CN117165942A - Plating process of diamond/copper composite material - Google Patents
Plating process of diamond/copper composite material Download PDFInfo
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- CN117165942A CN117165942A CN202311154301.5A CN202311154301A CN117165942A CN 117165942 A CN117165942 A CN 117165942A CN 202311154301 A CN202311154301 A CN 202311154301A CN 117165942 A CN117165942 A CN 117165942A
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- diamond
- composite material
- copper composite
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- plating
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- 239000002131 composite material Substances 0.000 title claims abstract description 127
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 125
- 239000010432 diamond Substances 0.000 title claims abstract description 125
- 239000010949 copper Substances 0.000 title claims abstract description 116
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 115
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 238000007747 plating Methods 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000008569 process Effects 0.000 title claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 164
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 81
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052737 gold Inorganic materials 0.000 claims abstract description 44
- 239000010931 gold Substances 0.000 claims abstract description 44
- 238000009713 electroplating Methods 0.000 claims abstract description 23
- 238000005238 degreasing Methods 0.000 claims abstract description 20
- 206010070834 Sensitisation Diseases 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 230000008313 sensitization Effects 0.000 claims abstract description 14
- 238000005488 sandblasting Methods 0.000 claims abstract description 10
- 238000000137 annealing Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 61
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- 230000003213 activating effect Effects 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 6
- 229960003975 potassium Drugs 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims description 6
- 239000004576 sand Substances 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- 238000005282 brightening Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- MXZVHYUSLJAVOE-UHFFFAOYSA-N gold(3+);tricyanide Chemical compound [Au+3].N#[C-].N#[C-].N#[C-] MXZVHYUSLJAVOE-UHFFFAOYSA-N 0.000 claims description 5
- 239000001119 stannous chloride Substances 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000001508 potassium citrate Substances 0.000 claims description 3
- 229960002635 potassium citrate Drugs 0.000 claims description 3
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 3
- 235000011082 potassium citrates Nutrition 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000001509 sodium citrate Substances 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
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- 238000003466 welding Methods 0.000 abstract description 10
- 238000004381 surface treatment Methods 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 230000008719 thickening Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000017525 heat dissipation Effects 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- 229910018104 Ni-P Inorganic materials 0.000 description 4
- 229910018536 Ni—P Inorganic materials 0.000 description 4
- 238000001994 activation Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000004100 electronic packaging Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- YTQVHRVITVLIRD-UHFFFAOYSA-L thallium sulfate Chemical compound [Tl+].[Tl+].[O-]S([O-])(=O)=O YTQVHRVITVLIRD-UHFFFAOYSA-L 0.000 description 3
- 229940119523 thallium sulfate Drugs 0.000 description 3
- 229910000374 thallium(I) sulfate Inorganic materials 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 241000080590 Niso Species 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- JVPLOXQKFGYFMN-UHFFFAOYSA-N gold tin Chemical group [Sn].[Au] JVPLOXQKFGYFMN-UHFFFAOYSA-N 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000013072 incoming material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005493 welding type Methods 0.000 description 1
Landscapes
- Chemically Coating (AREA)
Abstract
The invention belongs to the technical field of surface treatment, and particularly relates to a plating process of a diamond/copper composite material. The process of the invention comprises the following steps: degreasing, drying, sand blasting, degreasing, acid washing, sensitization, activation, electroless nickel plating, impact nickel, electroplating nickel, pre-plating gold, electroplating gold, and low-temperature annealing. According to the invention, aiming at the diamond grain size corresponding to different electroplating pretreatment process parameters, the uniform and compact plating layer is deposited on the surface of the diamond, and the stress between the surface of the composite material and the plating layer is reduced in a stepped heating mode, so that the binding force is improved, and the technical requirements of diamond/copper welding are met.
Description
Technical Field
The invention belongs to the technical field of surface treatment, and particularly relates to a plating process of a diamond/copper composite material.
