CN103755738A - Complexing agent and preparation method and use thereof - Google Patents
Complexing agent and preparation method and use thereof Download PDFInfo
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- CN103755738A CN103755738A CN201410015187.2A CN201410015187A CN103755738A CN 103755738 A CN103755738 A CN 103755738A CN 201410015187 A CN201410015187 A CN 201410015187A CN 103755738 A CN103755738 A CN 103755738A
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- complexing agent
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- organic acid
- electroplate liquid
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- 239000008139 complexing agent Substances 0.000 title claims abstract description 125
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 69
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 20
- 150000007524 organic acids Chemical class 0.000 claims abstract description 20
- 238000009713 electroplating Methods 0.000 claims abstract description 16
- 125000002252 acyl group Chemical group 0.000 claims abstract description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 238000007747 plating Methods 0.000 claims description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 25
- 229910052802 copper Inorganic materials 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 16
- 239000002585 base Substances 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 5
- 229910000906 Bronze Inorganic materials 0.000 claims description 4
- 239000010974 bronze Substances 0.000 claims description 4
- 229910000531 Co alloy Inorganic materials 0.000 claims description 3
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 3
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- WDHWFGNRFMPTQS-UHFFFAOYSA-N cobalt tin Chemical compound [Co].[Sn] WDHWFGNRFMPTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- GGZZISOUXJHYOY-UHFFFAOYSA-N 8-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C(N)=CC=CC2=C1O GGZZISOUXJHYOY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 16
- 238000001035 drying Methods 0.000 abstract description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000536 complexating effect Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 3
- 230000000379 polymerizing effect Effects 0.000 abstract 2
- 150000008043 acidic salts Chemical class 0.000 abstract 1
- 229910001431 copper ion Inorganic materials 0.000 abstract 1
- 238000005406 washing Methods 0.000 description 38
- 239000000243 solution Substances 0.000 description 35
- 239000000843 powder Substances 0.000 description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 238000002474 experimental method Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- 239000003921 oil Substances 0.000 description 9
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 8
- 238000005238 degreasing Methods 0.000 description 7
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005554 pickling Methods 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000011020 pilot scale process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910000926 A-3 tool steel Inorganic materials 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- -1 gold-plated Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- 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 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 0 CCNCC(C)(*)OP(C(C)(C)OP(O*)(ON)=O)(ON)=O Chemical compound CCNCC(C)(*)OP(C(C)(C)OP(O*)(ON)=O)(ON)=O 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 102000004867 Hydro-Lyases Human genes 0.000 description 1
- 108090001042 Hydro-Lyases Proteins 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002498 deadly effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BYGOPQKDHGXNCD-UHFFFAOYSA-N tripotassium;iron(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] BYGOPQKDHGXNCD-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
The invention relates to a complexing agent and a preparation method and use thereof. The general formula of the complexing agent is MxHyPnO3(n+1)Rz, wherein M is any one or more of alkali metal ions and NH<4+>; R is acyl; x, n and z are positive integers, y is 0 or a positive integer, and x+y+z=n+2. The preparation method of the complexing agent comprises the following steps: mixing M-containing alkali, carbonate or hydrocarbonate and phosphoric acid and acidic salt of an R group-containing unitary organic acid or polybasic organic acid in a molar ratio to react; then, directly polymerizing the reaction liquid for 0.5-10 hours at 100-800 DEG C to obtain a complexing agent product; or first, drying the reaction liquid, and then, polymerizing the reaction liquid for 0.5-10 hours at 100-800 DEG C to obtain the complexing agent product. The complexing agent provided by the invention applied to producing an electroplating liquid is convenient to process, and the prepared electroplating liquid is strong in complexing ability to metals, and has the complexing constant to copper ions of 10<26-27>; the complexing agent is far superior to a cyanide-free complexing agent in the prior art. The electroplating liquid prepared by the complexing agent is stable in quality, good in dispersibility, wider in technical current density range adopted and wide in application range.
Description
Technical field
The present invention relates to a kind of compound, relate to specifically a kind of complexing agent and its production and use, belong to chemical technology field.
Background technology
Complexing agent is for can form with metal ion the compound of complexing ion, in electroplating solution, except minority electroplate liquid, as acidic solution plating iron, nickel plating, chromium plating, copper facing are not used and maybe needn't be used outside complexing agent, other most of electroplate liquids, as silver-plated in basic solution, gold-plated, copper facing, zinc-plated, zinc-plated, bronze (copper-tin alloy) electroplating etc. all need to use complexing agent.
