CN112458506B - Electroplating solution for metal substrate - Google Patents
Electroplating solution for metal substrate Download PDFInfo
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- CN112458506B CN112458506B CN202011425678.6A CN202011425678A CN112458506B CN 112458506 B CN112458506 B CN 112458506B CN 202011425678 A CN202011425678 A CN 202011425678A CN 112458506 B CN112458506 B CN 112458506B
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- 238000009713 electroplating Methods 0.000 title claims description 46
- 239000000758 substrate Substances 0.000 title claims description 30
- 239000002184 metal Substances 0.000 title claims description 27
- 229910052751 metal Inorganic materials 0.000 title claims description 27
- 239000000243 solution Substances 0.000 claims abstract description 69
- 238000007747 plating Methods 0.000 claims abstract description 68
- 235000015655 Crocus sativus Nutrition 0.000 claims abstract description 22
- 244000124209 Crocus sativus Species 0.000 claims abstract description 22
- 235000013974 saffron Nutrition 0.000 claims abstract description 22
- 239000004248 saffron Substances 0.000 claims abstract description 22
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 claims abstract description 22
- BWHOZHOGCMHOBV-UHFFFAOYSA-N Benzalacetone Natural products CC(=O)C=CC1=CC=CC=C1 BWHOZHOGCMHOBV-UHFFFAOYSA-N 0.000 claims abstract description 21
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000007974 sodium acetate buffer Substances 0.000 claims abstract description 13
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940035044 sorbitan monolaurate Drugs 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims description 29
- 238000000576 coating method Methods 0.000 claims description 29
- 239000004094 surface-active agent Substances 0.000 claims description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 150000001868 cobalt Chemical class 0.000 claims description 11
- 239000008139 complexing agent Substances 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 11
- 150000002505 iron Chemical class 0.000 claims description 11
- 239000001509 sodium citrate Substances 0.000 claims description 11
- 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 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 2
- 229910003321 CoFe Inorganic materials 0.000 claims 1
- 229910002056 binary alloy Inorganic materials 0.000 abstract description 12
- 239000007853 buffer solution Substances 0.000 abstract description 9
- 229910020598 Co Fe Inorganic materials 0.000 abstract description 5
- 229910002519 Co-Fe Inorganic materials 0.000 abstract description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract description 5
- 239000004327 boric acid Substances 0.000 abstract description 5
- 238000013329 compounding Methods 0.000 abstract description 2
- 230000009044 synergistic interaction Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000151 deposition Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- 238000000089 atomic force micrograph Methods 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000000696 magnetic material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002546 FeCo Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000001211 (E)-4-phenylbut-3-en-2-one Substances 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 235000003255 Carthamus tinctorius Nutrition 0.000 description 1
- 244000020518 Carthamus tinctorius Species 0.000 description 1
- 229910001313 Cobalt-iron alloy Inorganic materials 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- 229910000976 Electrical steel Inorganic materials 0.000 description 1
- 229910017061 Fe Co Inorganic materials 0.000 description 1
- 239000006173 Good's buffer Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 229940069428 antacid Drugs 0.000 description 1
- 239000003159 antacid agent Substances 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229930008407 benzylideneacetone Natural products 0.000 description 1
- UDSAIICHUKSCKT-UHFFFAOYSA-N bromophenol blue Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C2=CC=CC=C2S(=O)(=O)O1 UDSAIICHUKSCKT-UHFFFAOYSA-N 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001004 magnetic alloy Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000889 permalloy Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The application provides a Co-Fe binary alloy plating solution, which adopts an acetic acid-sodium acetate buffer system to replace boric acid buffer solution, can effectively maintain pH=3.70+/-0.02, and effectively avoids uneven plating when the thickness of the plating layer exceeds 50 microns by adding sorbitan monolaurate into the plating solution and compounding blue-light saffron and benzalacetone through mutual synergistic interaction.
Description
Technical Field
The application relates to a metal substrate electroplating solution, in particular to a method for improving flatness of a cobalt-iron binary alloy coating, and belongs to the field of electroplating alloys.