Background
The electronic packaging shell is used for bearing the basic requirements of electronic components, such as certain mechanical strength, conductivity, heat dissipation, sealing and the like, and with the development of modern science and technology, the electronic packaging shell has the requirements of small volume, light weight and densification, so that the traditional metal packaging material cannot meet the requirement of heat dissipation of modern electronic components. The diamond/copper composite material has excellent performance of copper and diamond, has higher heat conductivity and adjustable thermal expansion coefficient, can replace materials such as Cu, W-Cu, mo-Cu and the like which are conventionally used as a base, a heat sink and the like of a high-power electronic component, and effectively solves the heat dissipation problem of the microwave power component.
However, the diamond and copper metal have high interface energy, and are not easy to be infiltrated by the metal and the brazing filler metal, and can not be directly welded, so that the diamond copper composite material is subjected to surface treatment, and a solderable coating with good adhesion performance is formed on the surface of the diamond copper composite material, so that a good heat path can be formed between the diamond copper composite material and a heat dissipation substrate, and the purpose of heat dissipation is achieved. In the electronic packaging process, the most commonly used solder is gold-tin solder (80 wt% Au20wt% Sn), so that nickel plating and gold plating treatment are required to be carried out on the surface of a welding piece, wherein nickel is used as a prime plating layer, and the gold plating layer on the surface can ensure good wettability and spreadability of the solder on the surface of a workpiece and prevent defects such as cold joint, air holes and the like.
Since diamond is an elemental crystal composed of one carbon element formed under high temperature and high pressure conditions. The C-C bond in the diamond is strong, all valence electrons participate in the formation of covalent bonds, and free electrons are not available, so that the conductivity of the diamond is poor, the diamond/copper composite material cannot be directly electroplated on the surface of the composite material by an electroplating technology, and even if the electroplating technology is used for directly electroplating nickel on the surface of the composite material, the bonding force of the diamond and a coating is poor, the coating is easy to peel off, and the application requirements cannot be met, and the method specifically comprises the following steps:
1. when the catalysis of the diamond/copper composite material surface is deficient, the plating leakage phenomenon exists on the diamond surface plating layer;
2. when the surface catalysis of the diamond/copper composite material is excessive, the deposited chemical nickel layer is caused to be nodulated, the binding force is poor and the like;
3. after the surface of the diamond/copper composite material is plated with thicker nickel and gold plating layers, the interface stress between the plating layers and the base material is increased, and the problem of poor binding force exists when the diamond/copper composite material is directly used.
Disclosure of Invention
To overcome the above-described drawbacks of the prior art, the present invention provides a diamond/copper composite plating process. The invention reduces the stress between the surface of the composite material and the plating layer in a stepped heating mode, thereby improving the binding force and meeting the technical requirements of diamond/copper welding.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a plating process of a diamond/copper composite material comprises the following specific steps:
s1, degreasing: placing the diamond/copper composite material into a degreasing liquid, treating the composite material for 10 to 15 minutes by using ultrasonic waves of 28 to 40KHz, taking out the composite material, and cleaning the composite material with water;
s2, drying: drying the diamond/copper composite material at 80-120 ℃ for 30-40 min;
s3, sand blasting:coarsening and leveling the surface of the diamond/copper composite material by using 100-400 mesh silicon carbide sand (or glass beads, etc.), wherein the sand blasting pressure is 0.2-2 kg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The surface roughness of the composite material can be increased by sand blasting, so that the surface is more uniform, and a certain amount of roughness is an effective measure for improving the binding force between the substrate and the coating;
s4, degreasing: soaking the diamond/copper composite material in deoiling liquid at 50-70 deg.c for 10-15 min, taking out and rinsing with water;
s5, acid washing: soaking the diamond/copper composite material in pickling solution at 40-70 deg.c for 1-2 min, taking out and rinsing with water;
s6, sensitization: soaking the diamond/copper composite material in sensitization solution with the solution temperature of 30-40 ℃ for 1-5 min, taking out and rinsing with water;
s7, activating: soaking the diamond/copper composite material in an activating solution with the solution temperature of 30-40 ℃ for 0.5-3 min, taking out and rinsing with water;
s8, chemical nickel plating: placing the diamond/copper composite material into an electroless nickel plating solution with the solution temperature of 85-92 ℃ for 20-30 min;
s9, impact nickel: placing the diamond/copper composite material into an impact nickel solution with the solution temperature of 30-50 ℃ for plating for 1-3 min, taking out and rinsing with water;
s10, electroplating nickel: placing the diamond/copper composite material into a nickel plating solution with the solution temperature of 50-55 ℃ for plating for 20-40 min, taking out and rinsing with water;
s11, pre-plating gold: placing the diamond/copper composite material into a preplating solution with the solution temperature of 50-60 ℃ for plating for 10-30 s, taking out and rinsing with water;
s12, electroplating gold: placing the diamond/copper composite material into a neutral cyanide gold plating solution with the solution temperature of 55-70 ℃ for plating for 5-10 min, taking out, rinsing with water, and drying;
s13, low-temperature annealing: and the temperature is raised stepwise to discharge water vapor in the diamond/copper base material and the coating of the diamond/copper composite material, the baking temperature is 100-420 ℃, and the baking time is 3-5 h.
