CN102534732B - Pulse-electrodeposited Ni-Co-P/HBN composite plating and preparation method thereof - Google Patents
Pulse-electrodeposited Ni-Co-P/HBN composite plating and preparation method thereof Download PDFInfo
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Abstract
A pulse-electrodeposited Ni-Co-P/HBN composite plating and a preparation method thereof. The preparation method adopts a metal material as a substrate, and comprises the following steps: firstly pretreating the substrate surface, preparing a composite plating solution with nickel sulfate, cobalt chloride, sodium hypophosphite, citric acid, trisodium citrate, boric acid, and polyvinyl alcohol as main components and hexagonal boron nitride HBN powder as a dispersed phase, performing surface modification and dispersion treatment of the HBN particles by using a surfactant through ultrasonic vibration, allowing the HBN particles to disperse uniformly in the plating solution through reasonable setting of pulse electrodeposition parameters and full stirring, performing codeposition and heat treatment of the HBN particles and the substrate metal nickel cobalt phosphor in a state of applying pulsed current so as to obtain a corrosion-resistant, wear-resistant and antifriction pulse-electrodeposited Ni-Co-P/HBN composite plating. The invention overcomes defects of single component of current composite plating, coarse plating crystal grain, low interface bonding strength with the substrate, non-ideal comprehensive properties of corrosion resistance, wear resistance, and antifriction, and the like; the pulse-electrodeposited Ni-Co-P/HBN composite plating of the invention is applicable to wear-resistant, antifriction and corrosion-resistant surface plating of friction kinematic pair parts in industries of machinery, metallurgy, chemical engineering, and the like.
Description
Technical field
The present invention relates to pulse electrodeposition Ni-Co-P/HBN composite deposite and preparation method thereof.
Background technology
The high rigidity of Ni-P alloy layer, high-wearing feature and high corrosion resistance, make it at machinery, oil, be used widely in the fields such as chemical industry, particularly in nickel-phosphor bath, add insoluble solia particle, make matrix metal and solia particle codeposition and form better nickel-phosphorus composite deposit, such nickel-phosphorus composite deposit can further improve structure of plating layer and performance, as finer and close in the weave construction of composite deposite, their physical and chemical performance, thermal stability, wear resistant friction reducing performance is further enhanced, multi-functional composite deposite has become matrix material preparation, the new developing direction of material surface modifying, its research contents relates to bath system, dispersed particle is at the electrochemical properties of cathode surface, the surface tissue of dispersed particle on the Cathodic polarization behavior of particle and in matrix metal deposition affect the aspects such as rule.Even in bath system of the same race, different dispersed particles is due to surface tissue and charged different in kind, their depositions in matrix metal have very big difference, be that some particle is easier to deposition in certain plating solution, and the deposition of some particle seldom or hardly deposits, thereby the finishing of dispersed particle is very crucial for the successful preparation of composite deposite; The bath stability of chemical Ni-P plating composite deposite is poor, and dispersed particle more easily aggravates plating solution and decomposes, and makes plating solution short work-ing life, and secondly, the required bath temperature of chemical Ni-P plating composite deposite is higher, and sedimentation velocity is slower, and energy consumption is many, and tooling cost is high; In recent years, impulse electrodeposition technology, because its current efficiency is high, coating is fine and close, crystal grain is tiny, arouses extensive attention at home and abroad.Hexagonal boron nitride HBN belongs to hexagonal system, it is a kind of laminate structure of similar graphite, there is chemistry, Heat stability is good and good antifriction performance, study new bath system, the modification of surfactant types to HBN particle, refinement coating tissue, improve the deposition of HBN particle in composite deposite, the antifriction characteristic of performance HBN particle in composite deposite, makes electro-deposition techniques in industrial applications, bring into play larger effect.
Summary of the invention
The object of this invention is to provide a kind of pulse electrodeposition Ni-Co-P/HBN composite deposite and preparation method thereof, the pulse electrodeposition Ni-Co-P/HBN composite deposite of preparing by this preparation method had both had excellent wear resistant friction reducing performance, there is again good anti-corrosion performance, also there is preparation technology simple, reliable, processing ease, is beneficial to suitability for industrialized production, and production cost is low, free from environmental pollution, be convenient to penetration and promotion.
For achieving the above object, a kind of pulse electrodeposition Ni-Co-P/HBN composite deposite, with metallic substance, make matrix, first matrix surface is carried out to pre-treatment, being equipped with nickel is the composite plating bath that main ingredient, hexagonal boron nitride HBN powder are disperse phase again, the matrix that pre-treatment is good is inserted in composite plating bath after surface active, carry out pulse electrodeposition Ni-Co-P/HBN composite deposite, through thermal treatment, obtain anti-corrosion, wear resistant friction reducing pulse electrodeposition Ni-Co-P/HBN composite deposite again, its preparation is as follows with operation steps:
I, technical process
Select metallic substance to do the pre-treatment of matrix-substrate material surface: to deoil, eliminate rust, finishing and ultrasonic wave dispersion treatment-configuration nickel cobalt phosphorus/HBN composite plating bath-substrate material surface activation-pulse electrodeposition Ni-Co-P/HBN composite deposite-thermal treatment-product of polishing, acetone cleaning-HBN particulate;
II, operation steps
1. select metallic substance to make matrix, standby;
2. the processing of deoiling of matrix, its formula is massfraction: sodium hydroxide 20g/L, sodium carbonate 30g/L, sodium phosphate 8g/L, OP-10 emulsifying agent 2ml/L volume fraction, 80 ℃ of temperature;
3. the processing of rust removing of matrix, its formula is: sulfuric acid 100ml/L volume fraction, hexamethylenetetramine 12g/L massfraction, temperature 50 C;
4. with 180#, 360#, 600# sand paper, successively the matrix deoiling after processing of rust removing is polished, then with acetone, matrix surface is carried out to ultrasonic cleaning, dry for standby;
5. the finishing of HBN particulate is processed:
5.-1 use volumetric concentration is that 20%HCl solution carries out deironing impurity elimination processing to HBN powder, soaks 24 hours, then washs and wash 6 times with deionized water;
5. it is, in the deionized water solution of 2.0ml/L POLYSORBATE 80 tensio-active agent, HBN particulate is carried out to finishing that-2 HBN powder after deironing impurity elimination is processed are inserted containing volume fraction, and soak time is 10 hours, and with glass stick, carries out intermittent stirring every 2 hours;
6. configure nickel cobalt phosphorus composite plating bath, in every liter of plating solution, the content massfraction of each composition is: NiSO
46H
2o 150~180g/L, CoCl
26H
2o 1~2g/L, NaH
2pO
2h
2o 10~15g/L, H
3bO
315~30g/L, citric acid 50~60g/L, trisodium citrate 10~20g/L, Padil 2g/L, polyvinyl alcohol 0.1~0.2g/L, HBN powder 10~25g/L; By volumetric concentration, be 10%H
2sO
4or mass concentration is pH value to 3.8~4.2 that 10%NaOH solution regulates composite plating bath, then, with deionized water, composite plating bath is added to specified volume;
7. body material activation;
8. pulse electrodeposition Ni-Co-P/HBN composite deposite:
8.-1 by the composite plating bath heating having configured, and temperature is controlled at 45~55 ℃;
8. before-2 platings, composite plating bath is placed in ultrasonic vibrator and carries out ultrasonic vibration dispersion treatment, the time is 20 minutes;
8.-3 use electrolytic nickels are as anode, and the body material that activation treatment is good is connected and is placed in composite plating bath with negative electrode; Unbalanced pulse power supply, adopts control current mode to carry out pulse electrodeposition Ni-Co-P/HBN composite deposite, and pulse electrodeposition processing parameter is: Mean Forward Current density 4~6A/dm
2, forward work is than 0.2~0.4, oppositely average current density 0.1~0.3A/dm
2, reverse operation is than 0.1~0.2, pulse-repetition 100Hz; Plating time is 2 hours;
8. in-4 plating processes, with electric mixer, carry out continuously stirring, stirring velocity is 100~250r/min, makes HBN particulate fully be suspended in plating solution;
9. thermal treatment: pulse electrodeposition Ni-Co-P/HBN composite deposite sample is positioned in chamber type electric resistance furnace, is warmed up to 300~450 ℃ with stove, heat-up rate is 5 ℃/min, is incubated 80 minutes, cools to room temperature with the furnace;
10. in stove, take out composite deposite, be pulse electrodeposition Ni-Co-P/HBN composite deposite product.
Best effect for achieving the above object, its further step is:
Body material is 45 steel.
Body material is red copper T2.
Body material is aluminum silicon alloy ZL109.
Body material is stainless steel 1Cr13.
Body material activation is: by volumetric concentration, be that 50%HCl solution carries out activation treatment to 45 steel, red copper T2 surface, soak time is 20 seconds.
Body material activation is: by volume ratio, be H
2sO
4: HCl: HNO
3: H
2o=1: the mixing acid of 1: 1: 7 carries out activation treatment to stainless steel 1Cr13 surface, soak time is 30 seconds.
Body material activation is: with phosphatase 11 00ml/L, sulfuric acid 40ml/L, citric acid 20g/L mixing acid, activation treatment is carried out in aluminum silicon alloy ZL109 surface, soak time is 20 seconds, and the aluminum silicon alloy ZL109 after activation treatment is inserted to FeCl fast
3h
2o20g/L, NiSO
46H
2o 20g/L, H
2sO
4in 20ml/L solution, carry out preimpregnation iron, prevent the front aluminum silicon alloy surface oxidation of plating.
