CN101550546B - A preparation method of surface metallized composite material through chemical plating under photocatalysis - Google Patents
A preparation method of surface metallized composite material through chemical plating under photocatalysis Download PDFInfo
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- CN101550546B CN101550546B CN200910081920XA CN200910081920A CN101550546B CN 101550546 B CN101550546 B CN 101550546B CN 200910081920X A CN200910081920X A CN 200910081920XA CN 200910081920 A CN200910081920 A CN 200910081920A CN 101550546 B CN101550546 B CN 101550546B
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Abstract
The present invention pertains to the technical field of the preparation of surface metallized composite material and relates to a preparation method of surface metallized composite material through chemical plating under photocatalysis, wherein the fibre, plastic, fabric, resin, glass, ceramic, monocrystalline silicon or metal encapsulated with semiconductor nano inorganic powder is used as substrate material, or the semiconductor nano inorganic powder is used as substrate material, the photocatalytic technique integrates the reducer effect in conventional chemical plating, metal is carried on the surface of substrate material effectively, and surface metallized composite material is prepared. The advantage is that it makes use of the feature that semiconductor nano inorganic powder will be excited and generate a large number of electron-cavity pairs under the irradiation of photons of which energy is equal to or greater than band-gap energy, while electrons have a reducing effect andhelp accelerate the reduction of metal ions, and combines this feature with the reducer effect in conventional chemical plating to raise plating speed and production efficiency, reduce product cost a nd prepare surface metallized composite material with uniform surface metal layer, tiny metal particles, high quality and low cost.
Description
Technical field
The invention belongs to the surface metallized composite material preparing technical field, relate to a kind of photochemical catalysis chemically plating Preparation Method of surface metallized composite material.
Background technology
Area load metal at macromolecular material, ceramic and metallic substance, the preparation surface metallized composite material, make it have the not available distinct advantages of single-material, have broad application prospects, be present one of research focus in Materials Science and Engineering field in the world, and improve the quality of products, shortened process, raising preparation efficiency, reduce production costs, reduce the key content that environmental pollution is these class surface metallized composite material research and development.
Electroless plating is a kind of typical method of preparation surface metallized composite material, its principle is: under the situation that does not add extrinsic current, utilize reductive agent self catalyzed reduction deposition on the activation substrate material surface to obtain metal plating [Jiang Xiaoxia, Shen Wei. the theoretical and practice of electroless plating. Beijing: National Defense Industry Press, 2000].But the electroless plating plating has a wide range of applications in fields such as weaving chemical industry, electronic information, automobile mechanical, space flight and aviation, health care, defence and military and daily lifes in materials such as fiber, plastics, fabric, resin, glass, pottery, silicon single crystal, metal and powders.
At present, carry out electroless plating to realize metallization at substrate material surface, traditional technology is at first to carry out sensitization, activation treatment (pre-treatment), make and on the process body material of surface preparation, adsorb a certain amount of metal nucleus with catalytic activity, and then under the effect of reductive agent, carry out electroless plating [Xu Lina, Liao Jianhui, Huang Lan, et al.Surface-bound nanoparticles for initiating metal deposition.Thin Solid Film, 2003,434 (1-2): 121-125].But this technology catalyzer commonly used is precious metals such as palladium metal, silver, and not only the waste of precious metal is serious, and whole process device complexity, and technical process is long, and the operative technique difficulty is bigger, and preparation efficiency is low, causes product cost higher; Various pretreatment fluid instabilities, composition are wayward, and big area plating qualification rate is low, and quality product is difficult to meet the demands; In addition, the use of a large amount of chemical reagent also makes and the production process heavy contamination does not meet Sustainable development requirement economic and society.
