CN103436869B - A kind of method obtaining nanometer gold coating at Glass Containers inwall - Google Patents
A kind of method obtaining nanometer gold coating at Glass Containers inwall Download PDFInfo
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- CN103436869B CN103436869B CN201310350279.1A CN201310350279A CN103436869B CN 103436869 B CN103436869 B CN 103436869B CN 201310350279 A CN201310350279 A CN 201310350279A CN 103436869 B CN103436869 B CN 103436869B
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Abstract
The present invention relates to the method for a kind of chemical method at Glass Containers plated with gold nanoparticle.First oil removing, alligatoring erosion, sensitization pre-treatment are carried out to Glass Containers, by the Glass Containers after processing above, add the hydrochloro-auric acid of 0.1wt% and the aqueous povidone solution of 5wt% and mix, add the hydrazine hydrate of 0.5wt% again, pour out solution after soaking for some time and rinse with water, evenly bright nanometer gold coating can be obtained at Glass Containers inwall.According to Performance Detection, by nanometer gold on the inner glass tube plated surface of Gas LASER Tube, the power of the Gas LASER Tube of 1.2m can be made to be increased to 98W by 60W before, to adopt method of the present invention to plate the laser tube life longer of nanometer gold to 10-20 month.
Description
Technical field
The present invention relates to nanoparticle preparing technical field, be specifically related to the method for a kind of chemical method at Glass Containers plated with gold nanoparticle.
Background technology
Golden nanometer particle has special physical and chemical performance, as having high electron density, dielectric characteristics and katalysis, can be combined with multiple biomacromolecule, and do not affect its biological activity, the special shape of golden nanometer particle and optical property, make it in food safety detection, catalysis, the application of photoelectron device and biomedical aspect is more and more extensive, has very large using value.
Golden nanometer particle has excellent stability and unique optics, electrical properties, show potential using value in a lot of fields, metal and semiconductor material are when its size is reduced to Nano grade, there will be " quantum size effect " and show special optics, electronic properties, thus have broad application prospects in opto-electronic device, sensor field, golden nanometer particle is expected to develop the excellent performance made new advances, can in order to the optics of various ion detection.
As far back as 4th century of Christian era, Rome glazier has just understood at glass-doped gold, the metallic particles such as silver, prepare have abundant, the glasswork of beautiful colors, nowadays, along with the development of nonlinear optics, especially after the third-order non-linear performance after nineteen eighty-three American scientist jian and Lind have studied glass-doped nano particle, people start to bias toward its optical property aspect to the research of doping metals particle in glass, when metal nanoparticle is impregnated in glass, particle is isolated from each other by glass matrix, form quantum dot, the limitation of electronics and coherency are strengthened, cause quantum confined effect, simultaneously, when the size of metal nanoparticle is much smaller than optical field wavelength, the electric field acted on particle is also obviously different from the medium macroscopic field of surrounding, its polarization process will change the specific inductivity of local, thus generation Dielectric confinement effect, this effect all can cause significantly improving of the non-linear optical property of glass, make the matrix material with non-linear optical property in optical storage, there is important application advantage in the fields such as transmission and switch.
A few days ago, in glass matrix, prepare the significant effort direction that equally distributed nanoparticle has become international physics, region of chemistry.The Glass tubing of plating nanometer gold can be applied in a lot of place, such as making the discharge tube of laser tube, and general CO
2the static voltage of laser tube is between 185-220V, and the laser tube static voltage of plating nanometer gold can be down to 160-220V, can reduce electric current thus, thus make the work of laser tube more stable.Because laser tube is as the running stores of laser engraving machine, therefore, become that user is topmost chooses index the life-span, the working life of general domestic laser tube was about 2-3 month (60W was example); Its processing object realized of domestic amorphous laser (i.e. laser tube) and import laser apparatus with apply substantially identical.In outward appearance, in the life-span, in performance, there is very big-difference in structure.Also differing greatly in price, equal-wattage, tens times of the price of import laser apparatus the chances are domestic laser apparatus, the same life-span also differs greatly, import CO
2laser apparatus can inflate use repeatedly, and domestic glass laser pipe is generally as single use, and therefore, domestic amorphous laser, price is generally on the low side.