Background
With the continuous development of miniaturization and high frequency of electronic equipment, the high frequency soft magnetic material applied to electromagnetic devices becomes a very active research field. Magnetic thin films are the most active field in the development of new materials of high and new technology at present. Functional materials having a thickness of several nanometers to several tens of micrometers and magnetic properties are called magnetic thin film materials, and as electronic components are developed toward miniaturization, integration, and high frequency, development of magnetic thin films having a high quality factor at microwave frequencies is strongly demanded.
Traditional soft magnetic materials include silicon steel sheets, permalloy, electrical soft iron, and amorphous, nanocrystalline alloy ribbons emerging in recent years, but these materials all suffer from several drawbacks. Although these materials can satisfy the performance in terms of soft magnetism, they have drawbacks in terms of use, high cost, difficulty in producing thin films having a thickness of less than 20 μm, and huge and expensive equipment, complicated operation, and severe conditions. The FeCo alloy has a series of excellent magnetic properties as a soft magnetic material, such as high saturation magnetization, high initial permeability and maximum permeability, small hysteresis elongation, high Curie temperature, and the like. Theory and experiment show that Co (Fe) based soft magnetic film is superior to other magnetic film in obtaining high microwave magnetic permeability, so that the Co (Fe) based soft magnetic film has been paid more attention to in research and application of integrated micro magnetic devices, magnetic head materials, anti-electromagnetic interference materials and microwave absorbing materials.
Although FeCo is an excellent soft magnetic material, the following technical problem exists that (1) the thickness of a plating layer is generally thinner, and as disclosed in CN201010196022, an Fe-Co magnetic alloy plating carbon fiber and a preparation method and application thereof are disclosed. The high-purity metal plate is used as an anode, the continuous carbon fiber oxidized at high temperature and strong acid is used as a cathode, and the sulfate of iron and cobalt is used as main salt. The preparation method is that electroplating is carried out under the condition of constant temperature electromagnetic stirring, and the thickness of the plating layer is controlled by the plating temperature and time. The magnetic carbon fiber provided by the application has a uniform and compact magnetic coating, the thickness of the coating is about 0.5-1.5 mu m, and the component of the magnetic coating is Co3Fe7. The preparation process of the magnetic carbon fiber is simple, the production efficiency is high, the magnetic performance is excellent, the magnetic carbon fiber is expected to be used as a novel wave-absorbing material with high mechanical property and low density, namely, the coating can be kept compact and flat in a lower thickness range, but if the thickness of the coating is increased, the technical problems of obvious coating roughness rise and coating flatness reduction can occur.
Disclosure of Invention
Based on the technical problems, the application provides the cobalt-iron soft magnetic coating which is simple in process, low in cost, high in thickness and high in flatness, and the technical problem of uneven surface caused by the rising of the thickness of the coating can be effectively solved.
A metal substrate electroplating solution is characterized in that the electroplating solution comprises the following components:
cobalt salt: coSO 4 . 7H2O(281): X mol，X=0.1-0.4；
Iron salt: feSO 4 . 7H2O(278):0.5-X mol；
Acetic acid-sodium acetate buffer system;
conductive salt: naCl 5-7 g/L;
and (2) a surfactant: sorbitan monolaurate, 0.5-1g/L;
composite leveling agent: blue light saffron and benzalacetone, wherein the blue light saffron is 1-1.5g/L; 1.5-2g/L of benzalacetone;
complexing agent: sodium citrate
The balance of deionized water.
Further, the ph=3.70±0.02, and the binary alloy plating layers obtained from the plating solutions all have extremely high flatness.
Further, the plating parameters of the plating solution: temperature is 20-30 DEG o C, the time is 60-120min, and the current density is 20-30mA/cm 2 。
Further, the roughness of the plating layer is 0.4-0.5 mu m, and the relative flatness is 63.2-69.3%.
Further, the deposition rate of the plating layer is less than 1 μm/min.
Further, the thickness of the coating is more than 50 μm and less than 100 μm.
Further, the error rate of the mole fraction of Fe in the plating solution to the mole fraction of Fe in the plating layer is more than 15%.
Further, the average particle size of CoFed in the plating layer is 10-20nm.
Further, the plating layer is a magnetic plating layer, and the coercive force Hc of the rapid plating layer is 8-30Oe.
Further, the substrate to be plated is a metal substrate.
