CN112425843A - Preparation method of mask - Google Patents
Preparation method of mask Download PDFInfo
- Publication number
- CN112425843A CN112425843A CN202011423536.6A CN202011423536A CN112425843A CN 112425843 A CN112425843 A CN 112425843A CN 202011423536 A CN202011423536 A CN 202011423536A CN 112425843 A CN112425843 A CN 112425843A
- Authority
- CN
- China
- Prior art keywords
- mask
- layer
- oxide film
- titanium
- tio
- 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
- 238000002360 preparation method Methods 0.000 title claims description 20
- 239000010410 layer Substances 0.000 claims abstract description 98
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 50
- 230000003647 oxidation Effects 0.000 claims abstract description 49
- 239000004744 fabric Substances 0.000 claims abstract description 34
- -1 polypropylene Polymers 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000004743 Polypropylene Substances 0.000 claims abstract description 29
- 229920001155 polypropylene Polymers 0.000 claims abstract description 29
- 229920000742 Cotton Polymers 0.000 claims abstract description 21
- 239000004750 melt-blown nonwoven Substances 0.000 claims abstract description 19
- 239000011241 protective layer Substances 0.000 claims abstract description 17
- 230000002378 acidificating effect Effects 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- 238000006722 reduction reaction Methods 0.000 claims abstract description 11
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 9
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010407 anodic oxide Substances 0.000 claims description 54
- 239000010936 titanium Substances 0.000 claims description 53
- 229910052719 titanium Inorganic materials 0.000 claims description 52
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 51
- 229910052751 metal Inorganic materials 0.000 claims description 47
- 239000002184 metal Substances 0.000 claims description 47
- 229910052709 silver Inorganic materials 0.000 claims description 31
- 239000004332 silver Substances 0.000 claims description 30
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 23
- 239000011148 porous material Substances 0.000 claims description 21
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 16
- 238000002048 anodisation reaction Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 230000003247 decreasing effect Effects 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 235000010323 ascorbic acid Nutrition 0.000 claims description 10
- 229960005070 ascorbic acid Drugs 0.000 claims description 10
- 239000011668 ascorbic acid Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 230000010355 oscillation Effects 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000004381 surface treatment Methods 0.000 claims description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 10
- 238000005238 degreasing Methods 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 8
- 239000011775 sodium fluoride Substances 0.000 claims description 8
- 235000013024 sodium fluoride Nutrition 0.000 claims description 8
- 239000001433 sodium tartrate Substances 0.000 claims description 8
- 229960002167 sodium tartrate Drugs 0.000 claims description 8
- 235000011004 sodium tartrates Nutrition 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000004831 Hot glue Substances 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims 2
- 238000005554 pickling Methods 0.000 claims 1
- 230000001954 sterilising effect Effects 0.000 abstract description 19
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 15
- 238000001914 filtration Methods 0.000 abstract description 9
- 230000000241 respiratory effect Effects 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 82
- 239000000243 solution Substances 0.000 description 23
- 239000011162 core material Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000002131 composite material Substances 0.000 description 10
- 230000002829 reductive effect Effects 0.000 description 10
- 239000002585 base Substances 0.000 description 8
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002344 surface layer Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 230000006870 function Effects 0.000 description 6
- 210000000214 mouth Anatomy 0.000 description 6
- 239000003929 acidic solution Substances 0.000 description 5
- 239000012670 alkaline solution Substances 0.000 description 5
- 239000003242 anti bacterial agent Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 241000700605 Viruses Species 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000001815 facial effect Effects 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000029058 respiratory gaseous exchange Effects 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- NGBNXJUWQPLNGM-UHFFFAOYSA-N silver;azane Chemical compound N.[Ag+] NGBNXJUWQPLNGM-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000606153 Chlamydia trachomatis Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 241000588653 Neisseria Species 0.000 description 1
- 101100396546 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) tif-6 gene Proteins 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 206010035664 Pneumonia Diseases 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 208000036142 Viral infection Diseases 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940038705 chlamydia trachomatis Drugs 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 230000003930 cognitive ability Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 230000009385 viral infection Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
- A41D13/05—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches protecting only a particular body part
- A41D13/11—Protective face masks, e.g. for surgical use, or for use in foul atmospheres
- A41D13/1192—Protective face masks, e.g. for surgical use, or for use in foul atmospheres with antimicrobial agent
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/02—Layered materials
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
- A41D31/30—Antimicrobial, e.g. antibacterial
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/024—Anodisation under pulsed or modulated current or potential
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D2500/00—Materials for garments
- A41D2500/30—Non-woven
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D2500/00—Materials for garments
- A41D2500/50—Synthetic resins or rubbers
- A41D2500/52—Synthetic resins or rubbers in sheet form
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Physical Education & Sports Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Respiratory Apparatuses And Protective Means (AREA)
Abstract
The invention provides a method for preparing a mask, wherein the mask body sequentially comprises all-cotton spunlace non-woven fabric, polypropylene melt-blown non-woven fabric protective layer and TiO from inside to outside2An oxide film layer, a polypropylene melt-blown non-woven fabric protective layer and a polypropylene spun-bonded fabric layer, wherein the TiO layer2The oxidation film layer is prepared by alkaline anodic oxidation, silver nanoparticles are attached to the inner wall of the through hole, the silver nanoparticles are prepared by acidic chemical reduction, and the mask has extremely high sterilization rate and filtering effect and keeps lower internal respiratory resistance.
Description
Technical Field
The invention relates to the technical field of medical protection, in particular to a preparation method of a mask.