A kind of pulse electrodeposition Ni-Co-P/HBN of the present invention composite deposite and preparation method thereof, it adopts metallic substance to make matrix, first matrix surface is carried out to pre-treatment, be equipped with again single nickel salt, cobalt chloride, sodium hypophosphite, citric acid, trisodium citrate, boric acid, polyvinyl alcohol is main ingredient, the composite plating bath that hexagonal boron nitride HBN powder is disperse phase, with tensio-active agent, ultrasonic vibration is carried out finishing and dispersion treatment to HBN particulate, by pulse electrodeposition parameter is rationally set, fully stir HBN particulate is dispersed in plating solution, applying HBN particulate and matrix metal nickel cobalt phosphorus generation codeposition and thermal treatment under pulsed current state and obtaining anti-corrosion, the technical scheme of wear resistant friction reducing pulse electrodeposition Ni-Co-P/HBN composite deposite, it is more single that it has overcome existing composite deposite component, coating coarse grains, the defect such as low with the interface bond strength of matrix, anti-corrosion, wear resistant friction reducing over-all properties is undesirable.
The beneficial effect that the present invention produced compared to existing technology.
[1] electrodeposition efficiency of Ni-Co-P/HBN composite plating bath of the present invention is high, reaches 90%; Composite plating bath is used safety, reliable, and environment is not produced to pollution, and composite deposite weave construction and corrosion resisting property and their chemical property, thermal stability, wear resistant friction reducing performance are all improved significantly, and extend work-ing life;
[2] the present invention adopts POLYSORBATE 80 tensio-active agent to carry out finishing to HBN particulate, has significantly increased the deposition of HBN particulate in matrix metal, and has effectively eliminated in plating process HBN particulate in reunion and the foaming phenomenon on plating solution surface;
[3] the present invention adopts Ni-Co-P/HBN composite deposite prepared by pulse electrodeposition, and its crystal grain is tiny, and surface compact light, has metalluster; Machinery part surface deposits after this composite deposite, does not need to carry out machining order;
[4] average microhardness under the composite deposite plated state condition that prepared by the present invention is 580.6HV
0.2, the average microhardness of 400 ℃ of thermal treatments composite deposite after 80 minutes reaches 930.8HV
0.2, to compare with deposit N i-P/HBN composite deposite, chemical Ni-P plating/HBN composite deposite, its microhardness is significantly increased; After thermal treatment, Ni-Co-P/HBN composite deposite and matrix have higher interface bond strength;
[5] after heat treatment the dry friction coefficient when rubbing is 0.12 to the Ni-Co-P/HBN composite deposite that prepared by the present invention with 45 quenched and tempered steel, and wear resistance is 5 times of Ni-P alloy layer, has excellent wear resistant friction reducing performance;
[6] the Ni-Co-P/HBN composite deposite that prepared by the present invention has good antioxidant property and thermal fatigue resistance below at 500 ℃, can be used as the self-lubricating coating material of the component such as the sliding surface bearing of working under the industry hot environments such as metallurgy, chemical industry, piston;
[7] Ni-Co-P/HBN composite deposite of the present invention, no matter under plated state condition or after thermal treatment, at NaCl, HCl, H
2sO
4with in NaOH corrosive medium, all show good corrosion resistance, can be used as the surfacecti proteon coating on the secondary component of fricting movement in corrosive medium;
[8] preparation technology of the present invention is simple, reliable, and processing ease, is beneficial to suitability for industrialized production, and production cost is low, free from environmental pollution, is convenient to penetration and promotion, and commercial promise is wide;
The present invention is applicable to doing wear resistant friction reducing, the anti-corrosion overlay coating of the secondary component of fricting movement in the industries such as machinery, metallurgy, chemical industry;
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Accompanying drawing explanation
Fig. 1 is Ni-Co-P/HBN composite deposite preparation technology general flow chart of the present invention.
Fig. 2 is the surface topography of the pulse electrodeposition Ni-Co-P/HBN composite deposite prepared of the present invention.
Fig. 3 is the Cross Section Morphology of the pulse electrodeposition Ni-Co-P/HBN composite deposite prepared of the present invention.
Fig. 4 is the x-ray diffraction pattern under the pulse electrodeposition Ni-Co-P/HBN composite deposite plated state state prepared of the present invention.
Fig. 5 is the x-ray diffraction patterns of 400 ℃ of thermal treatments of pulse electrodeposition Ni-Co-P/HBN composite deposite of preparing of the present invention after 80 minutes.
embodiment
Total embodiment
Explanation of tables:
The chemical component table that table 1 is the present invention's 45 steel used, red copper T2, aluminum silicon alloy ZL109 and stainless steel 1Cr13 body material.
Table 2 is chief component and the process parameter table of plating solution in pulse electrodeposition Ni-Co-P/HBN composite deposite embodiment 1-16 of the present invention.
In conjunction with figure, table, a kind of pulse electrodeposition Ni-Co-P/HBN of the present invention composite deposite and preparation method thereof, it adopts metallic substance to make matrix, first matrix surface is carried out to pre-treatment, be equipped with again single nickel salt, cobalt chloride, sodium hypophosphite, citric acid, trisodium citrate, boric acid, polyvinyl alcohol is main ingredient, the composite plating bath that the hexagonal boron nitride HBN powder of take is disperse phase, to after the good matrix surface activation of pre-treatment, insert in composite plating bath, by pulse electrodeposition processing parameter is rationally set, fully stir HBN particulate is dispersed in plating solution, applying HBN particulate and matrix metal Ni under pulsed current state, Co, there is codeposition and form Ni-Co-P/HBN composite deposite in P, finally pulse electrodeposition Ni-Co-P/HBN composite deposite sample is positioned in chamber type electric resistance furnace, with stove, be warmed up to 300~450 ℃, be incubated 80 minutes, cool to room temperature with the furnace, in stove, take out composite deposite sample, be anti-corrosion, wear resistant friction reducing pulse electrodeposition Ni-Co-P/HBN composite deposite product, its preparation and operation steps:
I, technical process
Select metallic substance 45 steel, red copper T2, aluminum silicon alloy ZL109 and stainless steel 1Cr13 to do the pre-treatment of matrix-substrate material surface: to deoil, eliminate rust, finishing and ultrasonic wave dispersion treatment-configuration nickel cobalt phosphorus/HBN composite plating bath-substrate material surface activation-pulse electrodeposition Ni-Co-P/HBN composite deposite-thermal treatment-product of polishing, acetone cleaning-HBN particulate;
II, operation steps are shown in embodiment
Embodiment 1
Body material is 45 steel, and chemical composition is shown in figure (table), and specimen size is: 50mm * 12mm * 2mm, and the preparation manipulation step of 45 steel surface Ni-Co-P/HBN composite deposites:
1. the 45 steel surfaces processing of deoiling, its formula is massfraction: sodium hydroxide 20g/L, sodium carbonate 30g/L, sodium phosphate 8g/L, OP-10 emulsifying agent 2ml/L volume fraction; 80 ℃ of temperature;
2. the processing of rust removing on 45 steel surfaces, its formula is: sulfuric acid 100ml/L volume fraction, hexamethylenetetramine 12g/L massfraction, temperature 50 C;
3. with 180#, 360#, 600# sand paper, successively 45 steel that deoil after processing of rust removing are polished, then with acetone, matrix surface is carried out to ultrasonic cleaning, dry for standby;
4. the finishing of HBN particulate is processed: by volumetric concentration, be that 20%HCl solution carries out deironing impurity elimination processing to HBN powder, soak time is 24 hours, then washs and wash 6 times with deionized water; It is, in the deionized water solution of 2.0ml/L POLYSORBATE 80 tensio-active agent, HBN particulate is carried out to finishing that HBN powder after deironing impurity elimination is processed is inserted containing volume fraction, and soak time is 10 hours, and with glass stick, carries out intermittent stirring every 2 hours;
5. configure nickel cobalt phosphorus composite plating bath: in every liter of plating solution, the content of each composition is massfraction: NiSO
46H
2o 150g/L, CoCl
26H
2o 1.0g/L, NaH
2pO
2h
2o 10g/L, H
3bO
315g/L, citric acid 50g/L, trisodium citrate 20g/L, Padil 2g/L, polyvinyl alcohol 0.1g/L, HBN powder 10g/L;
6. by volumetric concentration, be that 50%HCl solution carries out activation treatment to 45 steel surfaces of pre-treatment, soak time is 20 seconds;
7. pulse electrodeposition Ni-Co-P/HBN composite deposite: before plating, composite plating bath is carried out in ultrasonic vibrator to ultrasonic dispersion treatment, the treatment time is 20 minutes; With electrolytic nickel, as anode, the body material that activation treatment is good is connected and is placed in composite plating bath with negative electrode; Unbalanced pulse power supply, adopts control current mode to carry out pulse electrodeposition Ni-Co-P/HBN composite deposite, and pulse electrodeposition processing parameter is: Mean Forward Current density 4A/dm
2, forward work ratio is 0.2, oppositely average current density 0.1A/dm
2, reverse operation ratio is 0.1, pulse-repetition 100Hz; PH is 3.8, and bath temperature is 45 ℃, and stirring velocity is 100r/min.The pulse electrodeposition time is 2 hours, and the sedimentation velocity of coating is about 10.5 μ m/h;
8. thermal treatment: pulse electrodeposition Ni-Co-P/HBN composite deposite sample is positioned in chamber type electric resistance furnace, with stove, be warmed up to 300 ℃, heat-up rate is 5 ℃/min, is incubated 80 minutes, after cooling to room temperature with the furnace, take out, obtain Ni-Co-P/HBN composite deposite after thermal treatment.
