CN105776892B - A kind of magnetic plating Ag glass microballoons and preparation method thereof - Google Patents
A kind of magnetic plating Ag glass microballoons and preparation method thereof Download PDFInfo
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- CN105776892B CN105776892B CN201610067823.5A CN201610067823A CN105776892B CN 105776892 B CN105776892 B CN 105776892B CN 201610067823 A CN201610067823 A CN 201610067823A CN 105776892 B CN105776892 B CN 105776892B
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- 239000011521 glass Substances 0.000 title claims abstract description 126
- 238000007747 plating Methods 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011229 interlayer Substances 0.000 claims abstract description 20
- 239000010410 layer Substances 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 47
- 239000007864 aqueous solution Substances 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 39
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000002131 composite material Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 19
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 18
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 18
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 18
- 239000003381 stabilizer Substances 0.000 claims description 18
- 235000002906 tartaric acid Nutrition 0.000 claims description 18
- 239000011975 tartaric acid Substances 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 17
- 239000012153 distilled water Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 229910018104 Ni-P Inorganic materials 0.000 claims description 15
- 229910018536 Ni—P Inorganic materials 0.000 claims description 15
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 15
- 229910045601 alloy Inorganic materials 0.000 claims description 14
- 239000000956 alloy Substances 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- 101150003085 Pdcl gene Proteins 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 claims description 5
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 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 claims description 3
- 239000011260 aqueous acid Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 229910001096 P alloy Inorganic materials 0.000 abstract description 6
- 239000000463 material Substances 0.000 description 9
- 239000000696 magnetic material Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000011026 diafiltration Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 235000011083 sodium citrates Nutrition 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000007788 roughening Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical class [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- 239000011324 bead Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3607—Coatings of the type glass/inorganic compound/metal
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3668—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties
- C03C17/3676—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties specially adapted for use as electromagnetic shield
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/31—Pre-treatment
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
- C03C2218/324—De-oxidation
Abstract
The present invention relates to a kind of magnetic plating Ag glass microballoons and preparation method thereof.A kind of magnetic plates Ag glass microballoons, including glass microballoon core, and a Ni P alloy interlayers are provided with the outer surface of glass microballoon core, is provided with Ag layers in the outer surface of Ni P alloy interlayers, a diameter of 30~60 μm of glass microballoon core.A kind of preparation method of magnetic plating Ag glass microballoons, comprises the following steps：(1) pretreated glass microballon；(2) Ni P alloy interlayers are prepared；(3) magnetic glass microballon is pre-processed；(4) Ag layers are prepared.
Description
Technical field
The invention belongs to field of material engineering technology, and in particular to a kind of magnetic plating Ag glass microballoons and preparation method thereof.
Background technology
In polymer matrix electromagnetic shielding composite material, to make composite that there is sufficiently high conductance to reflect or inhale
Receive electromagnetic wave, it will usually the metal powder material with high conductivity is dosed into nonconducting polymeric matrix, these metal powders
It is referred to as conducting filler.When conducting filler doses certain fraction (" diafiltration " threshold value), the volume electricity of composite
Resistance rate can acutely decline suddenly, " diafiltration " phenomenon occur；Also, when the filling fraction of electric conductor continues increase, composite
Specific insulation can tend towards stability quickly, now the conductive path of material internal is substantially perfect, is further added by conducting filler
Also the electric conductivity of material will not be significantly improved, the deadweight of composite can be increased on the contrary and reduce its mechanical property.Therefore, subtract
" diafiltration " threshold value of small composite is to improving the combination property of shielding composite and to reduce cost highly beneficial.And reduce
Material " diafiltration " threshold value the best way is exactly from the metal Ag powder that conductance is very high and performance is sufficiently stable.
