave-shaped structure is constructed in the multi-layer nanofiber membrane through growth and displacement of ice crystals and nondestructive replacement of gas-liquid in the freeze drying process, and the method can be applied in a large scale and has good universality.
Drawings
Fig. 1 is a schematic diagram of an action mechanism of a nuclear protection nanofiber aerogel with a bionic structure in the technical scheme.
Fig. 2 is a long-range ordered wave multistage structure electron microscope image of the core-protecting nanofiber aerogel of the bionic structure in example 1, wherein (a) is a structure display image, (b) is a partial enlarged image of (a), and (c) is a partial enlarged image of (b).
Fig. 3 is an XRD pattern of the core protective nanofiber aerogel of the biomimetic structure in example 2.
Fig. 4 is a tensile fracture graph of the core protective nanofiber aerogel of the biomimetic structure of example 3.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
In the technical scheme, the characteristics of preparation means, materials, structures or composition ratios and the like which are not explicitly described are 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 X-ray shielding efficiency of the existing nuclear protection materials in the prior art in the conception process, inspires the unique structure of mollusks, namely mollusk shells have natural protection capability on nuclear radiation, the main components of the nuclear protection materials are mainly calcium carbonate, the nuclear protection materials have unique adsorption efficacy on radionuclides, the shells have unique multi-scale and multi-level 'brick-mud' assembled structures, and the multi-level layered structures of the nuclear protection materials have excellent characteristics of good toughness, good X-ray reflectivity and the like, polyurethane/bismuth oxide nanofiber membranes are innovatively used as 'mud' components, gadolinium oxide nanosheets are used as 'brick' components, and the nuclear protection nanofiber aerogel with a bionic structure is prepared, and has a 'mud-brick' long-range multi-layer wave structure imitating mollusk shells; the bismuth oxide and gadolinium oxide components have different K absorption edges, so that the full-band absorption of X rays below 150keV can be realized; meanwhile, the multi-layer fiber realizes the repeated reflection of X-rays in the material, so that an excellent shielding effect on the X-rays is achieved, and the action mechanism is shown in the figure 1.
The invention selects different organic micromolecular ligands to lead bismuth oxide (Bi 2 O 3 ) The nano particles are subjected to surface hydrophobic modification, and after the modified bismuth oxide nano particles are dispersed in a solvent DMF by combining a micro-jet high-pressure homogenization method, polyurethane (PU) polymer slices are slowly added for multiple times, and a high-dispersivity spinning solution is prepared by a gradient ultrasonic method. The micromolecular ligand provides lone pair electrons for bismuth oxide nano-particles, so that electrostatic repulsion is generated in DMF by the nano-particles, and agglomeration of the nano-particles is avoided. Then, the phase separation rate of electrostatic jet flow in the spinning process is accelerated by utilizing a high-temperature electrostatic spinning method, the directional migration-fixation of nano particles in the polymer jet flow is promoted, and PU/Bi with uniform morphology, thickness of 30-50 mu m and fiber diameter of 200-300 nm is prepared 2 O 3 A nanofiber membrane. Then PU/Bi is added 2 O 3 The nanofiber membrane is immersed in an amine cationic surfactant, and positively charged amino groups can be introduced to the surface of the nanofiber membrane. Gadolinium oxide (Gd) is prepared by coprecipitation method 2 O 3 ) Nanoflakes whose surface unsaturated oxygen is adsorbed hydroxyl coordinates to negatively charge them, followed by Gd 2 O 3 Adding the nano-sheets and the aqueous hexamethylene diisocyanate cross-linking agent into water, and stirring at a high speed for 2 hours to obtain a homogeneously dispersed impregnating solution; PU/Bi 2 O 3 The nanofiber membrane is cut into the shape with the same size, stacked layer by layer in the impregnating solution, and subjected to ultrasonic soaking, so that the impregnating solution enters into gaps of the nanofiber membrane. In this process, gd 2 O 3 Nanoflakes and PU/Bi 2 O 3 The nanofiber membrane is stacked layer by layer due to electrostatic attraction, forming a mud-brick like structure resembling a mollusk shell. And then placing the layer-by-layer laid fiber membrane impregnating solution in a mould prepared in advance, pre-freezing the impregnating solution in the mould for 10-30 min at low temperature, taking the impregnating solution out of the mould after the impregnating solution is completely frozen, placing the impregnating solution in freezing equipment, and taking the impregnating solution out after low-temperature freeze drying for 10-24 h to obtain the long-range ordered lamellar wavy nanofiber aerogel. In the freezing forming process, the temperature of the slurry in the mould is rapidly reducedThe solvent in the slurry is quickly cooled to form crystal nucleus and grow quickly, and the nanofiber membrane is deformed along the growth direction of the ice crystals due to the displacement of the ice crystals, so that an arched wave structure is formed. And after the sample is thoroughly cooled and solidified, carrying out vacuum drying treatment on the sample, directly converting the frozen and solidified solvent into gas through sublimation without liquid state in the freeze drying treatment process, and removing the gas through volatilization, so that a wave structure formed by solid solvent crystals is maintained, and the nuclear protection nanofiber aerogel with a long-range ordered multilayer wave structure is obtained, but no interaction exists between interlayer fiber films, and the obtained structure is unstable, so that the subsequent crosslinking and solidification treatment is needed.