Preferably, the degreasing liquid in the step S1 and the step S4 are composed of 60-80 g/L sodium hydroxide, 30-50 g/L sodium carbonate, 10-20 g/L sodium metasilicate, 3-5 g/L sodium dodecyl sulfonate and deionized water. Since the oil stain in step S4 is less than that in step S1, the content of each component of the degreasing fluid other than deionized water in step S4 may be lower than that of each component of the degreasing fluid other than deionized water in step S1.
Preferably, the pickling solution in the step S5 consists of deionized water and 10-20% of concentrated sulfuric acid by volume, wherein the mass ratio of the concentrated sulfuric acid is 98%.
Preferably, in the step S6, the sensitizing solution consists of 10-30 g/L stannous chloride (SnCl) 2 ) 30-60 mL/L hydrochloric acid (HCl) and deionized water.
Preferably, the activating solution in step S7 is composed of 0.2 to 1.0g/L of palladium chloride (PdCl 2 ) 10-30 mL/L hydrochloric acid (HCl) and deionized water.
Preferably, the electroless nickel plating solution in step S8 is composed of 25 to 30g/L nickel sulfate (NiSO 4 ·6H 2 O), 20-30 g/L sodium hypophosphite (NaH) 2 PO 2 ·H 2 O), 15-20 g/L sodium acetate (NaAc.3H) 2 O), 10-15 g/L sodium citrate (Na) 3 C 6 H 5 O 7 ·2H 2 O), 1-4 mg/L of additive and deionized water; the pH value of the electroless nickel plating solution is 4.2-5.1; the temperature of the chemical nickel plating solution is 85-92 ℃, and the thickness of the nickel plating layer in the step S8 is 2-4 mu m. The additive is one of a stabilizer or a surfactant.
Preferably, the impact nickel solution in the step S9 consists of 120-200 mL/L of concentrated hydrochloric acid with the mass percentage of 37.5%, 180-240 g/L of nickel chloride and deionized water.
Preferably, the nickel plating solution in the step S10 consists of 220-450 g/L nickel sulfamate, 5-15 g/L nickel chloride, 25-50 g/L boric acid, 0.1-1 g/L sodium dodecyl sulfate and deionized water; the thickness of the nickel plating layer in the step S10 is 2-5 mu m.
Preferably, the pre-gold plating solution in the step S11 consists of 1-2 g/L of potassium aurous cyanide, 1-3 g/L of potassium cyanide, 15-25 g/L of dipotassium hydrogen phosphate, 1-2 g/L of brightening agent and deionized water.