Conventional complexing agent is as prussiate; because cryanide ion has outstanding complex ability; cyanide electroplating is best plating mode; be widely used in electroplating industry; it is deadly poisonous compound that but cyanide electroplating will be used NaCN, KCN, CuCN etc.; it is only 0.005g to people's lethal quantity; prussiate had both endangered the healthy of operator; while is contaminate environment again; and waste water is difficult to administer, its sewage disposal expense is high, therefore for protection of the environment; reduce public hazards, urgently develop a kind of complexing agent of substitute for cyanogenless electroplating technology.
At present cyanogenless electroplating technology and mainly containing without cyanogen complexing agent of using are following several: 1. pyrophosphate copper plating: using potassium pyrophosphate as complexing agent, potassium pyrophosphate has good complex performance, the Complex Stability Constants K of cupric ion and pyrophosphate formation
1=6.7, K
2=9.0, with potassium pyrophosphate, cook the electroplate liquid steady quality of complexing agent, adoptable processing range is wider, but deficiency is: on steel substrate, can not directly electroplate, otherwise matrix surface can produce displacement causes bonding force bad, therefore, with potassium pyrophosphate, cook being of limited application of electroplate liquid of complexing agent; 2. citrate copper-plating: citric acid complex ability is stronger, can produce with cupric ion highly stable material in plating solution, the Complex Stability Constants K of cupric ion and citrate
2=19.30, adopt this technique copper facing iron-based surface to there will not be displacement phenomenon, weak point is: the electroplate liquid quality of making complexing agent with citric acid is stable not, and the dispersiveness of electroplate liquid has much room for improvement, and electroplate liquid can go bad when high temperature; 3.HEDP copper facing: HEDP is a kind of organic phosphonate, there is good complex ability, doing the used time with various metals, can form more stable material, the electroplate liquid steady quality being made as complexing agent by HEDP, electroplate liquid good dispersity, weak point is: the process current density narrow range of finding this electroplate liquid in actual production, coating easily produces copper powder, iron contamination in plating solution can reduce sedimentation rate, make the bonding force variation of coating and matrix, the electroplate liquid therefore being made as complexing agent by HEDP is not widely used.
Summary of the invention
The object of the invention is to solve the deficiency without cyanogen complexing agent of the prior art, a kind of complexing agent is provided, this complexing agent complex ability is strong, can reach 10 with the complexing stability constant of cupric ion
26~27.
Another object of the present invention is to provide a kind of preparation method of complexing agent, and this preparation method is simple to operate, the complexing agent steady quality making, and purity is high.
A further object of the invention is to provide a kind of purposes of complexing agent, this complexing agent is for the preparation of electroplate liquid, can improve the complex ability of electroplate liquid to metal, the electroplate liquid steady quality being made by this complexing agent, electroplate liquid good dispersity, adoptable process current density a wider range, the applied range of electroplate liquid.
The technical solution adopted for the present invention to solve the technical problems is:
A complexing agent, the general formula of described complexing agent is M
xh
yp
no
3n+1r
z, wherein M be in alkalimetal ion and NH4+ any one or multiple; R is acyl group; X, n and z are positive integer, and y is 0 or positive integer, x+y+z=n+2.
Below with several examples to explain technique scheme:
A: work as x=1, during y=1, z=n, the general formula of complexing agent is MHP
no
3n+1r
n, its structural formula as the formula (1):
B: work as x=n, during y=0, z=2, is M in the time of complexing agent
np
no
3n+1r
2, its structural formula as the formula (2):
structural formula (2);
C: work as x=1, during y=n-1, R=2, the general formula of complexing agent is MH
n-1p
no
3n+1r
2, its structural formula as the formula (1):
As preferably, the general formula of described complexing agent is M
xh
yp
no
3n+1r, wherein M is Na
+, K
+with in NH4+ any one or multiple; R is acyl group; X and n are positive integer, and y is 0 or positive integer, x+y=n+1.
Below with several examples to explain technique scheme:
D: when y=0, x=n+1, the general formula of complexing agent is M
n+1p
no
3n+1r, its structural formula as the formula (4):
E: when y=1, x=n, the general formula of complexing agent is M
nhP
no
3n+1r, its structural formula as the formula (5):
structural formula (5);
F: when y=n-1, x=2, the general formula of complexing agent is M
2h
n-1p
no
3n+1r, its structural formula as the formula (6):
A kind of preparation method of complexing agent, concrete operations are as follows: by containing alkali, carbonate or the supercarbonate of M and phosphoric acid, containing the monobasic organic acid of R base or the acid salt of poly-basic organic acid hybrid reaction in molar ratio, then reaction solution is at next step polymerase 10 of 100~800 ℃ of conditions .5~10h acquisition complexing agent finished product; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5~10h obtains complexing agent finished product under 100~800 ℃ of conditions.