Embodiment 2
Body material is 45 steel, and chemical composition is shown in figure (table), and specimen size is: 50mm * 12mm * 2mm, and the preparation manipulation step of 45 steel surface Ni-Co-P/HBN composite deposites:
1. the 45 steel surfaces processing of deoiling, its formula is massfraction: sodium hydroxide 20g/L, sodium carbonate 30g/L, sodium phosphate 8g/L, OP-10 emulsifying agent 2ml/L volume fraction, 80 ℃ of temperature;
2. the processing of rust removing on 45 steel surfaces, its formula is: sulfuric acid 100ml/L volume fraction, hexamethylenetetramine 12g/L massfraction, temperature 50 C;
3. with 180#, 360#, 600# sand paper, successively 45 steel that deoil after processing of rust removing are polished, then with acetone, matrix surface is carried out to ultrasonic cleaning, dry for standby;
4. the finishing of HBN particulate is processed: by volumetric concentration, be that 20%HCl solution carries out deironing impurity elimination processing to HBN powder, soak time is 24 hours, with deionized water, wash and wash 6 times again, it is, in the deionized water solution of 2.0ml/L POLYSORBATE 80 tensio-active agent, HBN particulate is carried out to finishing that HBN powder after deironing impurity elimination is processed is inserted containing volume fraction, soak time is 10 hours, and with glass stick, carries out intermittent stirring every 2 hours;
5. configure nickel cobalt phosphorus composite plating bath: in every liter of plating solution, the content massfraction of each composition is: NiSO
46H
2o 160g/L, CoCl
26H
2o 1.5g/L, NaH
2pO
2h
2o 13g/L, H
3bO
320g/L, citric acid 55g/L, trisodium citrate 15g/L, Padil 2g/L, polyvinyl alcohol 0.15g/L, HBN powder 15g/L;
6. by volumetric concentration, be that 50%HCl solution carries out activation treatment to 45 steel surfaces of pre-treatment, soak time is 20 seconds;
7. pulse electrodeposition Ni-Co-P/HBN composite deposite: before plating, composite plating bath is carried out in ultrasonic vibrator to ultrasonic dispersion treatment, the treatment time is 20 minutes; With electrolytic nickel as anode, the body material that activation treatment is good is connected and is placed in composite plating bath with negative electrode, unbalanced pulse power supply, adopts control current mode to carry out pulse electrodeposition Ni-Co-P/HBN composite deposite, and pulse electrodeposition processing parameter is: Mean Forward Current density 5A/dm
2, forward work ratio is 0.3, oppositely average current density 0.2A/dm
2, reverse operation ratio is 0.15, pulse-repetition 100Hz, and pH is 4.0, and bath temperature is 50 ℃, and stirring velocity is 150r/min, and the pulse electrodeposition time is 2 hours, the sedimentation velocity of coating is about 13.8 μ m/h;
8. thermal treatment: pulse electrodeposition Ni-Co-P/HBN composite deposite sample is positioned in chamber type electric resistance furnace, with stove, be warmed up to 350 ℃, heat-up rate is 5 ℃/min, is incubated 80 minutes, after cooling to room temperature with the furnace, take out, obtain Ni-Co-P/HBN composite deposite after thermal treatment.
Embodiment 3
Body material is 45 steel, and chemical composition is shown in figure (table), and specimen size is: 50mm * 12mm * 2mm, and the preparation manipulation step of 45 steel surface Ni-Co-P/HBN composite deposites:
1. the 45 steel surfaces processing of deoiling, its formula is massfraction: sodium hydroxide 20g/L, sodium carbonate 30g/L, sodium phosphate 8g/L, OP-10 emulsifying agent 2ml/L volume fraction; 80 ℃ of temperature;
2. the processing of rust removing on 45 steel surfaces, its formula is: sulfuric acid 100ml/L volume fraction, hexamethylenetetramine 12g/L massfraction, temperature 50 C;
3. with 180#, 360#, 600# sand paper, successively 45 steel that deoil after processing of rust removing are polished, then with acetone, matrix surface is carried out to ultrasonic cleaning, dry for standby;
4. the finishing of HBN particulate is processed: by volumetric concentration, be that 20%HCl solution carries out deironing impurity elimination processing to HBN powder, soak time is 24 hours, then washs and wash 6 times with deionized water; It is, in the deionized water solution of 2.0ml/L POLYSORBATE 80 tensio-active agent, HBN particulate is carried out to finishing that HBN powder after deironing impurity elimination is processed is inserted containing volume fraction, and soak time is 10 hours, and with glass stick, carries out intermittent stirring every 2 hours;
5. configure nickel cobalt phosphorus composite plating bath: in every liter of plating solution, the content massfraction of each composition is: NiSO
46H
2o 170g/L, CoCl
26H
2o 2.0g/L, NaH
2pO
2h
2o 15g/L, H
3bO
325g/L, citric acid 60g/L, trisodium citrate 10g/L, Padil 2g/L, polyvinyl alcohol 0.2g/L, HBN powder 20g/L;
6. by volumetric concentration, be that 50%HCl solution carries out activation treatment to 45 steel surfaces of pre-treatment, soak time is 20 seconds;
7. pulse electrodeposition Ni-Co-P/HBN composite deposite: before plating, composite plating bath is carried out in ultrasonic vibrator to ultrasonic dispersion treatment, the treatment time is 20 minutes; With electrolytic nickel, as anode, the body material that activation treatment is good is connected and is placed in composite plating bath with negative electrode; Unbalanced pulse power supply, adopts control current mode to carry out pulse electrodeposition Ni-Co-P/HBN composite deposite, and pulse electrodeposition processing parameter is: Mean Forward Current density 6A/dm
2, forward work ratio is 0.4, oppositely average current density 0.3A/dm
2, reverse operation ratio is 0.2, pulse-repetition 100Hz; PH is 4.2, and bath temperature is 55 ℃, and stirring velocity is 200r/min.The pulse electrodeposition time is 2 hours, and the sedimentation velocity of coating is about 15.3 μ m/h;
8. thermal treatment: pulse electrodeposition Ni-Co-P/HBN composite deposite sample is positioned in chamber type electric resistance furnace, with stove, be warmed up to 400 ℃, heat-up rate is 5 ℃/min, is incubated 80 minutes, after cooling to room temperature with the furnace, take out, obtain Ni-Co-P/HBN composite deposite after thermal treatment.
Embodiment 4
Body material is 45 steel, and chemical composition is shown in figure (table), and specimen size is: 50mm * 12mm * 2mm, and the preparation manipulation step of 45 steel surface Ni-Co-P/HBN composite deposites:
1. the 45 steel surfaces processing of deoiling, its formula is massfraction: sodium hydroxide 20g/L, sodium carbonate 30g/L, sodium phosphate 8g/L, OP-10 emulsifying agent 2ml/L volume fraction; 80 ℃ of temperature;
2. the processing of rust removing on 45 steel surfaces, its formula is: sulfuric acid 100ml/L volume fraction, hexamethylenetetramine 12g/L massfraction, temperature 50 C;
3. with 180#, 360#, 600# sand paper, successively 45 steel that deoil after processing of rust removing are polished, then with acetone, matrix surface is carried out to ultrasonic cleaning, dry for standby;
4. the finishing of HBN particulate is processed: by volumetric concentration, be that 20%HCl solution carries out deironing impurity elimination processing to HBN powder, soak time is 24 hours, then washs and wash 6 times with deionized water; It is, in the deionized water solution of 2.0ml/L POLYSORBATE 80 tensio-active agent, HBN particulate is carried out to finishing that HBN powder after deironing impurity elimination is processed is inserted containing volume fraction, and soak time is 10 hours, and with glass stick, carries out intermittent stirring every 2 hours;
5. configure nickel cobalt phosphorus composite plating bath: in every liter of plating solution, the content massfraction of each composition is: NiSO
46H
2o 180g/L, CoCl
26H
2o 1.5g/L, NaH
2pO
2h
2o 13g/L, H
3bO
330g/L, citric acid 55g/L, trisodium citrate 15g/L, Padil 2g/L, polyvinyl alcohol 0.15g/L, HBN powder 25g/L;
6. by volumetric concentration, be that 50%HCl solution carries out activation treatment to 45 steel surfaces of pre-treatment, soak time is 20 seconds;
7. pulse electrodeposition Ni-Co-P/HBN composite deposite: before plating, composite plating bath is carried out in ultrasonic vibrator to ultrasonic dispersion treatment, the treatment time is 20 minutes; With electrolytic nickel, as anode, the body material that activation treatment is good is connected and is placed in composite plating bath with negative electrode; Unbalanced pulse power supply, adopts control current mode to carry out pulse electrodeposition Ni-Co-P/HBN composite deposite, and pulse electrodeposition processing parameter is: Mean Forward Current density 5A/dm
2, forward work ratio is 0.3, oppositely average current density 0.3A/dm
2, reverse operation ratio is 0.1, pulse-repetition 100Hz; PH is 4.0, and bath temperature is 50 ℃, and stirring velocity is 250r/min.The pulse electrodeposition time is 2 hours, and the sedimentation velocity of coating is about 14.2 μ m/h;
8. thermal treatment: pulse electrodeposition Ni-Co-P/HBN composite deposite sample is positioned in chamber type electric resistance furnace, with stove, be warmed up to 450 ℃, heat-up rate is 5 ℃/min, is incubated 80 minutes, after cooling to room temperature with the furnace, take out, obtain Ni-Co-P/HBN composite deposite after thermal treatment.