Regarding the plating solution of the present application:
(1) Main salt: cobalt salt is selected as CoSO 4 . 7H2O, and the concentration plating is 0.1-0.4; iron salt: feSO 4 . 7H2O is 0.1-0.4 mol, the metal concentration is kept to be 0.5M, the concentration of main salt is reduced, the grain size and deposition flatness of a plating layer are improved, the relative proportion of cobalt and iron is regulated, the magnetic property of a film is mainly improved, and the technical problem of abnormal deposition of metal is avoided, and the application is not focused on the research and therefore is not described in detail.
(2) Buffering agent: the acetic acid-sodium acetate buffer system mainly adopts boric acid as buffer solution in the prior art, the boric acid is similar to phosphoric acid, the pH value of the solution is controlled through the release speed of three hydrogen ions, the buffer system has certain limitation, and the theory holds that the buffer effect of the boric acid is not in the solution body but in an electric double layer, no matter the action mechanism is, the pH value can be increased in the electroplating process, a buffer system with good buffer effect is needed,
the present application, however, for the first time proposes the use of sodium acetate-acetate as Co-Fe buffer system, said buffer system being present in HAc-NaAc buffer solution in the following balance: hac=h + +Ac - ;NaAc=Na + +Ac - Due to the homoionic effect, a large amount of HAc and Ac exist in the system - . When a small amount of acid is added, the acid dissociation equilibrium of acetic acid moves reversely, ac - Is reduced in the amount of Ac - Namely an antacid component. When a small amount of alkali is added, the vinegar acid dissociation equilibrium moves forward, the amount of HAc is reduced, and HAc is an alkali-resistant component. When (when)When water is added for dilution, on one hand, the concentration of H+ is reduced, on the other hand, the balance is moved rightward to supplement H+ due to the increase of dissociation degree of HAc and the weakening of homoionic effect, so that the pH value of the solution is almost unchanged, the buffer solution system is pH3.7,
the preparation process is as follows: pH3.7: taking 20g of anhydrous sodium acetate, adding 300ml of water for dissolution, adding 60-80ml of bromophenol blue indicator 3ml of glacial acetic acid until the solution turns from blue to pure green, adding water for dilution to 1000ml, adding a proper amount of sodium citrate, and controlling the pH value to be 3.70+/-0.02.
(3) Conductive salt: the conductivity of the plating solution is improved.
(4) And (2) a surfactant: the addition of the sorbitan monolaurate and the surfactant is the first factor for improving the Co-Fe binary alloy, if the surfactant is not added, pits and depressions appear on the surface of the coating, and after the surfactant is added, the Co-Fe coating gradually tends to be flat, mainly because uneven fluctuation can be formed due to uneven dispersion of deposition potential or current density in the Co-Fe electrodeposition process, the polarization effect of the plating solution is obviously improved in the presence of the surfactant, the deposition speed of the protrusions on the surface of the coating is reduced, the wetting effect of the surfactant also promotes the infiltration of the plating solution in the depressions, the active sites of crystallization are increased, the deposition speed of metal is increased, the depressions on the surface of a substrate are filled up along with the continuous increase of the electrodeposition process, the protrusions are weakened, and the leveling effect is obtained, the application range of the sorbitol monolaurate is proper, otherwise the plating solution is too hesive, the plating solution is controlled to be in the range of 0.5-1g/L, in addition, the surface tension and the solid-liquid interfacial free energy of the plating solution are reduced, the plating solution can be better contacted with the substrate, the critical dimension of the plating layer is better, and the leveling effect of the hydrogen desorption of the plating layer is improved.
(5) Composite leveling agent: the leveling agent used in the application is blue-light saffron and benzalacetone, wherein the structural formula of the blue-light saffron is as follows:
the additive has a C=N structure, is connected with a larger conjugated structure, is a positively charged compound containing nitrogen, has strong electropositivity in an acidic solution with PH of 3.70+/-0.02, is easy to adsorb on a cathode, generates competitive reaction with Co ions and Fe ions to prevent metal ions from depositing, and contains C=O, the structure of the functional groups determines the adsorption strength of the composite leveling agent, the structure is not shared by electron pairs filled in an empty track of metal to realize continuous action with a substrate, the compounded additive is generally sulfur-containing molecules, the molecules have extremely strong adsorption characteristics, usually thiourea, and the molecules containing C=O in the benzalacetone are not strong in adsorption, but the benzalacetone can show strong adsorption performance through the conjugation of carbonyl groups and benzene ring and other structures of safflower when the leveling agent with high ring-shaped structure such as blue saffron is used, namely the benzalacetone is conjugated with the ring-shaped structure of the blue saffron, and the blue positively charged C=N has extremely strong adsorption characteristics of the cathode, so that the adsorption characteristic of a plating layer is achieved.