Utilize nano inorganic powder to have characteristics such as surfactivity height, specific surface area is big, catalytic activity is strong, precious metal palladium in the plating of replacement traditional chemical, silver etc. are as surface with autocatalytic activity, do not need through treatment process such as the sensitization in the traditional chemical plating, activation, can directly obtain the matrix material [Liu Xuefeng of surface metalation, Sui Shoujun thanks and builds new .Cu/n-TiO
2The preparation of/PBO conjugated fibre. matrix material journal, 2008,25 (1): 28-34], have the saving noble metal, reduce product cost, shortened process reduces advantages such as environmental pollution, can overcome the deficiency of above-mentioned traditional chemical electroplating method.But, only with nano inorganic powder as surface with autocatalytic activity, adopt traditional chemical plating method to realize metallization at substrate material surface, exist problems such as plating speed is slow, production efficiency is low, surface metal-layer is owed evenly, metallic particles is thicker, thereby cause quality product to be difficult to satisfy service requirements.
Summary of the invention
The object of the present invention is to provide a kind of photochemical catalysis chemically plating Preparation Method of surface metallized composite material, utilize the semiconductor nano inorganic powder to be equal to or greater than under the photon irradiation of its band-gap energy at energy, can excite and produce a large amount of electron-hole pairs, and electronics has reductive action, help to quicken metal ion reductive characteristics, combine with the reductive agent effect in the traditional chemical plating, improve plating speed, prepare the surface metallized composite material that bed thickness is even, particle is tiny efficiently, thereby reach the purpose of improving the quality of products, reduce preparation cost.
A kind of photochemical catalysis chemically plating Preparation Method of surface metallized composite material, it is characterized in that fiber, plastics, fabric, resin, glass, pottery, silicon single crystal or metal with surface coating semiconductor nano inorganic powder are body material, or with the semiconductor nano inorganic powder this as body material, reductive agent effect in adopting photocatalysis technology and traditional chemical plating combines, at substrate material surface loaded metal efficiently, preparation high quality, surface metallized composite material cheaply.
Semiconductor nano inorganic powder of the present invention is: the semiconductor nano inorganic powder of nano titanium oxide, nano silicon oxide, nano zine oxide, nano tin dioxide or process doping vario-property.
Semiconductor nano inorganic powder through doping vario-property of the present invention is: rare earth-doped semiconductor nano inorganic powder, doped with rare-earth oxide semiconductor nano inorganic powder, metal-doped semiconductor nano inorganic powder or nitrogen doped semiconductor nanocrystal inorganic powder.
Area load metal of the present invention is: the alloy that copper, silver, nickel, aluminium, gold, magnesium, titanium, iron or this several metals are formed.
The photochemical catalysis chemical plating technology of surface metallized composite material of the present invention is as follows:
1, the body material with semiconductor nano inorganic powder or surface coating semiconductor nano inorganic powder directly immerses in the chemical plating fluid of the metal-salt that contains surperficial required loaded metal, and 0～80 ℃ of temperature range does not stop to stir;
2, shine 0.1～40min under wavelength is the UV-light of 200～400nm and carry out electroless plating, keeping bath pH value with alkaline solution between the reaction period is 7～13;
3, the matrix material with the coating surface metal takes out, washing, and 30～180min is handled in oven dry under 50～200 ℃ of vacuum or protective gas atmosphere, can make surface metallized composite material.
Metal-salt of the present invention is mantoquita, silver salt, nickel salt, aluminium salt, golden salt, magnesium salts, titanium salt or molysite; It is metal-salt 40～20%, reductive agent 35～20%, complexing agent 25～30%, additive 0～30% that described chemical plating fluid prescription is formed (massfraction).Wherein reductive agent is HCHO, NaH
2PO
2H
2O or HO (CH
2CH
2O)
nH (n=4～450), complexing agent is KNaC
4H
4O
64H
2O, Na
2EDTA2H
2O or C
6H
5Na
3O
72H
2O, additive are C
10H
8N
2Or K
4Fe (CN)
6H
2O.
The invention has the advantages that, utilize the semiconductor nano inorganic powder to be equal to or greater than under the photon irradiation of its band-gap energy at energy, can excite and produce a large amount of electron-hole pairs, and electronics has reductive action, help to quicken metal ion reductive characteristics, combine, improve plating speed and production efficiency with reductive agent effect in the traditional chemical plating, reduce product cost, preparation surface metal-layer is even, metallic particles is tiny high quality, low-cost surface metallized composite material.