First acid-base neutralisation reaction in the preparation method of complexing agent of the present invention, be about to mix in molar ratio with phosphoric acid, the monobasic organic acid that contains R base or the acid salt of poly-basic organic acid containing alkali, carbonate or the supercarbonate of M, and then dehydration polyreaction obtains complexing agent finished product, the mode of dehydration polymerization has two kinds: 1, directly reaction solution is sprayed into and in rotary kiln, under 100~800 ℃ of conditions, dry polymerisation step and complete and obtain complexing agent finished product; 2, reaction solution is obtained to partially polymerized intermediate powder by the dry or expansion drying mode of spraying at utmost point short period of time inner drying, intermediate powder is placed in the equipment that is similar to rake type drier and obtains complexing agent finished product in 100~800 ℃ of polymerase 10 .5~10h.
As preferably, when M is Na
+time, by sodium hydroxide, sodium carbonate or sodium bicarbonate and phosphoric acid, containing the monobasic organic acid of R base or the acid salt of poly-basic organic acid hybrid reaction in molar ratio, then reaction solution obtains complexing agent finished product at next step polymerase 10 of 200~400 ℃ of conditions .5~10h; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5~10h obtains complexing agent finished product under 200~400 ℃ of conditions.
As: M is Na
+, work as x=1, during y=1, z=n, the general formula of complexing agent is NaHP
no
3n+1r
n, R base is ethanoyl, its structural formula as the formula (7):
The preparation method of the complexing agent shown in structural formula (7) is as follows: by sodium hydroxide and phosphoric acid, acetic acid 1:n:n hybrid reaction in molar ratio, reaction finishes rear reaction solution and obtains partially polymerized intermediate powder through expansion drying, described partially polymerized intermediate powder is placed in mixer. in 200~400 ℃ of polymerase 10 .5~10h, obtains the complexing agent finished product as shown in structural formula (7).
As preferably, when M is K
+time, by potassium hydroxide, salt of wormwood or saleratus and phosphoric acid, containing the monobasic organic acid of R base or the acid salt of poly-basic organic acid hybrid reaction in molar ratio, then reaction solution obtains complexing agent finished product at next step polymerase 10 of 250~800 ℃ of conditions .5~10h; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5~10h obtains complexing agent finished product under 250~800 ℃ of conditions.
As: M is K
+, work as x=n, during y=0, z=2, the general formula of complexing agent is KP
no
3n+1r
2, R base is ethanoyl, its structural formula as the formula (8):
The preparation method of the complexing agent shown in structural formula (8) is as follows: by potassium hydroxide and phosphoric acid, acetic acid n:n:2 hybrid reaction in molar ratio, reaction finishes rear reaction solution through the partially polymerized intermediate powder of the dry acquisition of spraying, described partially polymerized intermediate powder is placed in mixer. in 250~800 ℃ of polymerase 10 .5~10h, obtains the complexing agent finished product as shown in structural formula (8).
As preferably, when M is NH4+, by ammoniacal liquor, volatile salt or bicarbonate of ammonia and phosphoric acid, containing the monobasic organic acid of R base or the acid salt of poly-basic organic acid hybrid reaction in molar ratio, then reaction solution obtains complexing agent finished product at next step polymerase 10 of 100~300 ℃ of conditions .5~10h; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5~10h obtains complexing agent finished product under 100~300 ℃ of conditions.
An application for complexing agent, for the preparation of electroplate liquid.
As preferably, described electroplate liquid is any one in copper facing, zinc-plated, copper-plated zinc alloy, bronze (copper-tin alloy) electroplating, nickel plating tin alloy, nickel-cobalt plating, zinc-plated cobalt-base alloy and nickel plating tin-cobalt alloy.
As preferably, in described electroplate liquid, to be calculated in mass percent be 1~60% to the consumption of complexing agent.
The invention has the beneficial effects as follows: raw material sources are extensive, cheap, preparation technology, transportation, storage and use are simple, and production cost is low; Complexing agent of the present invention is applied to produce electroplate liquid, easy to process, and the electroplate liquid making is strong to the complex ability of metal, as complexing agent of the present invention can reach 10 to the complexation constant of cupric ion
26~27, be far superior to conventional complexing agent of the prior art, the electroplate liquid steady quality being made by this complexing agent, electroplate liquid good dispersity, adoptable process current density a wider range, the applied range of electroplate liquid.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail.
Reagent in following each embodiment or raw material are all commercial conventional raw material, and purity is analytical pure.