Embodiment 5
Body material is red copper T2, and chemical composition is shown in figure (table), and specimen size is: 50mm * 15mm * 3mm, and the preparation manipulation step of red copper T2 surface Ni-Co-P/HBN composite deposite:
1. the red copper T2 processing of deoiling on surface, its formula is massfraction: sodium hydroxide 20g/L, sodium carbonate 30g/L, sodium phosphate 8g/L, OP-10 emulsifying agent 2ml/L volume fraction; 80 ℃ of temperature;
2. the oxide film on red copper T2 surface is processed, and its formula is: sulfuric acid 100ml/L volume fraction, hexamethylenetetramine 12g/L massfraction, temperature 50 C;
3. with 180#, 360#, 600# sand paper, successively the red copper T2 deoiling after processing of rust removing is polished, then with acetone, matrix surface is carried out to ultrasonic cleaning, dry for standby;
4. the finishing of HBN particulate is processed: by volumetric concentration, be that 20%HCl solution carries out deironing impurity elimination processing to HBN powder, soak time is 24 hours, then washs and wash 6 times with deionized water; It is, in the deionized water solution of 2.0ml/L POLYSORBATE 80 tensio-active agent, HBN particulate is carried out to finishing that HBN powder after deironing impurity elimination is processed is inserted containing volume fraction, and soak time is 10 hours, and with glass stick, carries out intermittent stirring every 2 hours;
5. configure nickel cobalt phosphorus composite plating bath: in every liter of plating solution, the content massfraction of each composition is: NiSO
46H
2o 150g/L, CoCl
26H
2o 1.0g/L, NaH
2pO
2h
2o 10g/L, H
3bO
315g/L, citric acid 50g/L, trisodium citrate 20g/L, Padil 2g/L, polyvinyl alcohol 0.1g/L, HBN powder 10g/L;
6. by volumetric concentration, be that 50%HCl solution carries out activation treatment to the red copper T2 surface of pre-treatment, soak time is 20 seconds;
7. pulse electrodeposition Ni-Co-P/HBN composite deposite: before plating, composite plating bath is carried out in ultrasonic vibrator to ultrasonic dispersion treatment, the treatment time is 20 minutes; With electrolytic nickel, as anode, the body material that activation treatment is good is connected and is placed in composite plating bath with negative electrode; Unbalanced pulse power supply, adopts control current mode to carry out pulse electrodeposition Ni-Co-P/HBN composite deposite, and pulse electrodeposition processing parameter is: Mean Forward Current density 4A/dm
2, forward work ratio is 0.2, oppositely average current density 0.1A/dm
2, reverse operation ratio is 0.1, pulse-repetition 100Hz; PH is 3.8, and bath temperature is 45 ℃, and stirring velocity is 100r/min.The pulse electrodeposition time is 2 hours, and the sedimentation velocity of coating is 9.6 μ m/h;
8. thermal treatment: pulse electrodeposition Ni-Co-P/HBN composite deposite sample is positioned in chamber type electric resistance furnace, with stove, be warmed up to 300 ℃, heat-up rate is 5 ℃/min, is incubated 80 minutes, after cooling to room temperature with the furnace, take out, obtain Ni-Co-P/HBN composite deposite after thermal treatment.
Embodiment 6
Body material is red copper T2, and chemical composition is shown in figure (table), and specimen size is: 50mm * 15mm * 3mm, and the preparation manipulation step of red copper T2 surface Ni-Co-P/HBN composite deposite:
1. the red copper T2 processing of deoiling on surface, its formula is massfraction: sodium hydroxide 20g/L, sodium carbonate 30g/L, sodium phosphate 8g/L, OP-10 emulsifying agent 2ml/L volume fraction; 80 ℃ of temperature;
2. the oxide film on red copper T2 surface is processed, and its formula is: sulfuric acid 100ml/L volume fraction, hexamethylenetetramine 12g/L massfraction, temperature 50 C;
3. with 180#, 360#, 600# sand paper, successively the red copper T2 deoiling after processing of rust removing is polished, then with acetone, matrix surface is carried out to ultrasonic cleaning, dry for standby;
4. the finishing of HBN particulate is processed: by volumetric concentration, be that 20%HCl solution carries out deironing impurity elimination processing to HBN powder, soak time is 24 hours, then washs and wash 6 times with deionized water; It is, in the deionized water solution of 2.0ml/L POLYSORBATE 80 tensio-active agent, HBN particulate is carried out to finishing that HBN powder after deironing impurity elimination is processed is inserted containing volume fraction, and soak time is 10 hours, and with glass stick, carries out intermittent stirring every 2 hours;
5. configure nickel cobalt phosphorus composite plating bath: in every liter of plating solution, the content massfraction of each composition is: NiSO
46H
2o 160g/L, CoCl
26H
2o 1.5g/L, NaH
2pO
2h
2o 13g/L, H
3bO
320g/L, citric acid 55g/L, trisodium citrate 15g/L, Padil 2g/L, polyvinyl alcohol 0.15g/L, HBN powder 15g/L;
6. by volumetric concentration, be that 50%HCl solution carries out activation treatment to the red copper T2 surface of pre-treatment, soak time is 20 seconds;
7. pulse electrodeposition Ni-Co-P/HBN composite deposite: before plating, composite plating bath is carried out in ultrasonic vibrator to ultrasonic dispersion treatment, the treatment time is 20 minutes; With electrolytic nickel, as anode, the body material that activation treatment is good is connected and is placed in composite plating bath with negative electrode; Unbalanced pulse power supply, adopts control current mode to carry out pulse electrodeposition Ni-Co-P/HBN composite deposite, and pulse electrodeposition processing parameter is: Mean Forward Current density 5A/dm
2, forward work ratio is 0.3, oppositely average current density 0.2A/dm
2, reverse operation ratio is 0.15, pulse-repetition 100Hz; PH is 4.0, and bath temperature is 50 ℃, and stirring velocity is 150r/min.The pulse electrodeposition time is 2 hours, and the sedimentation velocity of coating is 11.5 μ m/h;
8. thermal treatment: pulse electrodeposition Ni-Co-P/HBN composite deposite sample is positioned in chamber type electric resistance furnace, with stove, be warmed up to 350 ℃, heat-up rate is 5 ℃/min, is incubated 80 minutes, after cooling to room temperature with the furnace, take out, obtain Ni-Co-P/HBN composite deposite after thermal treatment.
Embodiment 7
Body material is red copper T2, and chemical composition is shown in figure (table), and specimen size is: 50mm * 15mm * 3mm, and the preparation manipulation step of red copper T2 surface Ni-Co-P/HBN composite deposite:
1. the red copper T2 processing of deoiling on surface, its formula is massfraction: sodium hydroxide 20g/L, sodium carbonate 30g/L, sodium phosphate 8g/L, OP-10 emulsifying agent 2ml/L volume fraction; 80 ℃ of temperature;
2. the oxide film on red copper T2 surface is processed, and its formula is: sulfuric acid 100ml/L volume fraction, hexamethylenetetramine 12g/L massfraction, temperature 50 C;
3. with 180#, 360#, 600# sand paper, successively the red copper T2 deoiling after processing of rust removing is polished, then with acetone, matrix surface is carried out to ultrasonic cleaning, dry for standby;
4. the finishing of HBN particulate is processed: by volumetric concentration, be that 20%HCl solution carries out deironing impurity elimination processing to HBN powder, soak time is 24 hours, then washs and wash 6 times with deionized water; It is, in the deionized water solution of 2.0ml/L POLYSORBATE 80 tensio-active agent, HBN particulate is carried out to finishing that HBN powder after deironing impurity elimination is processed is inserted containing volume fraction, and soak time is 10 hours, and with glass stick, carries out intermittent stirring every 2 hours; Before plating, the HBN microparticle suspending liquid after finishing is processed carries out ultrasonic dispersion treatment at ultrasonic vibrator, and the treatment time is 20 minutes;
5. configure nickel cobalt phosphorus composite plating bath: in every liter of plating solution, the content massfraction of each composition is: NiSO
46H
2o 170g/L, CoCl
26H
2o 2.0g/L, NaH
2pO
2h
2o 15g/L, H
3bO
325g/L, citric acid 60g/L, trisodium citrate 10g/L, Padil 2g/L, polyvinyl alcohol 0.2g/L, HBN powder 20g/L;
6. by volumetric concentration, be that 50%HCl solution carries out activation treatment to the red copper T2 surface of pre-treatment, soak time is 20 seconds;
7. pulse electrodeposition Ni-Co-P/HBN composite deposite: before plating, composite plating bath is carried out in ultrasonic vibrator to ultrasonic dispersion treatment, the treatment time is 20 minutes; With electrolytic nickel, as anode, the body material that activation treatment is good is connected and is placed in composite plating bath with negative electrode; Unbalanced pulse power supply, adopts control current mode to carry out pulse electrodeposition Ni-Co-P/HBN composite deposite, and pulse electrodeposition processing parameter is: Mean Forward Current density 6A/dm
2, forward work ratio is 0.4, oppositely average current density 0.3A/dm
2, reverse operation ratio is 0.2, pulse-repetition 100Hz; PH is 4.2, and bath temperature is 55 ℃, and stirring velocity is 200r/min.The pulse electrodeposition time is 2 hours, and the sedimentation velocity of coating is 13.4 μ m/h;
8. thermal treatment: pulse electrodeposition Ni-Co-P/HBN composite deposite sample is positioned in chamber type electric resistance furnace, with stove, be warmed up to 400 ℃, heat-up rate is 5 ℃/min, is incubated 80 minutes, after cooling to room temperature with the furnace, take out, obtain Ni-Co-P/HBN composite deposite after thermal treatment.
