CN105970262A - Wear-resistant and corrosion-resistant material with Ni-P-Ce-B4C (Cu) composite coating and preparation technology of material - Google Patents

Wear-resistant and corrosion-resistant material with Ni-P-Ce-B4C (Cu) composite coating and preparation technology of material Download PDF

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Publication number
CN105970262A
CN105970262A CN201610548085.6A CN201610548085A CN105970262A CN 105970262 A CN105970262 A CN 105970262A CN 201610548085 A CN201610548085 A CN 201610548085A CN 105970262 A CN105970262 A CN 105970262A
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coating
plating
solution
corrosion
base material
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CN105970262B (en
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周宏明
胡建红
胡雪仪
刘亚雄
简帅
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Changsha Crown Machinery Manufacturing Co Ltd
Central South University
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Changsha Crown Machinery Manufacturing Co Ltd
Central South University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/04—Electroplating with moving electrodes
    • C25D5/06—Brush or pad plating

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Chemically Coating (AREA)

Abstract

The invention discloses a wear-resistant and corrosion-resistant material with a Ni-P-Ce-B4C (Cu) composite coating and a preparation technology of the material. The preparation technology is simple, and a prepared product is excellent in performance and suitable for industrial production. The hardness, the wear resistance and the corrosion resistance of the obtained material are greatly improved.