And placing the freeze-dried and formed blocky nanofiber aggregate in heating equipment, heating to 140 ℃ and preserving heat, and performing high-temperature heating treatment to enable diisocyanate among fiber layers and polyurethane components in the fibers to be polymerized and cured in situ, so that stable crosslinking points are established among the fiber layers, and finally, the nuclear protection nanofiber aerogel with good mechanical properties and X-ray shielding properties is obtained. In this process, the reason why PU does not shrink due to high temperature is that the inorganic component Bi 2 O 3 、Gd 2 O 3 So that the nanofiber aerogel has good heat curing stability.
Example 1
The embodiment provides a preparation method of a nuclear protection nanofiber aerogel with a bionic structure, which takes a polyurethane/bismuth oxide nanofiber membrane as a mud component and gadolinium oxide nanosheets as a brick component, and prepares the nuclear protection nanofiber aerogel with the bionic structure by stacking layer by layer, and comprises the following steps:
the first step: carrying out surface hydrophobic modification on bismuth oxide nano particles (average particle diameter of 50 nm) by using 1, 3-propanedithiol to obtain modified bismuth oxide nano particles, dispersing the modified bismuth oxide nano particles in DMF (dimethyl formamide) by combining a micro-jet high-pressure homogenization method and mechanical stirring to obtain a dispersion liquid in which the nano particles are homogeneously dispersed, wherein the particle content in the dispersion liquid is 5wt%;
and a second step of: adding polyurethane polymer slices into the obtained dispersion liquid by using a gradient ultrasonic dispersion method (200 Hz, 220Hz and 240 Hz) while ultrasonic stirring to obtain a homogeneous and stable spinning liquid, wherein the polyurethane content in the spinning liquid is 15wt%;
and a third step of: spinning the homogeneous stable spinning solution by using a high-temperature electrostatic spinning process (the temperature of a drawing area is 35 ℃) to prepare a polyurethane/bismuth oxide nanofiber membrane with uniform morphology, wherein the thickness is 50 mu m;
fourth step: immersing the polyurethane/bismuth oxide nanofiber membrane in a polyallylamine solution (2 wt%) to impart positive charge to the fiber membrane;
fifth step: by Gd 2 O 3 Preparing gadolinium oxide nano-flakes by a coprecipitation method of powder (50 nm), dispersing the gadolinium oxide nano-flakes and a water-based hexamethylene diisocyanate cross-linking agent into deionized water together, stirring the mixture at a high speed at a rotating speed of 500rad/min for 2 hours, and obtaining a homogeneously dispersed water-based impregnating solution;
sixth step: cutting a polyurethane/bismuth oxide nanofiber membrane with the thickness of 50 mu m into a shape with the same size, stacking 50 layers layer by layer in the impregnating solution, and carrying out ultrasonic soaking for 30 minutes (bath ratio of 1:50);
seventh step: placing the fiber membrane impregnating solution laid layer by layer in a mould prepared in advance, pre-freezing the fiber membrane impregnating solution at a low temperature by utilizing liquid nitrogen, taking the fiber membrane impregnating solution out of the mould after the fiber membrane impregnating solution is completely frozen, placing the fiber membrane impregnating solution in a vacuum freeze dryer (the temperature of a cold plate is minus 25 ℃, the temperature of a cold trap is minus 55 ℃ and the vacuum degree is 50 Pa), and taking the fiber membrane impregnating solution out of the vacuum freeze dryer after low-temperature freeze drying to obtain a long-range ordered lamellar wavy blocky nanofiber aggregate;
eighth step: and placing the freeze-dried and formed blocky nanofiber aggregate in a blast oven, heating to 140 ℃ and preserving heat for 1h, and establishing stable crosslinking points on interlayer fibers to finally obtain the nuclear protection nanofiber aerogel with a bionic structure and good mechanical properties and X-ray shielding properties.