Embodiment 8
Body material is red copper T2, and chemical composition is shown in figure (table), and specimen size is: 50mm * 15mm * 3mm, and the preparation manipulation step of red copper T2 surface Ni-Co-P/HBN composite deposite:
1. the red copper T2 processing of deoiling on surface, its formula is massfraction: sodium hydroxide 20g/L, sodium carbonate 30g/L, sodium phosphate 8g/L, OP-10 emulsifying agent 2ml/L volume fraction; 80 ℃ of temperature;
2. the oxide film on red copper T2 surface is processed, and its formula is: sulfuric acid 100ml/L volume fraction, hexamethylenetetramine 12g/L massfraction, temperature 50 C;
3. with 180#, 360#, 600# sand paper, successively the red copper T2 deoiling after processing of rust removing is polished, then with acetone, matrix surface is carried out to ultrasonic cleaning, dry for standby;
4. the finishing of HBN particulate is processed: by volumetric concentration, be that 20%HCl solution carries out deironing impurity elimination processing to HBN powder, soak time is 24 hours, then washs and wash 6 times with deionized water; It is, in the deionized water solution of 2.0ml/L POLYSORBATE 80 tensio-active agent, HBN particulate is carried out to finishing that HBN powder after deironing impurity elimination is processed is inserted containing volume fraction, and soak time is 10 hours, and with glass stick, carries out intermittent stirring every 2 hours;
5. configure nickel cobalt phosphorus composite plating bath: in every liter of plating solution, the content massfraction of each composition is: NiSO
46H
2o 180g/L, CoCl
26H
2o 1.5g/L, NaH
2pO
2h
2o 13g/L, H
3bO
330g/L, citric acid 55g/L, trisodium citrate 15g/L, Padil 2g/L, polyvinyl alcohol 0.15g/L, HBN powder 25g/L;
6. by volumetric concentration, be that 50%HCl solution carries out activation treatment to the red copper T2 surface of pre-treatment, soak time is 20 seconds;
7. pulse electrodeposition Ni-Co-P/HBN composite deposite: before plating, composite plating bath is carried out in ultrasonic vibrator to ultrasonic dispersion treatment, the treatment time is 20 minutes; With electrolytic nickel, as anode, the body material that activation treatment is good is connected and is placed in composite plating bath with negative electrode; Unbalanced pulse power supply, adopts control current mode to carry out pulse electrodeposition Ni-Co-P/HBN composite deposite, and pulse electrodeposition processing parameter is: Mean Forward Current density 5A/dm
2, forward work ratio is 0.3, oppositely average current density 0.3A/dm
2, reverse operation ratio is 0.1, pulse-repetition 100Hz; PH is 4.0, and bath temperature is 50 ℃, and stirring velocity is 250r/min.The pulse electrodeposition time is 2 hours, and the sedimentation velocity of coating is 13.4 μ m/h;
8. thermal treatment: pulse electrodeposition Ni-Co-P/HBN composite deposite sample is positioned in chamber type electric resistance furnace, with stove, be warmed up to 450 ℃, heat-up rate is 5 ℃/min, is incubated 80 minutes, after cooling to room temperature with the furnace, take out, obtain Ni-Co-P/HBN composite deposite after thermal treatment.
Embodiment 9
Body material is aluminum silicon alloy ZL109, and chemical composition is shown in figure (table), and specimen size is: 50mm * 12mm * 2mm, and the preparation manipulation step of aluminum silicon alloy ZL109 surface Ni-Co-P/HBN composite deposite:
1. the aluminum silicon alloy ZL109 processing of deoiling on surface, its formula is massfraction: sodium hydroxide 20g/L, sodium carbonate 30g/L, sodium phosphate 8g/L, OP-10 emulsifying agent 2ml/L volume fraction; 80 ℃ of temperature;
2. with 180#, 360#, 600# sand paper, successively the aluminum silicon alloy ZL109 deoiling after processing is polished, then with acetone, matrix surface is carried out to ultrasonic cleaning, dry for standby;
3. the finishing of HBN particulate is processed: by volumetric concentration, be that 20%HCl solution carries out deironing impurity elimination processing to HBN powder, soak time is 24 hours, then washs and wash 6 times with deionized water; It is, in the deionized water solution of 2.0ml/L POLYSORBATE 80 tensio-active agent, HBN particulate is carried out to finishing that HBN powder after deironing impurity elimination is processed is inserted containing volume fraction, and soak time is 10 hours, and with glass stick, carries out intermittent stirring every 2 hours;
4. configure nickel cobalt phosphorus composite plating bath: in every liter of plating solution, the content massfraction of each composition is: NiSO
46H
2o 150g/L, CoCl
26H
2o 1.0g/L, NaH
2pO
2h
2o 10g/L, H
3bO
315g/L, citric acid 50g/L, trisodium citrate 20g/L, Padil 2g/L, polyvinyl alcohol 0.1g/L, HBN powder 10g/L;
5. with phosphatase 11 00ml/L, sulfuric acid 40ml/L, citric acid 20g/L mixing acid, activation treatment is carried out in aluminum silicon alloy ZL109 surface, soak time is 20 seconds;
6. the aluminum silicon alloy ZL109 after activation treatment is inserted to FeCl fast
3h
2o 20g/L, NiSO
46H
2o 20g/L, H
2sO
4in 20ml/L solution, carry out preimpregnation iron, prevent the front aluminum silicon alloy ZL109 surface oxidation of plating;
7. pulse electrodeposition Ni-Co-P/HBN composite deposite: before plating, composite plating bath is carried out in ultrasonic vibrator to ultrasonic dispersion treatment, the treatment time is 20 minutes; With electrolytic nickel, as anode, the body material that activation treatment is good is connected and is placed in composite plating bath with negative electrode; Unbalanced pulse power supply, adopts control current mode to carry out pulse electrodeposition Ni-Co-P/HBN composite deposite, and pulse electrodeposition processing parameter is: Mean Forward Current density 4A/dm
2, forward work ratio is 0.2, oppositely average current density 0.1A/dm
2, reverse operation ratio is 0.1, pulse-repetition 100Hz; PH is 3.8, and bath temperature is 45 ℃, and stirring velocity is 100r/min.The pulse electrodeposition time is 2 hours, and the sedimentation velocity of coating is 8.2 μ m/h;
8. thermal treatment: pulse electrodeposition Ni-Co-P/HBN composite deposite sample is positioned in chamber type electric resistance furnace, with stove, be warmed up to 300 ℃, heat-up rate is 5 ℃/min, is incubated 80 minutes, after cooling to room temperature with the furnace, take out, obtain Ni-Co-P/HBN composite deposite after thermal treatment.
Embodiment 10
Body material is aluminum silicon alloy ZL109, and chemical composition is shown in figure (table), and specimen size is: 50mm * 12mm * 2mm, and the preparation manipulation step of aluminum silicon alloy ZL109 surface Ni-Co-P/HBN composite deposite:
1. the aluminum silicon alloy ZL109 processing of deoiling on surface, its formula is massfraction: sodium hydroxide 20g/L, sodium carbonate 30g/L, sodium phosphate 8g/L, OP-10 emulsifying agent 2ml/L volume fraction; 80 ℃ of temperature;
2. with 180#, 360#, 600# sand paper, successively the aluminum silicon alloy ZL109 deoiling after processing is polished, then with acetone, matrix surface is carried out to ultrasonic cleaning, dry for standby;
3. the finishing of HBN particulate is processed: by volumetric concentration, be that 20%HCl solution carries out deironing impurity elimination processing to HBN powder, soak time is 24 hours, then washs and wash 6 times with deionized water; It is, in the deionized water solution of 2.0ml/L POLYSORBATE 80 tensio-active agent, HBN particulate is carried out to finishing that HBN powder after deironing impurity elimination is processed is inserted containing volume fraction, and soak time is 10 hours, and with glass stick, carries out intermittent stirring every 2 hours;
4. configure nickel cobalt phosphorus composite plating bath: in every liter of plating solution, the content massfraction of each composition is: NiSO
46H
2o 160g/L, CoCl
26H
2o 1.5g/L, NaH
2pO
2h
2o 13g/L, H
3bO
320g/L, citric acid 55g/L, trisodium citrate 15g/L, Padil 2g/L, polyvinyl alcohol 0.15g/L, HBN powder 15g/L;
5. with phosphatase 11 00ml/L, sulfuric acid 40ml/L, citric acid 20g/L mixing acid, activation treatment is carried out in aluminum silicon alloy ZL109 surface, soak time is 20 seconds;
6. the aluminum silicon alloy ZL109 after activation treatment is inserted to FeCl fast
3h
2o 20g/L, NiSO
46H
2o 20g/L, H
2sO
4in 20ml/L solution, carry out preimpregnation iron, prevent the front aluminum silicon alloy ZL109 surface oxidation of plating;
7. pulse electrodeposition Ni-Co-P/HBN composite deposite: before plating, composite plating bath is carried out in ultrasonic vibrator to ultrasonic dispersion treatment, the treatment time is 20 minutes; With electrolytic nickel, as anode, the body material that activation treatment is good is connected and is placed in composite plating bath with negative electrode; Unbalanced pulse power supply, adopts control current mode to carry out pulse electrodeposition Ni-Co-P/HBN composite deposite, and pulse electrodeposition processing parameter is: Mean Forward Current density 5A/dm
2, forward work ratio is 0.3, oppositely average current density 0.2A/dm
2, reverse operation ratio is 0.15, pulse-repetition 100Hz; PH is 4.0, and bath temperature is 50 ℃, and stirring velocity is 150r/min.The pulse electrodeposition time is 2 hours, and the sedimentation velocity of coating is 10.8 μ m/h,
8. thermal treatment: pulse electrodeposition Ni-Co-P/HBN composite deposite sample is positioned in chamber type electric resistance furnace, with stove, be warmed up to 350 ℃, heat-up rate is 5 ℃/min, is incubated 80 minutes, after cooling to room temperature with the furnace, take out, obtain Ni-Co-P/HBN composite deposite after thermal treatment.