In recent years, to some cheap, lightweights, green, material easy to process carry out surface metalation come replace costliness and
The excessive Ag powder of density again a, it has also become important trend of conductive filler development.It fact proved, plating Ag glass microballoons are as pure
The substitute of Ag powder complies fully with the requirement in technology and market.However, making rapid progress with science and technology, is electromagnetically shielded at present
The requirement to more Gao Gengxin and target fast forward through for the development of material, wherein the requirement to " widescreen is covered " effect is most challenged
Property.This means the simple conductance for improving composite can not meet to require, it is necessary to another while high conductivity is met
The new function of composite is assigned to strengthen its shield effectiveness；And the introducing of magnetic material by for improve composite electromagnetic screen
Cover performance injection new vitality.Because in the presence of electromagnetic wave, dynamic process is presented in the magnetization of magnetic material, now not only deposits
In the magnetic hystersis loss not available for common dielectric, it there is also and produced by effects such as magnetic aftereffect, domain wall resonance, natural resonances
Raw energy loss, and the magnetic loss of these different mechanisms is respectively acting on the electromagnetic wave of different frequency range.For example, in 10kHz
In~1MHz intermediate frequency range, dimensional resonance and magnetic force resonance phenomenon can occur for magnetic material；In 1~100MHz high frequency rank
Section, magnetic material will appear from domain wall resonance or relaxation；In 100MHz~10GHz uhf-ranges, magnetic material can occur certainly
So resonance.Therefore, the introducing of magnetic material will largely strengthen the shield effectiveness of shielding material and widen shielding material
Shield ranges.
The content of the invention
Goal of the invention：The present invention has made improvements in view of the above-mentioned problems of the prior art, i.e., and disclosed by the invention first
Individual purpose is to disclose a kind of magnetic plating Ag glass microballoons.Second object of the present invention is to disclose a kind of magnetic plating Ag glass
The preparation method of microballon.
Technical scheme：A kind of magnetic plates Ag glass microballoons, including glass microballoon core, in the outer of the glass microballoon core
Surface is provided with a Ni-P alloy interlayers, and Ag layers are provided with the outer surface of Ni-P alloy interlayers,
A diameter of 30~60 μm of the glass microballoon core.
Further, the thickness of the Ni-P alloy interlayers is 1~3 μm.
Further, the thickness of the Ag layers is 1~3 μm.
A kind of preparation method of magnetic plating Ag glass microballoons, comprises the following steps：
(1) pretreated glass microballon
(11) first with the Na that concentration is 5~40wt%2CO3The aqueous solution cleans to glass microballoon, then with 2~10wt%
Aqueous hydrochloric acid solution glass microballoon is cleaned, finally glass microballoon is carried out with the 60~70wt% industrial alcohol aqueous solution
Cleaning；
(12) glass microballoon that step (11) obtains is put into 0.1~3wt% hydrofluoric acid aqueous solution and carries out roughening quarter
Erosion processing 5~15 minutes；
(13) glass microballoon obtained to step (12) is put into SnCl2In HCl mixed aqueous solution, 10~40 points are stirred
Clock；
(14) it is 0.02~0.1wt%PdCl the glass microballoon that step (13) obtains to be put into concentration2In aqueous solution,
Stirring 10~40 minutes；
(2) Ni-P alloy interlayers are prepared
(21) plating solution is prepared
By 2~8 parts of NiCl2·6H2O, 1~5 part of sodium citrate, 0.1~1 part of sodium potassium tartrate tetrahydrate are dissolved in 50~150 parts of distillations
In water, then take the NaH that 50~150 parts of concentration are 3~5wt%2PO2·H2The O aqueous solution is added thereto, and finally adds 6 thereto again
~9 parts of concentration are 25~28wt% ammoniacal liquor, and plating solution is obtained after stirring；
(22) plating
The glass microballoon that step (14) obtains is put into the plating solution that step (21) obtains, with 2~5 under stirring
℃·min-1Heating rate be heated to 70 DEG C after be incubated 20~40min, filtering, with distillation water washing after be made magnetic glass it is micro-
Pearl；
(3) magnetic glass microballon is pre-processed
(31) by 1~5 part of SnCl2, 2~8 parts of concentrated hydrochloric acids and 5~30 parts of polyethylene glycol 2000s be dissolved in 50~150 parts of distillations
In water, stir and obtain cleaning fluid；
(32) the magnetic glass microballon that step (22) obtains is put into the cleaning fluid that step (31) obtains, stirring 20~
40min, filtering, then obtain magnetic glass microballon with after distilling water washing 2~3 times；
(33) the magnetic glass microballon that step (32) obtains is put into the PdCl that concentration is 0.02~0.1wt%2The aqueous solution
In, 10~30min, filtering are stirred, then magnetic glass microballon is obtained 2~3 times with water washing is distilled；
(4) Ag layers are prepared
(41) plating solution is prepared
By 1~5 part of AgNO3Be dissolved in 1~5 part of compound stabilizer in 100 parts of distilled water, add 3~9 parts of concentration be 25~
28wt% ammoniacal liquor, stirs to precipitation to be completely dissolved and obtains plating solution；
(42) complex reducing agent is prepared
0.5~3 part of hydrazine hydrate is dissolved in formation composite reduction agent solution in 40~60 parts of methanol；
(43) plating
The magnetic glass microballon that step (33) obtains is put into the plating solution that step (41) obtains and stirred, is then added dropwise
The composite reduction agent solution that step (42) obtains, react 10~30min after filtering, washing, dry after i.e. obtain magnetic plating Ag glass
Glass microballon.