China's number of applying for a patent: 200910189682.4 publication numbers: CN102001829A provides a kind of preparation method of the sintered glass containing golden nanometer particle; the method adopts hydrochloro-auric acid as Jin Yuan; Trisodium Citrate, hydrazine hydrate etc. prepare golden nanometer particle as reductive agent at glass inner wall; the nm gold particles do not prepared with protective material PVP is spherical and torispherical, and local has agglomeration.And this invention sintered glass is not also through the preprocessing process of oil removing, alligatoring, sensitization.
Summary of the invention
The object of the present invention is to provide that a kind of cost is low, the method at Glass Containers inwall plated with gold nanoparticle of good stability, creating conditions for producing high performance laser tube further.
The technical scheme adopted is as follows:
Obtain a method for nanometer gold coating at Glass Containers inwall, comprise the following steps:
1) oil removing: degreaser is poured in clean Glass Containers, soak, rear hot water is clean by glass container cleaning;
2) alligatoring and erosion: pour alligatoring agent in the Glass Containers that oil removal treatment is crossed, soak, then clean up with water, then pour salt acid attack wherein into, rear water cleans up;
3) sensitization: also corrode in the Glass Containers processed to alligatoring and pour sensitizing agent into, soaks, cleans up with water;
4) by the Glass Containers after processing above, be incorporated as the hydrochloro-auric acid of 0.1wt% and the aqueous povidone solution of 5wt% and mix, add the hydrazine hydrate of 0.5wt% again, pour out solution after soaking for some time and rinse with water, evenly bright nanometer gold coating can be obtained at Glass Containers inwall.
By such scheme, degreaser described in step 1) is NaOH, Na
3pO
4, Na
2cO
3with the mixed aqueous solution of OP-10; Wherein NaOH:Na
3pO
4: Na
2cO
3: OP-10(technical grade, main component is alkylphenol polyoxyethylene) be 2.98:5.95:2.98:1 in mass ratio, mixed aqueous solution concentration is 108.4g/L; Except oil temperature is 50 ~ 60 DEG C, the oil removing time is 10 ~ 15min.
By such scheme, step 2) described in alligatoring agent be NH
4the mixed aqueous solution of F and HF; Wherein NH
4f:HF is 1:1.55 in mass ratio, and mixed aqueous solution concentration is 102.04g/L; Alligatoring agent coarsening time is 5 ~ 15min, and hydrochloric acid erosion time is 3 ~ 10min.
By such scheme, sensitizing agent described in step 3) is the mixed aqueous solution of tin protochloride and HCl; Wherein tin protochloride: HCl is 1:4.72 in mass ratio, and mixed aqueous solution concentration is 57.16g/L; Sensitizing temperature is 40 ~ 100 DEG C, and sensitization time is 10 ~ 15min.
By such scheme, described in step 4) hydrochloro-auric acid, polyvinylpyrrolidone, hydrazine hydrate be 1:0.5 ~ 1.5:0.1 ~ 0.8 by volume, soak time is 1 ~ 2.5h.
By such scheme, Glass Containers is Glass tubing or laser tube.
By such scheme, the concentration of hydrochloric acid is 10wt%.
The present invention has carried out oil removing, alligatoring and sensitization in the early stage of Glass Containers in process, craft of gilding is carried out again after this three steps pre-treatment, nano Au particle can more easily be attached to Glass tubing inwall, and coating is more more even than what process without this step, the golden nanometer particle of generation is more intensive, and the production cycle of the present invention will shorter than other, considerably increase the efficiency of production, according to Performance Detection, by nanometer gold on the inner glass tube plated surface of Gas LASER Tube, the power of the Gas LASER Tube of 1.2m can be made to be increased to 98W by 60W before, method of the present invention is adopted to plate laser tube life longer to 10-20 month of nanometer gold, reason is exactly be the katalysis of nanometer gold at laser tube, the gas that can reduce in laser tube, thus the work-ing life of laser tube can be extended, this not only can change the history of domestic laser tube by import, and popularize nanoparticle laser tube and can produce certain economic benefit and social benefit.