The long-range ordered layered wavy structure of the nuclear 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 films are stacked layer by layer to form a layered structure similar to a pearl layer; meanwhile, an arch wave structure is formed between the fiber films, and the fiber films are characterized by long-range order and short-range disorder; and gadolinium oxide nano-sheets are dispersed between the fiber membranes.
Example 2
The embodiment provides a preparation method of a nuclear protection nanofiber aerogel with a bionic structure, which takes a polyurethane/bismuth oxide nanofiber membrane as a mud component and gadolinium oxide nanosheets as a brick component, and prepares the nuclear protection nanofiber aerogel with the bionic structure by stacking layer by layer, and comprises the following steps:
the first step: carrying out surface hydrophobic modification on bismuth oxide nano particles (average particle diameter of 50 nm) by using 1, 4-butanedithiol to obtain modified bismuth oxide nano particles, dispersing the modified bismuth oxide nano particles in DMF (dimethyl formamide) by combining a micro-jet high-pressure homogenization method and mechanical stirring to obtain a dispersion liquid in which the nano particles are homogeneously dispersed, wherein the particle content in the dispersion liquid is 10wt%;
and a second step of: adding polyurethane polymer slices into the obtained dispersion liquid by using a gradient ultrasonic dispersion method (300 Hz, 320Hz and 340 Hz) while ultrasonic stirring to obtain a homogeneous and stable spinning liquid, wherein the polyurethane content in the spinning liquid is 20wt%;
and a third step of: spinning the homogeneous stable spinning solution by using a high-temperature electrostatic spinning process (the temperature of a drawing area is 40 ℃), and preparing a polyurethane/bismuth oxide nanofiber membrane with uniform morphology, wherein the thickness is 100 mu m;
fourth step: immersing the polyurethane/bismuth oxide nanofiber membrane in an octadecyl ammonium acetate solution (2 wt%) to impart positive charge to the fiber membrane;
fifth step: by Gd 2 O 3 Preparing gadolinium oxide nano-flakes by a powder (100 nm) coprecipitation method, dispersing the gadolinium oxide nano-flakes and a water-based hexamethylene diisocyanate cross-linking agent into deionized water together, stirring the mixture at a high speed at a rotating speed of 1000rad/min for 2 hours, and obtaining a homogeneously dispersed water-based impregnating solution;
sixth step: cutting a polyurethane/bismuth oxide nanofiber membrane with the thickness of 100 mu m into a shape with the same size, stacking 40 layers layer by layer in the impregnating solution, and carrying out ultrasonic soaking for 60 minutes (bath ratio of 1:100);
seventh step: placing the fiber membrane impregnating solution laid layer by layer in a mould prepared in advance, pre-freezing the fiber membrane impregnating solution at a low temperature by utilizing liquid nitrogen, taking the fiber membrane impregnating solution out of the mould after the fiber membrane impregnating solution is completely frozen, placing the fiber membrane impregnating solution in a vacuum freeze dryer (the temperature of a cold plate is minus 22 ℃, the temperature of a cold trap is minus 54 ℃ and the vacuum degree is 100 Pa), and taking the fiber membrane impregnating solution out of the vacuum freeze dryer after low-temperature freeze drying to obtain a long-range ordered lamellar wavy blocky nanofiber aggregate;
eighth step: and placing the freeze-dried and formed blocky nanofiber aggregate in a blast oven, heating to 140 ℃ and preserving heat for 2 hours, and establishing stable crosslinking points on interlayer fibers to finally obtain the nuclear 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 with the bionic structure in this embodiment is shown in fig. 3, and it can be seen from fig. 3 that the surface of the bionic nanofiber aerogel has gadolinium oxide and bismuth oxide at the same time.