Further, in the mixed aqueous solution in step (13), SnCl2Concentration be 1~8wt%, HCl concentration is 5
~15wt%.
Further, the compound stabilizer in step (41) is the mixture of thiocarbamide, EDTA and tartaric acid, tartaric acid,
The mass ratio of EDTA and thiocarbamide is (0.5~6)：(0.1~2)：(0.03~0.1).
Beneficial effect：The invention discloses a kind of magnetic plating Ag glass microballoons and preparation method thereof to have below beneficial to effect
Fruit：
1st, in silver plating process, due to using compound stabilizer, therefore plating solution is sufficiently stable, place longer time and
Also undergone no deterioration within the scope of wider temperature, be beneficial to industrialized production；
2nd, in silver plating process, the reproducibility of complex reducing agent is stronger, both shortens the reaction time, ensures that silver coating causes again
Close property；
3rd, silver-plated glass beads have certain magnetic.
Brief description of the drawings
Fig. 1 is a kind of stereoscan photograph of magnetic plating Ag glass microballoons disclosed by the invention；
Fig. 2 is a kind of XRD spectrum of magnetic plating Ag glass microballoons disclosed by the invention；
Fig. 3 is a kind of magnetic hysteresis regression curve of magnetic plating Ag glass microballoons disclosed by the invention.
Embodiment：
The embodiment of the present invention is described in detail below.
Specific embodiment 1
A kind of magnetic plates Ag glass microballoons, including glass microballoon core, and a Ni- is provided with the outer surface of glass microballoon core
P alloy interlayers, Ag layers are provided with the outer surface of Ni-P alloy interlayers,
A diameter of 30 μm of glass microballoon core.
Further, the thickness of Ni-P alloy interlayers is 1 μm.
Further, the thickness of Ag layers is 1 μm.
A kind of preparation method of magnetic plating Ag glass microballoons, comprises the following steps：
(1) pretreated glass microballon
(11) Na for being first 5wt% with concentration2CO3The aqueous solution cleans to glass microballoon, then the hydrochloric acid water with 2wt%
Solution is cleaned to glass microballoon, and finally glass microballoon is cleaned with the 60wt% industrial alcohol aqueous solution；
(12) glass microballoon that step (11) obtains is put into 0.1wt% hydrofluoric acid aqueous solution and be roughened at etching
Reason 5 minutes；
(13) glass microballoon obtained to step (12) is put into SnCl2In HCl mixed aqueous solution, stir 10 minutes；
(14) it is 0.02wt%PdCl the glass microballoon that step (13) obtains to be put into concentration2In aqueous solution, stirring
10 minutes；
(2) Ni-P alloy interlayers are prepared
(21) plating solution is prepared
By 2 parts of NiCl2·6H2O, 1 part of sodium citrate, 0.1 part of sodium potassium tartrate tetrahydrate are dissolved in 50 parts of distilled water, then take 50 parts
Concentration is 3wt% NaH2PO2·H2The O aqueous solution is added thereto, and it is 25wt% ammoniacal liquor finally to add 6 parts of concentration thereto again, is stirred
Plating solution is obtained after mixing uniformly；
(22) plating
The glass microballoon that step (14) obtains is put into the plating solution that step (21) obtains, with 2 DEG C under stirring
min-1Heating rate be heated to 70 DEG C after be incubated 20min, filtering, with magnetic glass microballon is made after distillation water washing；
(3) magnetic glass microballon is pre-processed
(31) by 1 part of SnCl2, 2 parts of concentrated hydrochloric acids and 5 parts of polyethylene glycol 2000s be dissolved in 50 parts of distilled water, stir i.e.