The beneficial effect that the present invention possesses is summarized as follows:
(1) easy and simple to handle, preparation cycle is short, can effectively save production cost.
(2) golden nanometer particle in Glass Containers inwall is evenly distributed.
(3) for doing the inner glass tube of Gas LASER Tube after the process of plating nanometer gold, greatly power can be improved.
(4) with low cost, only use a small amount of cheap chemical reagent (except required hydrochloro-auric acid).
Accompanying drawing explanation
Fig. 1 is the SEM photo of golden nanometer particle prepared by the embodiment of the present invention 1.
Fig. 2 is the SEM photo of golden nanometer particle prepared by the embodiment of the present invention 2.
Fig. 3 is the SEM photo of golden nanometer particle prepared by the embodiment of the present invention 3.
Fig. 4 is the SEM photo of golden nanometer particle prepared by the embodiment of the present invention 4.
Embodiment
Following examples are used for explaining the present invention further, not as limiting the scope of the invention.
Preparation degreaser: get NaOH, Na
3pO
4, Na
2cO
3with OP-10 be in mass ratio 2.98:5.95:2.98:1 batching, add water and be prepared into the aqueous solution that concentration is 108.4g/L.
Preparation alligatoring agent: get NH
4f and HF is 1:1.55 batching in mass ratio, adds water and is prepared into the mixed aqueous solution that concentration is 102.04g/L.
Preparation sensitizing agent: get SnCl
2.H
2o and HCl is 1:4.72 batching in mass ratio, and the degree of being prepared into that adds water is that the mixed aqueous solution of 57.16g/L is dense.
Embodiment 1
Pre-treatment: poured into by the degreaser prepared in clean Glass tubing, soak 15min at 55 DEG C, reusable heat water cleans up; Pour alligatoring agent into, at room temperature soak 10min, the HCl cleaning up rear 10wt% with water at room temperature corrodes 5min, cleans up with water; To entering sensitizing agent, at 70 DEG C, soaking 10min, clean up with water.
Coating: pour the hydrochloro-auric acid of 0.1wt% and the aqueous povidone solution of 5wt% into and mix in pretreated Glass tubing, add the hydrazine hydrate of 0.5wt% again, the volume ratio of guarantee hydrochloro-auric acid and aqueous povidone solution and hydrazine hydrate is 1:1:0.1, ambient temperatare is poured out solution after putting 2h and is rinsed with water, can obtain evenly bright nanometer gold coating at Glass tubing inwall.
Fig. 1 is the SEM photo of golden nanometer particle prepared by embodiment 1.In FIG, scale is 500nm; As seen from Figure 1, product is the spherical nm gold particles of dispersion, and the median size of nano Au particle is 30nm, and pattern is homogeneous, and coating is even, and do not have particle agglomeration phenomenon, stability is better.
By nanometer gold on the inner glass tube plated surface of Gas LASER Tube, the power of the Gas LASER Tube of 1.2m can be made to be increased to 98W by 60W before, adopt method of the present invention to plate laser tube life longer to 10-20 month of nanometer gold.Following examples are identical.
Embodiment 2:
Pre-treatment: poured into by the degreaser prepared in clean Glass tubing, soak 15min at 60 DEG C, reusable heat water cleans up; Pour alligatoring agent into, at room temperature soak 15min, the HCl cleaning up rear 10wt% with water at room temperature corrodes 10min, cleans up with water; To entering sensitizing agent, at 100 DEG C, soaking 15min, clean up with water.
Coating: pour the hydrochloro-auric acid of 0.1wt% and the aqueous povidone solution of 5wt% into and mix in pretreated Glass tubing, add the hydrazine hydrate of 0.5wt% again, the volume ratio of guarantee hydrochloro-auric acid and aqueous povidone solution and hydrazine hydrate is 1:1.5:0.4, ambient temperatare is poured out solution after putting 2.5h and is rinsed with water, can obtain evenly bright nanometer gold coating at Glass tubing inwall.