Background
The mask is a protective article, and is a tool which is worn at the mouth and nose parts of a person and is used for filtering air entering the mouth and nose so as to prevent harmful gas, smell, dust, spray and the like from entering and exiting the mouth and nose of the wearer. The mask has various forms, and has the main function of forming an air filter layer between the nose, mouth and the outside to prevent germs, smoke dust and dust from directly entering the mouth and the nose. In recent years, a wide range of virus epidemic outbreaks has brought people to realize the importance of the mask. Under the continuous call of medical professionals, the cognitive ability of people to the gauze mask is continuously strengthened. Medical masks are generally classified into medical protective masks, medical surgical masks, and disposable medical masks. The medical mask is required to be worn so that the mask fits to the face to a certain extent. If the inherent shape of the face and mask do not conform to one another and a tight fit is not achieved, respiratory protection may fail, resulting in an increased risk of viral infection during an epidemic.
The traditional mask mostly adopts a simple rectangular plane structure formed by stacking multiple layers of sterile gauze, generally adopts a three-layer structure filter piece (SMS structure), namely a spunbonded layer (S), a melt-blown layer (M) and a spunbonded layer (S), the spunbonded layer is tightly attached to the face, the oral cavity and the nostril positions are covered, and the mask is tied on the auricle by means of a mask belt. However, the new crown pneumonia epidemic situation occurred in the early 2020, which causes a lot of defects of the mask, and the production amount of the mask at present is difficult to meet the daily requirement of one mask per person.
Chinese CN106307711A patent discloses a warm mask with detachable self-heating patches, which comprises a mask body, self-heating patches and ear hanging belts arranged at two sides of the mask body, wherein the mask body comprises an outer surface layer and a cotton bag, the outer surface layer and the lower edge of the cotton bag are connected by sewing threads, the self-heating patches are inserted between the outer surface layer and the cotton bag, a cotton wadding layer is arranged in the cotton bag, an opening is arranged on the cotton bag, a zipper is arranged in the opening, the mask is adopted, the detachable self-heating patches are arranged in the mask, the self-heating patches can be disposable heating patches mature in the market, when in use, release paper at the back of the self-heating patches is torn off and is attached to the inside of the mask, the cotton bag capable of adjusting the thickness of the cotton wadding layer is adopted, the opening at the upper part can be opened by the zipper, the cotton wadding layer is taken out or the cotton wadding layer is added, the effect of automatically adjusting the distance between the self-heating patch and the face is achieved, and the problem that the warm-keeping effect cannot be achieved due to chronic scalding caused by overhigh temperature or low temperature is solved. A filter disc, a degerming disc, a peculiar smell removing disc, a pollen removing disc and the like can be arranged between the outer surface layer and the cotton bag. The invention realizes the effects of keeping warm, filtering, degerming, removing peculiar smell and removing pollen by adding different functional sheets, can realize the combination of various functions by combining different functional sheets, and creates a more suitable facial air environment, however, the combination of the multiple functional sheets inevitably leads to the increase of the volume of the facial protective article and is inconvenient to use. Furthermore, the disposable heat-generating patch generally generates heat by oxidation of a plurality of compound powders in contact with air. The heating patch is easy to leak into the respiratory tract or hurt the facial skin when the sealing performance is not good, and the heating patch can cause larger air resistance when the sealing performance is good, so that the user is labored to breathe.
In the prior art, the examples of using a porous metal alloy film as a sterilization layer are few, for example, CN201810088912.7 in china aims at the defects that the structure of a nano-porous copper-silver filtering sterilization layer in the prior art is single, nano-copper-silver bimetallic powder is easy to accumulate and cannot be self-supported, and the like, and provides a breathable layered nano-porous copper-silver composite material and a preparation method thereof. The material comprises a nano-porous copper-silver (C layer) in the middle, and nano-porous copper (B layer), nano-porous copper-silver (A layer, surface layers on two sides of a thin strip) which are arranged on two sides in sequence, namely, the composite material with a five-layer nano-porous structure (nano-porous copper-silver (A layer, surface layer on one side) -nano-porous copper (B layer) -nano-porous copper-silver (C layer) -nano-porous copper (B layer) -nano-porous copper-silver (A layer, surface layer on the other side) is arranged on one side of the composite material to the other side in sequence). Because the composite material has five layers of nano-porous metal, nano holes on each layer are completely transparent and have adjustable pore diameters, and the layers are communicated with each other through the nano holes. The composite not only acts as a multi-layer barrier, but is also completely breathable. The preparation method comprises the steps of carrying out heat treatment on the prepared amorphous alloy thin strip to remove surface stress, so that the mechanical integrity of the composite material after alloy removal is ensured. Then preparing the breathable layered nano porous copper-silver composite material by using an electrochemical dealloying process. Compared with the reported novel composite material, the novel composite material prepared by the invention has more nano porous metal layers, and the layers are communicated through nano holes, so that the novel composite material has better filtering and sterilizing performance in the field of mask filter material.
International patent WO2012/023713a2 provides a mask capable of blocking viruses and a method of manufacturing such a mask. Forming an inhalation port and an exhalation port in the mask body; and fitting an inhalation part and an exhalation part including an inhalation filter into the inhalation part insertion port and the exhalation part insertion port, respectively. The suction filter may be formed by forming an alumina thin film formed by anodizing aluminum to form pores, and by arranging a mesh separator and fibers at both surfaces of the alumina thin film.
