CN115153279B - Titanium cup with trace element supplementing function and preparation method thereof - Google Patents
Titanium cup with trace element supplementing function and preparation method thereof Download PDFInfo
- Publication number
- CN115153279B CN115153279B CN202210533784.9A CN202210533784A CN115153279B CN 115153279 B CN115153279 B CN 115153279B CN 202210533784 A CN202210533784 A CN 202210533784A CN 115153279 B CN115153279 B CN 115153279B
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- CN
- China
- Prior art keywords
- titanium cup
- zinc
- nano
- titanium
- solution
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000010936 titanium Substances 0.000 title claims abstract description 95
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 95
- 239000011573 trace mineral Substances 0.000 title claims abstract description 51
- 235000013619 trace mineral Nutrition 0.000 title claims abstract description 51
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 60
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000011701 zinc Substances 0.000 claims abstract description 54
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 54
- 239000002131 composite material Substances 0.000 claims abstract description 39
- 239000011248 coating agent Substances 0.000 claims abstract description 37
- 238000000576 coating method Methods 0.000 claims abstract description 37
- 108010038807 Oligopeptides Proteins 0.000 claims abstract description 35
- 102000015636 Oligopeptides Human genes 0.000 claims abstract description 35
- 239000011787 zinc oxide Substances 0.000 claims abstract description 30
- 239000002103 nanocoating Substances 0.000 claims abstract description 27
- 244000269722 Thea sinensis Species 0.000 claims abstract description 25
- 150000002500 ions Chemical class 0.000 claims abstract description 18
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 16
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 15
- 235000013616 tea Nutrition 0.000 claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000005342 ion exchange Methods 0.000 claims abstract description 13
- 239000000284 extract Substances 0.000 claims abstract description 11
- 235000006468 Thea sinensis Nutrition 0.000 claims abstract description 9
- 235000020279 black tea Nutrition 0.000 claims abstract description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 9
- KSHPUQQHKKJVIO-UHFFFAOYSA-N [Na].[Zn] Chemical compound [Na].[Zn] KSHPUQQHKKJVIO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940094952 green tea extract Drugs 0.000 claims abstract description 8
- 235000020688 green tea extract Nutrition 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 150000008442 polyphenolic compounds Chemical class 0.000 claims abstract description 8
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000013522 chelant Substances 0.000 claims abstract description 6
- 238000010348 incorporation Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 53
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 229910001868 water Inorganic materials 0.000 claims description 22
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 17
- 238000010828 elution Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000002086 nanomaterial Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000004246 zinc acetate Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 7
- 229910020264 Na2TiO3 Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 230000003746 surface roughness Effects 0.000 claims description 4
- UOGBMDMLDZZHGP-UHFFFAOYSA-N 2,2,2-triethoxyethanol Chemical compound CCOC(CO)(OCC)OCC UOGBMDMLDZZHGP-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910003122 ZnTiO3 Inorganic materials 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000013589 supplement Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 238000010335 hydrothermal treatment Methods 0.000 abstract 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 8
- 235000013305 food Nutrition 0.000 description 8
- 229940091251 zinc supplement Drugs 0.000 description 8
- 230000035622 drinking Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920001202 Inulin Polymers 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
- 235000020188 drinking water Nutrition 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000008821 health effect Effects 0.000 description 3
- 229940029339 inulin Drugs 0.000 description 3
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 108090000765 processed proteins & peptides Proteins 0.000 description 3
- 239000012460 protein solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- 241000190070 Sarracenia purpurea Species 0.000 description 2
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 206010012601 diabetes mellitus Diseases 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 235000003599 food sweetener Nutrition 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000003765 sweetening agent Substances 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 239000011670 zinc gluconate Substances 0.000 description 2
- 229960000306 zinc gluconate Drugs 0.000 description 2
- 235000011478 zinc gluconate Nutrition 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229940092124 calcium citrate malate Drugs 0.000 description 1
- MPCMQXRREZMSPJ-UHFFFAOYSA-L calcium;2-hydroxybutanedioate;2-hydroxypropane-1,2,3-tricarboxylic acid;pentahydrate Chemical compound O.O.O.O.O.[Ca+2].[O-]C(=O)C(O)CC([O-])=O.OC(=O)CC(O)(C(O)=O)CC(O)=O MPCMQXRREZMSPJ-UHFFFAOYSA-L 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002354 daily effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000009982 effect on human Effects 0.000 description 1
- 229960001617 ethyl hydroxybenzoate Drugs 0.000 description 1
- 235000010228 ethyl p-hydroxybenzoate Nutrition 0.000 description 1
- 239000004403 ethyl p-hydroxybenzoate Substances 0.000 description 1
