CN101811835B - Phosphate laser glass surface enhanced ion exchange method - Google Patents
Phosphate laser glass surface enhanced ion exchange method Download PDFInfo
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- CN101811835B CN101811835B CN2010101712912A CN201010171291A CN101811835B CN 101811835 B CN101811835 B CN 101811835B CN 2010101712912 A CN2010101712912 A CN 2010101712912A CN 201010171291 A CN201010171291 A CN 201010171291A CN 101811835 B CN101811835 B CN 101811835B
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- Prior art keywords
- sample
- laser glass
- ion exchange
- phosphate laser
- deionized water
- Prior art date
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- 239000000087 laser glass Substances 0.000 title claims abstract description 35
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 33
- 239000010452 phosphate Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000005342 ion exchange Methods 0.000 title claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical class [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 abstract description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical class [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 abstract description 10
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical class [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 abstract description 5
- 235000010333 potassium nitrate Nutrition 0.000 abstract description 5
- 238000005086 pumping Methods 0.000 abstract description 5
- 235000010344 sodium nitrate Nutrition 0.000 abstract description 5
- 230000006378 damage Effects 0.000 abstract description 3
- 229910052724 xenon Inorganic materials 0.000 abstract description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 2
- 238000004140 cleaning Methods 0.000 abstract 2
- 239000007853 buffer solution Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 239000011833 salt mixture Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 17
- 229910002651 NO3 Inorganic materials 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 8
- 229910001422 barium ion Inorganic materials 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 4
- 229910001414 potassium ion Inorganic materials 0.000 description 4
- 238000000227 grinding Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000005365 phosphate glass Substances 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 101000652229 Homo sapiens Suppressor of cytokine signaling 7 Proteins 0.000 description 1
- 102100030529 Suppressor of cytokine signaling 7 Human genes 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- -1 rare earth ion Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Abstract
The invention discloses a phosphate laser glass surface enhanced ion exchange method comprising the following steps: processing phosphate laser glass with 4.0 mol/L of NaOH solution at the temperature of 60 DEG C for 50 minutes, and cleaning with deionized water; processing with 1.0 mol/L of hydrofluoric acid buffer solution at the temperature of 80 DEG C for 40 minutes, cleaning with deionized water at normal temperature, and drying; putting prepared NaNO3, KNO3 and Ba(NO3)2 salt mixture and a sample into an ion exchange utensil; preserving heat of the ion exchange utensil and the sample thereof in a muffle furnace at the temperature of 320-430 DEG C for 12-16 hours, and then cooling to 50-100 DEG C at the rate of 80-100 DEG C/ hour; and taking out the sample, processing with 1.0 mol/L of hydrochloric acid, washing with deionized water, and drying. The invention greatly improves the mechanical property of the phosphate laser glass and greatly improves the repetition frequency and the thermal destruction threshold value under xenon lamp pumping.
Description
Technical field
The present invention relates to phosphate laser glass, particularly a kind of phosphate laser glass surface surface enhanced ion exchange method.
Background technology
Phosphate glass has advantageous properties such as phonon energy is moderate, high to rare earth ion solubleness, nonlinear factor is little makes it become the widest laser glass medium of use.The Application Areas of phosphate laser glass has contained laser-produced fusion, laser weapon, laser ranging, optical communication orthoron, ultrashort pulse laser application.
High repetition frequency, high-average power laser require increasingly high to the thermal shock resistance of laser glass under the high-strength light pumping condition.But phosphate glass is that typical brittleness material, the coefficient of expansion are big and chemicalstability is relatively poor; Surface and the inferior surperficial defective that exists processing to cause; Cause that crack propagation very easily takes place instability under external force, medium and thermal environment effect; So the surface imperfection especially influence of tiny crack makes the thermal shock resistance of phosphate laser glass under the high-strength light pumping condition lower, has limited the application of phosphate laser glass.