Embodiment 11
Body material is aluminum silicon alloy ZL109, and chemical composition is shown in figure (table), and specimen size is: 50mm * 12mm * 2mm, and the preparation manipulation step of aluminum silicon alloy ZL109 surface Ni-Co-P/HBN composite deposite:
1. the aluminum silicon alloy ZL109 processing of deoiling on surface, its formula is massfraction: sodium hydroxide 20g/L, sodium carbonate 30g/L, sodium phosphate 8g/L, OP-10 emulsifying agent 2ml/L volume fraction; 80 ℃ of temperature;
2. with 180#, 360#, 600# sand paper, successively the aluminum silicon alloy ZL109 deoiling after processing is polished, then with acetone, matrix surface is carried out to ultrasonic cleaning, dry for standby;
3. the finishing of HBN particulate is processed: by volumetric concentration, be that 20%HCl solution carries out deironing impurity elimination processing to HBN powder, soak time is 24 hours, then washs and wash 6 times with deionized water; It is, in the deionized water solution of 2.0ml/L POLYSORBATE 80 tensio-active agent, HBN particulate is carried out to finishing that HBN powder after deironing impurity elimination is processed is inserted containing volume fraction, and soak time is 10 hours, and with glass stick, carries out intermittent stirring every 2 hours;
4. configure nickel cobalt phosphorus composite plating bath: in every liter of plating solution, the content massfraction of each composition is: NiSO
46H
2o 170g/L, CoCl
26H
2o 2.0g/L, NaH
2pO
2h
2o 15g/L, H
3bO
325g/L, citric acid 60g/L, trisodium citrate 10g/L, Padil 2g/L, polyvinyl alcohol 0.2g/L, HBN powder 20g/L;
5. with phosphatase 11 00ml/L, sulfuric acid 40ml/L, citric acid 20g/L mixing acid, activation treatment is carried out in aluminum silicon alloy ZL109 surface, soak time is 20 seconds;
6. the aluminum silicon alloy ZL109 after activation treatment is inserted to FeCl fast
3h
2o 20g/L, NiSO
46H
2o 20g/L, H
2sO
4in 20ml/L solution, carry out preimpregnation iron, prevent the front aluminum silicon alloy ZL109 surface oxidation of plating;
7. pulse electrodeposition Ni-Co-P/HBN composite deposite: before plating, composite plating bath is carried out in ultrasonic vibrator to ultrasonic dispersion treatment, the treatment time is 20 minutes; With electrolytic nickel, as anode, the body material that activation treatment is good is connected and is placed in composite plating bath with negative electrode; Unbalanced pulse power supply, adopts control current mode to carry out pulse electrodeposition Ni-Co-P/HBN composite deposite, and pulse electrodeposition processing parameter is: Mean Forward Current density 6A/dm
2, forward work ratio is 0.4, oppositely average current density 0.3A/dm
2, reverse operation ratio is 0.2, pulse-repetition 100Hz; PH is 4.2, and bath temperature is 55 ℃, and stirring velocity is 200r/min.The pulse electrodeposition time is 2 hours, and the sedimentation velocity of coating is 12.7 μ m/h,
8. thermal treatment: pulse electrodeposition Ni-Co-P/HBN composite deposite sample is positioned in chamber type electric resistance furnace, with stove, be warmed up to 400 ℃, heat-up rate is 5 ℃/min, is incubated 80 minutes, after cooling to room temperature with the furnace, take out, obtain Ni-Co-P/HBN composite deposite after thermal treatment.
Embodiment 12
Body material is aluminum silicon alloy ZL109, and chemical composition is shown in figure (table), and specimen size is: 50mm * 12mm * 2mm, and the preparation manipulation step of aluminum silicon alloy ZL109 surface Ni-Co-P/HBN composite deposite:
1. the aluminum silicon alloy ZL109 processing of deoiling on surface, its formula is massfraction: sodium hydroxide 20g/L, sodium carbonate 30g/L, sodium phosphate 8g/L, OP-10 emulsifying agent 2ml/L volume fraction; 80 ℃ of temperature;
2. with 180#, 360#, 600# sand paper, successively the aluminum silicon alloy ZL109 deoiling after processing is polished, then with acetone, matrix surface is carried out to ultrasonic cleaning, dry for standby;
3. the finishing of HBN particulate is processed: by volumetric concentration, be that 20%HCl solution carries out deironing impurity elimination processing to HBN powder, soak time is 24 hours, then washs and wash 6 times with deionized water; It is, in the deionized water solution of 2.0ml/L POLYSORBATE 80 tensio-active agent, HBN particulate is carried out to finishing that HBN powder after deironing impurity elimination is processed is inserted containing volume fraction, and soak time is 10 hours, and with glass stick, carries out intermittent stirring every 2 hours;
4. configure nickel cobalt phosphorus composite plating bath: in every liter of plating solution, the content massfraction of each composition is: NiSO
46H
2o 180g/L, CoCl
26H
2o 1.5g/L, NaH
2pO
2h
2o 13g/L, H
3bO
330g/L, citric acid 55g/L, trisodium citrate 15g/L, Padil 2g/L, polyvinyl alcohol 0.15g/L, HBN powder 25g/L;
5. with phosphatase 11 00ml/L, sulfuric acid 40ml/L, citric acid 20g/L mixing acid, activation treatment is carried out in aluminum silicon alloy ZL109 surface, soak time is 20 seconds;
6. the aluminum silicon alloy ZL109 after activation treatment is inserted to FeCl fast
3h
2o 20g/L, NiSO
46H
2o 20g/L, H
2sO
4in 20ml/L solution, carry out preimpregnation iron, prevent the front aluminum silicon alloy ZL109 surface oxidation of plating;
7. pulse electrodeposition Ni-Co-P/HBN composite deposite: before plating, composite plating bath is carried out in ultrasonic vibrator to ultrasonic dispersion treatment, the treatment time is 20 minutes; With electrolytic nickel, as anode, the body material that activation treatment is good is connected and is placed in composite plating bath with negative electrode; Unbalanced pulse power supply, adopts control current mode to carry out pulse electrodeposition Ni-Co-P/HBN composite deposite, and pulse electrodeposition processing parameter is: Mean Forward Current density 5A/dm
2, forward work ratio is 0.3, oppositely average current density 0.3A/dm
2, reverse operation ratio is 0.1, pulse-repetition 100Hz; PH is 4.0, and bath temperature is 50 ℃, and stirring velocity is 250r/min.The pulse electrodeposition time is 2 hours, and the sedimentation velocity of coating is 11.8 μ m/h;
8. thermal treatment: pulse electrodeposition Ni-Co-P/HBN composite deposite sample is positioned in chamber type electric resistance furnace, with stove, be warmed up to 450 ℃, heat-up rate is 5 ℃/min, is incubated 80 minutes, after cooling to room temperature with the furnace, take out, obtain Ni-Co-P/HBN composite deposite after thermal treatment.
Embodiment 13
Body material is stainless steel 1Cr13, and chemical composition is shown in figure (table), and specimen size is: 50mm * 12mm * 2mm, and the preparation manipulation step of stainless steel 1Cr13 surface Ni-Co-P/HBN composite deposite:
1. the stainless steel 1Cr13 processing of deoiling on surface, its formula is massfraction: sodium hydroxide 20g/L, sodium carbonate 30g/L, sodium phosphate 8g/L, OP-10 emulsifying agent 2ml/L volume fraction; 80 ℃ of temperature;
2. the oxide film on stainless steel 1Cr13 surface is processed, and its formula volume fraction is: sulfuric acid 80ml/L, nitric acid 20ml/L, temperature 50 C;
3. with 180#, 360#, 600# sand paper, successively the stainless steel 1Cr13 deoiling after processing of rust removing is polished, then with acetone, matrix surface is carried out to ultrasonic cleaning, dry for standby;
4. the finishing of HBN particulate is processed: by volumetric concentration, be that 20%HCl solution carries out deironing impurity elimination processing to HBN powder, soak time is 24 hours, then washs and wash 6 times with deionized water; It is, in the deionized water solution of 2.0ml/L POLYSORBATE 80 tensio-active agent, HBN particulate is carried out to finishing that HBN powder after deironing impurity elimination is processed is inserted containing volume fraction, and soak time is 10 hours, and with glass stick, carries out intermittent stirring every 2 hours;
5. configure nickel cobalt phosphorus composite plating bath: in every liter of plating solution, the content massfraction of each composition is: NiSO
46H
2o 150g/L, CoCl
26H
2o 1.0g/L, NaH
2pO
2h
2o 10g/L, H
3bO
315g/L, citric acid 50g/L, trisodium citrate 20g/L, Padil 2g/L, polyvinyl alcohol 0.10g/L, HBN powder 10g/L;
6. by volume ratio, be H
2sO
4: HCl: HNO
3: H
2o=1: the mixing acid of 1: 1: 7 carries out activation treatment to stainless steel 1Cr13 surface, soak time is 30 seconds;
7. pulse electrodeposition Ni-Co-P/HBN composite deposite: before plating, composite plating bath is carried out in ultrasonic vibrator to ultrasonic dispersion treatment, the treatment time is 20 minutes; With electrolytic nickel, as anode, the body material that activation treatment is good is connected and is placed in composite plating bath with negative electrode; Unbalanced pulse power supply, adopts control current mode to carry out pulse electrodeposition Ni-Co-P/HBN composite deposite, and pulse electrodeposition processing parameter is: Mean Forward Current density 4A/dm
2, forward work ratio is 0.2, oppositely average current density 0.1A/dm
2, reverse operation ratio is 0.1, pulse-repetition 100Hz; PH is 3.8, and bath temperature is 45 ℃, and stirring velocity is 100r/min.The pulse electrodeposition time is 2 hours, and the sedimentation velocity of coating is 8.3 μ m/h;
8. thermal treatment: pulse electrodeposition Ni-Co-P/HBN composite deposite sample is positioned in chamber type electric resistance furnace, with stove, be warmed up to 300 ℃, heat-up rate is 5 ℃/min, is incubated 80 minutes, after cooling to room temperature with the furnace, take out, obtain Ni-Co-P/HBN composite deposite after thermal treatment.