- NUVBSKCKDOMJSU-UHFFFAOYSA-N ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000009569 green tea Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- AIHDCSAXVMAMJH-GFBKWZILSA-N levan Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@@H]1[C@@H](O)[C@H](O)[C@](CO)(CO[C@@H]2[C@H]([C@H](O)[C@@](O)(CO)O2)O)O1 AIHDCSAXVMAMJH-GFBKWZILSA-N 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 235000021340 zinc rich food Nutrition 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47G—HOUSEHOLD OR TABLE EQUIPMENT
- A47G19/00—Table service
- A47G19/22—Drinking vessels or saucers used for table service
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
-
- 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
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/02—Pretreatment of the material to be coated
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/80—After-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a titanium cup with a trace element supplementing function and a preparation method thereof, and the titanium cup comprises a titanium cup, wherein a composite coating with 2 trace element ion sources is synthesized on the inner wall surface of the titanium cup through a combination process, the composite coating is a micro-nano coating with a leaf-shaped network structure, and the 2 trace element ion sources are respectively metal titanate and nano metal oxide; when the titanium cup contains a solution containing protein or oligopeptide or a black tea extract solution or a green tea extract solution, the composite coating can release trace element ions permanently and quantitatively and form chelate with the protein or oligopeptide or tea polyphenol; the preparation method comprises the following preparation steps: s1: surface pretreatment; s2: crystallizing to obtain TiO2 oxide film; s3: performing hydrothermal treatment; s4: zinc-sodium ion exchange; s5: preparing nano zinc oxide; s6: incorporation of nano zinc oxide. The invention opens up a new way for people to permanently supplement zinc in trace quantity, and makes up the defects in the prior art.
Description
Technical Field
The invention relates to the technical field of surface treatment of metallic titanium or titanium alloy, in particular to a titanium cup with a trace element supplementing function and a preparation method thereof.
Background
In the state that normal foods are difficult to ensure nutrition and lack zinc, world health organization recommends to supplement zinc salts. There are typically three zinc sources 1) inorganic zinc such as zinc sulfate; 2) Zinc salts of organic acids such as zinc gluconate; 3) Biological zinc such as protein zinc or oligopeptide zinc can be used for zinc supplementation. As known from chinese patent, in patent literature, such as "CN102716150B" and "a zinc sulfate syrup oral liquid preparation", chen Ping et al, use inorganic zinc sulfate as main ingredient, sucrose as sweetener, ethylparaben as preservative, citric acid, sodium citrate as pH stabilizer. In patent literature with the authority bulletin number of CN103599113B and the name of a composition for supplementing calcium and zinc, cheng Gang is developed to prepare a composition which takes organic zinc gluconate and calcium citrate malate as main medicines and can supplement zinc and calcium simultaneously. In recent years, the biological zinc of the third generation has the advantages of high activity, easy absorption by human body and quick effect, and has no stimulation and toxic side effect on human body safety due to low zinc content (equivalent to that of food), so the application of the biological zinc is widely paid attention. For example, in patent documents with the authorized bulletin number of CN104231099B, the name of "an inulin zinc and an oral liquid containing inulin zinc", wang Yijun inulin zinc prepared by chelating levan molecules with zinc ions, and patent documents with the authorized bulletin number of CN107337709B, the name of "a high zinc chelating active zinc chelating peptide and application thereof", xie Ningning et al chelate small molecule active peptide with zinc ions to prepare oligopeptide zinc, which are examples of biological zinc preparation and application. Recently Quan Gui controls the single zinc particle dissolution amount through engineering design of drinking water cup (CN 213085555U, a children zinc supplement element cup) so as to ensure the safety of zinc supplement at the same time.
Although the various zinc source preparations and the water cup for controlling the zinc dissolution amount through the utility model engineering design developed in the above patent have certain zinc supplementing application value, the zinc supplementing preparations in the patent technologies usually contain a plurality of auxiliary agents such as sweeteners, preservatives, dissolution assisting stabilizers and the like which are not needed by human bodies, so that not only are unnecessary preparation cost increased and potential harm to the human bodies caused, but also the zinc supplementing preparations are inconvenient to be used together with various drinking foods and are difficult to be accepted by consumers. The external zinc supplementing medicine has far different zinc supplementing effect from food in ideal. Therefore, the development of an effective way which is cheap and convenient and can simply convert various drinking foods into zinc-rich foods, and the health effect of low zinc supplement is achieved while people conveniently enjoy the delicious beverage, so that the zinc supplement is the most ideal zinc supplement way expected by people.
Disclosure of Invention
Aiming at the defects that the effect of supplementing trace elements, particularly zinc, by human bodies through foods or medicines in the prior art is still not ideal, a new ideal method for supplementing trace elements needs to be found, and the like, the invention provides a novel titanium cup with the function of supplementing trace elements and a preparation method thereof.