Example 3
The embodiment provides a preparation method of a nuclear protection nanofiber aerogel with a bionic structure, which takes a polyurethane/bismuth oxide nanofiber membrane as a mud component and gadolinium oxide nanosheets as a brick component, and prepares the nuclear protection nanofiber aerogel with the bionic structure by stacking layer by layer, and comprises the following steps:
the first step: carrying out surface hydrophobic modification on bismuth oxide nano particles (average particle diameter is 50 nm) by using thiophenol to obtain modified bismuth oxide nano particles, dispersing the modified bismuth oxide nano particles in DMF (dimethyl formamide) by combining a micro-jet high-pressure homogenization method and mechanical stirring to obtain a dispersion liquid in which the nano particles are homogeneously dispersed, wherein the particle content in the dispersion liquid is 15wt%;
and a second step of: adding polyurethane polymer slices into the obtained dispersion liquid while ultrasonic stirring by using a gradient ultrasonic dispersion method (400 Hz, 420Hz and 440 Hz) to obtain a homogeneous and stable spinning liquid, wherein the polyurethane content in the spinning liquid is 15wt%;
and a third step of: spinning the homogeneous stable spinning solution by using a high-temperature electrostatic spinning process (the temperature of a drawing area is 50 ℃), and preparing a polyurethane/bismuth oxide nanofiber membrane with uniform morphology, wherein the thickness is 200 mu m;
fourth step: immersing the polyurethane/bismuth oxide nanofiber membrane into a mixed solution (3 wt%) of polydimethyl diallyl ammonium chloride and polyacrylamide, wherein the mass ratio of the polydimethyl diallyl ammonium chloride to the polyacrylamide is 7:3, and endowing the nanofiber membrane with positive charges;
fifth step: by Gd 2 O 3 Preparing gadolinium oxide nano-flakes by a coprecipitation method of powder (200 nm), dispersing the gadolinium oxide nano-flakes and a water-based hexamethylene diisocyanate cross-linking agent into deionized water together, stirring the mixture at a high speed for 2 hours at a rotating speed of 1500rad/min to obtain a homogeneously dispersed water-based impregnating solution;
sixth step: cutting a polyurethane/bismuth oxide nanofiber membrane with the thickness of 200 mu m into a shape with the same size, stacking 20 layers layer by layer in the impregnating solution, and carrying out ultrasonic soaking for 90 minutes (bath ratio of 1:200);
seventh step: placing the fiber membrane impregnating solution laid layer by layer in a mould prepared in advance, pre-freezing the fiber membrane impregnating solution at a low temperature by utilizing liquid nitrogen, taking the fiber membrane impregnating solution out of the mould after the fiber membrane impregnating solution is completely frozen, placing the fiber membrane impregnating solution in a vacuum freeze dryer (the temperature of a cold plate is minus 20 ℃, the temperature of a cold trap is minus 50 ℃ and the vacuum degree is 10 Pa), and taking the fiber membrane impregnating solution out of the vacuum freeze dryer after low-temperature freeze drying to obtain a long-range ordered lamellar wavy blocky nanofiber aggregate;
eighth step: and placing the freeze-dried and formed blocky nanofiber aggregate in a blast oven, heating to 140 ℃ and preserving heat for 0.5h, and establishing stable crosslinking points on interlayer fibers to finally obtain the nuclear protection nanofiber aerogel with a bionic structure and good mechanical properties and X-ray shielding properties.