Although the international patent proposes the use of an anodic oxide film as a mask filter material for the first time, there are several problems as follows: (1) the anodic oxide film has only a filtering function, and as described in the specification, it is possible to produce masks 100 that block dust and viruses of different sizes depending on the purpose and environment of use, i.e., the anodic oxide film itself does not have a sterilization function and is physically protected only by a pore size molecular sieve structure; (2) the key technical means are ambiguous, as shown in figure 5: in this way, after the aluminum oxide layer 51 is formed by anodic oxidation, an etching process is performed in order to adjust the size of the hole formed in the aluminum oxide layer 51. When a portion of the alumina layer 51 is etched, alumina pillars 51a and an alumina lower layer 51b are formed, and thus a hole of an appropriate size is formed according to the use of the mask 100. The person skilled in the art would expect to be able to obtain a through-hole type anodic oxide film, but due to the barrier of the substrate and the shielding layer at the bottom of the anodic oxide film, the preparation of the through-hole anodic oxide film itself is the focus of the prior art:
various techniques are commonly used to remove the aluminum substrate and the shielding layer to obtain a porous alumina material, mainly as follows:
(a) the chemical method comprises the following steps: directly adopting CuCl2-HCl solution or SnCl4And replacing and removing the aluminum material at the bottom of the anodic oxide film, then soaking the anodic aluminum oxide in a phosphoric acid solution, dissolving and removing the shielding layer, and obviously corroding and dissolving part of the anodic oxide porous layer.
(b) A step-by-step pressurization method: the principle is that the thickness of the anode oxidized shielding layer is in direct proportion to the voltage, the thickness of the shielding layer is reduced in the process of reducing the voltage, and the shielding layer is considered to be removed when the voltage is reduced to 0V, but the nano-pore structure of the anode oxidized shielding layer is necessarily damaged in the process of reducing the voltage because the voltage is closely related to the pore size and the uniformity of the pore structure, and although the shielding layer is removed.
(c) A counter-pressure method: the main principle is that after the anode oxidation is finished, a reverse voltage H is provided in the electrolyte+Migration to the bottom of the hole, local high concentration of H+The ions accelerate the dissolution of the barrier layer alumina, and once the barrier layer is dissolved through, H + ions are reduced on the metal cathode to form H2The resulting gas pressure causes the porous film to peel off the aluminum substrate. Although the theory is simple, the actual operation process is extremely difficult to control.
(d) A complete oxidation method: the over-oxidation method is to extend the electrolysis time to completely anodize the aluminum sheet from one side to penetrate through to the lower layer metal to directly obtain the self-supporting through hole film, and the method has the obvious defect that the one-side oxidation is needed, otherwise, the array structure cannot be obtained.
Disclosure of Invention
Based on the problems in the prior art, the invention provides a preparation method of a mask, which comprises the following steps:
(1) preparing all-cotton spunlaced non-woven fabric;
(2) preparing a polypropylene melt-blown non-woven fabric protective layer;
(3) preparation of TiO2Oxidizing the film layer;
(4) preparing a polypropylene melt-blown non-woven fabric protective layer;
(5) preparing a polypropylene spun-bonded fabric layer;
(6) sequentially stacking the cloth in the steps (1) to (5) from inside to outside to obtain a mask main part, and cutting the mask main part to a required size;
(7) a nose clip is inserted and installed above the mask main part, the outer side edge of the mask main part is imprinted and sealed, and ear bands are fixedly bonded at the four corners of the mask main part through hot melt adhesive and imprinting;
the step (3) of preparing TiO2The process of oxidizing the film layer is as follows:
(a) the metal titanium is used as a base material, and the surface treatment is carried out on the base material.
(b) Carrying out anodic oxidation in alkaline electrolyte by taking metal titanium as an anode and inert metal as a cathode;
(c) reducing the anodic oxidation voltage parameter to 0.5V in a gradient manner;
(d) the anodization voltage parameter is increased to 130V instantaneously,
(e) meanwhile, in the step (d), high-frequency ultrasonic vibration is applied to the vicinity of the titanium anode to peel off the anodic oxide film from the surface of the titanium substrate.
(f) Fishing the anodic oxide film and placing the anodic oxide film in a silver acid solution containing a reducing agent.
(g) Vacuum freeze drying to obtain TiO2And (5) oxidizing the film layer.
Further, the TiO2The oxide film layer is a through-hole type nano-pore array, and the TiO is2The thickness of the oxide film layer is 10-20 microns, the aperture of the through hole is 200-300nm, silver nanoparticles are attached to the inner wall of the through hole, and the particle size of the nanoparticles is 50-80 nm.
Further, the metal titanium is pure titanium.
Further, the preparation process of the acid chemical reduction is as follows: placing the anodic oxide film stripped in the step (5) in an acidic reducing solution, wherein the acidic reducing solution comprises: 5-7 wt% of silver nitrate, 3-5 wt% of ascorbic acid, 1-2wt% of hydrogen peroxide, 1-2wt% of polyvinylpyrrolidone and 2-3 of pH, and fishing the mixture after reduction for vacuum freeze drying.
Further, the surface treatment comprises mechanical polishing, degreasing and acid cleaning, wherein the degreasing liquid is inorganic alkaline degreasing liquid and comprises sodium hydroxide and sodium carbonate, and the mixed liquid of acidic nitric acid and hydrofluoric acid.
Further, the alkaline anodization solution and electrolysis parameters are as follows: 150-170g/L of NaOH, 10-20g/L of sodium tartrate, 2-8g/L of sodium fluoride, 50-60V of voltage and 50-80min of time.
Further, the gradient decreased anodization voltage from 10-15s to 20V, held for 30s, then 10-15s to 5V, held for 60s, then 10-15s to 0.5V, and held for 60 s.
Further, after the anodic oxidation voltage parameter is increased to 130V instantly, the anodic oxidation voltage parameter is kept for 1min, and high-frequency ultrasonic oscillation treatment is assisted.