Obtain cleaning fluid；
(32) the magnetic glass microballon that step (22) obtains is put into the cleaning fluid that step (31) obtains, stirs 20min,
Filtering, then obtain magnetic glass microballon with after distilling water washing 2 times；
(33) the magnetic glass microballon that step (32) obtains is put into the PdCl that concentration is 0.02wt%2In the aqueous solution, stir
10min is mixed, is filtered, then magnetic glass microballon is obtained 2 times with water washing is distilled；
(4) Ag layers are prepared
(41) plating solution is prepared
By 3 parts of AgNO3It is dissolved in 3.86 parts of compound stabilizers in 100 parts of distilled water, adds the ammonia that 3 parts of concentration are 25wt%
Water, stirs to precipitation to be completely dissolved and obtains plating solution；
(42) complex reducing agent is prepared
1.5 parts of hydrazine hydrates are dissolved in formation composite reduction agent solution in 55 parts of methanol；
(43) plating
The magnetic glass microballon that step (33) obtains is put into the plating solution that step (41) obtains and stirred, is then added dropwise
The composite reduction agent solution that step (42) obtains, react 10min after filtering, washing, dry after i.e. obtain magnetic plating Ag glass it is micro-
Pearl.
Further, in the mixed aqueous solution in step (13), SnCl2Concentration be 1wt%, HCl concentration is
5wt%.
Further, the compound stabilizer in step (41) is the mixture of thiocarbamide, EDTA and tartaric acid, tartaric acid,
The mass ratio of EDTA and thiocarbamide is 3：0.8：0.06.
The magnetic plating Ag glass microballoons being prepared are characterized.
As shown in Figure 1, the surface of magnetic plating Ag glass microballoons has densification, clad complete.
As shown in Figure 2, magnetic plating Ag glass microballoons are amorphous state, and the crystallization degree of Ni-P alloy-layers is also very low, but
The diffraction peak intensity of Ag layers is higher and wideization to a certain degree occurs, illustrates the crystal grain for being deposited on the outermost Ag particles of compound particle
Spend very little.
From the figure 3, it may be seen that magnetic plating Ag glass microballoons hysteresis occur under external magnetic field, there is magnetic.
Specific embodiment 2
A kind of magnetic plates Ag glass microballoons, including glass microballoon core, and a Ni- is provided with the outer surface of glass microballoon core
P alloy interlayers, Ag layers are provided with the outer surface of Ni-P alloy interlayers,
A diameter of 60 μm of glass microballoon core.
Further, the thickness of Ni-P alloy interlayers is 3 μm.
Further, the thickness of Ag layers is 3 μm.