Embodiment 14
Body material is stainless steel 1Cr13, and chemical composition is shown in figure (table), and specimen size is: 50mm * 12mm * 2mm, and the preparation manipulation step of stainless steel 1Cr13 surface Ni-Co-P/HBN composite deposite:
1. the stainless steel 1Cr13 processing of deoiling on surface, its formula is massfraction: sodium hydroxide 20g/L, sodium carbonate 30g/L, sodium phosphate 8g/L, OP-10 emulsifying agent 2ml/L volume fraction; 80 ℃ of temperature;
2. the oxide film on stainless steel 1Cr13 surface is processed, and its formula volume fraction is: sulfuric acid 80ml/L, nitric acid 20ml/L, temperature 50 C;
3. with 180#, 360#, 600# sand paper, successively the stainless steel 1Cr13 deoiling after processing of rust removing is polished, then with acetone, matrix surface is carried out to ultrasonic cleaning, dry for standby;
4. the finishing of HBN particulate is processed: by volumetric concentration, be that 20%HCl solution carries out deironing impurity elimination processing to HBN powder, soak time is 24 hours, then washs and wash 6 times with deionized water; It is, in the deionized water solution of 2.0ml/L POLYSORBATE 80 tensio-active agent, HBN particulate is carried out to finishing that HBN powder after deironing impurity elimination is processed is inserted containing volume fraction, and soak time is 10 hours, and with glass stick, carries out intermittent stirring every 2 hours;
5. configure nickel cobalt phosphorus composite plating bath: in every liter of plating solution, the content massfraction of each composition is: NiSO
46H
2o 160g/L, CoCl
26H
2o 1.5g/L, NaH
2pO
2h
2o 13g/L, H
3bO
320g/L, citric acid 55g/L, trisodium citrate 15g/L, Padil 2g/L, polyvinyl alcohol 0.15g/L, HBN powder 15g/L;
6. by volume ratio, be H
2sO
4: HCl: HNO
3: H
2o=1: the mixing acid of 1: 1: 7 carries out activation treatment to stainless steel 1Cr13 surface, soak time is 30 seconds;
7. pulse electrodeposition Ni-Co-P/HBN composite deposite: before plating, composite plating bath is carried out in ultrasonic vibrator to ultrasonic dispersion treatment, the treatment time is 20 minutes; With electrolytic nickel, as anode, the body material that activation treatment is good is connected and is placed in composite plating bath with negative electrode; Unbalanced pulse power supply, adopts control current mode to carry out pulse electrodeposition Ni-Co-P/HBN composite deposite, and pulse electrodeposition processing parameter is: Mean Forward Current density 5A/dm
2, forward work ratio is 0.3, oppositely average current density 0.2A/dm
2, reverse operation ratio is 0.15, pulse-repetition 100Hz; PH is 4.0, and bath temperature is 50 ℃, and stirring velocity is 150r/min.The pulse electrodeposition time is 2 hours, and the sedimentation velocity of coating is 10.6 μ m/h;
8. thermal treatment: pulse electrodeposition Ni-Co-P/HBN composite deposite sample is positioned in chamber type electric resistance furnace, with stove, be warmed up to 350 ℃, heat-up rate is 5 ℃/min, is incubated 80 minutes, after cooling to room temperature with the furnace, take out, obtain Ni-Co-P/HBN composite deposite after thermal treatment.
Embodiment 15
Body material is stainless steel 1Cr13, and chemical composition is shown in figure (table), and specimen size is: 50mm * 12mm * 2mm, and the preparation manipulation step of stainless steel 1Cr13 surface Ni-Co-P/HBN composite deposite:
1. the stainless steel 1Cr13 processing of deoiling on surface, its formula is massfraction: sodium hydroxide 20g/L, sodium carbonate 30g/L, sodium phosphate 8g/L, OP-10 emulsifying agent 2ml/L volume fraction; 80 ℃ of temperature;
2. the oxide film on stainless steel 1Cr13 surface is processed, and its formula volume fraction is: sulfuric acid 80ml/L, nitric acid 20ml/L, temperature 50 C;
3. with 180#, 360#, 600# sand paper, successively the stainless steel 1Cr13 deoiling after processing of rust removing is polished, then with acetone, matrix surface is carried out to ultrasonic cleaning, dry for standby;
4. the finishing of HBN particulate is processed: by volumetric concentration, be that 20%HCl solution carries out deironing impurity elimination processing to HBN powder, soak time is 24 hours, then washs and wash 6 times with deionized water; It is, in the deionized water solution of 2.0ml/L POLYSORBATE 80 tensio-active agent, HBN particulate is carried out to finishing that HBN powder after deironing impurity elimination is processed is inserted containing volume fraction, and soak time is 10 hours, and with glass stick, carries out intermittent stirring every 2 hours;
5. configure nickel cobalt phosphorus composite plating bath: in every liter of plating solution, the content massfraction of each composition is: NiSO
46H
2o 170g/L, CoCl
26H
2o 2.0g/L, NaH
2pO
2h
2o 15g/L, H
3bO
325g/L, citric acid 60g/L, trisodium citrate 10g/L, Padil 2g/L, polyvinyl alcohol 0.2g/L, HBN powder 20g/L;
6. by volume ratio, be H
2sO
4: HCl: HNO
3: H
2o=1: the mixing acid of 1: 1: 7 carries out activation treatment to stainless steel 1Cr13 surface, soak time is 30 seconds;
7. pulse electrodeposition Ni-Co-P/HBN composite deposite: before plating, composite plating bath is carried out in ultrasonic vibrator to ultrasonic dispersion treatment, the treatment time is 20 minutes; With electrolytic nickel, as anode, the body material that activation treatment is good is connected and is placed in composite plating bath with negative electrode; Unbalanced pulse power supply, adopts control current mode to carry out pulse electrodeposition Ni-Co-P/HBN composite deposite, and pulse electrodeposition processing parameter is: Mean Forward Current density 6A/dm
2, forward work ratio is 0.4, oppositely average current density 0.3A/dm
2, reverse operation ratio is 0.2, pulse-repetition 100Hz; PH is 4.2, and bath temperature is 55 ℃, and stirring velocity is 200r/min.The pulse electrodeposition time is 2 hours, and the sedimentation velocity of coating is 13.8 μ m/h;
8. thermal treatment: pulse electrodeposition Ni-Co-P/HBN composite deposite sample is positioned in chamber type electric resistance furnace, with stove, be warmed up to 400 ℃, heat-up rate is 5 ℃/min, is incubated 80 minutes, after cooling to room temperature with the furnace, take out, obtain Ni-Co-P/HBN composite deposite after thermal treatment.
Embodiment 16
Body material is stainless steel 1Cr13, and chemical composition is shown in figure (table), and specimen size is: 50mm * 12mm * 2mm, and the preparation manipulation step of stainless steel 1Cr13 surface Ni-Co-P/HBN composite deposite:
1. the stainless steel 1Cr13 processing of deoiling on surface, its formula is massfraction: sodium hydroxide 20g/L, sodium carbonate 30g/L, sodium phosphate 8g/L, OP-10 emulsifying agent 2ml/L volume fraction; 80 ℃ of temperature;
2. the oxide film on stainless steel 1Cr13 surface is processed, and its formula volume fraction is: sulfuric acid 80ml/L, nitric acid 20ml/L, temperature 50 C;
3. with 180#, 360#, 600# sand paper, successively the stainless steel 1Cr13 deoiling after processing of rust removing is polished, then with acetone, matrix surface is carried out to ultrasonic cleaning, dry for standby;
4. the finishing of HBN particulate is processed: by volumetric concentration, be that 20%HCl solution carries out deironing impurity elimination processing to HBN powder, soak time is 24 hours, then washs and wash 6 times with deionized water; It is, in the deionized water solution of 2.0ml/L POLYSORBATE 80 tensio-active agent, HBN particulate is carried out to finishing that HBN powder after deironing impurity elimination is processed is inserted containing volume fraction, and soak time is 10 hours, and with glass stick, carries out intermittent stirring every 2 hours;
5. configure nickel cobalt phosphorus composite plating bath: in every liter of plating solution, the content massfraction of each composition is: NiSO
46H
2o 180g/L, CoCl
26H
2o 1.5g/L, NaH
2pO
2h
2o 13g/L, H
3bO
330g/L, citric acid 55g/L, trisodium citrate 15g/L, Padil 2g/L, polyvinyl alcohol 0.15g/L, HBN powder 25g/L;
6. by volume ratio, be H
2sO
4: HCl: HNO
3: H
2o=1: the mixing acid of 1: 1: 7 carries out activation treatment to stainless steel 1Cr13 surface, soak time is 30 seconds;
7. pulse electrodeposition Ni-Co-P/HBN composite deposite: before plating, composite plating bath is carried out in ultrasonic vibrator to ultrasonic dispersion treatment, the treatment time is 20 minutes; With electrolytic nickel, as anode, the body material that activation treatment is good is connected and is placed in composite plating bath with negative electrode; Unbalanced pulse power supply, adopts control current mode to carry out pulse electrodeposition Ni-Co-P/HBN composite deposite, and pulse electrodeposition processing parameter is: Mean Forward Current density 5A/dm
2, forward work ratio is 0.3, oppositely average current density 0.3A/dm
2, reverse operation ratio is 0.1, pulse-repetition 100Hz; PH is 4.0, and bath temperature is 50 ℃, and stirring velocity is 250r/min.The pulse electrodeposition time is 2 hours, and the sedimentation velocity of coating is 11.6 μ m/h;
8. thermal treatment: pulse electrodeposition Ni-Co-P/HBN composite deposite sample is positioned in chamber type electric resistance furnace, with stove, be warmed up to 450 ℃, heat-up rate is 5 ℃/min, is incubated 80 minutes, after cooling to room temperature with the furnace, take out, obtain Ni-Co-P/HBN composite deposite after thermal treatment.