Furthermore, the ultrasonic oscillation frequency is 20-30KHz, the power is 300-.
Further, the size of the mask is 18cm by 9cm or 15cm by 9cm
The mechanical polishing means included in the prior art includes sand blasting, shot blasting, grinding, sand paper grinding and polishing, and the main functions of the mechanical polishing means are to remove an oxide film on the surface of metal and obtain certain flatness, if sand blasting or shot blasting is used, the metal is strictly forbidden to be used for carrying out pretreatment on the titanium metal, because impurities can be obviously introduced into the metal, the subsequent anodic oxidation treatment is influenced.
After simple surface treatment, the surface oil stain is removed by alkali notification, and the method can be adopted for removing the oil stain on the surface, such as steam degreasing, ultrasonic cleaning and organic solvent degreasing, the invention adopts inorganic liquid saponification reaction of sodium hydroxide and sodium carbonate for degreasing, and the treatment temperature is 40-50 DEGoC, the time is 1-2 min.
The main function of the acid cleaning after the alkali cleaning is to achieve the mirror surface effect due to the polishing, effectively improve the plane roughness of the titanium material, and use HNO as the polishing solution345wt.% and HF15 wt%, temperature 25%oC, the time is 1-2 min.
The surface pretreatment process only carries out pretreatment when the oxide film is prepared for one time, and then carries out … for the second time and the third time.
Furthermore, the metal titanium is pure titanium, the size of the metal titanium is 18cm by 9cm or 15cm by 9cm, and the size of the metal titanium is matched with that of the mask.
The metal base material adopted by the invention is pure titanium alloy instead of titanium alloy, the main purpose is to obtain uniform and regular anode oxide film pore passages instead of wear-resistant or other high-density corrosion-resistant anode oxide films, and chromium, aluminum, copper and other materials in alloy elements have obvious influence on the regularity of the anode oxide film and the electrolysis parameters of the anode oxide film, so that the pure titanium metal base material with the simplest use and the best effect is adopted in the invention.
In addition, the size of the metal substrate is required to be consistent with the size of the prior art masks, 18cm by 9cm adults or 15cm by 9cm children, and if the core of the present invention is used as a pull-in or detachable mask, the size can be reduced as needed.
Further, the alkaline electrolyte comprises the following components: 150-170g/L of NaOH, 10-20g/L of sodium tartrate, 2-8g/L of sodium fluoride, 50-60V of voltage and 50-80min of time.
The anodic oxidation solution used in the invention is alkaline anodic oxidation solution, and acidic anodic oxidation solution is abandoned, and due to the limitation of acidic electrolyte, the technicians in the field know that in the prior art, the electrolyte for anodizing titanium metal is mainly divided into two types of acidity and alkalinity, the acidic electrolyte comprises adjustment or combination of sulfuric acid, nitric acid, hydrochloric acid, oxalic acid, or organic acid such as malonic acid, lactic acid, malic acid, tartaric acid, but the thickness of the commonly obtained anodic oxidation film is concentrated in the range of 50-400nm, and a high-thickness inner core carrier is difficult to obtain. In contrast, although the alkaline bath is less acidic in pore regularity, it is easier to obtain an anodic oxide film of ten microns or more, even 100 microns in the alkaline bath, and when the thickness is thicker, the subsequent stripping is more convenient, and the anodic oxide film is more suitable as a core carrier.
The invention obtains the anodic oxidation with the aperture of 200-300nm, the thickness of TiO2 of 10-20 microns and the thickness of the shielding layer of 40-50nm at the voltage of 50-60V and the time of 50-80 min.
Further, the gradient decreased anodization voltage from 10-15s to 20V, held for 30s, then 10-15s to 5V, held for 60s, then 10-15s to 0.5V, and held for 60 s.
As known to those skilled in the art, the anodic oxidation material mainly comprises a metal substrate with a bottom part, an anodic oxidation porous layer on the top part and an intermediate shielding layer on the bottom part and the top part, wherein the shielding layer is difficult to remove, especially difficult to select, and the shielding layer is formed by dynamic equilibrium of dissolution and deposition of the metal substrate in the anodic oxidation process of the metal substrate, namely the shielding layer is closely related to voltage, the shielding layer is easier to dissolve and inhibits the sedimentation process when the voltage is smaller in a certain range, and further the thickness of the shielding layer is obviously reduced.
Further, after the anodic oxidation voltage parameter is increased to 130V instantly, the anodic oxidation voltage parameter is kept for 1min, and high-frequency ultrasonic oscillation treatment is assisted.
In alkaline electrolysis, the anode should react with Ti +4OH-→TiO2+2H2O+4e-Mainly of said OH-Mainly comes from OH in alkaline NaOH, but in a tiny anodic oxidation pore channel, the mass transfer process is severely limited, and under the condition of extremely large voltage, the electrolysis of water occurs, H2O → OH-+H+Said OH is-Continue to react with the substrate while excess H+Under the premise of mass transfer limitation, the acid ions cannot be gathered to the cathode and can be moved away by OH even if the acid ions move away-Capture, neutralization, and thus localized formation of acidic H+The reaction TiO2+6F- +4H + → [ TiF6 ] takes place]2-+2H2O, the end result in the above process is H in the vicinity of the substrate+The shielding layer in close contact with the substrate is consumed and the excess or remote H is moved+Does not occur with TiO of the porous layer2And reacting with OH rich in a remote place, finally generating the stripping effect of the positioning corrosion shielding layer and the anodic oxide film, and simultaneously assisting ultrasonic oscillation after the electrolysis is finished to facilitate the separation of the anodic oxide film, wherein the ultrasonic oscillation frequency is 20-30KHz, the power is 300 ion-doped 500W, and the time is 2-5min, the anodic oxide film floats on the surface of the electrolyte under the premise of oscillation assistance, and a stirring rod or magnetic stirring is strictly forbidden to avoid deformation of the film form.