Description

The wear-and corrosion-resistant material of a kind of band Ni-P-Ce-B4C (Cu) composite deposite and preparation technology thereof
Technical field
The present invention relates to a kind of Wear-resistant corrosion-resistant coating and preparation method thereof, be specifically related to a kind of band Ni-P-Ce-B4C (Cu) multiple Close wear-and corrosion-resistant material and the preparation technology thereof of coating.
Background technology
Last century, the eighties started, and people use Brush Electroplating Technique to obtain composite deposite, for coating hardness, wear-resisting and resistance to The raising of corrosive nature, currently mainly by mixing the second phase microgranule or metal to Ni-P coating, utilizes plating or chemical plating side Method makes metal or solid solution codeposition of WC particles to prepare tri compound coating.Second phase microgranule mainly has SiC, WC, cube B4C, Al2O3, Si3N4Deng composite particles for the purpose of improving hardness and wearability, and CuF2, (CF)n, PTFE, MoS2Deng For improving the composite particles of coating self lubricity.
In conventional composite Resisting Property of Brush Electroplating Coating, the second phase insoluble granule closes difference with the bond of alloy, and boundary moisture performance is poor, Can easily produce the second phase insoluble granule, easy to fall off, cause coating surface porosity to increase, ultimately cause corrosion resisting property Reduce.
Nanometer B4C powder is a kind of electrically non-conductive material, and in traditional Brush Plating deposition process, it is mainly by matrix metal Mechanical entrapment effect in growth course enters coating, and in the composite deposite obtained, the content of nano powder is low, and nano powder is in plating Skewness in Ceng.
And existing prepare in Brush Plating Ni-Cu-P coating, and the brush plating plating solution of preparation is the most complicated, for the brush plating effect obtained, In plating solution, each component ratio is difficult to hold, and operating procedure also is difficult to control.
There is the defect that hardness is not high enough, wear and corrosion behavior is the best in the existing wear-and corrosion-resistant all materials containing composite deposite, The requirements such as the highest wear-and corrosion-resistant can not be met.
Summary of the invention
Present invention aims to the deficiencies in the prior art, it is provided that the band that a kind of high rigidity, Wear-resistant corrosion-resistant are substantially improved The wear-and corrosion-resistant material of Ni-P-Ce-B4C (Cu) composite deposite.
Another object of the present invention is to provide a kind of preparation method is simple, obtain material hardness and wear-resisting erosion resistance to obtain very The preparation technology of the wear-and corrosion-resistant material of band Ni-P-Ce-B4C (Cu) composite deposite that big degree is improved.
The invention provides the wear-and corrosion-resistant material of a kind of band Ni-P-Ce-B4C (Cu) composite deposite, described wear-and corrosion-resistant material is from inner To including base material, a Ni coating, Ni-P-Ce coating, the 2nd Ni coating, Ni-P-Ce-B4C (Cu) coating successively outward.
The present invention farther includes following preferred scheme:
Preferably in scheme, a described Ni coating, the thickness of the 2nd Ni coating are 0.5-1.5 μm.It is preferably 0.5-1.0 μm, further preferred 0.5 μm.
Preferably in scheme, the thickness of described Ni-P-Ce coating is 5.0-7.0 μm, preferably 5.0-6.0 μm, the most excellent Elect 5.0 μm as.
Preferably in scheme, the thickness of described Ni-P-Ce-B4C (Cu) coating is 6.0-8.0 μm, preferably 6.0-7.0 μm, enters One step is preferably 7.0 μm.
The invention further relates to the preparation technology of a kind of band Ni-P-Ce-B4C (Cu) wear-and corrosion-resistant composite deposite, substrate surface Brush plating the oneth Ni coating, Ni-P-Ce coating, the 2nd Ni coating, Ni-P-Ce-B4C (Cu) coating successively after pretreatment.
Preferably in scheme, described preparation technology comprises the following steps that:
Step one:
Under the conditions of 40-50 DEG C, base material clean for activation processing rear surface is used the brush plating carrying out nickel containing nickel plating bath, obtains Base material/Ni coating；
Step 2:
Base material/Ni coating sample use water is cleaned, carries out the brush plating of plating solution A-1, obtain base material/Ni coating / Ni-P-Ce coating sample, reuses the brush plating carrying out nickel containing nickel plating bath, obtains base material/Ni coating after cleaning with water / Ni-P-Ce coating/the 2nd Ni coating and the remaining liquid B of plating；Cu is coated with B4C granule add in the remaining liquid B of plating, controls Cu Cladding B4C concentration in the remaining liquid B of plating is 35-75g/L, carries out ultrasonic disperse, and stirring obtains plating solution A-2, uses subsequently Plating solution A-2 implements brush plating, obtains a base material/Ni coating/Ni-P-Ce coating/the 2nd Ni coating/Ni-P-Ce-B4C (Cu) plating Layer sample；
Described include following components containing nickel plating bath: six hydration nickel sulfate 320-350g/L, citric acid 60-80g/L, boric acid 15-30g/L, carboxylic acid, during plating, is 1-3 containing nickel plating bath pH；