Thereby utilize chemical process to be called chemical enhancement method, claim that again IX strengthens method in the method that the prefabricated compressive stress layer of glass surface improves the glass machinery performance.It is that the glass surface enhanced is a kind of that IX strengthens; Its principle is that the mechanism according to ion diffusion changes glass surface and forms, and is immersed in glass in the high-temperature molten salt at a certain temperature, and alkalimetal ion in the glass and the alkalimetal ion in the fused salt because of diffusion mutual exchange take place; The IX that radius is big in the fused salt goes out the little ion of glass surface radius; Make glass surface produce " jammed " phenomenon, produce stress, thereby improve glass intensity at glass surface.
Na is used in general IX more
+The Li of exchange glass surface
+, K
+The Na of exchange glass surface
+, the little ion of IX radius that promptly radius is big produces stress, makes glass get intensity and is improved.But surface, exchange back can't effectively be repaired, and the chemicalstability of glass can reduce relatively.
Summary of the invention
The invention provides a kind of phosphate laser glass surface surface enhanced ion exchange method; This method can make folding strength, microhardness, the embrittlement temperature of phosphate laser glass be greatly improved, and therefore can significantly improve repetition rate and the thermal destruction threshold value of phosphate laser glass under xenon flash lamp pumping.And make the surface obtain repairing.The surface that can be widely used in phosphate laser glass strengthens.
Technical solution of the present invention is following:
A kind of phosphate laser glass surface surface enhanced ion exchange method, characteristics are may further comprise the steps:
The first step: pending phosphate laser glass; Hereinafter to be referred as sample; With handling 50 minutes and cleaned at 60 ℃ in the NaOH solution of 4.0mol/L, handled 40 minutes with the 1.0mol/L buffered hydrofluoric acid solution at 80 ℃ afterwards, at last at normal temperatures with deionized water wash and oven dry with deionized water;
Second step: with the NaNO of preparation
3, KNO
3, Ba (NO
3)
2Mixing salt is put into the IX vessel, and the sample after then the first step being handled is put into described IX vessel;
The 3rd step: described IX vessel and sample thereof under the 320-430oC, are incubated after 12～16 hours in retort furnace, are cooled to 50～100 ℃ with 80-100 ℃/hour speed;
The 4th step: take out sample with the s.t. of 1.0mol/L salt after with drying behind the deionized water wash.
Described NaNO
3, KNO
3, Ba (NO
3)
2Mixing salt composition and weight percent following:
Form wt%
NaNO
3 10～30
KNO
3 20～40
Ba(NO
3)
2 40～70
The invention has the advantages that:
1, potassium ion that radius of the present invention is big and barium ion can both get into glass surface and form compressive stress layer, and compressive stress layer can stop the expansion of glass surface tiny crack.
2, ion-exchange temperature of the present invention is higher, and potassium ion and the barium ion exchange degree of depth is deep, and the compressive stress layer of formation is thicker, physical strength that can bigger raising glass.
3, barium ion of the present invention at high temperature can combine with phosphate glass surface unsaturated link(age), thereby the repair of playing surperficial key improves the Surface Physical performance
Phosphate laser glass after the present invention handles can form thicker better compressive stress layer; Make it have higher microhardness, folding strength, embrittlement temperature, therefore can increase substantially repetition rate and the thermal destruction threshold value of phosphate laser glass under xenon flash lamp pumping.
Description of drawings
Fig. 1 is the sodium ion exchange back case depth distribution plan that the inventive method is handled the back phosphate laser glass:
Fig. 2 is the potassium ion exchange back case depth distribution plan that the inventive method is handled the back phosphate laser glass
Fig. 3 is the barium ion exchange back case depth distribution plan that the inventive method is handled the back phosphate laser glass
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is described further, but should limit protection scope of the present invention with this.
First embodiment:
Present embodiment phosphate laser glass surface surface enhanced ion exchange method may further comprise the steps:
The first step: sample was handled 50 minutes and was cleaned with deionized water at 60 ℃ with 4.0mol/LNaOH, handled sample 40 minutes at 80 ℃ with the 1.0mol/L buffered hydrofluoric acid solution afterwards, also dried with the deionized water wash sample at normal temperature at last.
Second step: the first step is handled the back sample put into the IX vessel that the mixed nitrate of preparing to ratio in institute is housed.