In order to solve the technical problems, the invention is realized by the following technical scheme:
The titanium cup with the trace element supplementing function comprises a titanium cup, wherein a TiO 2 oxide film is crystallized on the inner wall surface of the titanium cup, the TiO 2 oxide film is synthesized into a composite coating with 2 trace element ion sources through a hydrothermal method, metal ion exchange and nano material doping modification combined process, the composite coating is a micro-nano coating with a leaf-shaped network structure, the 2 trace element ion sources are respectively metal titanate and nano metal oxide, the metal titanate contains one or more trace elements of zinc, calcium and iron, and the nano metal oxide is one or more trace element oxides of nano zinc oxide, nano calcium oxide and nano iron oxide; the titanium element content of the composite coating is 84.91%, the trace element content is 6.79%, and the oxygen element content is 8.3%;
when the titanium cup contains a solution containing protein or oligopeptide or a black tea extract solution or a green tea extract solution, the composite coating can release trace element ions permanently and quantitatively and form chelate with the protein or oligopeptide or tea polyphenol.
The TiO 2 oxide film has extremely high crystallinity, and compared with a naturally formed titanium oxide film, the TiO2 oxide film has the advantages of low defect and low doping degree, and further has excellent corrosion resistance, wear resistance and biocompatibility.
The invention takes TiO 2 oxide film as a substrate, forms layered titanate nano material on the surface of a titanium cup through a hydrothermal method and a metal ion exchange process, and then mixes nano metal oxide into the layered titanate nano material through doping modification to finally form a nano coating with a leaf-shaped network structure.
According to the invention, two zinc source materials capable of releasing trace element ions are introduced into a nano structure on the surface of a titanium cup: 1) Metal titanate: the metal titanate is obtained by carrying out ion exchange between water-soluble trace element ions and sodium ions in sodium titanate generated by a titanium cup surface hydrothermal method; 2) Nano metal oxide: the ultrasonic technology is applied to dope and fix the nano-scale metallic zinc oxide into the special nano-structure on the surface of the titanium cup. Because the elution speed of titanate to trace element ions is greater than that of nano metal oxide, the titanate is suitable for short-term quick release of trace element ions, and the nano metal oxide particles are suitable for long-term slow release of trace element ions.
The invention supplements microelements of zinc, calcium and iron by drinking chelates formed by other biological organic molecules of protein, oligopeptide or tea polyphenol in liquid solution and microelements ions on the inner wall of a titanium cup. The supplementing trace elements can be quantitatively controlled according to the dosage of the liquid solution in the titanium cup, namely the concentration of oligopeptides or other biological organic molecules of tea polyphenol which form chelates with the trace elements, and the temperature and the time.
In summary, the invention forms chelate with protein, oligopeptide or tea polyphenol biological organic molecules in the drinking food through zinc ions on the inner wall of the titanium cup to release trace zinc ions quantitatively for a long time, so that the invention not only can be used for accurately supplementing zinc with high absorptivity and bioavailability, but also does not need any auxiliary agent, and maintains the original taste and flavor of the drinking food before and after zinc enrichment, and most importantly, consumers can convert the common drinking solution into the corresponding zinc-enriched solution very conveniently and cheaply through the invention, thereby opening up a new way for people to supplement zinc for a long time and making up the defects in the prior art.
Preferably, the titanium cup with the function of supplementing trace elements is characterized in that the metal titanate is zinc titanate, the nano metal oxide is nano zinc oxide with the wavelength of 0.5-50 nm, the composite coating is immersed in water, and the elution release amount of zinc ions is 15.2 ug/L.10h-26.6 ug/L.10h within 8 days.
Zinc is one of the most important and most desirable trace elements of the human body. Cai Lou and Li Cai (trace element zinc and diabetes, science Press, 1 month 1 year 2010) and a large number of scientific papers in international journal all report that zinc ions can activate enzymes related to diabetes, which is helpful for controlling blood sugar of diabetics. Therefore, the trace zinc ions can achieve the health care effect through the zinc supplement of daily drinking water.
According to the invention, two zinc source materials capable of releasing trace element zinc ions are introduced into a nano structure on the surface of a titanium cup: the metal zinc titanate and the nano zinc oxide are prepared by doping and fixing nano zinc oxide with the particle size of 0.5-50 nm into a special nano structure on the surface of a titanium cup by an ultrasonic technology. Because the elution speed of zinc titanate on zinc ions is greater than that of nano zinc oxide, zinc titanate is suitable for short-term quick release of trace element zinc ions, and zinc oxide nano particles are suitable for long-term slow release of trace element zinc ions.
Preferably, the titanium cup with the function of supplementing trace elements is characterized in that the composite coating is immersed in an oligopeptide aqueous solution with the concentration of 50g/L, and the elution release amount of zinc ions is not higher than 18 mg/L.10h.
The composite coating can release zinc ions permanently and quantitatively after being immersed in the oligopeptide aqueous solution.