The anodic oxide film that is effectively peeled off can be obtained by applying a voltage and an instantaneous voltage through the above-mentioned gradient, the anodic oxide film is of a through hole type, but since the shielding layer of each pore channel cannot be guaranteed to be corroded in the stripping process, under the condition that part of the shielding layer is not completely corroded, because the shielding layer of other parts is corroded, under the assistance of ultrasonic oscillation, the part which is not corroded and shielded is peeled off due to stress tearing, rather than peeling off the shielding layer due to consumption, which results in that the current anodized film of the present invention is not a complete through-hole type anodized film, if the anodic oxide film is of a non-through hole type, the sterilization effect of the mask in the breathing process can not be exerted, while also causing discomfort to the wearer of the mask, it should be understood that the non-through holes are only a small percentage, by number, approximately 1/10.
Further, the silver acid solution containing the reducing agent is prepared according to the following ratio: 5-7 wt% of silver nitrate, 3-5 wt% of ascorbic acid, 1-2wt% of hydrogen peroxide, 1-2wt% of polyvinylpyrrolidone and 2-3 of pH =.
The main content of this step is the chemical reduction active component, i.e. the antibacterial agent, generally classified into three types, inorganic antibacterial agent, organic antibacterial agent and natural antibacterial agent. Inorganic antibacterial agents have been widely used and studied in various fields because of their low toxicity, heat resistance, sustainability, and the like. It is prepared by utilizing the sterilization and bacteriostasis of Ag, Cu, Zn, Ti and other metals or ions thereof, wherein the silver system has the best sterilization effect.
Silver (NanoSilver) is a metallic silver simple substance having a particle size of a nanometer order. By processing silver simple substance or silver ions, nano silver particles (AgNPs) with the particle size of 1-100 nm can be prepared, and the nano silver particles have effective inhibiting and killing effects on dozens of pathogenic microorganisms such as escherichia coli, gonococcus, chlamydia trachomatis and the like.
In the prior art, acidic reduced silver and alkaline reduced silver are provided, and currently, alkaline reduction is mainly used, such as silver ammonium solution, but if the alkaline reducing solution is adopted, the effect is not as good as that of the acidic reducing solution, probably because of the alkaline electrolyte adopted by anodic oxidation, the formed titanium oxide has certain alkali resistance, hydroxyl groups on the surface have lower sensitivity to the reducing solutions such as alkaline silver ammonium and the like, and by using the acidic solution, 1 can corrode the shielding layer which is not corroded due to stress tearing in the process to obtain the through hole anodic oxide film; 2, the acidic reduction is beneficial to improving the adsorption force of Ag on the surface of titanium oxide; 3, reducing with acid to obtain nanometer particles with size lower than that of the alkaline solution, and intensively distributing the obtained silver nanometer particles in 50-80 nm.
Wherein, polyvinylpyrrolidone is used as dispersant and is adsorbed on the surface of silver ion, and the reaction formula is as follows under the condition of acid ascorbic acid
Ag++PVP→Ag(PVP)+
2Ag(PVP)++C6H8O6→2Ag↓+2H++C6H6O6+2PVP
The pH =2-3, wherein the existence of hydrogen peroxide can improve the reducibility of ascorbic acid, and finally silver nanoparticles with uniform size are obtained.
Further, the preparation process of the silver acid solution containing the reducing agent comprises the following steps of firstly, sequentially adding polyvinylpyrrolidone, ascorbic acid and hydrogen peroxide into a proper amount of water to prepare a mixed solution; and then putting a porous titanium oxide array into the mixed solution, slowly adding silver nitrate, and slowly stirring by magnetic force for 10-15min at normal temperature and at the magnetic stirring speed of 100 rpm.
The sequence of addition of the main reagents should be strict in the above process to avoid premature reduction and deposition of silver ions, which would result in undesirable agglomeration of silver particles.
The scheme of the invention has the following beneficial effects:
(1) the anodic oxide film with extremely high through-hole rate can be obtained by sequentially reducing the anodic oxidation voltage in a gradient manner, instantly increasing the anodic oxidation voltage, and carrying out acid reduction deposition.
(2) The prepared anode oxide film layer can effectively protect the metal substrate and can be oxidized and stripped for multiple times.
(3) Ag/through-hole TiO2The inner core of the sterilizing layer is used as the inner core of the mask, so that the mask has extremely high sterilizing effect and filtering effect, and good air suction and exhalation effects.
Drawings
FIG. 1 is an SEM image of an all-cotton spunlace nonwoven fabric, a polypropylene meltblown nonwoven fabric and a polypropylene spunbonded fabric of the present invention.
FIG. 2 is an optical diagram of the anode oxide film sterilization inner core prepared by the invention.
FIG. 3 is a top SEM image of a via hole anodized film pore channel of the present invention.
FIG. 4 is an SEM image of a cross section of a via hole of the through hole anodized film of the present invention.
FIG. 5 is a SEM thickness diagram of a cross section of a via hole of a through hole anodized film of the present invention.
FIG. 6 is a top SEM image of an anodic oxide film pore channel array according to the present invention.
FIG. 7 is a TEM image of the distribution of silver ions in the pores of the anodic oxide film.