Embodiment
Below in conjunction with embodiment the present invention is specifically described; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the those of skill in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1:
Nano-titanium dioxide powder 1g is immersed in the 1L chemical bronze plating liquid, and 20～50 ℃ of temperature ranges do not stop to stir.
Be to shine 0.1～10min under the UV-light of 254nm to carry out electroless plating at wavelength, use NaOH 14gL between the reaction period
-1Keeping bath pH value is 11.5～12.
The nano-titanium dioxide powder matrix material of coating surface metallic copper is taken out, washing, 60～150min is handled in oven dry under 80～200 ℃ of argon gas atmosphere, makes metallic copper clad nano titanium dioxide powder composite material.
It is 30%CuSO that the prescription of chemical plating fluid is formed (massfraction)
45H
2O16gL
-1, 20% HCHO 16mLL
-1, 20% mixed twine mixture (KNaC
4H
4O
64H
2O 15gL
-1, Na
2EDTA2H
2O 24gL
-1), 30% mixed additive (C
10H
8N
224mgL
-1, K
4Fe (CN)
6H
2O 12mgL
-1).
Embodiment 2:
Nano-titanium dioxide powder is coated pbo fiber matrix material 1.5g immerse in the 2L chemical bronze plating liquid, 20～80 ℃ of temperature ranges do not stop to stir.
Be to shine 1～30min under the UV-light of 360nm to carry out electroless plating at wavelength, use NaOH 14gL between the reaction period
-1Keeping bath pH value is 11.5～12.5.
The pbo fiber matrix material of coating surface metallic copper is taken out, and washing is dried processing 60～180min down in 50～200 ℃ of hydrogen atmospheres, makes metallic copper and coats the pbo fiber matrix material.
It is 30%CuSO that the prescription of chemical plating fluid is formed (massfraction)
45H
2O16gL
-1, 30% HCHO16mLL
-1, 20% mixed twine mixture (KNaC
4H
4O
64H
2O 15gL
-1, Na
2EDTA2H
2O 24gL
-1), 20% mixed additive (C
10H
8N
224mgL
-1, K
4Fe (CN)
6H
2O 12mgL
-1).
Embodiment 3:
Nanometer Zinc oxide powder carbon coated fibre composite 2g is immersed in the 3L chemical bronze plating liquid, and 0～50 ℃ of temperature range does not stop to stir.
Be to shine 20～40min under the UV-light of 254nm to carry out electroless plating at wavelength, use NaOH 14gL between the reaction period
-1Keeping bath pH value is 11～12.
The carbon-fibre composite of coating surface metallic copper is taken out, washing, 60～120min is handled in oven dry under 50～100 ℃ of vacuum, makes metallic copper carbon coated fibre composite.
It is 20%CuSO that the prescription of chemical plating fluid is formed (massfraction)
45H
2O 16gL
-1, 30% HCHO 16mLL
-1, 30% mixed twine mixture (KNaC
4H
4O
64H
2O 15gL
-1, Na
2EDTA2H
2O 24gL
-1), 20% mixed additive (C
10H
8N
224mgL
-1, K
4Fe (CN)
6H
2O 12mgL
-1).
Embodiment 4:
Nano-titanium dioxide powder is coated glass composite material 7g immerse in the 1.5L chemical nickel-plating liquid, 20～40 ℃ of temperature ranges do not stop to stir.
Be to shine 10～30min under the UV-light of 400nm to carry out electroless plating at wavelength, use NaOH 14gL between the reaction period
-1Keeping bath pH value is 9～10.
The glass composite material of coating surface metallic nickel is taken out, washing, 30～90min is handled in oven dry under 50～120 ℃ of vacuum, makes metallic nickel and coats glass composite material.
It is 35%NiSO that the prescription of chemical plating fluid is formed (massfraction)
46H
2O 30gL
-1, 35% NaH
2PO
2H
2O 30gL
-1, 30%C
6H
5Na
3O
72H
2O 20gL
-1
Embodiment 5:
Nano-titanium dioxide powder is coated pbo fiber matrix material 2g immerse in the 2L chemical nickel-plating liquid, 20～70 ℃ of temperature ranges do not stop to stir.