Embodiment 1:
A complexing agent, the general formula of described complexing agent is M
xh
yp
no
3n+ 1R
z, x=3 wherein, y=0, n=2, z=1, M is K
+, R is ethanoyl, concrete structure formula is as follows:
The preparation method of this complexing agent is as follows: by potassium hydroxide, phosphoric acid and acetic acid 3:2:1 hybrid reaction in molar ratio, reaction solution is dried and is obtained partially polymerized intermediate powder by spraying, this intermediate powder is placed in to rake type drier interior in 250 ℃ of polyreaction 10h, polyreaction finishes rear acquisition complexing agent finished product.
Embodiment 2:
A complexing agent, the general formula of described complexing agent is M
xh
yp
no
3n+ 1R
z, x=3 wherein, y=0, n=3, z=2, M is K
+and Na
+, R is ethanoyl, concrete structure formula is as follows:
The preparation method of this complexing agent is as follows: by sodium hydroxide, phosphoric acid and acetic acid 3:3:2 hybrid reaction in molar ratio, reaction solution obtains partially polymerized intermediate powder by expansion drying, this intermediate powder is placed in to rake type drier interior in 200 ℃ of polyreaction 10h, polyreaction finishes rear acquisition complexing agent finished product.
Embodiment 3:
A complexing agent, the general formula of described complexing agent is M
xh
yp
no
3n+ 1R
z, x=5 wherein, y=0, n=5, z=2, M is Na
+, R is the acyl group forming after ethanoyl and sodium hydrotartrate dehydration, concrete structure formula is as follows:
The preparation method of this complexing agent is as follows: by sodium bicarbonate, phosphoric acid, acetic acid and sodium hydrotartrate 5:5:1:1 hybrid reaction in molar ratio, then reaction solution obtains partially polymerized intermediate powder by expansion drying, this intermediate powder is placed in to rake type drier interior in 400 ℃ of polyreaction 0.5h, polyreaction finishes rear acquisition complexing agent finished product.
Embodiment 4:
A complexing agent, the general formula of described complexing agent is M
xh
yp
no
3n+ 1R
z, x=10 wherein, y=1, n=10, z=1, M is K
+and Na
+, R is the acyl group forming after sodium hydrotartrate dehydration, concrete structure formula is as follows:
The preparation method of this complexing agent is as follows: by sodium hydroxide, potassium hydroxide, phosphoric acid and sodium hydrotartrate 1:9:10:1 hybrid reaction in molar ratio, reaction solution is dried and is obtained partially polymerized intermediate powder by spraying, this intermediate powder is placed in to rake type drier interior in 800 ℃ of polyreaction 0.5h, polyreaction finishes rear acquisition complexing agent finished product.
Embodiment 5:
A complexing agent, the general formula of described complexing agent is M
xh
yp
no
3n+ 1R
z, x=10 wherein, y=1, n=10, z=1, M is Na
+, R is the acyl group forming after Monobasic sodium citrate dehydration, concrete structure formula is as follows:
The preparation method of this complexing agent is as follows: by sodium carbonate, phosphoric acid and Monobasic sodium citrate 5:10:1 hybrid reaction in molar ratio, reaction solution obtains partially polymerized intermediate powder by expansion drying, this intermediate powder is placed in to rake type drier interior in 400 ℃ of polyreaction 0.5h, polyreaction finishes rear acquisition complexing agent finished product.
Embodiment 6:
A complexing agent, the general formula of described complexing agent is M
xh
yp
no
3n+ 1R
z, x=1 wherein, y=100, n=100, z=1, M is Na
+, R is the amide group forming after ala dehydratase, concrete structure formula is as follows:
The preparation method of this complexing agent is as follows: by sodium bicarbonate, phosphoric acid and L-Ala 1:100:1 hybrid reaction in molar ratio, reaction solution obtains partially polymerized intermediate powder by expansion drying, this intermediate powder is placed in to rake type drier interior in 300 ℃ of polyreaction 2.5h, polyreaction finishes rear acquisition complexing agent finished product.
Embodiment 7:
A complexing agent, the general formula of described complexing agent is M
xh
yp
no
3n+ 1R
z, x=1 wherein, y=100, n=100, z=1, M is Na
+, R is ethanoyl, concrete structure formula is as follows:
The preparation method of this complexing agent is as follows: by sodium bicarbonate, phosphoric acid and acetic acid 1:100:1 hybrid reaction in molar ratio, reaction solution obtains partially polymerized intermediate powder by expansion drying, this intermediate powder is placed in to rake type drier interior in 300 ℃ of polyreaction 2.5h, polyreaction finishes rear acquisition complexing agent finished product.