Preferably, the titanium cup with the trace element supplementing function is characterized in that the composite coating is immersed into a protein powder solution with the concentration of 40g/L, and the elution release amount of zinc ions is not higher than 4 mg/L.10h.
The composite coating can release zinc ions permanently and quantitatively after being immersed in the protein powder solution.
Preferably, the titanium cup with the trace element supplementing function is characterized in that the composite coating is immersed in black tea extract or green tea extract solution with the concentration of 1.5g/L, and the elution release amount of zinc ions is not higher than 16 mg/L.10h.
The composite coating can release zinc ions permanently and quantitatively after being immersed in black tea extract or green tea extract solution.
A preparation method of a titanium cup with a trace element supplementing function comprises the following preparation steps:
S1: surface pretreatment: uniformly mixing sodium hydroxide, absolute ethyl alcohol, a detergent and deionized water according to the volume ratio of 4:2:0.3:10 to prepare a pretreatment cleaning solution, immersing the titanium cup in the pretreatment cleaning solution, standing for 5min, taking out, washing with deionized water, and airing;
S2: crystallizing a TiO 2 oxide film on the titanium cup through a vacuum high-temperature oxidation process;
S3: treatment by a hydrothermal method: immersing the titanium cup treated in the step S2 into 10mol/L sodium hydroxide solution A, standing and reacting for 24 hours at the normal pressure and 60 ℃, and carrying out the following chemical reaction on the TiO 2 oxide film on the titanium cup:
TiO2+2NaOH＝Na2TiO3+H2O，
after the reaction is finished, a micro-nano structure with low surface roughness and good hydrophilicity is formed on the titanium cup, then the titanium cup is gently rinsed by deionized water, and then the titanium cup is put into an oven with 220 ℃ to be baked for 3 hours, and then the titanium cup is taken out for natural cooling;
s4: zinc-sodium ion exchange: the cooled titanium cup is immersed into 0.05mol/L zinc acetate solution A again, and the reaction is carried out for 12 hours at 40 ℃ through the following zinc-sodium ion exchange reaction:
Zn2++Na2TiO3＝ZnTiO3+2Na+，
So as to form a nano coating with a leaf-shaped network structure on the titanium cup, lightly flushing the nano coating with deionized water for 4-5 times, drying the nano coating at 40 ℃ for 30min, and then taking out the nano coating for natural cooling;
S5: preparation of nano zinc oxide: preparing 0.1mol/L sodium hydroxide solution B and 0.1mol/L zinc acetate solution B again, uniformly mixing 10ml zinc acetate solution B and 200ml triethoxyethanol, placing on a magnetic stirrer, stirring at a rotating speed of 500rmp, gradually dripping 10ml sodium hydroxide solution B, and continuously stirring for 10min to obtain a solution containing nano zinc oxide particles;
S6: incorporation of nano zinc oxide: and (3) immersing the titanium cup cooled in the step (S4) into a solution containing nano zinc oxide particles, carrying out ultrasonic vibration for 120min by adopting an ultrasonic cleaner, doping the nano zinc oxide particles into the nano coating with the leaf-shaped network structure, washing for 4-5 times by deionized water after ultrasonic vibration, drying for 30min at 40 ℃, taking out, naturally cooling, and finally preparing the composite coating on the titanium cup.
In the step S1, the pretreatment cleaning solution can remove greasy dirt and impurities on the surface of the titanium cup, so that the purity of the titanium cup is ensured.
In the step S2, the surface of the titanium cup is crystallized to form an extremely thin compact rutile TiO 2 oxide film after being oxidized at high temperature under vacuum. The titanium cup has a titanium element content of 99.43% and an oxygen element content of 0.57% after high-temperature crystallization.