Detailed Description
Example 1
A preparation method of the mask comprises the following steps:
(1) preparing all-cotton spunlaced non-woven fabric;
(2) preparing a polypropylene melt-blown non-woven fabric protective layer;
(3) preparation of TiO2Oxidizing the film layer;
(4) preparing a polypropylene melt-blown non-woven fabric protective layer;
(5) preparing a polypropylene spun-bonded fabric layer;
(6) sequentially stacking the cloth in the steps (1) to (5) from inside to outside to obtain a mask main part, and cutting the mask main part to a required size;
(7) a nose clip is inserted and installed above the mask main part, the outer side edge of the mask main part is imprinted and sealed, and ear bands are fixedly bonded at the four corners of the mask main part through hot melt adhesive and imprinting;
the step (3) of preparing TiO2The process of oxidizing the film layer is as follows:
(a) the metal titanium is used as a base material, and the surface treatment is carried out on the base material.
(b) Taking metal titanium as an anode and inert metal as a cathode, and carrying out anodic oxidation in alkaline electrolyte, wherein the alkaline electrolyte comprises the following components: 150g/L NaOH, 10g/L sodium tartrate, 2g/L sodium fluoride, 50V voltage and 50min time.
(c) The anodization voltage parameter was decreased to 0.5V by a gradient of 10s to 20V, held for 30s, then 10s to 5V, held for 60s, then 10s to 0.5V, held for 60 s.
(d) And (4) instantly increasing the anodic oxidation voltage parameter to 130V, and keeping for 1min after the anodic oxidation voltage parameter is instantly increased to 130V.
(e) And (d) applying high-frequency ultrasonic vibration near the titanium anode to strip the anodic oxide film from the surface of the titanium substrate and float the anodic oxide film on the surface of the anodic oxide solution, wherein the ultrasonic vibration frequency is 30KHz, the power is 500W, and the time is 2 min.
(f) Fishing the anodic oxide film, and placing the anodic oxide film in a silver alkaline solution containing a reducing agent, wherein the silver acidic solution containing the reducing agent is prepared from the following components in percentage by weight: 5wt% of silver nitrate, 3 wt% of ascorbic acid, 1wt% of hydrogen peroxide, 1wt% of polyvinylpyrrolidone and 2-3 of pH.
(g) And (5) vacuum freeze drying.
The metal titanium is pure titanium.
Example 2
A preparation method of the mask comprises the following steps:
(1) preparing all-cotton spunlaced non-woven fabric;
(2) preparing a polypropylene melt-blown non-woven fabric protective layer;
(3) preparation of TiO2Oxidizing the film layer;
(4) preparing a polypropylene melt-blown non-woven fabric protective layer;
(5) preparing a polypropylene spun-bonded fabric layer;
(6) sequentially stacking the cloth in the steps (1) to (5) from inside to outside to obtain a mask main part, and cutting the mask main part to a required size;
(7) a nose clip is inserted and installed above the mask main part, the outer side edge of the mask main part is imprinted and sealed, and ear bands are fixedly bonded at the four corners of the mask main part through hot melt adhesive and imprinting;
the step (3) of preparing TiO2The process of oxidizing the film layer is as follows:
(a) the metal titanium is used as a base material, and the surface treatment is carried out on the base material.
(b) Taking metal titanium as an anode and inert metal as a cathode, and carrying out anodic oxidation in alkaline electrolyte, wherein the alkaline electrolyte comprises the following components: NaOH160g/L, sodium tartrate 15g/L, sodium fluoride 5g/L, voltage 55V, time 65 min.
(c) The anodization voltage parameter was decreased to 0.5V by a gradient, the anodization voltage was decreased to 20V by a gradient of 13s, held for 30s, then 13s to 5V, held for 60s, then 13s to 0.5V, held for 60 s.
(d) And (4) instantly increasing the anodic oxidation voltage parameter to 130V, and keeping for 1min after the anodic oxidation voltage parameter is instantly increased to 130V.
(e) And (4) applying high-frequency ultrasonic vibration near the titanium anode to strip the anodic oxide film from the surface of the titanium substrate and float the anodic oxide film on the surface of the anodic oxide solution, wherein the ultrasonic vibration frequency is 30KHz, the power is 500W, and the time is 3.5 min.
(f) Fishing the anodic oxide film, and placing the anodic oxide film in a silver alkaline solution containing a reducing agent, wherein the silver acidic solution containing the reducing agent is prepared from the following components in percentage by weight: 6 wt% of silver nitrate, 4 wt% of ascorbic acid, 1.5wt% of hydrogen peroxide, 1.5wt% of polyvinylpyrrolidone and 2-3 of pH.
(g) And (5) vacuum freeze drying.
The metal titanium is pure titanium.
Example 3
A preparation method of the mask comprises the following steps:
(1) preparing all-cotton spunlaced non-woven fabric;
(2) preparing a polypropylene melt-blown non-woven fabric protective layer;
(3) preparation of TiO2Oxidizing the film layer;
(4) preparing a polypropylene melt-blown non-woven fabric protective layer;
(5) preparing a polypropylene spun-bonded fabric layer;
(6) sequentially stacking the cloth in the steps (1) to (5) from inside to outside to obtain a mask main part, and cutting the mask main part to a required size;
(7) a nose clip is inserted and installed above the mask main part, the outer side edge of the mask main part is imprinted and sealed, and ear bands are fixedly bonded at the four corners of the mask main part through hot melt adhesive and imprinting;
the step (3) of preparing TiO2The process of oxidizing the film layer is as follows:
(a) the metal titanium is used as a base material, and the surface treatment is carried out on the base material.