The 3rd step: IX vessel and sample thereof are incubated 430oC under in retort furnace that the speed with 100 ℃/hour is cooled to 100 ℃ after 14 hours.
The 4th step: take out sample and dry with deionized water wash after with the s.t. of 1.0mol/L salt.
The composition of described mixed nitrate is following:
Form wt%
NaNO3 10％
KNO3 20％
Ba(NO3)2 70％
Second embodiment:
The composition of described mixed nitrate is following:
Form wt%
NaNO3 20％
KNO3 20％
Ba(NO3)2 60％
The phosphate laser glass surface surface enhanced ion exchange method may further comprise the steps:
The first step:
Sample was handled 50 minutes and was cleaned with deionized water at 60 ℃ with 4.0mol/LNaOH, handled sample 40 minutes at 80 ℃ with the 1.0mol/L buffered hydrofluoric acid solution afterwards, also dried with the deionized water wash sample at normal temperature at last.
Second step: the first step is handled the back sample put into the IX vessel that the mixed nitrate of preparing to ratio in institute is housed.
The 3rd step: be incubated 420oC under in retort furnace that the speed with 90 ℃/hour is cooled to 100 ℃ after 13 hours.
The 4th step: take out sample and dry with deionized water wash after with the s.t. of 1.0mol/L salt.
The 3rd embodiment:
The composition of described mixed nitrate is following:
Form wt%
NaNO3 30％
KNO3 30％
Ba(NO3)2 40％
The phosphate laser glass surface surface enhanced ion exchange method may further comprise the steps:
The first step:
Sample was handled 50 minutes and was cleaned with deionized water at 60 ℃ with 4.0mol/LNaOH, handled sample 40 minutes at 80 ℃ with the 1.0mol/L buffered hydrofluoric acid solution afterwards, also dried with the deionized water wash sample at normal temperature at last.
Second step: the first step is handled the back sample put into the IX vessel that the mixed nitrate of preparing to ratio in institute is housed.
The 3rd step: be incubated 410oC under in retort furnace that the speed with 80 ℃/hour is cooled to 90 ℃ after 16 hours.
The 4th step: take out sample and dry with deionized water wash after with the s.t. of 1.0mol/L salt.
The 4th embodiment:
The composition of described mixed nitrate is following:
Form wt%
NaNO3 25％
KNO3 35％
Ba(NO3)2 40％
Present embodiment phosphate laser glass surface surface enhanced ion exchange method may further comprise the steps:
The first step:
Sample was handled 50 minutes and was cleaned with deionized water at 60 ℃ with 4.0mol/LNaOH, handled sample 40 minutes at 80 ℃ with the 1.0mol/L buffered hydrofluoric acid solution afterwards, also dried with the deionized water wash sample at normal temperature at last.
Second step: the first step is handled the back sample put into the IX vessel that the mixed nitrate of preparing to ratio in institute is housed.
The 3rd step: be incubated 415oC under in retort furnace that the speed with 80 ℃/hour is cooled to 80 ℃ after 14 hours.
The 4th step: take out sample and dry with deionized water wash after with the s.t. of 1.0mol/L salt.
Phosphate laser glass surface enhancing to handling through the inventive method is tested; Fig. 1 is the sodium ion exchange back case depth distribution plan that the inventive method is handled the back phosphate laser glass; Fig. 2 is the potassium ion exchange back case depth distribution plan that the inventive method is handled the back phosphate laser glass, and Fig. 3 is the barium ion exchange back case depth distribution plan that the inventive method is handled the back phosphate laser glass.
Below table 1～3 provided the present invention and handle the back and handle the physical strength of back phosphate laser glass and the comparison of thermal shock resistance with respect to additive method.