In the steps S3-S4, the special micro-nano coating with small surface roughness, good hydrophilicity and leaf-shaped network structure can be formed on the surface of the titanium cup by a hydrothermal method. The surface of the titanium cup forms a special micro-nano coating by a hydrothermal method, wherein the titanium element content is 89.19%, the oxygen element content is 8.99%, and the sodium element content is 1.83%. Forming a nano coating on the surface of the titanium cup through zinc-sodium ion exchange;
in the steps S5-S6, the surface of the titanium cup is doped by nano zinc oxide to form a composite coating, wherein the content of titanium element is 84.91%, the content of oxygen element is 8.30% and the content of zinc element is 6.79%.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of a TiO 2 oxide film in step S2 of the present invention;
FIG. 2 is an Energy Dispersive Spectroscopy (EDS) of the TiO 2 oxide film of step S2 of the present invention;
FIG. 3 is a Scanning Electron Microscope (SEM) photograph of the micro-nano structure of the present invention in step S3;
FIG. 4 is an Energy Dispersive Spectroscopy (EDS) of the micro-nano structure of the present invention in step S3;
FIG. 5 is a Scanning Electron Microscope (SEM) photograph of the nanocoating of step S4 of the present invention;
FIG. 6 is an Energy Dispersive Spectroscopy (EDS) of the nanocoating of step S4 of the present invention;
FIG. 7 is a Scanning Electron Microscope (SEM) photograph of the composite coating layer in step S6 of the present invention;
FIG. 8 is an Energy Dispersive Spectroscopy (EDS) of the composite coating of step S6 of the present invention;
FIG. 9 is an x-ray photoelectron spectroscopy (XPS) of the TiO 2 oxide film of step S2 of the present invention;
FIG. 10 is an x-ray photoelectron spectroscopy (XPS) of the nanocoating of step S6 of the present invention;
FIG. 11 is a graph showing the experimental results of example 4 of the present invention;
FIG. 12 is a graph showing the experimental results of example 5 of the present invention;
FIG. 13 is a graph II showing the experimental results of example 5 of the present invention;
FIG. 14 is a graph showing the experimental results of example 6 in the present invention.
Detailed Description
The invention is described in further detail below in connection with figures 1-14 and the detailed description, which are not intended to limit the invention:
Example 1
The titanium cup with the trace element supplementing function comprises a titanium cup, wherein a TiO 2 oxide film is crystallized on the inner wall surface of the titanium cup, the TiO 2 oxide film is synthesized into a composite coating with 2 trace element ion sources through a hydrothermal method, metal ion exchange and nano material doping modification combined process, the composite coating is a micro-nano coating with a leaf-shaped network structure, the 2 trace element ion sources are respectively metal titanate and nano metal oxide, the metal titanate contains one or more trace elements of zinc, calcium and iron, and the nano metal oxide is one or more trace element oxides of nano zinc oxide, nano calcium oxide and nano iron oxide; the titanium element content of the composite coating is 84.91%, the trace element content is 6.79%, and the oxygen element content is 8.3%;
when the titanium cup contains a solution containing protein or oligopeptide or a black tea extract solution or a green tea extract solution, the composite coating can release trace element ions permanently and quantitatively and form chelate with the protein or oligopeptide or tea polyphenol.
Preferably, the metal titanate is zinc titanate, the nano metal oxide is 10nm nano zinc oxide, and the composite coating is immersed in water, and the elution release amount of zinc ions is 15.2 ug/L.10h-26.6 ug/L.10h within 8 days.
Preferably, the composite coating is immersed in an oligopeptide aqueous solution with the concentration of 50g/L, and the elution release amount of zinc ions is not higher than 18 mg/L.10h.
Preferably, the composite coating is immersed in a protein powder solution with the concentration of 40g/L, and the elution release amount of zinc ions is not higher than 4 mg/L.10h.
Preferably, the composite coating is immersed in black tea extract or green tea extract solution with the concentration of 1.5g/L, and the elution release amount of zinc ions is not higher than 16 mg/L.10h.
A preparation method of a titanium cup with a trace element supplementing function comprises the following preparation steps:
S1: surface pretreatment: uniformly mixing sodium hydroxide, absolute ethyl alcohol, a detergent and deionized water according to the volume ratio of 4:2:0.3:10 to prepare a pretreatment cleaning solution, immersing the titanium cup in the pretreatment cleaning solution, standing for 5min, taking out, washing with deionized water, and airing;
S2: crystallizing a TiO 2 oxide film on the titanium cup through a vacuum high-temperature oxidation process;
S3: treatment by a hydrothermal method: immersing the titanium cup treated in the step S2 into 10mol/L sodium hydroxide solution A, standing and reacting for 24 hours at the temperature of 60 ℃ under normal pressure, and carrying out the following chemical reaction on a TiO2 oxide film on the titanium cup:
TiO2+2NaOH＝Na2TiO3+H2O，
after the reaction is finished, a micro-nano structure with low surface roughness and good hydrophilicity is formed on the titanium cup, then the titanium cup is gently rinsed by deionized water, and then the titanium cup is put into an oven with 220 ℃ to be baked for 3 hours, and then the titanium cup is taken out for natural cooling;
s4: zinc-sodium ion exchange: the cooled titanium cup is immersed into 0.05mol/L zinc acetate solution A again, and the reaction is carried out for 12 hours at 40 ℃ through the following zinc-sodium ion exchange reaction:
Zn2++Na2TiO3＝ZnTiO3+2Na+，
So as to form a nano coating with a leaf-shaped network structure on the titanium cup, lightly flushing the nano coating with deionized water for 4-5 times, drying the nano coating at 40 ℃ for 30min, and then taking out the nano coating for natural cooling;
S5: preparation of nano zinc oxide: preparing 0.1mol/L sodium hydroxide solution B and 0.1mol/L zinc acetate solution B again, uniformly mixing 10ml zinc acetate solution B and 200ml triethoxyethanol, placing on a magnetic stirrer, stirring at a rotating speed of 500rmp, gradually dripping 10ml sodium hydroxide solution B, and continuously stirring for 10min to obtain a solution containing nano zinc oxide particles;
S6: incorporation of nano zinc oxide: and (3) immersing the titanium cup cooled in the step (S4) into a solution containing nano zinc oxide particles, carrying out ultrasonic vibration for 120min by adopting an ultrasonic cleaner, doping the nano zinc oxide particles into the nano coating with the leaf-shaped network structure, washing for 4-5 times by deionized water after ultrasonic vibration, drying for 30min at 40 ℃, taking out, naturally cooling, and finally preparing the composite coating on the titanium cup.