A kind of preparation method of magnetic plating Ag glass microballoons, comprises the following steps：
(1) pretreated glass microballon
(11) Na for being first 40wt% with concentration2CO3The aqueous solution cleans to glass microballoon, then the hydrochloric acid with 10wt%
The aqueous solution is cleaned to glass microballoon, and finally glass microballoon is cleaned with the 70wt% industrial alcohol aqueous solution；
(12) glass microballoon that step (11) obtains is put into 3wt% hydrofluoric acid aqueous solution and carries out roughening etching processing
15 minutes；
(13) glass microballoon obtained to step (12) is put into SnCl2In HCl mixed aqueous solution, stir 40 minutes；
(14) it is 0.1wt%PdCl the glass microballoon that step (13) obtains to be put into concentration2In aqueous solution, stirring 40
Minute；
(2) Ni-P alloy interlayers are prepared
(21) plating solution is prepared
By 8 parts of NiCl2·6H2O, 5 parts of sodium citrates, 1 part of sodium potassium tartrate tetrahydrate are dissolved in 150 parts of distilled water, then take 150 parts
Concentration is 5wt% NaH2PO2·H2The O aqueous solution is added thereto, and it is 28wt% ammoniacal liquor finally to add 9 parts of concentration thereto again, is stirred
Plating solution is obtained after mixing uniformly；
(22) plating
The glass microballoon that step (14) obtains is put into the plating solution that step (21) obtains, with 5 DEG C under stirring
min-1Heating rate be heated to 70 DEG C after be incubated 40min, filtering, with magnetic glass microballon is made after distillation water washing；
(3) magnetic glass microballon is pre-processed
(31) by 5 parts of SnCl2, 8 parts of concentrated hydrochloric acids and 30 parts of polyethylene glycol 2000s be dissolved in 150 parts of distilled water, stir
Obtain cleaning fluid；
(32) the magnetic glass microballon that step (22) obtains is put into the cleaning fluid that step (31) obtains, stirs 40min,
Filtering, then obtain magnetic glass microballon with after distilling water washing 3 times；
(33) the magnetic glass microballon that step (32) obtains is put into the PdCl that concentration is 0.1wt%2In the aqueous solution, stirring
30min, filtering, then obtain magnetic glass microballon 3 times with water washing is distilled；
(4) Ag layers are prepared
(41) plating solution is prepared
By 5 parts of AgNO3It is dissolved in 5 parts of compound stabilizers in 100 parts of distilled water, adds the ammoniacal liquor that 9 parts of concentration are 28wt%,
Stirring is completely dissolved to precipitation obtains plating solution；
(42) complex reducing agent is prepared
3 parts of hydrazine hydrates are dissolved in formation composite reduction agent solution in 60 parts of methanol；
(43) plating
The magnetic glass microballon that step (33) obtains is put into the plating solution that step (41) obtains and stirred, is then added dropwise
The composite reduction agent solution that step (42) obtains, react 30min after filtering, washing, dry after i.e. obtain magnetic plating Ag glass it is micro-
Pearl.
Further, in the mixed aqueous solution in step (13), SnCl2Concentration be 8wt%, HCl concentration is
15wt%.
Further, the compound stabilizer in step (41) is the mixture of thiocarbamide, EDTA and tartaric acid, tartaric acid,
The mass ratio of EDTA and thiocarbamide is 3：0.1：0.03.
Specific embodiment 3
A kind of magnetic plates Ag glass microballoons, including glass microballoon core, and a Ni- is provided with the outer surface of glass microballoon core
P alloy interlayers, Ag layers are provided with the outer surface of Ni-P alloy interlayers,
A diameter of 40 μm of glass microballoon core.
Further, the thickness of Ni-P alloy interlayers is 2 μm.
Further, the thickness of Ag layers is 2 μm.
A kind of preparation method of magnetic plating Ag glass microballoons, comprises the following steps：
(1) pretreated glass microballon
(11) Na for being first 20wt% with concentration2CO3The aqueous solution cleans to glass microballoon, then the hydrochloric acid water with 5wt%
Solution is cleaned to glass microballoon, and finally glass microballoon is cleaned with the 65wt% industrial alcohol aqueous solution；
(12) glass microballoon that step (11) obtains is put into 1wt% hydrofluoric acid aqueous solution and carries out roughening etching processing
10 minutes；
(13) glass microballoon obtained to step (12) is put into SnCl2In HCl mixed aqueous solution, stir 20 minutes；
(14) it is 0.05wt%PdCl the glass microballoon that step (13) obtains to be put into concentration2In aqueous solution, stirring