Preferably, the neutral cyanide gold plating solution in the step S12 consists of 8-12 g/L of potassium aurous cyanide, 1-3 g/L of potassium cyanide, 50-125 g/L of potassium citrate, 3-3 g/L of additives (such as brightening agent (thallium sulfate), stabilizing agent and the like) and deionized water; the thickness of the gold plating layer in the step S12 is 1.3-5.7 mu m; step S13, wherein the temperature is raised stepwise and is sequentially kept at 100 ℃ for 30min, 150 ℃ for 30min, 200 ℃ for 30min, 250 ℃ for 120min and 380 ℃ for 30min; the diamond particle size in the diamond/copper composite material is 50 to 400 mesh, preferably 100 to 250 mesh.
The invention has the advantages that:
(1) The invention solves the problems of poor bonding force and missed plating of the composite material with the diamond granularity of 50-400 meshes in the prior plating technology, and realizes the plating process of the diamond/copper composite material by carrying out chemical nickel plating, electroplating nickel and gold plating on the surface of the diamond/copper composite material.
(2) The invention designs a process formula matched with the diamond/copper composite material and the diamond grain size in the diamond/copper composite material to correspond to different electroplating pretreatment process parameters, so that a uniform and compact plating layer is deposited on the surface of the diamond/copper composite material, and the stress between the surface of the composite material and the plating layer is reduced in a stepped heating mode, thereby improving the binding force and meeting the technical requirements of diamond/copper welding.
(3) The invention is suitable for the nickel plating and gold plating process with the diamond granularity of 50-400 meshes in diamond/copper, the plating layer meets the welding requirement of less than or equal to 450 ℃, the welding type has wider application range, the pretreatment formula is simple, the parameter range is wide, the management and control are mature, and the yield is high.
(5) The key of the nickel plating and gold plating process technology of the diamond/copper composite material is that a layer of uniform catalytic crystal nucleus is formed on the surface of the diamond/copper after sensitization and activation, so that a layer of uniform and compact Ni-P layer can be deposited, and the nickel plating layer and the gold plating layer with certain thickness can be plated in the subsequent working procedure; the diamond/copper composite material plating process of the invention coarsens, sensitizes and activates the surface of the base material through the pretreatment process, firstly deposits a uniform and compact chemical nickel plating layer, then carries out nickel and gold electroplating, and ensures that the surface of the diamond/copper composite material is plated with a uniform and compact plating layer with good bonding force by an auxiliary low-temperature annealing method.
Drawings
Fig. 1 is a schematic view of a diamond/copper composite structure according to the present invention.
Fig. 2 is a schematic diagram of a sensitization process of a diamond/copper composite material according to the present invention.
Fig. 3 is a schematic representation of the activation process of the diamond/copper composite material of the present invention.
Fig. 4 is a schematic diagram of the chemical nickel plating deposition principle of the diamond/copper composite material of the invention.
Detailed Description
The present invention will be further described in detail with reference to the drawings and examples, wherein all other examples, which are obtained by a person skilled in the art without making any inventive effort, are included in the scope of the present invention.
As shown in fig. 1-4, a diamond/copper composite plating process comprises the steps of:
s1, degreasing: and (3) machining greasy dirt on the surface of the diamond/copper composite material (figure 1) by using a degreasing solution, performing ultrasonic treatment for 10-15 min at 28-40 KHz, taking out, and cleaning with water.
S2, drying: the cleaning water on the surface of the diamond/copper composite material is removed, the temperature is 80-120 ℃, and the drying time is 30-40 min.
S3, sand blasting: coarsening and leveling the surface of the diamond/copper composite material, using 100-400 mesh silicon carbide sand (cutting sand), and the sand blasting pressure is 0.2-2 kg/cm 2；
S4, degreasing: removing fingerprint and greasy dirt on the surface of the diamond/copper composite material, soaking the diamond/copper composite material in the degreasing liquid at the solution temperature of 50-70 ℃ for 10-15 min, taking out and rinsing with water.