Table 1: the present invention handles the back and handles back embrittlement temperature contrast with other surface treatment modes
Table 2: the present invention handles the back and handles back folding strength contrast with other surface treatment modes
| Sample (NAP4) | Folding strength (Mpa) |
| 303 sand fine grind 1 | 84 |
| 303 sand fine grind 2 | 81 |
| Treatment samples 1 of the present invention | 168 |
| Treatment samples 2 of the present invention | 185 |
| Treatment samples 3 of the present invention | 198 |
| Monovalence hybrid ionic exchange appearance 1 after the 303 sand fine grindings | 158 |
| Monovalence hybrid ionic exchange appearance 2 after the 303 sand fine grindings | 157 |
| Monovalence hybrid ionic exchange appearance 3 after the 303 sand fine grindings | 136 |
Table 3: the present invention handles the back and handles back microhardness contrast with other surface treatment modes
Claims (2)
1. phosphate laser glass surface surface enhanced ion exchange method is characterised in that may further comprise the steps:
1. pending phosphate laser glass; Hereinafter to be referred as sample; With handling 50 minutes and cleaned at 60 ℃ in the NaOH solution of 4.0mol/L, handled 40 minutes with the 1.0mol/L buffered hydrofluoric acid solution at 80 ℃ afterwards, at last at normal temperatures with deionized water wash and oven dry with deionized water;
2. with the NaNO for preparing
3, KNO
3, Ba (NO
3)
2Mixing salt and described sample are put into the IX vessel;
3. described IX vessel and sample thereof under 320-430 ℃, are incubated after 12～16 hours in retort furnace, are cooled to 50～100 ℃ with 80-100 ℃/hour speed;
4. take out sample with the s.t. of 1.0mol/L salt after, with drying behind the deionized water wash.
2. phosphate laser glass surface surface enhanced ion exchange method according to claim 1 is characterized in that described NaNO
3, KNO
3, Ba (NO
3)
2Mixing salt composition and weight percent following:
Form wt%
NaNO
3 10～30
KNO
3 20～40
Ba(NO
3)
2 40～70
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101712912A CN101811835B (en) | 2010-05-11 | 2010-05-11 | Phosphate laser glass surface enhanced ion exchange method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101712912A CN101811835B (en) | 2010-05-11 | 2010-05-11 | Phosphate laser glass surface enhanced ion exchange method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101811835A CN101811835A (en) | 2010-08-25 |
| CN101811835B true CN101811835B (en) | 2012-01-04 |
Family
ID=42619227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101712912A Expired - Fee Related CN101811835B (en) | 2010-05-11 | 2010-05-11 | Phosphate laser glass surface enhanced ion exchange method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101811835B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8834962B2 (en) * | 2011-06-03 | 2014-09-16 | WD Media, LLC | Methods for improving the strength of glass substrates |
| CN108623189A (en) * | 2017-12-29 | 2018-10-09 | 长春理工大学 | The processing method of phosphate laser glass surface enhancing |
| CN108623177A (en) * | 2017-12-29 | 2018-10-09 | 长春理工大学 | A kind of processing method of phosphate laser glass surface enhancing |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6652972B1 (en) * | 1999-11-01 | 2003-11-25 | Schott Glass Technologies Inc. | Low temperature joining of phosphate glass |
| CN1424271A (en) * | 2002-12-26 | 2003-06-18 | 上海莹力科技有限公司 | Ion exchange surface enhancing method for glass substrates of magnet recording discs |
| CN100556839C (en) * | 2005-10-28 | 2009-11-04 | 比亚迪股份有限公司 | Be used for composition and enhancement method that glass is strengthened |
| CN101561533A (en) * | 2009-05-26 | 2009-10-21 | 电子科技大学 | Ion exchange technical condition based on neodymium doped phosphate glass channeling optical waveguide |
-
2010
- 2010-05-11 CN CN2010101712912A patent/CN101811835B/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN101811835A (en) | 2010-08-25 |
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| GR01 | Patent grant | ||
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Owner name: SHANGHAI DAHENG OPTICS AND FINE MECHANICS CO., LTD Effective date: 20130109 |
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| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20130109 Address after: 201800 Shanghai 800-211 post office box Patentee after: Shanghai Optical Precision Machinery Inst., Chinese Academy of Sciences Patentee after: Shanghai Daheng Optics And Fine Mechanics Co., Ltd. Address before: 201800 Shanghai 800-211 post office box Patentee before: Shanghai Optical Precision Machinery Inst., Chinese Academy of Sciences |
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Granted publication date: 20120104 Termination date: 20130511 |