(b) Taking metal titanium as an anode and inert metal as a cathode, and carrying out anodic oxidation in alkaline electrolyte, wherein the alkaline electrolyte comprises the following components: NaOH170g/L, sodium tartrate 20g/L, sodium fluoride 8g/L, voltage 60V, time 80 min.
(c) The anodization voltage parameter was decreased to 0.5V by a gradient, the anodization voltage was decreased to 20V by a gradient of 15s, held for 30s, then 15s to 5V, held for 60s, then 15s to 0.5V, held for 60 s.
(d) And (4) instantly increasing the anodic oxidation voltage parameter to 130V, and keeping for 1min after the anodic oxidation voltage parameter is instantly increased to 130V.
(e) And (4) applying high-frequency ultrasonic vibration near the titanium anode to strip the anodic oxide film from the surface of the titanium substrate and float the anodic oxide film on the surface of the anodic oxide solution, wherein the ultrasonic vibration frequency is 30KHz, the power is 500W, and the time is 5 min.
(f) Fishing the anodic oxide film, and placing the anodic oxide film in a silver alkaline solution containing a reducing agent, wherein the silver acidic solution containing the reducing agent is prepared from the following components in percentage by weight: 7 wt% of silver nitrate, 5wt% of ascorbic acid, 2wt% of hydrogen peroxide, 2wt% of polyvinylpyrrolidone and 2-3 wt% of pH.
(g) And (5) vacuum freeze drying.
The metal titanium is pure titanium.
Comparative example 1:
purchase a prior art 3M9002V mask;
comparative example 2:
a bactericidal and bacteriostatic mask comprises a mask body, a nose clip and an ear band, wherein the mask body sequentially comprises all cotton spunlace nonwoven fabric from inside to outsideCloth, polypropylene melt-blown non-woven fabric protective layer and TiO2An oxide film layer, a polypropylene melt-blown non-woven fabric protective layer and a polypropylene spun-bonded fabric layer, wherein the TiO layer2The oxide film layer is a through-hole type nanometer pore canal array, and the preparation process comprises the following steps:
(1) the metal titanium is used as a base material, and the surface treatment is carried out on the base material.
(2) Taking metal titanium as an anode and inert metal as a cathode, and carrying out anodic oxidation in alkaline electrolyte, wherein the alkaline electrolyte comprises the following components: NaOH160g/L, sodium tartrate 15g/L, sodium fluoride 5g/L, voltage 55V, time 65 min.
(3) The anodization voltage parameter was decreased to 0.5V by a gradient, the anodization voltage was decreased to 20V by a gradient of 13s, held for 30s, then 13s to 5V, held for 60s, then 13s to 0.5V, held for 60 s.
(4) And (4) instantly increasing the anodic oxidation voltage parameter to 130V, and keeping for 1min after the anodic oxidation voltage parameter is instantly increased to 130V.
(5) And (4) applying high-frequency ultrasonic vibration near the titanium anode to strip the anodic oxide film from the surface of the titanium substrate and float the anodic oxide film on the surface of the anodic oxide solution, wherein the ultrasonic vibration frequency is 30KHz, the power is 500W, and the time is 3.5 min.
(6) Vacuum freeze drying to obtain through-hole TiO2An inner core.
The metal titanium is pure titanium.
Comparative example 3
A sterilization and bacteriostasis mask is prepared by the following specific preparation process:
(1) the metal titanium is used as a base material, and the surface treatment is carried out on the base material.
(2) Taking metal titanium as an anode and inert metal as a cathode, and carrying out anodic oxidation in alkaline electrolyte, wherein the alkaline electrolyte comprises the following components: NaOH160g/L, sodium tartrate 15g/L, sodium fluoride 5g/L, voltage 55V, time 65 min.
(3) The anodization voltage parameter was decreased to 0.5V by a gradient, the anodization voltage was decreased to 20V by a gradient of 13s, held for 30s, then 13s to 5V, held for 60s, then 13s to 0.5V, held for 60 s.
(4) And applying high-frequency ultrasonic vibration near the titanium anode to strip the anodic oxide film from the surface of the titanium substrate and float the anodic oxide film on the surface of the anodic oxidation solution, wherein the ultrasonic vibration frequency is 30KHz, the power is 500W, and the time is 3.5 min.
(5) Fishing the anodic oxide film, and placing the anodic oxide film in a silver alkaline solution containing a reducing agent, wherein the silver acidic solution containing the reducing agent is prepared from the following components in percentage by weight: 6 wt% of silver nitrate, 4 wt% of ascorbic acid, 1.5wt% of hydrogen peroxide, 1.5wt% of polyvinylpyrrolidone and 2-3 of pH.
(6) Vacuum freeze drying to obtain Ag/through-hole TiO2An inner core of the sterilization layer.
The metal titanium is pure titanium.
The mask comprises an all-cotton spunlace non-woven fabric, a polypropylene melt-blown non-woven fabric protective layer, Ag/TiO from inside to outside in sequence2The sterilization test conditions comprise that an oxidation film layer, a polypropylene melt-blown non-woven fabric protective layer and polypropylene spun-bonded fabric are as follows: the area is 45cm2, and the flow rate is 30L/min, which are all golden yellow glucose bacteria.
As can be clearly seen from the above table, the mask obtained by the present invention has a lower respiratory resistance than the mask of the market 3M, is more comfortable, and has higher sterilization and filtration efficiency than the comparison document 1.