By reference to the accompanying drawings, structural principle of the present invention and function: the pulse electrodeposition Ni-Co-P/HBN composite deposite obtaining through pulse electrodeposition Ni-Co-P/HBN composite deposite preparation method of the present invention, to its pattern observe, composition analysis and performance test, consequently: HBN particulate is after the finishing of POLYSORBATE 80 tensio-active agent and ultrasonic wave dispersion treatment, can effectively promote the deposition of HBN particulate in coating, and eliminate in plating process HBN particulate in reunion and the foaming phenomenon on plating solution surface; Coating surface is smooth smooth, and crystal grain is tiny; EDAX results shows, the composition of pulse electrodeposition composite deposite be take Ni as main, and content is about 76.3wt%, and Co content is about 3.8wt%, and P content is about 12.5wt%, and all the other are HBN; X-ray analysis shows that under composite deposite plated state condition be amorphous structure, and has occurred obvious HBN diffraction peak, and by 400 ℃ of thermal treatments of composite deposite, after 80 minutes, composite deposite is complete crystallization, has produced Ni in coating
3p cenotype, the microhardness of 400 ℃ of thermal treatment composite deposites reaches 930.8HV
0.2, friction and wear behavior improves a lot compared with Ni-P alloy layer, and this is mainly the Ni separating out in coating
3p has played the effect of dispersion-strengthened mutually, thereby improves the drag of alloy layer matrix to local plastic deformation, and the wear resistance of matrix is increased; Secondly, the HBN particle in composite deposite is a kind of laminate structure of similar graphite, in layer, between atom, is very strong covalent attachment, close structure; Interlayer is molecular linkage combination, a little less than bonding force, easily causes slippage under shearing stress effect, at friction surface, forms one deck self-lubricating film, has reduced the frictional coefficient to the couple of rubbing, and frictional stress is reduced, and has reduced fatigue wear; Composite deposite and Ni-P alloy layer all have good anti-3.5%NaCl, 10%HCl, 10%H under plated state condition
2sO
4with 10%NaOH corrosive nature, but after thermal treatment Ni-P alloy layer crystallization, corrosion resisting property significantly reduces, and thermal treatment composite deposite still keeps good corrosion resistance nature, and this is mainly because HBN particulate stops Ni in heat treatment process
3growing up of P precipitated phase, has prevented the tendency of coating generation galvanic corrosion, and it is conducive to improve the work-ing life of the secondary component of the fricting movement of composite deposite under complicated environmental condition.
Table 1
Body material | Chemical composition (massfraction %) |
45 steel | C:0.42~0.5,Mn:0.5~0.8,Si:0.17~0.37,Cr≤0.25,Cu≤0.25,Ni≤0.3 |
Red copper (T2) | Cu+Ag: >=99.90, impurity summation :≤0.1 |
Aluminum silicon alloy (ZL109) | Si:11.0~13.0, Cu:0.5~1.5, Mg:0.8~1.3, Ni:0.8~1.5, Al: surplus |
Stainless steel (1Cr13) | C :≤0.15, Si :≤1.0, Mn :≤1.0, S≤0.03, P≤0.035, Cr:11.50~13.5, Fe: surplus |
Table 2
Claims (4)
1. a pulse electrodeposition Ni-Co-P/HBN composite deposite, it is characterized in that selecting 45 steel or red copper T2 or aluminum silicon alloy ZL109 or stainless steel 1Cr13 is body material, first matrix surface is carried out to pre-treatment, being equipped with nickel is the composite plating bath that main ingredient, hexagonal boron nitride HBN powder are disperse phase again, the matrix that pre-treatment is good is inserted in composite plating bath after surface active, carry out pulse electrodeposition Ni-Co-P/HBN composite deposite, through thermal treatment, obtain pulse electrodeposition Ni-Co-P/HBN composite deposite again, its preparation is as follows with operation steps:
I, technical process
Select metallic substance to do the pre-treatment of matrix-substrate material surface: to deoil, eliminate rust, finishing and ultrasonic wave dispersion treatment-configuration nickel cobalt phosphorus/HBN composite plating bath-substrate material surface activation-pulse electrodeposition Ni-Co-P/HBN composite deposite-thermal treatment-product of polishing, acetone cleaning-HBN particulate;
II, operation steps
1. select metallic substance to make matrix, standby;
2. the processing of deoiling of matrix, its formula is massfraction: sodium hydroxide 20g/L, sodium carbonate 30g/L, sodium phosphate 8g/L, OP-10 emulsifying agent 2ml/L volume fraction, 80 ℃ of temperature;
3. the processing of rust removing of matrix, its formula is: sulfuric acid 100ml/L volume fraction, hexamethylenetetramine 12g/L massfraction, temperature 50 C;
4. with 180#, 360#, 600# sand paper, successively the matrix deoiling after processing of rust removing is polished, then with acetone, matrix surface is carried out to ultrasonic cleaning, dry for standby;
5. the finishing of HBN particulate is processed:
5.-1 use volumetric concentration is that 20%HCl solution carries out deironing impurity elimination processing to HBN powder, soaks 24 hours, then washs and wash 6 times with deionized water;
5. it is, in the deionized water solution of 2.0ml/L POLYSORBATE 80 tensio-active agent, HBN particulate is carried out to finishing that-2 HBN powder after deironing impurity elimination is processed are inserted containing volume fraction, and soak time is 10 hours, and with glass stick, carries out intermittent stirring every 2 hours;
6. configure nickel cobalt phosphorus composite plating bath, in every liter of plating solution, the content massfraction of each composition is: NiSO
46H
2o150~180g/L, CoCl
26H
2o1~2g/L, NaH
2pO
2h
2o10~15g/L, H
3bO
315~30g/L, citric acid 50~60g/L, trisodium citrate 10~20g/L, Padil 2g/L, polyvinyl alcohol 0.1~0.2g/L, HBN powder 10~25g/L; By volumetric concentration, be 10%H
2sO
4or mass concentration is pH value to 3.8~4.2 that 10%NaOH solution regulates composite plating bath, then, with deionized water, composite plating bath is added to specified volume;
7. body material activation;
8. pulse electrodeposition Ni-Co-P/HBN composite deposite:
8.-1 by the composite plating bath heating having configured, and temperature is controlled at 45~55 ℃;
8. before-2 platings, composite plating bath is placed in ultrasonic vibrator and carries out ultrasonic vibration dispersion treatment, the time is 20 minutes;
8.-3 use electrolytic nickels are as anode, and the body material that activation treatment is good is connected and is placed in composite plating bath with negative electrode; Unbalanced pulse power supply, adopts control current mode to carry out pulse electrodeposition Ni-Co-P/HBN composite deposite, and pulse electrodeposition processing parameter is: Mean Forward Current density 4~6A/dm
2, forward work is than 0.2~0.4, oppositely average current density 0.1~0.3A/dm
2, reverse operation is than 0.1~0.2, pulse-repetition 100Hz; Plating time is 2 hours;
8. in-4 plating processes, with electric mixer, carry out continuously stirring, stirring velocity is 100~250r/min, makes HBN particulate fully be suspended in plating solution;
9. thermal treatment: pulse electrodeposition Ni-Co-P/HBN composite deposite sample is positioned in chamber type electric resistance furnace, is warmed up to 300~450 ℃ with stove, heat-up rate is 5 ℃/min, is incubated 80 minutes, cools to room temperature with the furnace;
10. in stove, take out composite deposite, be pulse electrodeposition Ni-Co-P/HBN composite deposite product.
2. the pulse electrodeposition Ni-Co-P/HBN composite deposite of stating according to claim 1, is characterized in that body material activation is: by volumetric concentration, be that 50%HCl solution carries out activation treatment to 45 steel, red copper T2 surface, soak time is 20 seconds.
3. the pulse electrodeposition Ni-Co-P/HBN composite deposite of stating according to claim 1, is characterized in that body material activation is: by volume ratio, be H
2sO
4: HCl: HNO
3: H
2o=1: the mixing acid of 1: 1: 7 carries out activation treatment to stainless steel 1Cr13 surface, soak time is 30 seconds.
4. the pulse electrodeposition Ni-Co-P/HBN composite deposite of stating according to claim 1, it is characterized in that body material activation is: with phosphatase 11 00ml/L, sulfuric acid 40ml/L, citric acid 20g/L mixing acid, activation treatment is carried out in aluminum silicon alloy ZL109 surface, soak time is 20 seconds, and the aluminum silicon alloy ZL109 after activation treatment is inserted to FeCl fast
3h
2o20g/L, NiSO
46H
2o20g/L, H
2sO
4in 20ml/L solution, carry out preimpregnation iron, prevent the front aluminum silicon alloy surface oxidation of plating.
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