Be to shine 5～20min under the UV-light of 200nm to carry out electroless plating at wavelength, use NaOH 14gL between the reaction period
-1Keeping bath pH value is 9～10.
The pbo fiber matrix material of coating surface metallic nickel is taken out, washing, 60～100min is handled in oven dry under 50～150 ℃ of vacuum, makes metallic nickel and coats the pbo fiber matrix material.
It is 40% NiSO that the prescription of chemical plating fluid is formed (massfraction)
46H
2O 30gL
-1, 35% NaH
2PO
2H
2O 30gL
-1, 25% C
6H
5Na
3O
72H
2O 20gL
-1
Claims (1)
1. the photochemical catalysis chemically plating Preparation Method of a surface metallized composite material, it is characterized in that fiber, plastics, fabric, resin, glass, pottery, silicon single crystal or metal with surface coating semiconductor nano inorganic powder are body material, or with the semiconductor nano inorganic powder this as body material, reductive agent effect in adopting photocatalysis technology and traditional chemical plating combines, at substrate material surface loaded metal efficiently, the preparation surface metallized composite material;
Described semiconductor nano inorganic powder is: the semiconductor nano inorganic powder of nano titanium oxide, nano silicon oxide, nano zine oxide, nano tin dioxide or process doping vario-property;
Described semiconductor nano inorganic powder through doping vario-property is: rare earth-doped semiconductor nano inorganic powder, doped with rare-earth oxide semiconductor nano inorganic powder, metal-doped semiconductor nano inorganic powder or nitrogen doped semiconductor nanocrystal inorganic powder;
Described area load metal is: the alloy that copper, silver, nickel, aluminium, gold, magnesium, titanium, iron or this several metals are formed;
The photochemical catalysis chemical plating technology is as follows:
1) body material with semiconductor nano inorganic powder or surface coating semiconductor nano inorganic powder directly immerses in the chemical plating fluid of the metal-salt that contains surperficial required loaded metal, and 0～80 ℃ of temperature range does not stop to stir;
2) shine 0.1～40min under wavelength is the UV-light of 200～400nm and carry out electroless plating, keeping bath pH value with alkaline solution between the reaction period is 7～13;
3) matrix material with the coating surface metal takes out, washing, and 30～180min is handled in oven dry under 50～200 ℃ of vacuum or protective gas atmosphere, can make surface metallized composite material;
Metal-salt of the present invention is mantoquita, silver salt, nickel salt, aluminium salt, golden salt, magnesium salts, titanium salt or molysite; It is metal-salt 40～20%, reductive agent 35～20%, complexing agent 25～30%, additive 0～30% that described chemical plating fluid prescription is formed massfraction, and wherein reductive agent is HCHO, NaH
2PO
2H
2O or HO (CH
2CH
2O)
nH (n=4～450), complexing agent is KNaC
4H
4O
64H
2O, Na
2EDTA2H
2O or C
6H
5Na
3O
72H
2O, additive are C
10H
8N
2Or K
4Fe (CN)
6H
2O.
Priority Applications (1)
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|---|---|---|---|
| CN200910081920XA CN101550546B (en) | 2009-04-08 | 2009-04-08 | A preparation method of surface metallized composite material through chemical plating under photocatalysis |
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| CN200910081920XA CN101550546B (en) | 2009-04-08 | 2009-04-08 | A preparation method of surface metallized composite material through chemical plating under photocatalysis |
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| CN101550546B true CN101550546B (en) | 2010-08-18 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI414630B (en) * | 2010-10-11 | 2013-11-11 | Nat Applied Res Laboratories | A method for producing a metal-titanium dioxide composite material using a micro-localized metal precursor |
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| CN102254704A (en) * | 2011-05-06 | 2011-11-23 | 海南科技职业学院 | Dye sensitized noble metal deposited titanium dioxide light anode and preparation method thereof |
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Cited By (1)
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| TWI414630B (en) * | 2010-10-11 | 2013-11-11 | Nat Applied Res Laboratories | A method for producing a metal-titanium dioxide composite material using a micro-localized metal precursor |
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