20 minutes；
(2) Ni-P alloy interlayers are prepared
(21) plating solution is prepared
By 5 parts of NiCl2·6H2O, 3 parts of sodium citrates, 0.5 part of sodium potassium tartrate tetrahydrate are dissolved in 100 parts of distilled water, then take 100
The NaH that part concentration is 4wt%2PO2·H2The O aqueous solution is added thereto, and it is 26wt% ammoniacal liquor finally to add 7 parts of concentration thereto again,
Plating solution is obtained after stirring；
(22) plating
The glass microballoon that step (14) obtains is put into the plating solution that step (21) obtains, with 3 DEG C under stirring
min-1Heating rate be heated to 70 DEG C after be incubated 30min, filtering, with magnetic glass microballon is made after distillation water washing；
(3) magnetic glass microballon is pre-processed
(31) by 3 parts of SnCl2, 5 parts of concentrated hydrochloric acids and 20 parts of polyethylene glycol 2000s be dissolved in 100 parts of distilled water, stir
Obtain cleaning fluid；
(32) the magnetic glass microballon that step (22) obtains is put into the cleaning fluid that step (31) obtains, stirs 30min,
Filtering, then obtain magnetic glass microballon with after distilling water washing 3 times；
(33) the magnetic glass microballon that step (32) obtains is put into the PdCl that concentration is 0.05wt%2In the aqueous solution, stir
20min is mixed, is filtered, then magnetic glass microballon is obtained 2 times with water washing is distilled；
(4) Ag layers are prepared
(41) plating solution is prepared
By 1 part of AgNO3It is dissolved in 1.07 parts of compound stabilizers in 100 parts of distilled water, adds the ammonia that 6 parts of concentration are 26wt%
Water, stirs to precipitation to be completely dissolved and obtains plating solution；
(42) complex reducing agent is prepared
0.5 part of hydrazine hydrate is dissolved in formation composite reduction agent solution in 40 parts of methanol；
(43) plating
The magnetic glass microballon that step (33) obtains is put into the plating solution that step (41) obtains and stirred, is then added dropwise
The composite reduction agent solution that step (42) obtains, react 20min after filtering, washing, dry after i.e. obtain magnetic plating Ag glass it is micro-
Pearl.
Further, in the mixed aqueous solution in step (13), SnCl2Concentration be 5wt%, HCl concentration is
10wt%.
Further, the compound stabilizer in step (41) is the mixture of thiocarbamide, EDTA and tartaric acid, tartaric acid,
The mass ratio of EDTA and thiocarbamide is 3：2：0.1.
Specific embodiment 4
It is roughly the same with specific embodiment 1, differ only in：
Step (41) is by 3 parts of AgNO3It is dissolved in 3.78 parts of compound stabilizers in 100 parts of distilled water, adding 3 parts of concentration is
25wt% ammoniacal liquor, stirs to precipitation to be completely dissolved and obtains plating solution；
Compound stabilizer in step (41) is the mixture of thiocarbamide, EDTA and tartaric acid, tartaric acid, EDTA and thiocarbamide
Mass ratio is 0.5：0.1：0.03.
Specific embodiment 5
It is roughly the same with specific embodiment 2, differ only in：
Compound stabilizer in step (41) is the mixture of thiocarbamide, EDTA and tartaric acid, tartaric acid, EDTA and thiocarbamide
Mass ratio is 0.5：2：0.1.
Specific embodiment 6
It is roughly the same with specific embodiment 3, differ only in：
By 1 part of AgNO in step (41)3It is dissolved in 1.02 parts of compound stabilizers in 100 parts of distilled water, adding 6 parts of concentration is
26wt% ammoniacal liquor, stirs to precipitation to be completely dissolved and obtains plating solution；
Compound stabilizer in step (41) is the mixture of thiocarbamide, EDTA and tartaric acid, tartaric acid, EDTA and thiocarbamide
Mass ratio is 6：0.1：0.03.
Specific embodiment 7
It is roughly the same with specific embodiment 1, differ only in：
By 3 parts of AgNO in step (41)3It is dissolved in 3.43 parts of compound stabilizers in 100 parts of distilled water, adding 3 parts of concentration is
25wt% ammoniacal liquor, stirs to precipitation to be completely dissolved and obtains plating solution；
Compound stabilizer in step (41) is the mixture of thiocarbamide, EDTA and tartaric acid, tartaric acid, EDTA and thiocarbamide
Mass ratio is 6：0.8：0.06.
Embodiments of the present invention are elaborated above.But the present invention is not limited to above-mentioned embodiment,
In art those of ordinary skill's possessed knowledge, it can also be done on the premise of present inventive concept is not departed from
Go out various change.