Embodiment 8
A complexing agent, the general formula of described complexing agent is M
xh
yp
no
3n+ 1R
z, x=3 wherein, y=0, n=2, z=1, M is Na
+, R is the acyl group that methyl acid phosphate dehydration has formation, concrete structure formula is as follows:
The preparation method of this complexing agent is as follows: by sodium hydroxide, phosphoric acid and methyl acid phosphate 3:2:1 hybrid reaction in molar ratio, reaction solution obtains partially polymerized intermediate powder by expansion drying, this intermediate powder is placed in to rake type drier interior in 300 ℃ of polyreaction 5h, polyreaction finishes rear acquisition complexing agent finished product.
Above-mentioned complexing agent is for the preparation of electroplate liquid, and described electroplate liquid is any one in copper facing, zinc-plated, copper-plated zinc alloy, bronze (copper-tin alloy) electroplating, nickel plating tin alloy, nickel-cobalt plating, zinc-plated cobalt-base alloy and nickel plating tin-cobalt alloy.
Plating solution for copper-plating used take below as example, specific as follows:
Embodiment 9:
The complexing agent making with embodiment 7 is for the preparation of non-cyanide pre-plating copper plating solution, and the preparation method of described electroplate liquid is as follows:
(1) preparation of mantoquita: the complexing agent that embodiment 7 is made and copper sulfate in molar ratio 2:1 mix, in normal-temperature reaction 1.0h, after reaction finishes, through centrifugation the dry mantoquita that to obtain, the structural formula of this mantoquita is as follows;
(2) mantoquita that the preparation of electroplate liquid: by 1%(mass percent) complexing agent of embodiment 7,0.5% step (1) make and 98.5% purified water mix in proportion, and then use potassium hydroxide adjust pH to 8.5, obtain non-cyanide pre-plating copper plating solution.
Embodiment 10:
The complexing agent making with embodiment 8 is for the preparation of non-cyanide pre-plating copper plating solution, and the preparation method of described electroplate liquid is as follows:
(1) preparation of mantoquita: the complexing agent that embodiment 8 is made and copper sulfate in molar ratio 2:3 mix, in normal-temperature reaction 1.0h, after reaction finishes, through centrifugation the dry mantoquita that to obtain, the structural formula of this mantoquita is as follows;
(2) mantoquita that the complexing agent of embodiment 1 preparation of electroplate liquid: by 60%(mass percent), 5% step (1) obtain and 35% purified water mix in proportion, and then potassium hydroxide adjust pH to 9.5, obtains pre-plating copper plating solution.
The non-cyanide pre-plating copper plating solution that embodiment 9 and 10 is made has carried out following research:
1, Hull groove test (267ml)
1.1 tentative experiments: the electroplate liquid that embodiment 9 and embodiment 10 are made is 25 ℃ of temperature, circuit 1A(current stabilization), the lower sheet of beating of the condition of pneumatic blending, time 5min, beat in sheet process and observe under current stabilization condition, groove presses also relatively stable and plating sheet in larger area, to show half luminous point, the careful feature of crystal.
Current density range is determined in the test of 1.2Hull groove:
The electroplate liquid making with embodiment 9 and embodiment 10 is 55 ℃ of temperature, electric current 1A, and time 10min, beats sheet by Hull and determines optimum current density range, makes the A3 steel disc that sheet material that sheet selects adopts 0.5*70*100,600# silicon carbide paper sanding and polishing.With reference to experimental formula J
k=I(5.1-5.24LgL) calculate the current density of test piece every bit.By beating sheet and current density, calculate and can draw, the current density range of the electroplate liquid that embodiment 9 and embodiment 10 make is 0.5A/dm
2to 2.5A/dm
2between.
2 electroplate liquids and plating performance test
The mensuration of 2.1 current efficiency: adopt copper voltameter to measure, the current efficiency of the electroplate liquid that embodiment 9 makes is that the current efficiency of the electroplate liquid that makes of 93.0%, embodiment 10 is 93.8%.
2.2 electroplate liquid dispersive abilities are measured
The dispersive ability of surveying electroplate liquid by bending cathode method, condition is electric current 1A, oil-free air stirs, 55 ℃ of temperature, time 30min, examination material is selected the A3 copper sheet of 0.5*70*100,600# silicon carbide paper sanding and polishing.
The dispersive ability of the electroplate liquid of the embodiment 9 recording is that the dispersive ability of the electroplate liquid of 93.5%, embodiment 10 is 93.1%.