The tensile fracture graph of the nuclear protection nanofiber aerogel with the bionic structure in this embodiment is shown in fig. 4, and it can be seen from fig. 4 that the tensile strength of the prepared nuclear protection nanofiber aerogel with the bionic structure is 3.8MPa.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments 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-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (9)
1. The preparation method of the nuclear protection nanofiber aerogel with the bionic structure is characterized in that polyurethane/bismuth oxide nanofiber membranes are used as mud components, gadolinium oxide nanosheets are used as brick components, and the nuclear protection nanofiber aerogel with the bionic structure is prepared by stacking layer by layer;
the method comprises the following steps:
the first step: carrying out 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%;
and a second step of: adding polyurethane polymer slices into the dispersion liquid obtained in the first step by utilizing a gradient ultrasonic dispersion method while ultrasonic stirring to obtain a homogeneous and stable spinning liquid, wherein the polyurethane content is 10-30wt%;
and a third step of: 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 morphology;
fourth step: immersing the polyurethane/bismuth oxide nanofiber membrane obtained in the third step into a cationic surfactant to endow the nanofiber membrane with positive charges to obtain a positively charged polyurethane/bismuth oxide nanofiber membrane;
fifth step: preparing gadolinium oxide nano-sheets by using a coprecipitation method of gadolinium oxide powder, dispersing the obtained gadolinium oxide nano-sheets and a water-based hexamethylene diisocyanate cross-linking agent in water, and stirring at a high speed for 2 hours to obtain a homogeneously dispersed water-based impregnating solution;
sixth step: shearing the positively charged polyurethane/bismuth oxide nanofiber membrane obtained in the fourth step, stacking layer by layer in the aqueous impregnating solution obtained in the fifth step, and carrying out ultrasonic soaking to obtain a fiber membrane impregnating solution;
seventh step: pre-freezing the fiber membrane impregnating solution obtained in the sixth step in a mold for 10-30 min, taking out the fiber membrane impregnating solution from the mold after the fiber membrane impregnating solution is completely frozen, and performing low-temperature freeze drying in freezing equipment for 10-24 h to obtain a long-range ordered lamellar wavy blocky nanofiber aggregate;
eighth step: heating the blocky nanofiber aggregate obtained in the seventh step to 140 ℃ in heating equipment, preserving heat, and establishing stable crosslinking points on interlayer fibers to obtain the nuclear protection nanofiber aerogel with a bionic structure and good mechanical properties and X-ray shielding properties.
2. The method for preparing a core-protecting nanofiber aerogel with a bionic structure according to claim 1, wherein in the first step, the solvent is DMF;
the average particle size of the bismuth oxide nano particles is 50nm;
the small molecule ligand is one or a combination of more of fluoro-di (propan-2-yloxy) -sulfhydryl phosphine alkane, dimethoxy- [ (2-methyl-1, 3-oxathiolane-2-yl) methyl thio ] -sulfhydryl phosphine alkane, 1-chloro-4- [ (4-chlorophenyl) sulfhydryl methyl ] 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.
3. The method for preparing a core-protecting nanofiber aerogel of a biomimetic structure according to claim 1, wherein in the second step, the gradient ultrasonic method is that ultrasonic frequency is increased in a gradient manner in the process of adding polyurethane polymer slices; the number of the gradients is 3, and the gradient is 20HZ.
4. The method for preparing a core-protecting nanofiber aerogel with a bionic structure according to claim 1, wherein in the third step, the high-temperature electrostatic spinning process is to arrange a real-time heating plate in a jet drawing area; the temperature of the jet flow drafting zone 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.
5. The method for preparing a biomimetic-structured nuclear protection nanofiber aerogel according to claim 1, wherein in the fourth step, the cationic surfactant is one or a combination of several of dodecylammonium acetate, octadecylammonium acetate, polyallylamine, sodium dodecylbenzenesulfonate, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, polydimethyldiallylammonium chloride, and polyacrylamide;
the particle size of the gadolinium oxide powder is 50-500 nm.
6. The method for preparing a core-protecting nanofiber aerogel with a bionic structure according to claim 1, wherein in the fifth step, the addition amount of the aqueous hexamethylene diisocyanate cross-linking agent is 0.5-5 wt%;
the rotating speed of the high-speed stirring is 200-2000 rad/min.