Complexing agent: sodium citrate, complex metal ions, avoids strong abnormal metal deposition behavior, and causes strong differences between the plating solution and the metal components of the plating layer.
The beneficial technical effects are as follows:
(1) The first proposal is that an acetic acid-sodium acetate buffer system is used for replacing boric acid buffer solution in the ferrocobalt plating solution, so that the pH=3.70+/-0.02 can be effectively maintained;
(2) By adding sorbitan monolaurate into the electroplating solution and compounding blue-light saffron and benzalacetone, the phenomenon of uneven plating layer when the thickness of the plating layer exceeds 50 microns is effectively avoided through mutual synergistic effect.
Drawings
FIG. 1 is an AFM image of a coating according to example 2 of the present application.
FIG. 2 is an AFM image of the coating of comparative example 2 of the present application.
FIG. 3 is an AFM image of the coating of comparative example 3 of the present application.
FIG. 4 is an AFM image of the coating of comparative example 4 of the present application.
FIG. 5 is an AFM image of the coating of comparative example 5 of the present application.
Detailed Description
The following describes in detail the examples of the present application, which are implemented on the premise of the technical solution of the present application, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present application is not limited to the following examples.
Example 1
A metal substrate electroplating solution is characterized in that the electroplating solution comprises the following components:
cobalt salt: coSO 4 . 7H2O: 0.1 mol；
Iron salt: feSO 4 . 7H2O:0.4 mol；
Acetic acid-sodium acetate buffer system;
conductive salt: naCl 5g/L;
and (2) a surfactant: sorbitan monolaurate, 0.5g/L;
composite leveling agent: blue light saffron and benzalacetone, wherein the blue light saffron is 1g/L; 1.5g/L of benzalacetone;
complexing agent: sodium citrate 2g/L
The balance of deionized water.
The pH=3.70+/-0.02, and the binary alloy plating layers obtained by the plating solution have extremely high flatness.
Electroplating parameters of the electroplating solution: temperature 20 o C, time 60min, current density 20mA/cm 2 。
Example 2
A metal substrate electroplating solution is characterized in that the electroplating solution comprises the following components:
cobalt salt: coSO 4 . 7H2O: 0.25mol/L；
Iron salt: feSO 4 . 7H2O:0.25 mol/L；
Acetic acid-sodium acetate buffer system;
conductive salt: 6g/L NaCl;
and (2) a surfactant: sorbitan monolaurate, 0.75g/L;
composite leveling agent: blue light saffron and benzalacetone, wherein the blue light saffron is 1.25g/L; 1.75g/L of benzalacetone;
complexing agent: sodium citrate 2.3g/L
The balance of deionized water.
The pH=3.70+/-0.02, and the binary alloy plating layers obtained by the plating solution have extremely high flatness.
Electroplating parameters of the electroplating solution: temperature 25 o C, time 90min, current density 25mA/cm 2 。
Designated S-2.
Example 3
A metal substrate electroplating solution is characterized in that the electroplating solution comprises the following components:
cobalt salt: coSO 4 . 7H2O: 0.4mol/L；
Iron salt: feSO 4 . 7H2O:0.1 mol；
Acetic acid-sodium acetate buffer system;
conductive salt: naCl 7 g/L;
and (2) a surfactant: sorbitan monolaurate, 1g/L;
composite leveling agent: blue light saffron and benzalacetone, wherein the blue light saffron is 1.5g/L; 2g/L of benzalacetone;
complexing agent: sodium citrate 2.5g/L
The balance of deionized water.
The pH=3.70+/-0.02, and the binary alloy plating layers obtained by the plating solution have extremely high flatness.
Electroplating parameters of the electroplating solution: temperature 30 o C, time 120min, current density 30mA/cm 2 。
Comparative example 1
A metal substrate electroplating solution is characterized in that the electroplating solution comprises the following components:
cobalt salt: coSO 4 . 7H2O: 0.25mol/L；
Iron salt: feSO 4 . 7H2O:0.25 mol/L；
Acetic acid-sodium acetate buffer system;
conductive salt: 6g/L NaCl;
complexing agent: sodium citrate 2.3g/L
The balance of deionized water.