The mensuration of 2.3 covering powers
Adopt endoporus method to measure the covering power of plating solution, copper pipe size 10mm*100mm, adopts through hole and Blind Hole Method, and temperature of electroplating solution is 55 ℃, and cathode current density is 0.5A/dm
2, time 5min.After experiment, cut iron pipe open, coating situation in observation tube.
Take embodiment 9 and 10 electroplate liquid as experiment electroplate liquid, after experiment, find that through hole and blind hole have all plated copper layer, illustrate that the covering power of the electroplate liquid that embodiment 9 and embodiment 10 make is good.
2.4 bonding force tests
2.4.1 crooked experiment: adopt the polishing iron plate (A3) that thickness is 0.5mm, the temperature of electroplate liquid is 55 ℃, and cathode current density is 2A/dm
2, time 15min.
The electroplate liquid of embodiment 9 and 10 of take is experiment electroplate liquid, after experiment by the test piece alternating bending of plate to rupturing, breach place, without the phenomenon of peeling, proves that coating is not separated with matrix.
2.4.2 thermal shock experiment: adopt the polishing iron plate (A3) that thickness is 0.5mm, the temperature of electroplate liquid is 55 ℃, and cathode current density is 2A/dm
2, time 15min.
Take the electroplate liquid of embodiment 9 and 10 as experiment electroplate liquid, after experiment, the test piece of plate is placed in baking oven and is baked to 200 ℃, toast continuously 1h, immerse immediately quenching in 0 ℃ of water after taking-up, result is not found coating foaming and the phenomenon of peeling.
2.5 ductility of electrodeposited film experiments: by the thick A3 steel disc chromic acid passivation of 1mm, directly hang in the electroplate liquid that embodiment 9 and 10 makes after cleaning, the thickness of coating reaches after 20 μ m, coating is stripped down, crooked 180 ℃, and push knee, coating does not rupture, and shows that ductility of electrodeposited film is good.
2.6 coating porosity experiments: adopt the polishing iron plate (A3) that thickness is 0.5mm, 55 ℃ of the temperature of electroplate liquid, cathode current density 1A/dm
2, time 20min, pastes filter paper laboratory method with potassium ferricyanide solution and carries out porosity experiment.
Tripotassium iron hexacyanide 10g/L; Sodium-chlor 20g/L.
Experimental result shows, the porosity of the electrolytic coating that the electroplate liquid that embodiment 9 and embodiment 10 make forms as experimental subjects all≤1/dm
2.
The mensuration of 2.7 sedimentation velocities: set electric current 1A, 55 ℃ of temperature, time 30min, measurement result shows, and the sedimentation velocity of the electroplate liquid that embodiment 9 makes is 0.6 μ m/min, and the sedimentation velocity of the electroplate liquid that embodiment 10 makes is 0.52 μ m/min.
The electroplate liquid that embodiment 9 and embodiment 10 are made further carries out pilot experiment, and pilot process parameter is as follows:
Technical process: iron and steel parts → ultrasonic wave oil removing → washing 1 → washing 2 → anode electrolysis oil removing → washing 1 → washing 2 → pickling degreasing → washing 1 → washing 2 → salt pickling → washing 1 → washing 2 → terminal electrolytic degreasing → washing 1 → washing 2 → acid activation → washing 1 → washing 2 → embodiment 9 or electroplate liquid → recovery → washing 1 → washing 2 → acid activation → sour copper of 10.
Ultrasonic wave oil removing: degreasing powder concentration 50 ± 5g/L, 70 ± 5 ℃ of temperature, current density 1-5A/dm2,5 minutes time.
Catholyte oil removing: electrolytic degreasing powder concentration 50 ± 5g/L, 70 ± 5 ℃ of temperature, current density 1-5A/dm2,5~7 minutes time.
Anode electrolysis oil removing: electrolytic degreasing powder concentration 50 ± 5g/L, 70 ± 5 ℃ of temperature, current density 1-5A/dm
2, 3~5 minutes time.
Pickling: technical hydrochloric acid concentration 15~20%, time 8~10min, room temperature.
Activation: technical hydrochloric acid concentration 5~10%, time 3~5min, room temperature.
Embodiment 9 or 10 electroplate liquid: degree Beaume 32-36, pH value 8.5~9.5,50~55 ℃ of temperature, current density 0.5~2.5A/dm
2, time 5min to a few hours not etc., facts have proved, be plating to 100 μ m leveling property, luminance brightness is also very good.
By 50L pilot scale electroplating assembly line, move 20 months continuously, 350L pilot scale electroplating assembly line moves 11 months continuously, has verified that the electroplate liquid that embodiment 9 or 10 makes has reliability, and plating solution performance is stable, and the consumption of plating solution is 10~50ml/KAH.
