CN100484430C - A method for nano TiO2 polymerization synergistic modification of natural pearls - Google Patents
A method for nano TiO2 polymerization synergistic modification of natural pearls Download PDFInfo
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- CN100484430C CN100484430C CNB2007100671114A CN200710067111A CN100484430C CN 100484430 C CN100484430 C CN 100484430C CN B2007100671114 A CNB2007100671114 A CN B2007100671114A CN 200710067111 A CN200710067111 A CN 200710067111A CN 100484430 C CN100484430 C CN 100484430C
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- Prior art keywords
- tio
- pearl
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- natural peral
- modification
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000004048 modification Effects 0.000 title claims description 36
- 238000012986 modification Methods 0.000 title claims description 36
- 230000002195 synergetic effect Effects 0.000 title claims description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract 6
- 239000011050 natural pearl Substances 0.000 title abstract 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 239000000839 emulsion Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 21
- 239000010936 titanium Substances 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 206010013786 Dry skin Diseases 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 150000003608 titanium Chemical class 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 3
- 239000011049 pearl Substances 0.000 abstract description 58
- 210000004243 sweat Anatomy 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000004383 yellowing Methods 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract 2
- 239000012467 final product Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 238000000985 reflectance spectrum Methods 0.000 description 23
- 239000013505 freshwater Substances 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 239000010984 cultured pearl Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 238000005299 abrasion Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010437 gem Substances 0.000 description 1
- 229910001751 gemstone Inorganic materials 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a method for producing nanoTiO2 Polymerization synergism-modified natural pearl. the method comprises the steps of: 1) preparing aqueous collosol, 2) carrying out a reaction between the natural pearl and aqueous collosol, drying, heat-treating to obtain intermediate state nano TiO2 modified natural pearl, 3) stirring the aqueous emulsion and deionized water for reaction to prepare precursor of aqueous solution, and 4) carrying out a polyreaction between the intermediate state nano TiO2 modified natural pearl and precursor Solution, drying, and heat-treating to obtain the final product. The product of the invention has the advantages of good uvioresistant oxidation and decay resistance performance. it is showed that the yellowing speed is reduced to 0 from the former 1.76% by 72h intensify experiment, polish descent speed is reduced to 0 from the former 2.87% by 10h sweat soaking experiment. The polish is improved with one or two rates than common pearl.
Description
Technical field
The present invention relates to nano-TiO
2The method of-polymerization synergistic modification natural peral.
Background technology
Pearl is a kind of organic jewel of preciousness, can be divided into natural peral and cultured pearl usually by its origin cause of formation, then can be divided into sea water pearls and fresh water pearl by producing environment, and modal on the market is freshwater cultured pearl.China is pearl culture big country, and the breed of fresh water pearl mainly concentrates on the provinces and regions of middle and lower reach of Yangtze River fresh water water system prosperity, and Zhejiang is the important producing region of fresh water pearl.Output to China fresh water pearl in 2002 has exceeded 2000 tons/year, accounts for global 90%.But the technology of states such as optimization process technological level that China is present and Japan, the U.S. has bigger gap, and the requirement of pearl quality and international market also has certain distance, and the pearl finished product is difficult to participate in competition in the international market, causes a large amount of former pearls of main exit.With China fresh water pearl quantity disproportionate be worth too low: disclosed statistics shows that China only accounts for 4%～10% in the international pearl share of trade in 1999 to 2002.Change this situation, it is very necessary with the use value that improves pearl to strengthen freshwater cultured pearl optimization process Study on Technology.
Because in use, be subjected to the effect of oxygen, dusty gas etc. in sunlight, ultraviolet ray and the air, aragonite of pearl and organic matter can wear out usually, go bad.Aragonite can become common calcite, is that the organic matter of main component then reaction of degeneration (RD) can take place with the keratoprotein, and organic group is oxidized easily and change chromophoric groups such as carbonyl, carboxyl into.Bleaching pearl will be become common yellow and the brightness reversion phenomenon be occurred by white, Here it is proverb said " in the sear and yellow ".Pearl can contact human sweat, grease, perfume, alcohol etc. in wearing process simultaneously, and the pearl surface can be destroyed because of weathering under these material effects, and pearl loses beautiful gloss.And color of pearl and gloss are two important factors of its value of decision, produce these destruction back pearls and have just lost its use value substantially.