Example 2
Preferably, the metal titanate is zinc titanate, the nano metal oxide is nano zinc oxide with the wavelength of 0.5nm, the composite coating is immersed in water, and the elution release amount of zinc ions is 15.2 ug/L.10h-26.6ug/L.10h within 8 days.
Further implementations of this example refer to example 1.
Example 3
Preferably, the metal titanate is zinc titanate, the nano metal oxide is nano zinc oxide with the wavelength of 50nm, and the composite coating is immersed in water, and the elution release amount of zinc ions is 15.2 ug/L.10h-26.6ug/L.10h within 8 days.
Further implementations of this example refer to example 1.
Example 4
The titanium cup of example 1 was used for a zinc ion release test, which was performed as follows:
200mL of boiled water is added into the sample, the sample is kept stand for 24 hours at room temperature, 200mL of water is poured out for zinc ion analysis, then 200mL of boiled water is added into the same sample after 24 hours, the sample is kept stand for 24 hours at room temperature for water sample analysis, after the experiment is continuously repeated for 8 days, all 8-day water samples collected from the sample are subjected to ICP-MS analysis, and the concentration of zinc ions in the water is determined, as shown in FIG. 11.
From the experimental results of zinc ion release for 1-8 days, the amount of zinc ions eluted and released every day is low, and the change is small (only 15.2 ug/L-26.6 ug/L), which shows that the zinc ions in the trace element composite micro-nano coating are very stable, and can slowly release low concentration zinc ions into water for a long time. Therefore, the titanium cup has the function of zinc supplement for drinking water with a lasting low amount.
Example 5
The titanium cup of example 1 was used for a zinc ion release test, which was performed as follows:
10 g of oligopeptide powder was dissolved in 200mL of boiled water to prepare 2 parts of oligopeptide aqueous solutions, namely oligopeptide sample 1 and oligopeptide sample 2, respectively, and the oligopeptide aqueous solutions were sampled and analyzed by ICP-MS (inductively coupled plasma-mass spectrometry) after being distributed for 2, 4, 6, 12, 24 and 144 hours, so as to determine the zinc ion concentration in the oligopeptide aqueous solutions, as shown in FIG. 12.
From the results of the zinc ion release experiment of the oligopeptide aqueous solution, the zinc ion release amount of the oligopeptide solution is not only much higher than that of pure water due to the chelation of the oligopeptide molecules and the zinc ions, but also is faster, and the maximum value is close to 2 hours.
Different amounts of oligopeptide powder (2, 4, 6, 8 and 10 g) are respectively dissolved in 200mL of boiled water in a sample to prepare oligopeptide aqueous solution (10 g/L-50 g/L), and meanwhile, raw material-protein solution (10 g/L-40 g/L) for preparing the oligopeptide is used as a comparison. Samples were taken after 2 hours for ICP-MS analysis to determine the zinc ion concentration in the oligopeptide aqueous solution and the protein aqueous solution as shown in FIG. 13.
The result shows that the release amount of zinc ions of the oligopeptide solution in the zinc-rich titanium cup is in direct proportion to the dosage of the oligopeptide, so that the double health effects of accurately supplementing the peptide and zinc can be realized by controlling the quantity of the oligopeptide in the zinc-rich titanium cup. Furthermore, since the oligopeptide has better water solubility and better zinc ion chelating ability than the protein solution, the oligopeptide solution has much higher zinc ion release amount than the protein solution.
Example 6
The titanium cup of example 1 was used for a zinc ion release test, which was performed as follows:
the concentration of zinc ions in tea water was determined by dissolving 0.3 g of green tea or black tea extract in 200mL of boiled water in a sample, or 3 g of tea was immersed in 200mL of boiled water, and after 24 hours, sampling was performed for ICP-MS analysis, respectively, as shown in FIG. 14.