Fig. 2 is the SEM photo of golden nanometer particle prepared by embodiment 2.In fig. 2, scale is 500nm, and product is the spherical nm gold particles of dispersion, and the median size of nano Au particle is 40nm, and pattern is homogeneous, and coating is even, and do not have particle agglomeration phenomenon, stability is better.
Embodiment 3
Pre-treatment: poured into by the degreaser prepared in clean Glass tubing, soak 10min at 50 DEG C, reusable heat water cleans up; Pour alligatoring agent into, at room temperature soak 5min, the HCl cleaning up rear 10wt% with water at room temperature corrodes 3min, cleans up with water; To entering sensitizing agent, at 40 DEG C, soaking 12min, clean up with water.
Coating: pour the hydrochloro-auric acid of 0.1wt% and the aqueous povidone solution of 5wt% into and mix in pretreated Glass tubing, add the hydrazine hydrate of 0.5wt% again, the volume ratio of guarantee hydrochloro-auric acid and aqueous povidone solution and hydrazine hydrate is 1:0.5:0.4, ambient temperatare is poured out solution after putting 1h and is rinsed with water, can obtain evenly bright nanometer gold coating at Glass tubing inwall.
Fig. 3 is the SEM photo of golden nanometer particle prepared by embodiment 3.In figure 3, scale is 500nm, and product is the spherical nm gold particles of dispersion, and the median size of nano Au particle is 40nm, and pattern is homogeneous, and coating is even, and accidental particle agglomeration phenomenon, stability is better.
Embodiment 4
Pre-treatment: poured into by the degreaser prepared in clean Glass tubing, soak 10min at 55 DEG C, reusable heat water cleans up; Pour alligatoring agent into, at room temperature soak 10min, the HCl cleaning up rear use 10% with water at room temperature corrodes 8min, cleans up with water; To entering sensitizing agent, at 70 DEG C, soaking 10min, clean up with water.
Coating: pour the hydrochloro-auric acid of 0.1wt% and the aqueous povidone solution of 5wt% into and mix in pretreated Glass tubing, add the hydrazine hydrate of 0.5wt% again, the volume ratio of guarantee hydrochloro-auric acid and aqueous povidone solution and hydrazine hydrate is 1:1:0.8, ambient temperatare is poured out solution after putting 2h and is rinsed with water, can obtain evenly bright nanometer gold coating at Glass tubing inwall.
Fig. 4 is the SEM photo of golden nanometer particle prepared by embodiment 4.In the diagram, scale is 500nm, and product is the spherical nm gold particles of dispersion, and the median size of nano Au particle is 40nm, and pattern is homogeneous, and coating is even, and accidental particle agglomeration phenomenon, stability is better.
Claims (3)
1. obtain a method for nanometer gold coating at Glass Containers inwall, it is characterized in that comprising the following steps:
1) oil removing: poured into by degreaser in clean Glass Containers, soaks, then with hot water, glass container cleaning is clean; Described degreaser is NaOH, Na
3pO
4, Na
2cO
3with the mixed aqueous solution of OP-10; Wherein NaOH:Na
3pO
4: Na
2cO
3: OP-10 are 2.98:5.95:2.98:1 in mass ratio, and mixed aqueous solution concentration is 108.4g/L; Except oil temperature is 50 ~ 60 DEG C, the oil removing time is 10 ~ 15min;
2) alligatoring and erosion: pour alligatoring agent in the Glass Containers that oil removal treatment is crossed, soak, then clean up with water, then pour salt acid attack wherein into, rear water cleans up; Described alligatoring agent is NH
4the mixed aqueous solution of F and HF; Wherein NH
4f:HF is 1:1.55 in mass ratio, and mixed aqueous solution concentration is 102.04g/L; Alligatoring agent coarsening time is 5 ~ 15min, and hydrochloric acid erosion time is 3 ~ 10min;
3) sensitization: also corrode in the Glass Containers processed to alligatoring and pour sensitizing agent into, soaks, cleans up with water; Described sensitizing agent is the mixed aqueous solution of tin protochloride and HCl; Wherein tin protochloride: HCl is 1:4.72 in mass ratio, and mixed aqueous solution concentration is 57.16g/L; Sensitizing temperature is 40 ~ 100 DEG C, and sensitization time is 10 ~ 15min;
4) by the Glass Containers after processing above, be incorporated as the hydrochloro-auric acid of 0.1wt% and the aqueous povidone solution of 5wt% and mix, add the hydrazine hydrate of 0.5wt% again, pour out solution after soaking for some time and rinse with water, evenly bright nanometer gold coating can be obtained at Glass Containers inwall; Described hydrochloro-auric acid, polyvinylpyrrolidone, hydrazine hydrate are 1:0.5 ~ 1.5:0.1 ~ 0.8 by volume, and soak time is 1 ~ 2.5h.