Solve the aging problem that is subjected to environmental attack easily that reaches of pearl, anti-aging, the erosion resistant pearl technology of preparing of exploitation high-quality is very necessary.
Obviously, if can handle by pearl being carried out the anti-aging and anti-erosion of surperficial uvioresistant, and finally obtaining the high-performance high quality pearl, will be the key that solves the yellowing sex change problem of pearl existence at present.Explore a kind of uvioresistant ageing resistace that can improve pearl, have corrosion-resistant property and the pearl process of surface treatment and the method that keep better surface gloss preferably again, just be expected to develop this field and make a breakthrough the high-performance pearl.
Summary of the invention
The object of the present invention is to provide a kind of anti-photooxidation, nano-TiO that decay resistance is good
2The method of-polymerization synergistic modification natural peral.
Nano-TiO of the present invention
2The method of-polymerization synergistic modification natural peral is characterized in that may further comprise the steps:
1) under 80～100 ℃, titanium salt and hydrogen peroxide mixed preparing are contained TiO
2Aqueous sol, Ti/H
2O
2Mol ratio be 1:1～1:4, collosol concentration is controlled at 0.1～0.5mol/L scope;
2) natural peral and aqueous sol were reacted 5～60 seconds, in 50～100 ℃ of dryings, in Muffle furnace, heat-treated for 10～600 seconds under 100～500 ℃ then, obtain the surface and form nano-TiO
2The intermediate state natural peral of modification;
3) water-based emulsion and the deionized water and stirring reaction with commodity AB-EP-20 by name and AB-HGF is mixed with aqueous solution precursor, and the volume ratio of deionized water: AB-EP-20:AB-HGF is (20～100): 4:1;
4) with step 2) nano-TiO that makes
2The precursor solution of the natural peral of intermediate state and step 3) preparation carried out polymerisation 5～60 seconds, after 50～100 ℃ of dryings, placed Muffle furnace 100-200 ℃ heat treatment 10～80 minutes, obtained nano-TiO
2The natural peral of-polymerization synergistic modification.
Above-mentioned titanium salt can be titanyl sulfate, Ti (OH)
4Or Ti (O
iPr)
4
The beneficial effect that the present invention compares with background technology is:
1, the nano-TiO of the inventive method acquisition
2-polymerization synergistic modification natural peral forms one deck nano-TiO on the surface of pearl
2-polymerization synergistic modification layer, it has uvioresistant oxidation preferably, decay resistance.Because sodium yellow and blue light are complementary colours, so former pearl is subjected to ultraviolet ray irradiation flavescence to show that 420nm～470nm blue segment reflectance spectrum intensity descends, and nano-TiO
2-polymerization synergistic modification coating can prevent that pearl is destroyed by ultraviolet ray.The gloss of pearl can represent that former pearl shows as 400nm～700nm visible light section when being subjected to the sweat corrosion reflectance spectrum intensity descends nano-TiO with the reflectance spectrum intensity of visible light section
2-polymerization synergistic modification coating can protect pearl to be avoided the sweat corrosion failure;
2, nano-TiO
2The gloss of-polymerization synergistic modification pearl can improve one to two grade than common pearl, and the abrasion resistance properties of pearl also increases.
3, because TiO
2Have automatically cleaning, performance such as antibiotic, so nano-TiO
2The pearl of-polymerization synergistic modification also can be realized automatically cleaning, characteristic such as antibiotic.
4, preparation technology is simple, utilizes the low temperature modification technology, has successfully formed TiO on the pearl top layer
2Nanocrystalline.By polymerization parcel TiO
2Nanocrystalline, realize modified synergic;
Description of drawings
Fig. 1 is a nano-TiO
2The schematic diagram of-polymerization synergistic modification natural peral.