S5, acid washing: removing rust and oxide on the surface of the diamond/copper composite material, soaking the diamond/copper composite material in pickling solution at the solution temperature of 40-70 ℃ for 1-2 min, taking out and rinsing with water; the pickling solution is formed by fully mixing 10-20% concentrated sulfuric acid (the mass ratio is 98%) and deionized water;
s6, sensitization: adsorption of Sn with reducing ability to the surface of diamond/copper composite (FIG. 2) 2+ Soaking in sensitization solution at 30-40 ℃ for 1-5 min, taking out and rinsing with water; the sensitization process formula comprises the following steps: stannous chloride (SnCl) 2 ) 10-30 g/L, 30-60 mL/L hydrochloric acid (HCl) and deionized water;
s7, activating: reducing a layer of simple substance Pd on the surface of the diamond/copper composite material (figure 3) to form a catalytic center, soaking the diamond/copper composite material in an activating solution with the solution temperature of 30-40 ℃ for 0.5-3 min, taking out and rinsing with water; the activating solution is prepared from palladium chloride (PdCl) 2 ) 0.2-1.0 g/L, 10-30 mL/L hydrochloric acid (HCl) and deionized water;
s8, chemical nickel plating: depositing a uniform Ni-P coating on the surface of the diamond/copper composite material (figure 4); the temperature of the chemical nickel solution is 85-92 ℃ and the time is 20-30 min; the chemical nickel solution is prepared from nickel sulfate (NiSO 4 ·6H 2 O) 25-30 g/L sodium hypophosphite (NaH) 2 PO 2 ·H 2 O) 20-30 g/L, sodium acetate (NaAc.3H) 2 O) 15-20 g/L, sodium citrate (Na) 3 C 6 H 5 O 7 ·2H 2 O) 10-15 g/L, other additives 1-4 mg/L, and rest deionized water, wherein the pH value is 4.2-5.1, the temperature is 85-92 ℃, and the thickness of the nickel plating layer is 2-4 mu m.
S9, impact nickel: enhancing the binding force of chemical nickel and an electroplated nickel layer, plating the diamond/copper composite material in an acidic nickel plating solution (namely an impact nickel solution) with the temperature of 30-50 ℃ for 1-3 min, taking out and rinsing with water; the impact nickel solution is formed by fully mixing 120-200 mL/L of concentrated hydrochloric acid with the mass percentage of 37.5 percent, 180-240 g/L of nickel chloride and deionized water.
S10, electroplating nickel: thickening a nickel layer by adopting nickel sulfamate, plating the diamond/copper composite material in a nickel plating solution with the temperature of 50-55 ℃ for 20-40 min, taking out and rinsing with water; the nickel sulfamate solution is formed by fully mixing 220-450 g/L of nickel sulfamate, 5-15 g/L of nickel chloride, 25-50 g/L of boric acid, 0.1-1 g/L of sodium dodecyl sulfate and deionized water, wherein the thickness of a nickel plating layer is 2-5 mu m.
S11, pre-plating gold: a thin gold layer is quickly plated on the surface of the diamond/copper composite material, the bonding force between the gold layer and the nickel layer is enhanced, acidic low-concentration gold solution is adopted to plate in a pre-gold plating solution with the temperature of 50-60 ℃ for 10-30 s, and the gold solution is taken out and rinsed with water; the pre-gold plating solution is formed by fully mixing 1-2 g/L of potassium aurous cyanide, 1-3 g/L of potassium cyanide, 15-25 g/L of dipotassium hydrogen phosphate, 1-2 g/L of brightening agent (such as thallium sulfate) and deionized water;
s12, electroplating gold: thickening the thickness of a gold layer on the surface of the diamond/copper composite material by adopting a neutral cyanide system gold plating solution, plating for 5-10 min in a gold plating solution with the temperature of 55-70 ℃, taking out, rinsing with water, and drying; the neutral cyanide gold plating solution is formed by fully mixing 8-12 g/L of potassium aurous cyanide, 1-3 g/L of potassium cyanide, 50-125 g/L of potassium citrate, 3-3 g/L of additives (brightening agent (thallium sulfate, stabilizing agent, etc.) and deionized water; the thickness of the gold plating layer is 1.3-5.7 mu m;
s13, low-temperature annealing: the temperature is raised stepwise to discharge water vapor in the diamond/copper base material and the coating, the molecular diffusion is facilitated to improve the bonding force of the coating at the temperature, the welding requirement is met, the baking temperature is 100-420 ℃, and the baking time is 3-5 h. The step-type temperature rise is specifically as follows: the heat preservation is carried out for 30min at 100 ℃, 30min at 150 ℃, 30min at 200 ℃, 120min at 250 ℃ and 30min at 380 ℃, so that water vapor between the substrate and the coating is discharged completely, stress is eliminated, intermolecular diffusion is facilitated, the bonding force of the coating is improved, and the welding requirement is met.