2. obtain the method for nanometer gold coating as claimed in claim 1 at Glass Containers inwall, it is characterized in that: Glass Containers is Glass tubing or laser tube.
3. obtain the method for nanometer gold coating as claimed in claim 1 at Glass Containers inwall, it is characterized in that: the concentration of hydrochloric acid is 10wt%.
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|---|---|---|---|
| CN201310350279.1A CN103436869B (en) | 2013-08-13 | 2013-08-13 | A kind of method obtaining nanometer gold coating at Glass Containers inwall |
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|---|---|---|---|
| CN201310350279.1A CN103436869B (en) | 2013-08-13 | 2013-08-13 | A kind of method obtaining nanometer gold coating at Glass Containers inwall |
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| CN103436869B true CN103436869B (en) | 2016-03-09 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105514769A (en) * | 2016-02-01 | 2016-04-20 | 上海凯溯激光科技有限公司 | Industrial sealed-off carbon dioxide laser tube |
| CN106917079B (en) * | 2017-03-06 | 2019-03-12 | 齐鲁工业大学 | Chemically plating for Au-Pt alloy nanotube method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1096826A (en) * | 1993-06-25 | 1994-12-28 | 刘振魁 | Method for showering metallizing on non-metallic material |
| EP0911301A1 (en) * | 1997-03-14 | 1999-04-28 | Nippon Sheet Glass Co., Ltd. | Composition for forming colored coating and process for producing glass article coated with colored coating |
| CN101845625A (en) * | 2010-06-01 | 2010-09-29 | 无锡阿尔法电子科技有限公司 | Method for chemically plating gold on surface of capacitive touch screen |
| CN102001829A (en) * | 2009-08-31 | 2011-04-06 | 海洋王照明科技股份有限公司 | Cellular glass containing gold nano particles and preparation method thereof |
| CN102085575A (en) * | 2009-12-03 | 2011-06-08 | 中国科学院化学研究所 | Method for rapidly and continuously preparing size and feature controllable metal nano particles |
-
2013
- 2013-08-13 CN CN201310350279.1A patent/CN103436869B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1096826A (en) * | 1993-06-25 | 1994-12-28 | 刘振魁 | Method for showering metallizing on non-metallic material |
| EP0911301A1 (en) * | 1997-03-14 | 1999-04-28 | Nippon Sheet Glass Co., Ltd. | Composition for forming colored coating and process for producing glass article coated with colored coating |
| CN102001829A (en) * | 2009-08-31 | 2011-04-06 | 海洋王照明科技股份有限公司 | Cellular glass containing gold nano particles and preparation method thereof |
| CN102085575A (en) * | 2009-12-03 | 2011-06-08 | 中国科学院化学研究所 | Method for rapidly and continuously preparing size and feature controllable metal nano particles |
| CN101845625A (en) * | 2010-06-01 | 2010-09-29 | 无锡阿尔法电子科技有限公司 | Method for chemically plating gold on surface of capacitive touch screen |
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