The specific embodiment
Embodiment 1
1) under 80 ℃, titanyl sulfate and hydrogen peroxide mixed preparing are contained TiO
2Aqueous sol, Ti/H
2O
2Mol ratio be 1:1, collosol concentration is controlled at 0.1mol/L;
2) with natural peral and aqueous sol reaction 5 seconds, 30RMP Rotary drying 10 minutes in 50 ℃ of insulating boxs was heat-treated under 100 ℃ 10 minutes in Muffle furnace more then, obtained the top layer and formed nano-TiO
2The intermediate state natural peral;
3) water-based emulsion and the deionized water and stirring reaction with commodity AB-EP-20 by name and AB-HGF is mixed with aqueous solution precursor, and the volume ratio of deionized water: AB-EP-20:AB-HGF is 20:4:1;
4) with step 2) nano-TiO that makes
2The precursor solution of intermediate state natural peral and step 3) preparation carried out polymerisation 5 seconds, and the 30RMP Rotary drying placed 100 ℃ of heat treatments of Muffle furnace 80 minutes after 1 hour in 50 ℃ of insulating boxs, obtained nano-TiO
2-polymerization synergistic modification natural peral (see figure 1).On the surface of natural peral 1 one deck nano-TiO is arranged as seen from the figure
2-polymerization synergistic modification layer 2.
Definition 420nm～470nm blue segment reflectance spectrum intensity rate of descent is:
Reflectance spectrum intensity rate of descent=(0 hour blue segment reflectance spectrum average strength-72 hour blue segment reflectance spectrum average strength)/0 hour blue segment reflectance spectrum average strength
Definition 400nm～700nm visible light section reflectance spectrum intensity rate of descent is:
Reflectance spectrum intensity rate of descent=(0 hour visible light section reflectance spectrum average strength-10 hour visible light section reflectance spectrum average strength)/0 hour visible light section reflectance spectrum average strength
The speed of pearl oxidation flavescence under ultraviolet ray irradiation is characterized by 420nm～470nm blue segment reflectance spectrum intensity rate of descent in 72 hours enhanced times, has promptly characterized its anti-ultraviolet property.The pearl speed that gloss descends under sweat corrosion is characterized by 400nm～700nm visible light section reflectance spectrum intensity rate of descent in 10 hours enhanced times, has promptly characterized its anti-sweat corrosive nature.
More former pearl and nano-TiO
2-polymerization synergistic modification natural peral is through the visible reflectance of ultraviolet ray irradiation after 72 hours, and the blue segment reflectance spectrum intensity rate of descent of former pearl is 1.76%, and the blue segment reflectance spectrum intensity rate of descent of modification pearl is 0%, this shows nano-TiO
2The uvioresistant oxidation susceptibility of-polymerization synergistic modification pearl is improved.
More former pearl and nano-TiO
2-polymerization synergistic modification natural peral is through the visible reflectance of sweat immersion after 10 hours, and the visible light section reflectance spectrum intensity rate of descent of former pearl is 2.87%, and modification pearl visible light section reflectance spectrum intensity rate drops to 0%, this shows nano-TiO
2The sweat proof corrosion performance of-polymerization synergistic modification pearl also is improved.
Embodiment 2
1) under 100 ℃, with Ti (OH)
4Contain TiO with the hydrogen peroxide mixed preparing
2Aqueous sol, Ti/H
2O
2Mol ratio be 1:4, collosol concentration is controlled at the 0.5mol/L scope;
2) natural peral and aqueous sol were reacted 60 seconds, in 100 ℃ of dryings, in Muffle furnace, heat-treated for 10 seconds under 500 ℃ then, obtain the surface and form nano-TiO
2The intermediate state natural peral of modification;
3) water-based emulsion and the deionized water and stirring reaction with commodity AB-EP-20 by name and AB-HGF is mixed with aqueous solution precursor, and the volume ratio of deionized water: AB-EP-20:AB-HGF is 100:4:1;
4) with step 2) nano-TiO that makes
2The precursor solution of the natural peral of intermediate state and step 3) preparation carried out polymerisation 60 seconds, after 100 ℃ of dryings, placed 200 ℃ of heat treatments of Muffle furnace 10 minutes, obtained nano-TiO
2The natural peral of-polymerization synergistic modification.