Wherein, the degreasing solution in the steps S1 and S4 is formed by fully mixing 60-80 g/L of sodium hydroxide, 30-50 g/L of sodium carbonate, 10-20 g/L of sodium metasilicate, 3-5 g/L of sodium dodecyl sulfate and the rest deionized water. In fig. 1: diamond particles (50-400 mesh) are distributed in the copper substrate. In fig. 2: diamond/copper substrate on Sn-containing 2+ Sensitization in solutionAnd (5) melting. In fig. 3: pd-containing diamond/copper substrate 2+ And (3) activating in the solution to form catalytic crystal nuclei. In fig. 4: the diamond/copper substrate was deposited with a nickel plating layer in an electroless nickel plating solution.
Example 1 (100 mesh diamond/copper composite Nickel plating gold plating Process)
S1, degreasing: and (3) carrying out ultrasonic treatment for 15min at 28KHz, and removing the machining greasy dirt on the surface of the diamond/copper composite material.
S2, drying: drying at 120 ℃ for 40min, and removing the cleaning moisture on the surface of the diamond/copper composite material.
S3, sand blasting: 0.5kg/cm 2 And (3) cutting sand, and carrying out physical roughening and leveling on the surface of the diamond/copper composite material.
S4, degreasing: and (3) removing fingerprint and greasy dirt on the surface of the diamond/copper composite material for 15 min.
S5, acid washing: and (3) removing oxide and rust products on the surface of the diamond/copper composite material for 1.5 min.
S6, sensitization: 2min, adsorbing a layer of Sn with reducing capability on the surface of the diamond/copper composite material 2+ Ensures that the reduction reaction occurs in the activation process to generate metallic palladium, thereby forming catalytic crystal nucleus.
S7, activating: and forming a layer of catalytic center on the surface of the diamond/copper composite material for 1 min.
S8, chemical nickel plating: depositing a uniform compact Ni-P coating on the surface of the diamond/copper composite material for 25min
S9, impact nickel: 2min, high-concentration nickel electroplating with stronger acidity is adopted, so that the binding force between the nickel electroplating layer and the bottom nickel is enhanced.
S10, electroplating nickel: and (3) thickening the nickel layer for 30min by adopting nickel sulfamate with higher nickel ion concentration, so that the uniformity of the nickel layer is improved.
S11, pre-plating gold: and 20s, the binding force of the gold layer and the nickel layer is enhanced.
S12, electroplating gold: and (3) thickening the gold layer by adopting a neutral cyanide system gold plating solution for 8 min.
S13, low-temperature annealing: and heating to 380 ℃ in a stepwise manner, and baking for 3 hours to obtain the composite material 1.
Example 2 (400 mesh diamond/copper composite Nickel plating gold plating Process)
S1, degreasing: and (3) carrying out ultrasonic treatment for 15min at 28KHz, and removing the machining greasy dirt on the surface of the diamond/copper composite material.
S2, drying: drying at 120 ℃ for 40min, and removing the cleaning moisture on the surface of the diamond/copper composite material.
S3, sand blasting: 2kg/cm 2 And (3) cutting sand, and carrying out physical roughening and leveling on the surface of the diamond/copper composite material.
S4, degreasing: and (3) removing fingerprint and greasy dirt on the surface of the diamond/copper composite material for 15 min.
S5, acid washing: and (3) removing oxide and rust products on the surface of the diamond/copper composite material for 2 min.