On the experiment basis of above-mentioned pilot scale, the electroplate liquid that acquisition embodiment 9 or 10 makes is for the processing condition of suitability for industrialized production.
1, iron and steel parts:
Technical process: iron and steel parts → ultrasonic wave oil removing → washing 1 → washing 2 → anode electrolysis oil removing → washing 1 → washing 2 → pickling degreasing → washing 1 → washing 2 → salt pickling → washing 1 → washing 2 → terminal electrolytic degreasing → washing 1 → washing 2 → acid activation → washing 1 → washing 2 → preimpregnation → embodiment 9 or electroplate liquid → recovery → washing 1 → washing 2 → acid activation → sour copper of 10.
Processing condition:
Electroplate liquid density: 32~36 degree Beaume
45~60 ℃ of temperature
PH value: 8.60~9.50
Stir: pneumatic blending adds movable cathode
Anode: electrolytic copper or anaerobic electrolytic copper
Negative and positive Area Ratio: 1:1.5~2.
Electric current: 0.5~2.5A/dm
2
2, zinc alloy workpiece:
Technical process: zinc alloy workpiece → hot dipping paraffin removal → ultrasonic wave paraffin removal → washing 1 → washing 2 → ultrasonic wave oil removing → washing 1 → washing 2 → anode electrolysis oil removing → washing 1 → washing 2 → acid salt activating → washing 1 → washing 2 → ultrasonic wave presoak preimpregnation 30s → embodiment 9 or 10 electroplate liquid (charged enter groove 25~35 ℃) → reclaim → washing 1 → washing 2 → acid activation → sour copper.
Processing condition:
Electroplate liquid density: 32~38 degree Beaume
25~35 ℃ of temperature
PH value: 8.60~9.50
Stir: pneumatic blending adds movable cathode
Anode: electrolytic copper or anaerobic electrolytic copper
Negative and positive Area Ratio: 1:1.5~2.
Electric current: 0.5~1.5A/dm
2
Above-described embodiment is a kind of preferably scheme of the present invention, not the present invention is done to any pro forma restriction, also has other variant and remodeling under the prerequisite that does not exceed the technical scheme that claim records.
Claims (9)
1. a complexing agent, is characterized in that: the general formula of described complexing agent is M
xh
yp
no
3n+1r
z, wherein M be in alkalimetal ion and NH4+ any one or multiple; R is acyl group; X, n and z are positive integer, and y is 0 or positive integer, x+y+z=n+2.
2. complexing agent according to claim 1, is characterized in that: the general formula of described complexing agent is M
xh
yp
no
3n+1r, wherein M is Na
+, K
+with in NH4+ any one or multiple; R is acyl group; X and n are positive integer, and y is 0 or positive integer, x+y=n+1.
3. the preparation method of the complexing agent described in a claim 1 or 2, it is characterized in that: concrete operations are as follows: by containing alkali, carbonate or the supercarbonate of M and phosphoric acid, containing the monobasic organic acid of R base or the acid salt of poly-basic organic acid hybrid reaction in molar ratio, then reaction solution is at next step polymerase 10 of 100~800 ℃ of conditions .5~10h acquisition complexing agent finished product; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5~10h obtains complexing agent finished product under 100~800 ℃ of conditions.
4. the preparation method of complexing agent according to claim 3, is characterized in that, when M is Na
+time, by sodium hydroxide, sodium carbonate or sodium bicarbonate and phosphoric acid, containing the monobasic organic acid of R base or the acid salt of poly-basic organic acid hybrid reaction in molar ratio, then reaction solution obtains complexing agent finished product at next step polymerase 10 of 200~400 ℃ of conditions .5~10h; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5~10h obtains complexing agent finished product under 200~400 ℃ of conditions.
5. the preparation method of complexing agent according to claim 3, is characterized in that, when M is K
+time, by potassium hydroxide, salt of wormwood or saleratus and phosphoric acid, containing the monobasic organic acid of R base or the acid salt of poly-basic organic acid hybrid reaction in molar ratio, then reaction solution obtains complexing agent finished product at next step polymerase 10 of 250~800 ℃ of conditions .5~10h; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5~10h obtains complexing agent finished product under 250~800 ℃ of conditions.
6. the preparation method of complexing agent according to claim 3, it is characterized in that, when M is NH4+, by ammoniacal liquor, volatile salt or bicarbonate of ammonia and phosphoric acid, containing the monobasic organic acid of R base or the acid salt of poly-basic organic acid hybrid reaction in molar ratio, then reaction solution obtains complexing agent finished product at next step polymerase 10 of 100~300 ℃ of conditions .5~10h; Or above-mentioned reaction solution is first dry, and then polymerase 10 .5~10h obtains complexing agent finished product under 100~300 ℃ of conditions.