More former pearl and nano-TiO
2-polymerization synergistic modification natural peral is through the visible reflectance of ultraviolet ray irradiation after 72 hours, and the blue segment reflectance spectrum intensity rate of descent of former pearl is 1.76%, and the blue segment reflectance spectrum intensity rate of descent of modification pearl is 0%, this shows nano-TiO
2The uvioresistant oxidation susceptibility of-polymerization synergistic modification pearl is improved.
More former pearl and nano-TiO
2-polymerization synergistic modification natural peral is through the visible reflectance of sweat immersion after 10 hours, and the visible light section reflectance spectrum intensity rate of descent of former pearl is 2.87%, and modification pearl visible light section reflectance spectrum intensity rate drops to 0%, this shows nano-TiO
2The sweat proof corrosion performance of-polymerization synergistic modification pearl also is improved.
Claims (3)
1. nano-TiO
2The method of-polymerization synergistic modification natural peral is characterized in that may further comprise the steps:
1) under 80～100 ℃, titanium salt and hydrogen peroxide mixed preparing are contained TiO
2Aqueous sol, Ti/H
2O
2Mol ratio be 1:1～1:4, collosol concentration is controlled at 0.1～0.5mol/L scope;
2) natural peral and aqueous sol were reacted 5～60 seconds, in 50～100 ℃ of dryings, in Muffle furnace, heat-treated for 10～600 seconds under 100～500 ℃ then, obtain the surface and form nano-TiO
2The intermediate state natural peral of modification;
3) water-based emulsion and the deionized water and stirring reaction with commodity AB-EP-20 by name and AB-HGF is mixed with aqueous solution precursor, and the volume ratio of deionized water: AB-EP-20:AB-HGF is (20～100): 4:1;
4) with step 2) nano-TiO that makes
2The precursor solution of the natural peral of intermediate state and step 3) preparation carried out polymerisation 5～60 seconds, after 50～100 ℃ of dryings, placed Muffle furnace 100-200 ℃ heat treatment 10～80 minutes, obtained nano-TiO
2The natural peral of-polymerization synergistic modification.
2. nano-TiO according to claim 1
2The method of-polymerization synergistic modification natural peral is characterized in that said titanium salt is a titanyl sulfate.
3. nano-TiO according to claim 1
2The method of-polymerization synergistic modification natural peral is characterized in that Ti (OH)
4Or Ti (O
1Pr)
4Substitute said titanium salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100671114A CN100484430C (en) | 2007-01-31 | 2007-01-31 | A method for nano TiO2 polymerization synergistic modification of natural pearls |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100671114A CN100484430C (en) | 2007-01-31 | 2007-01-31 | A method for nano TiO2 polymerization synergistic modification of natural pearls |
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|---|---|
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| CN100484430C true CN100484430C (en) | 2009-05-06 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260414B (en) * | 2010-05-21 | 2013-01-09 | 冀州市中意复合材料有限公司 | Material with reef-like structure and preparation method thereof |
| KR101918967B1 (en) * | 2017-03-30 | 2019-02-08 | (주) 내츄럴웰테크 | Wave providing ornaments using sawtooth waveforms |
| CN110973784B (en) * | 2019-12-24 | 2021-12-28 | 中国计量大学 | Pearl brightening method and device |
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2007
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Non-Patent Citations (2)
| Title |
|---|
| 淡水养殖珍珠的化学染色及其对珍珠表面形貌的影响. 吴广州等.宝石和宝石学杂志，第8卷第2期. 2006 |
| 淡水养殖珍珠的化学染色及其对珍珠表面形貌的影响. 吴广州等.宝石和宝石学杂志，第8卷第2期. 2006 * |
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