The result shows that the release amount of zinc ions of the fully-dissolved tea industry extract in the zinc-rich titanium cup is much higher than that of the corresponding tea industry soaking liquid, and the fully-dissolved tea industry extract contains higher concentration of tea polyphenol and other biological organic matters which can be chelated with the zinc ions. Also, by drinking the tea through the zinc-rich cup of the technology, the double health effects of Chinese tea and zinc supplement can be obtained simultaneously.
In summary, the foregoing description is only of the preferred embodiments of the present invention, and all equivalent changes and modifications that come within the scope of the present invention are desired to be covered thereby.
Claims (4)
1. A titanium cup with function of supplementing trace elements is characterized in that: the titanium cup comprises a titanium cup, wherein a TiO 2 oxide film is crystallized on the surface of the inner wall of the titanium cup, the TiO 2 oxide film is synthesized into a composite coating with 2 trace element ion sources through a hydrothermal method, metal ion exchange and nano material doping modification combined process, the composite coating is a micro-nano coating with a leaf-shaped network structure, and the 2 trace element ion sources are respectively metal titanate and nano metal oxide; the titanium element content of the composite coating is 84.91%, the trace element content is 6.79%, and the oxygen element content is 8.3%;
When the titanium cup contains a solution containing protein or oligopeptide or a black tea extract solution or a green tea extract solution, the composite coating can release trace element ions permanently and quantitatively and form chelate with the protein or oligopeptide or tea polyphenol;
The metal titanate is zinc titanate, the nano metal oxide is nano zinc oxide with the particle size of 0.5-50 nm, the composite coating is immersed in water, and the elution release amount of zinc ions is 15.2 ug/L.10 h-26.6 ug/L.10 h within 8 days;
The preparation method comprises the following preparation steps:
S1: surface pretreatment: uniformly mixing sodium hydroxide, absolute ethyl alcohol, a detergent and deionized water according to the volume ratio of 4:2:0.3:10 to prepare a pretreatment cleaning solution, immersing the titanium cup in the pretreatment cleaning solution, standing for 5min, taking out, washing with deionized water, and airing;
S2: crystallizing a TiO 2 oxide film on the titanium cup through a vacuum high-temperature oxidation process;
S3: treatment by a hydrothermal method: immersing the titanium cup treated in the step S2 into 10mol/L sodium hydroxide solution A, standing and reacting for 24 hours at the normal pressure and 60 ℃, and carrying out the following chemical reaction on the TiO 2 oxide film on the titanium cup:
TiO2+2NaOH=Na2TiO3+H2O，
after the reaction is finished, a micro-nano structure with low surface roughness and good hydrophilicity is formed on the titanium cup, then the titanium cup is gently rinsed by deionized water, and then the titanium cup is put into an oven with 220 ℃ to be baked for 3 hours, and then the titanium cup is taken out for natural cooling;
s4: zinc-sodium ion exchange: the cooled titanium cup is immersed into 0.05mol/L zinc acetate solution A again, and the reaction is carried out for 12 hours at 40 ℃ through the following zinc-sodium ion exchange reaction:
Zn2++Na2TiO3=ZnTiO3+2Na+，
Forming a nano coating with a leaf-shaped network structure on the titanium cup, lightly flushing the nano coating with deionized water for 4-5 times, drying the nano coating at 40 ℃ for 30min, and then taking out the nano coating for natural cooling;
S5: preparation of nano zinc oxide: preparing 0.1mol/L sodium hydroxide solution B and 0.1mol/L zinc acetate solution B again, uniformly mixing 10ml zinc acetate solution B and 200ml triethoxyethanol, placing on a magnetic stirrer, stirring at a rotating speed of 500rmp, gradually dripping 10ml sodium hydroxide solution B, and continuously stirring for 10min to obtain a solution containing nano zinc oxide particles;
S6: incorporation of nano zinc oxide: and (3) immersing the titanium cup cooled in the step (S4) into a solution containing nano zinc oxide particles, carrying out ultrasonic vibration for 120min by adopting an ultrasonic cleaner, doping the nano zinc oxide particles into the nano coating with the leaf-shaped network structure, washing for 4-5 times by deionized water after ultrasonic vibration, drying at 40 ℃ for 30min, taking out, naturally cooling, and finally preparing the composite coating on the titanium cup.
2. The titanium cup with the function of supplementing trace elements according to claim 1, wherein the titanium cup is characterized in that: the composite coating is immersed into oligopeptide aqueous solution with the concentration of 50g/L, and the elution release amount of zinc ions is not higher than 18 mg/L.10h.
3. The titanium cup with the function of supplementing trace elements according to claim 1, wherein the titanium cup is characterized in that: the composite coating is immersed into a protein powder solution with the concentration of 40g/L, and the elution release amount of zinc ions is not higher than 4 mg/L.10h.