The pH=3.70+/-0.02, and the binary alloy plating layers obtained by the plating solution have extremely high flatness.
Electroplating parameters of the electroplating solution: temperature 25 o C, time 90min, current density 25mA/cm 2 。
Designated as D-1.
Comparative example 2
A metal substrate electroplating solution is characterized in that the electroplating solution comprises the following components:
cobalt salt: coSO 4 . 7H2O: 0.25mol/L；
Iron salt: feSO 4 . 7H2O:0.25 mol/L；
Acetic acid-sodium acetate buffer system;
conductive salt: 6g/L NaCl;
composite leveling agent: blue light saffron and benzalacetone, wherein the blue light saffron is 1.25g/L; 1.75g/L of benzalacetone;
complexing agent: 2.3g/L
The balance of deionized water.
The pH=3.70+/-0.02, and the binary alloy plating layers obtained by the plating solution have extremely high flatness.
Electroplating parameters of the electroplating solution: temperature 25 o C, time 90min, current density 25mA/cm 2 。
Designated as D-2.
Comparative example 3
A metal substrate electroplating solution is characterized in that the electroplating solution comprises the following components:
cobalt salt: coSO 4 . 7H2O: 0.25mol/L；
Iron salt: feSO 4 . 7H2O:0.25 mol/L；
Acetic acid-sodium acetate buffer system;
conductive salt: 6g/L NaCl;
and (2) a surfactant: sorbitan monolaurate, 0.75g/L;
complexing agent: sodium citrate 2.3g/L
The balance of deionized water.
The pH=3.70+/-0.02, and the binary alloy plating layers obtained by the plating solution have extremely high flatness.
Electroplating parameters of the electroplating solution: temperature 25 o C, time 90min, current density 25mA/cm 2 。
Designated as D-3.
Comparative example 4
A metal substrate electroplating solution is characterized in that the electroplating solution comprises the following components:
cobalt salt: coSO 4 . 7H2O: 0.25mol/L；
Iron salt: feSO 4 . 7H2O:0.25 mol/L；
Acetic acid-sodium acetate buffer system;
conductive salt: 6g/L NaCl;
and (2) a surfactant: sorbitan monolaurate, 0.75g/L;
composite leveling agent: blue light saffron 1.25g/L;
complexing agent: sodium citrate 2.3g/L
The balance of deionized water.
The pH=3.70+/-0.02, and the binary alloy plating layers obtained by the plating solution have extremely high flatness.
Electroplating parameters of the electroplating solution: temperature 25 o C, time 90min, current density 25mA/cm 2 。
Designated as D-4.
Comparative example 5
A metal substrate electroplating solution is characterized in that the electroplating solution comprises the following components:
cobalt salt: coSO 4 . 7H2O: 0.25mol/L；
Iron salt: feSO 4 . 7H2O:0.25 mol/L；
Acetic acid-sodium acetate buffer system;
conductive salt: 6g/L NaCl;
and (2) a surfactant: sorbitan monolaurate, 0.75g/L;
composite leveling agent: benzylidene acetone, 1.75g/L;
complexing agent: sodium citrate 2.3g/L
The balance of deionized water.
The pH=3.70+/-0.02, and the binary alloy plating layers obtained by the plating solution have extremely high flatness.
Electroplating parameters of the electroplating solution: temperature 25 o C, time 90min, current density 25mA/cm 2 。
Designated as D-5.
First, the calculation formula of the relative flatness is as follows: the roughness of the substrate is about 1.3, and as those skilled in the art know, when the coating is lower, the flatness of the coating is closely related to the roughness of the substrate, and as the coating undulates and is electroplated, i.e., the flatness is generally absolute by the substrate, the lower the roughness of the substrate is, the uniformity of the coating is good, the flatness of the coating is high, and when the thickness of the coating, particularly the thickness of the cobalt-iron alloy coating of the present application is greater than 50 μm, a significant decrease in flatness occurs, thus requiring improvement with certain additives.