Claims (2)
1. a kind of preparation method of magnetic plating Ag glass microballoons, it is characterised in that comprise the following steps：
(1) pretreated glass microballon
(11) first with the Na that concentration is 5~40wt%2CO3The aqueous solution cleans to glass microballoon, then the salt with 2~10wt%
Aqueous acid is cleaned to glass microballoon, and finally glass microballoon is carried out clearly with the 60~70wt% industrial alcohol aqueous solution
Wash；
(12) glass microballoon that step (11) obtains is put into 0.1~3wt% hydrofluoric acid aqueous solution and be roughened at etching
Reason 5~15 minutes；
(13) glass microballoon obtained to step (12) is put into SnCl2In HCl mixed aqueous solution, stir 10~40 minutes；
(14) it is 0.02~0.1wt%PdCl the glass microballoon that step (13) obtains to be put into concentration2In aqueous solution, stirring
10~40 minutes；
(2) Ni-P alloy interlayers are prepared
(21) plating solution is prepared
By 2~8 parts of NiCl2·6H2O, 1~5 part of sodium citrate, 0.1~1 part of sodium potassium tartrate tetrahydrate are dissolved in 50~150 parts of distilled water
In, then take the NaH that 50~150 parts of concentration are 3~5wt%2PO2·H2The O aqueous solution is added thereto, finally again thereto add 6~
9 parts of concentration are 25~28wt% ammoniacal liquor, and plating solution is obtained after stirring；
(22) plating
The glass microballoon that step (14) obtains is put into the plating solution that step (21) obtains, with 2~5 DEG C under stirring
min-1Heating rate be heated to 70 DEG C after be incubated 20~40min, filtering, with magnetic glass microballon is made after distillation water washing；
(3) magnetic glass microballon is pre-processed
(31) by 1~5 part of SnCl2, 2~8 parts of concentrated hydrochloric acids and 5~30 parts of polyethylene glycol 2000s be dissolved in 50~150 parts of distilled water,
Stir and obtain cleaning fluid；
(32) the magnetic glass microballon that step (22) obtains is put into the cleaning fluid that step (31) obtains, stirs 20~40min,
Filtering, then obtain magnetic glass microballon with after distilling water washing 2~3 times；
(33) the magnetic glass microballon that step (32) obtains is put into the PdCl that concentration is 0.02~0.1wt%2In the aqueous solution, stir
10~30min is mixed, is filtered, then magnetic glass microballon is obtained 2~3 times with water washing is distilled；
(4) Ag layers are prepared
(41) plating solution is prepared
By 1~5 part of AgNO3Be dissolved in 1~5 part of compound stabilizer in 100 parts of distilled water, add 3~9 parts of concentration be 25~
28wt% ammoniacal liquor, stirs to precipitation to be completely dissolved and obtains plating solution, wherein：
Compound stabilizer is the mixture of thiocarbamide, EDTA and tartaric acid, the mass ratio of tartaric acid, EDTA and thiocarbamide for (0.5~
6)：(0.1~2)：(0.03~0.1)；
(42) complex reducing agent is prepared
0.5~3 part of hydrazine hydrate is dissolved in formation composite reduction agent solution in 40~60 parts of methanol；
(43) plating
The magnetic glass microballon that step (33) obtains is put into the plating solution that step (41) obtains and stirred, step is then added dropwise
(42) the composite reduction agent solution obtained, react 10~30min after filtering, washing, dry after i.e. obtain magnetic plating Ag glass it is micro-
Pearl.
2. the preparation method of a kind of magnetic plating Ag glass microballoons according to claim 1, it is characterised in that in step (13)
Mixed aqueous solution in, SnCl2Concentration be 1~8wt%, HCl concentration is 5~15wt%.
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| CN103130421A (en) * | 2013-04-03 | 2013-06-05 | 中国兵器工业集团第五三研究所 | Nickel plating silvered glass bead and preparation method thereof |
| CN104646663A (en) * | 2014-12-11 | 2015-05-27 | 薛世君 | Ag Cu coated powder preparation method |
| CN105273689A (en) * | 2014-07-18 | 2016-01-27 | 广东工业大学 | Novel multi-element structure composite conductive filling material |
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| CN103130421A (en) * | 2013-04-03 | 2013-06-05 | 中国兵器工业集团第五三研究所 | Nickel plating silvered glass bead and preparation method thereof |
| CN105273689A (en) * | 2014-07-18 | 2016-01-27 | 广东工业大学 | Novel multi-element structure composite conductive filling material |
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