4. The titanium cup with the function of supplementing trace elements according to claim 1, wherein the titanium cup is characterized in that: the composite coating is immersed into black tea extract or green tea extract solution with the concentration of 1.5g/L, and the elution release amount of zinc ions is not higher than 16 mg/L.10h.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6858294B1 (en) * | 1997-12-16 | 2005-02-22 | Catalyst & Chemicals Industries Co., Ltd. | Coating fluid for forming hard coating and substrates covered with hard coating |
| JP2005097712A (en) * | 2002-11-25 | 2005-04-14 | Toyo Seikan Kaisha Ltd | Surface-treated metallic material, method of surface treating therefor and resin-coated metallic material, metal can and can lid |
| CN1623910A (en) * | 2003-12-05 | 2005-06-08 | 朱星河 | Nano activation water cup and its preparation process |
| CN103396548A (en) * | 2013-08-14 | 2013-11-20 | 武汉一海数字工程有限公司 | Preparation method of high-dielectric polyimide/calcium copper titanate nanowire composite material |
| CN107029728A (en) * | 2017-05-11 | 2017-08-11 | 中国科学院新疆理化技术研究所 | A kind of Preparation method and use of the photochemical catalyst CaCu 3 Ti 4 O of the Lacking oxygen containing high density |
| CN109126821A (en) * | 2018-09-19 | 2019-01-04 | 平顶山学院 | A kind of preparation method of biomass carbon Base Metal modification auto-dope richness defect tin oxide nano composite photocatalyst material |
| CN111772446A (en) * | 2020-07-29 | 2020-10-16 | 上海超高环保科技股份有限公司 | Slow-release cup containing trace elements and manufacturing method thereof |
| CN113001124A (en) * | 2021-03-18 | 2021-06-22 | 浙江飞剑工贸有限公司 | Manufacturing method of vacuum cup with composite inner container |
| CN214595366U (en) * | 2021-03-18 | 2021-11-05 | 浙江飞剑工贸有限公司 | Thermos cup with composite inner container |
| CN113812819A (en) * | 2021-09-15 | 2021-12-21 | 四川泽南世家生物科技有限公司 | Sustained-release cup containing trace elements and manufacturing method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004053195A1 (en) * | 2002-11-25 | 2004-06-24 | Toyo Seikan Kaisha,Ltd. | Surface-treated metallic material, method of surface treating therefor and resin-coated metallic material, metal can and can lid |
| FI122800B (en) * | 2009-10-30 | 2012-07-13 | Laura Bougdanos | Teacup |
-
2022
- 2022-05-16 CN CN202210533784.9A patent/CN115153279B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6858294B1 (en) * | 1997-12-16 | 2005-02-22 | Catalyst & Chemicals Industries Co., Ltd. | Coating fluid for forming hard coating and substrates covered with hard coating |
| JP2005097712A (en) * | 2002-11-25 | 2005-04-14 | Toyo Seikan Kaisha Ltd | Surface-treated metallic material, method of surface treating therefor and resin-coated metallic material, metal can and can lid |
| CN1623910A (en) * | 2003-12-05 | 2005-06-08 | 朱星河 | Nano activation water cup and its preparation process |
| CN103396548A (en) * | 2013-08-14 | 2013-11-20 | 武汉一海数字工程有限公司 | Preparation method of high-dielectric polyimide/calcium copper titanate nanowire composite material |
| CN107029728A (en) * | 2017-05-11 | 2017-08-11 | 中国科学院新疆理化技术研究所 | A kind of Preparation method and use of the photochemical catalyst CaCu 3 Ti 4 O of the Lacking oxygen containing high density |
| CN109126821A (en) * | 2018-09-19 | 2019-01-04 | 平顶山学院 | A kind of preparation method of biomass carbon Base Metal modification auto-dope richness defect tin oxide nano composite photocatalyst material |
| CN111772446A (en) * | 2020-07-29 | 2020-10-16 | 上海超高环保科技股份有限公司 | Slow-release cup containing trace elements and manufacturing method thereof |
| CN113001124A (en) * | 2021-03-18 | 2021-06-22 | 浙江飞剑工贸有限公司 | Manufacturing method of vacuum cup with composite inner container |
| CN214595366U (en) * | 2021-03-18 | 2021-11-05 | 浙江飞剑工贸有限公司 | Thermos cup with composite inner container |
| CN113812819A (en) * | 2021-09-15 | 2021-12-21 | 四川泽南世家生物科技有限公司 | Sustained-release cup containing trace elements and manufacturing method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Zn-Incorporated Titanium Substrates with High Antibacterial Activity and Consecutive Release of Zinc;Xing Lin 等,;《Chemistry Select》;20230102;第8卷;第1-10 页 * |
| ZnO nanoparticle incorporated nanostructured metallic titanium for increased mesenchymal stem cell response and antibacterial activity;Elmy Elizabeth 等,;《Nanotechnology》;20140204;第25卷;第2 页 * |
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