As shown in the table, in the embodiment 2 of the application, S-2, the roughness of the plating layer is obviously refined under the condition of adding the surfactant, the blue saffron and the benzalacetone simultaneously, as shown in the attached figure 1, the roughness is high at the thickness of 82.3 mu m, the roughness is 0.43 mu m, and the leveling effect is 0.675, compared with the roughness of D-1 of 8.32 mu m under the condition of not adding the surfactant, the blue saffron and the benzalacetone, the relative leveling degree is-5.303, namely the leveling effect is extremely poor according to the prior art.
As shown in fig. 2, no surfactant was added to the D-2 sample,
as shown in fig. 3, no composite leveler was added to the D-3 sample,
as shown in fig. 4, in the D-4 sample containing only saffron,
as shown in FIG. 5, the sample D-5 contained only benzalacetone,
the influence of the additive on the roughness and the flatness of the coating can be obviously and intuitively seen.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the application.
Claims (7)
1. A metal substrate electroplating solution is characterized in that the electroplating solution comprises the following components:
cobalt salt: coSO 4 . 7H 2 O: X mol/L，X=0.1-0.4；
Iron salt: feSO 4 . 7H 2 O: 0.5-X mol/L；
Acetic acid-sodium acetate buffer system;
conductive salt: naCl 5-7 g/L;
and (2) a surfactant: sorbitan monolaurate, 0.5-1g/L;
composite leveling agent: blue light saffron and benzalacetone, wherein the blue light saffron is 1-1.5g/L; 1.5-2g/L of benzalacetone;
complexing agent: 2-2.5g/L of sodium citrate;
the balance of deionized water,
the substrate to be plated by the electroplating solution is a metal substrate,
electroplating parameters of the electroplating solution: the temperature is 20-30deg.C, the time is 60-120min, and the current density is 20-30mA/cm 2 ，pH=3.70±0.02。
2. A metal substrate plating solution according to claim 1, wherein said plating solution provides a plating layer having a roughness of 0.4 to 0.5 μm and a relative flatness of 63.2 to 69.3%.
3. A metal substrate plating solution according to claim 2, wherein said plating layer is deposited at a rate of less than 1 μm/min.
4. A metal substrate plating solution according to claim 2, wherein said coating thickness is greater than 50 μm and less than 100 μm.
5. A metal substrate plating solution according to claim 1, wherein the error rate of the mole fraction of Fe in the plating solution to the mole fraction of Fe in the plating layer is greater than 15%.
6. A metal substrate plating solution according to claim 2, wherein said average particle size of CoFe in said coating is 10-20nm.
7. A metal substrate plating solution according to claim 2, wherein said plating layer is a magnetic plating layer having a coercive force Hc of 8-30Oe.
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| CN1178259A (en) * | 1997-08-26 | 1998-04-08 | 北京科技大学 | Solution and coating method for chemically plating amorphous nickel, chromium and phosphur alloys |
| CN1362541A (en) * | 2001-12-20 | 2002-08-07 | 周益春 | Electroplasting solution for electrodeposition of bright ZnFe alloy with low Fe content from sulfate system |
| CN103014792A (en) * | 2012-12-13 | 2013-04-03 | 合肥华清方兴表面技术有限公司 | Tin-cobalt alloy decorative chromium-substituted electroplate liquid and electroplate method thereof |
| CN107142503A (en) * | 2017-05-27 | 2017-09-08 | 中国科学院金属研究所 | A kind of Fe Ni P or Fe Ni P RE amorphous alloy coatings and its electro-deposition plating solution and electro-deposition method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1178259A (en) * | 1997-08-26 | 1998-04-08 | 北京科技大学 | Solution and coating method for chemically plating amorphous nickel, chromium and phosphur alloys |
| CN1362541A (en) * | 2001-12-20 | 2002-08-07 | 周益春 | Electroplasting solution for electrodeposition of bright ZnFe alloy with low Fe content from sulfate system |
| CN103014792A (en) * | 2012-12-13 | 2013-04-03 | 合肥华清方兴表面技术有限公司 | Tin-cobalt alloy decorative chromium-substituted electroplate liquid and electroplate method thereof |
| CN107142503A (en) * | 2017-05-27 | 2017-09-08 | 中国科学院金属研究所 | A kind of Fe Ni P or Fe Ni P RE amorphous alloy coatings and its electro-deposition plating solution and electro-deposition method |
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