S6, sensitization: 1min, adsorbing a layer of Sn with reducing capability on the surface of the diamond/copper composite material 2+ Ensures that the reduction reaction occurs in the activation process to generate metallic palladium, thereby forming catalytic crystal nucleus.
S7, activating: and 30s, forming a layer of catalytic center on the surface of the diamond/copper composite material.
S8, chemical nickel plating: and (3) depositing a layer of uniform and compact Ni-P coating on the surface of the diamond/copper composite material for 25 min.
S9, impact nickel: 2min, high-concentration nickel electroplating with stronger acidity is adopted, so that the binding force between the nickel electroplating layer and the bottom nickel is enhanced.
S10, electroplating nickel: and (3) thickening the nickel layer for 30min by adopting nickel sulfamate with higher nickel ion concentration, so that the uniformity of the nickel layer is improved.
S11, pre-plating gold: and 20s, the binding force of the gold layer and the nickel layer is enhanced.
S12, electroplating gold: and (3) thickening the gold layer by adopting a neutral cyanide system gold plating solution for 8 min.
S13, low-temperature annealing: and heating to 380 ℃ in a stepwise manner, and baking for 3 hours to obtain the composite material 2.
1. The composite materials prepared in example 1 and example 2 were subjected to heat preservation at 450 ℃ for 5min, and then examined under a 25-fold microscope for no phenomena such as coating swelling, peeling, cracking, and the like.
2. The coating thickness of the composite material of examples 1-2 was measured using a phenanthrell X-Ray fluorescent thickness meter, germany, wherein the nickel layer thickness of the composite material 1 was 8.2 microns and the gold layer thickness was 1.33 microns; the nickel layer of the composite material 2 had a thickness of 6.7 microns and the gold layer had a thickness of 1.49 microns.
3. The surface roughness of the composite of examples 1-2 was tested, the roughness of the finished composite 1 was 0.96 microns and the roughness of the machined feed was 0.55 microns; the roughness of the composite material 2 was 0.91 microns and the roughness of the machined incoming material was 0.53 microns.
4. Detecting the welding performance of the composite materials of the examples 1-2, and welding by using gold-tin (80 wt%Au20wt%Sn) solder, wherein both the composite material 1 and the composite material 2 meet the requirements of solder flow and welding strength;
5. salt spray performance of the composite materials of examples 1-2 was tested, and both composite material 1 and composite material 2 met the test result of GJB548 condition C.
The above embodiments are merely preferred embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of the present invention.
Claims (10)
1. The plating process of the diamond/copper composite material is characterized by comprising the following specific steps:
s1, degreasing: placing the diamond/copper composite material into a degreasing liquid, treating the composite material for 10 to 15 minutes by using ultrasonic waves of 28 to 40KHz, taking out the composite material, and cleaning the composite material with water;
s2, drying: drying the diamond/copper composite material at 80-120 ℃ for 30-40 min;
s3, sand blasting: coarsening and leveling the surface of the diamond/copper composite material by using 100-400 mesh silicon carbide sand, wherein the sand blasting pressure is 0.2-2 kg/cm 2 ；
S4, degreasing: soaking the diamond/copper composite material in deoiling liquid at 50-70 deg.c for 10-15 min, taking out and rinsing with water;
s5, acid washing: soaking the diamond/copper composite material in pickling solution at 40-70 deg.c for 1-2 min, taking out and rinsing with water;
s6, sensitization: soaking the diamond/copper composite material in sensitization solution with the solution temperature of 30-40 ℃ for 1-5 min, taking out and rinsing with water;
s7, activating: soaking the diamond/copper composite material in an activating solution with the solution temperature of 30-40 ℃ for 0.5-3 min, taking out and rinsing with water;
s8, chemical nickel plating: placing the diamond/copper composite material into an electroless nickel plating solution with the solution temperature of 85-92 ℃ for 20-30 min;
s9, impact nickel: placing the diamond/copper composite material into an impact nickel solution with the solution temperature of 30-50 ℃ for plating for 1-3 min, taking out and rinsing with water;
s10, electroplating nickel: placing the diamond/copper composite material into a nickel plating solution with the solution temperature of 50-55 ℃ for plating for 20-40 min, taking out and rinsing with water;
s11, pre-plating gold: placing the diamond/copper composite material into a preplating solution with the solution temperature of 50-60 ℃ for plating for 10-30 s, taking out and rinsing with water;
s12, electroplating gold: placing the diamond/copper composite material into a neutral cyanide gold plating solution with the solution temperature of 55-70 ℃ for plating for 5-10 min, taking out, rinsing with water, and drying;
s13, low-temperature annealing: and the temperature is raised stepwise to discharge water vapor in the diamond/copper base material and the coating of the diamond/copper composite material, the baking temperature is 100-420 ℃, and the baking time is 3-5 h.