The difference between example 2 and comparative document 2 is that the active component silver is not applied to comparative document 2, and theoretically, if silver ions are not loaded, the pore channels of the anodic oxide film cannot be blocked by the silver ions, i.e. the breathing resistance of comparative document 2 should be lower than that of example 2, but the actual test effect is higher than that of example 2, mainly because the anodic oxide film is reduced by using an acidic silver solution after alkaline washing anodic oxidation, and the acidic silver solution can corrode a shielding layer remained in the alkaline anodic oxidation to obtain a higher pore rate of the anodic oxide film although the pore channels are inevitably blocked.
Example 2 is different from comparative example 3 in that no transient increase voltage was applied, which resulted in ineffective removal of the shielding layer, and peeling of the film was mainly due to tearing by ultrasonic oscillation, so that the obtained anodic oxide film was non-through-hole, resulting in extremely large resistance and high sterilization rate due to partial through-hole and sterilization effect by acid reduction.
As shown in figure 1, the all-cotton spunlace non-woven fabric-polypropylene fiber melt-blown non-woven fabric protective layer-Ag/TiO of the invention2The SEM image of the mask comprising the oxide film layer, the polypropylene melt-blown non-woven fabric protective layer and the polypropylene spun-bonded fabric shows that the fibrous material can obviously improve the filtering effect.
As shown in attached figure 2, the optical diagram of the anode oxide film sterilization inner core prepared by the invention obtains the anode oxide film which has certain flexibility and mechanical strength and is suitable for being used as the sterilization inner core of the mask.
As shown in the top view of fig. 3, the sectional view of fig. 4, and the thickness diagram of fig. 5, it can be seen that the obtained core material has regular cell channels and is in a through-hole type.
As shown in fig. 6, wherein the bottom of fig. 6 a is the shielding layer of the anodic oxide film, as shown in fig. 6 b, the shielding layer at the bottom can be significantly removed by reducing the anodic oxidation voltage in a gradient manner and increasing the anodic oxidation voltage instantaneously, but a part of the shielding layer still remains, the pore walls of the pore channels are significantly reduced by the acid reduced silver treatment, the shielding at the bottom is significantly disappeared, and the supported silver particles are shown in fig. 7.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A preparation method of the mask is characterized by comprising the following steps:
(1) preparing all-cotton spunlaced non-woven fabric;
(2) preparing a polypropylene melt-blown non-woven fabric protective layer;
(3) preparation of TiO2Oxidizing the film layer;
(4) preparing a polypropylene melt-blown non-woven fabric protective layer;
(5) preparing a polypropylene spun-bonded fabric layer;
(6) sequentially stacking the cloth in the steps (1) to (5) from inside to outside to obtain a mask main part, and cutting the mask main part to a required size;
(7) a nose clip is inserted and installed above the mask main part, the outer side edge of the mask main part is imprinted and sealed, and ear bands are fixedly bonded at the four corners of the mask main part through hot melt adhesive and imprinting;
the step (3) of preparing TiO2The process of oxidizing the film layer is as follows:
(a) the metallic titanium is taken as a base material, the surface treatment is carried out on the metallic titanium,
(b) carrying out anodic oxidation in alkaline electrolyte by taking metal titanium as an anode and inert metal as a cathode;
(c) reducing the anodic oxidation voltage parameter to 0.5V in a gradient manner;
(d) the anodization voltage parameter is increased to 130V instantaneously,
(e) meanwhile, in the step (d), high-frequency ultrasonic vibration is applied near the titanium anode to strip the anodic oxide film from the surface of the titanium substrate,
(f) fishing the anodic oxide film, placing the anodic oxide film in silver acid solution containing reducing agent,
(g) vacuum freeze drying to obtain TiO2And (5) oxidizing the film layer.
2. The method of making a mask according to claim 1 wherein said TiO is2The oxide film layer is a through-hole type nano-pore array, and the TiO is2The thickness of the oxide film layer is 10-20 microns, the aperture of the through hole is 200-300nm, silver nanoparticles are attached to the inner wall of the through hole, and the particle size of the nanoparticles is 50-80 nm.
3. The method of making a mask according to claim 1 wherein said titanium metal is pure titanium.
4. The method of making a mask according to claim 1 wherein said acid chemical reduction process comprises the steps of: placing the anodized film stripped in step (f) in an acidic reducing solution comprising: 5-7 wt% of silver nitrate, 3-5 wt% of ascorbic acid, 1-2wt% of hydrogen peroxide, 1-2wt% of polyvinylpyrrolidone and 2-3 of pH, and fishing the mixture after reduction for vacuum freeze drying.
5. The method of making a mask of claim 1 wherein said surface treatment comprises mechanical polishing, degreasing and pickling, said degreasing fluid is an inorganic alkaline degreasing fluid comprising a mixture of sodium hydroxide and sodium carbonate, and said acidic nitric acid and hydrofluoric acid.
6. The method of making a mask according to claim 1 wherein said alkaline anodization solution and electrolysis parameters are: 150-170g/L of NaOH, 10-20g/L of sodium tartrate, 2-8g/L of sodium fluoride, 50-60V of voltage and 50-80min of time.
7. The method of making a mask according to claim 1 wherein said voltage of anodic oxidation is decreased from 10-15s to 20V for 30s, then from 10-15s to 5V for 60s, then from 10-15s to 0.5V for 60 s.
8. The method of making a mask according to claim 1 wherein said step of adding an anodic oxidation voltage parameter instantaneously after 130V is maintained for 1min and assisted by high frequency ultrasonic oscillation.
9. The method of claim 1, wherein the ultrasonic oscillation frequency is 20-30KHz, the power is 300- & lt500W, and the time is 2-5 min.
10. A method of making a mask according to claim 1 wherein said cut is 18cm by 9cm or 15cm by 9 cm.
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| CN114622207A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Oxide film and preparation method and application thereof |
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