7. an application for the complexing agent described in claim 1 or 2, is characterized in that: for the preparation of electroplate liquid.
8. the application of complexing agent according to claim 7, is characterized in that: described electroplate liquid is any one in copper facing, zinc-plated, copper-plated zinc alloy, bronze (copper-tin alloy) electroplating, nickel plating tin alloy, nickel-cobalt plating, zinc-plated cobalt-base alloy and nickel plating tin-cobalt alloy.
9. the application of complexing agent according to claim 7, is characterized in that: in described electroplate liquid, to be calculated in mass percent be 1~60% to the consumption of complexing agent.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103938239A (en) * | 2014-05-11 | 2014-07-23 | 山东建筑大学 | Steel band continuous copper plating I |
WO2015103785A1 (en) * | 2014-01-13 | 2015-07-16 | 孙松华 | Complexing agent and preparation method and use thereof |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3298937A (en) * | 1963-01-12 | 1967-01-17 | Dehydag Gmbh | Electroplating baths and processes |
US3475292A (en) * | 1966-02-10 | 1969-10-28 | Technic | Gold plating bath and process |
US3933602A (en) * | 1973-04-27 | 1976-01-20 | Oxy Metal Industries Corporation | Palladium electroplating bath, process, and preparation |
FR2427404A1 (en) * | 1978-05-30 | 1979-12-28 | Oxy Metal Industries Corp | AQUEOUS ACIDIC RHODIUM COATING BATHS AND ELECTROLYTIC RHODIUM COATING COMPOSITIONS CONTAINING THESE BATHS |
US4262060A (en) * | 1978-11-09 | 1981-04-14 | Tokyo Shibaura Denki Kabushiki Kaisha | Solar heat absorber and a method of manufacturing the same |
CN101545123A (en) * | 2009-03-30 | 2009-09-30 | 哈尔滨汽轮机厂有限责任公司 | Method for non-cyanide copper electroplating of steel parts |
CN101622379A (en) * | 2007-02-14 | 2010-01-06 | 尤米科尔电镀技术有限公司 | Copper-tin electrolyte and method for depositing bronze layers |
CN101922027A (en) * | 2010-08-19 | 2010-12-22 | 武汉风帆电镀技术有限公司 | Cyanide-free alkaline copper plating solution and preparation method thereof |
CN102051648A (en) * | 2011-01-20 | 2011-05-11 | 广州市二轻工业科学技术研究所 | Cyanogen-free plating method of zinc alloy die casting |
-
2014
- 2014-01-13 CN CN201410015187.2A patent/CN103755738B/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3298937A (en) * | 1963-01-12 | 1967-01-17 | Dehydag Gmbh | Electroplating baths and processes |
US3475292A (en) * | 1966-02-10 | 1969-10-28 | Technic | Gold plating bath and process |
US3933602A (en) * | 1973-04-27 | 1976-01-20 | Oxy Metal Industries Corporation | Palladium electroplating bath, process, and preparation |
FR2427404A1 (en) * | 1978-05-30 | 1979-12-28 | Oxy Metal Industries Corp | AQUEOUS ACIDIC RHODIUM COATING BATHS AND ELECTROLYTIC RHODIUM COATING COMPOSITIONS CONTAINING THESE BATHS |
US4262060A (en) * | 1978-11-09 | 1981-04-14 | Tokyo Shibaura Denki Kabushiki Kaisha | Solar heat absorber and a method of manufacturing the same |
CN101622379A (en) * | 2007-02-14 | 2010-01-06 | 尤米科尔电镀技术有限公司 | Copper-tin electrolyte and method for depositing bronze layers |
CN101545123A (en) * | 2009-03-30 | 2009-09-30 | 哈尔滨汽轮机厂有限责任公司 | Method for non-cyanide copper electroplating of steel parts |
CN101922027A (en) * | 2010-08-19 | 2010-12-22 | 武汉风帆电镀技术有限公司 | Cyanide-free alkaline copper plating solution and preparation method thereof |
CN102051648A (en) * | 2011-01-20 | 2011-05-11 | 广州市二轻工业科学技术研究所 | Cyanogen-free plating method of zinc alloy die casting |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015103785A1 (en) * | 2014-01-13 | 2015-07-16 | 孙松华 | Complexing agent and preparation method and use thereof |
CN103938239A (en) * | 2014-05-11 | 2014-07-23 | 山东建筑大学 | Steel band continuous copper plating I |
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