2. A diamond/copper composite plating process according to claim 1, wherein: the oil removing liquid in the step S1 and the step S4 consists of 60-80 g/L sodium hydroxide, 30-50 g/L sodium carbonate, 10-20 g/L sodium metasilicate, 3-5 g/L sodium dodecyl sulfonate and deionized water.
3. A diamond/copper composite plating process according to claim 1, wherein: the pickling solution in the step S5 consists of deionized water and 10-20% of concentrated sulfuric acid by volume, wherein the mass ratio of the concentrated sulfuric acid is 98%.
4. A diamond/copper composite plating process according to claim 1, wherein: the sensitization liquid in the step S6 consists of 10-30 g/L stannous chloride, 30-60 mL/L hydrochloric acid and deionized water.
5. A diamond/copper composite plating process according to claim 1, wherein: the activating solution in the step S7 consists of 0.2-1.0 g/L palladium chloride, 10-30 mL/L hydrochloric acid and deionized water.
6. A diamond/copper composite plating process according to claim 1, wherein: the chemical nickel plating solution in the step S8 consists of 25-30 g/L nickel sulfate, 20-30 g/L sodium hypophosphite, 15-20 g/L sodium acetate, 10-15 g/L sodium citrate, 1-4 mg/L additive and deionized water; the pH value of the electroless nickel plating solution is 4.2-5.1; the temperature of the chemical nickel plating solution is 85-92 ℃, and the thickness of the nickel plating layer in the step S8 is 2-4 mu m.
7. A diamond/copper composite plating process according to claim 1, wherein: the impact nickel solution in the step S9 consists of concentrated hydrochloric acid with the mass percentage of 37.5% of 120-200 mL/L, nickel chloride with the mass percentage of 180-240 g/L and deionized water.
8. A diamond/copper composite plating process according to claim 1, wherein: the nickel plating solution in the step S10 consists of 220-450 g/L nickel sulfamate, 5-15 g/L nickel chloride, 25-50 g/L boric acid, 0.1-1 g/L sodium dodecyl sulfate and deionized water; the thickness of the nickel plating layer in the step S10 is 2-5 mu m.
9. A diamond/copper composite plating process according to claim 1, wherein: the pre-gold plating solution in the step S11 consists of 1-2 g/L of potassium aurous cyanide, 1-3 g/L of potassium cyanide, 15-25 g/L of dipotassium hydrogen phosphate, 1-2 g/L of brightening agent and deionized water.
10. A diamond/copper composite plating process according to claim 1, wherein: the neutral cyanide gold plating solution in the step S12 consists of 8-12 g/L of potassium aurous cyanide, 1-3 g/L of potassium cyanide, 50-125 g/L of potassium citrate, 3-3 g/L of additive and deionized water; the thickness of the gold plating layer in the step S12 is 1.3-5.7 mu m; the step-type heating in the step S13 is sequentially carried out at 100 ℃ for 30min, at 150 ℃ for 30min, at 200 ℃ for 30min, at 250 ℃ for 120min and at 380 ℃ for 30min; the diamond particle size of the diamond/copper composite material is 50-400 meshes.
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