7. The method for preparing a core-protecting nanofiber aerogel with a bionic structure according to claim 1, wherein in the sixth step, the thickness of the positively charged polyurethane/bismuth oxide nanofiber membrane is 50-200 μm;
the shearing 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: 50-1: 200.
8. the method for preparing the nuclear protection nanofiber aerogel with the bionic structure according to claim 1, 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 refrigeration equipment 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.
9. A core-protecting nanofiber aerogel of a biomimetic structure prepared by the method of any one of claims 1-8, characterized by a long-range ordered multi-layer wave structure of a mud-tile with mollusc-like shell.
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 CN115478430A (en) | 2022-12-16 |
| CN115478430B true 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 (10)
| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101468018B1 (en) * | 2013-05-21 | 2014-12-02 | 한국생산기술연구원 | EMI Shield sheet comprising carbon complex fiber manufactured by electrospinning and a preparation method thereof |
-
2022
- 2022-08-26 CN CN202211030728.XA patent/CN115478430B/en active Active
Patent Citations (10)
| 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 |
| 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 |
|---|---|
| CN115478430A (en) | 2022-12-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108525018B (en) | High-strength hydrogel based on three-dimensional network scaffold and preparation method thereof | |
| Asmatulu et al. | Synthesis and applications of electrospun nanofibers | |
| Mohammed et al. | Fabrication and characterization of zinc oxide nanoparticle-treated kenaf polymer composites for weather resistance based on a solar UV radiation | |
| US4576608A (en) | Porous body-implantable polytetrafluoroethylene | |
| Shuai et al. | Development of composite porous scaffolds based on poly (lactide-co-glycolide)/nano-hydroxyapatite via selective laser sintering | |
| Yu et al. | Cellulose nanocrystals/polyethylene glycol as bifunctional reinforcing/compatibilizing agents in poly (lactic acid) nanofibers for controlling long-term in vitro drug release | |
| DE102007044648B4 (en) | Bioresorbable gelatin non-woven fabric | |
| EP1165865A1 (en) | Auxetic materials | |
| CN115478430B (en) | Nuclear protection nanofiber aerogel with bionic structure and preparation method thereof | |
| CN105624821B (en) | A kind of barium sulfate/polyvinyl alcohol composite fiber and preparation method thereof, non-woven cloth | |
| CN103526329A (en) | Preparation method for radiation-proof fibers | |
| JPS5831117A (en) | Production of fiber composite material for neutron shielding | |
| CN108690274B (en) | Radiation-proof composite latex, preparation method and application thereof, and radiation-proof gloves | |
| CN114687202B (en) | X-ray-proof shielding fabric and preparation method and application thereof | |
| Wan et al. | Preparation and characterization of three-dimensional braided carbon/Kevlar/epoxy hybrid composites | |
| CN114411014A (en) | In-situ synthesized ZnO reinforced composite material under GPa grade high pressure and preparation method thereof | |
| CN108324997B (en) | Carbon-carbon composite bone fracture plate with BMP slow release coating and preparation method thereof | |
| PL244595B1 (en) | Method for producing composite bone implants, method for producing powdered raw material for the composite bone implants, powdered raw material for bone implants and the composite bone implant | |
| Li et al. | Fabrication and characterization of microencapsulated n-octadecane with silk fibroin–silver nanoparticles shell for thermal regulation | |
| Ward et al. | The Development of Load‐bearing Bone Substitute Materials | |
| Sosiati et al. | Improving the Tensile Properties of Curcuma Mangga Val Extract (CMVE)/PVA Nanofiber Mats by Using a Type of Non-Commercial CMVE | |
| KR102280102B1 (en) | Protective clothing | |
| Meng et al. | Large-Scale Fabrication of Highly Filled Polymer Fibers for Radiation Protection Safety and Wear Comfort of Multilayer Fabrics in Complex Radiations | |
| Meng et al. | Preparation of Nano-PbWO4 Particles by Polymaleic Acid Modification: A Highly Filled Nonwoven Membrane Used To Improve the Wearing Comfort and Radiation Safety of γ-ray Protection Products | |
| Mao et al. | The Cut-/Stab-Resistance of Protective Composite Textiles Reinforced with Particle Additives |
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 |