Described brush plating liquid A-1 includes following components: nickel sulfate 240g/L-280g/L, sodium hypophosphite 15-25g/L, Fructus Citri Limoniae Acid 20-30g/L, trisodium citrate 15-25g/L, sodium sulfate 15-20g/L, glacial acetic acid 20-30ml/L, lauryl sulphate acid Sodium 0.1-0.3g/L, cerous nitrate 25-45g/L；
During plating, the pH value of plating solution A-1 controls: 3.0-5.0.
Preferably in scheme, the granularity of described Cu cladding B4C granule is 100-350nm.
Preferably in scheme, described Cu cladding B4C granule is 8-12wt%'s by nanometer B4C powder is immersed concentration NH4In F solution after roughening treatment, solid-liquid separation adds 10-11g/L SnCl2With sensitization in 4-5g/L HCl solution, solid-liquid Separate, add 0.4-0.6g/L PdCl2Activate with in 20-22ml/L HCl activating solution, solid-liquid separation, and add secondary after drying In sodium phosphite aqueous solution, stirring forms suspension, adds in modification liquid, and after stirring reaction, solid-liquid separation obtains；
Wherein, modification liquid forms: copper sulfate 7.5g/L-15g/L, formaldehyde 15ml/L-25ml/L, sodium potassium tartrate tetrahydrate 20-30g/L, A, a` mono-bipyridyl 10mg-20mg/L, nickel potassium cyanide 50mg/L-100mg/L, sodium hydroxide 6-9/L；
The pH of modification liquid is 11.5-12.5, and useful load is 2-4dm2/ L, temperature is 45-60 DEG C.
Described useful load refers to that one square decimeter of surface area of Brush Plating needs the capacity of electroplating solution.
Not only solve powder by above cladding to co-deposit in coating and equally distributed problem, and the cladding of Cu is also The problem that can improve the corrosive nature decline that coating causes due to the addition of nano-particle.
Improving nanometer B4C granule agglomeration traits in the solution, Cu deposition in coating is possible not only to the thinnest Changing coating cellular structure, Cu also shows in saline solution system and preferentially corrodes mechanism, thus Ni alloy is provided negative electrode Protective effect, whole coating shows as the electrochemistry system being made up of a large amount of Ni-Cu uniform Two dimensional Distribution of microcosmic erosion unit System, compensate for owing to the addition of particle causes increasing interface and hole so that more microdefect occurs in coating, finally makes The corrosive nature becoming local corrosion galvanic element quantity to increase and to cause declines.
Preferably in scheme, when preparing nickel dam, the control brush plating time is 50s-90s.
Preferably in scheme, during preparation Ni-P-Ce coating, the control brush plating time is 3-4min.
Preferably in scheme, during preparation Ni-P-Ce-B4C (Cu) coating, the control brush plating time is 4-5min.
Preferably in scheme, the plating piece after brush plating being completed is at 400-430 DEG C, after constant temperature processes 0.5h-1.5h, takes out sample Air cooling, obtains finished product.
Preferably in scheme, carrying out controlling voltage during the brush plating of plating solution A-1 is 11V, uses the positive connection, brush plating speed to be 50-80mm/s。
Preferably in scheme, controlling voltage during brush plating nickel is 12V, and using positive connection, brush plating speed is 40-80mm/s.
Preferably in scheme, during brush plating nickel, the control brush plating time is 50s-90s.
Preferably in scheme, being coated with by Cu in the whipping process that B4C adds in the remaining liquid B of plating, controlling rotating speed is 200-300r/min。
Preferably in scheme, during brush plating Ni-P-Ce-B4C (Cu) coating, control voltage is 11V, uses positive connection, brush plating Speed is 40-80mm/s.
Preferably in scheme, the process of base material activation processing is:
1) base material wiping organic solvent-acetone being carried out manual oil removing, the time is 20-60s.
2) the clean oil removing of electricity, using positive connection, regulation voltage is 12V, dips the clean liquid of electricity by plated pen and base material is carried out brush plating, brush Plating speed is 60-100mm/s, and the time is 15s-30s.After brush plating is complete, clean with deionized water.
3) activating solution activation: an activating solution activation regulation voltage is 12V, uses opposition method, and brush plating speed is 90-130mm/s, the time is 20s-30s.Voltage 12V need to be regulated during No. three activating solution activation, use opposition method, brush plating speed For 90-130mm/s, the time is 50s-90s.
A number activating solution consists of: 98% concentrated sulphuric acid 44.6ml/L, ammonium sulfate 110.9g/l, pH=0.4；No. three activating solution compositions For citric acid 94.2g/L, trisodium citrate 141.2g/L, Nickel dichloride. 3g/L, pH=4.
The clean liquid of electricity consist of sodium hydroxide 25g/L, sodium carbonate 21.6g/L, sodium phosphate 50g/L, sodium chloride 2.4g/L, pH=13.
Preferably in scheme, described plating solution A-1 is prepared by following proposal:
Preferably in scheme, according to required plating solution in the component of designed plating solution A-1 and concentration and actual production process The volume of A-1 is joined and is taken nickel sulfate, sodium hypophosphite, citric acid, trisodium citrate, glacial acetic acid, sodium sulfate, dodecyl Sodium sulfate, cerous nitrate；Joined with a small amount of deionized water dissolving the most respectively take nickel sulfate, sodium hypophosphite, citric acid, Trisodium citrate, sodium sulfate, obtain nickel sulfate solution, ortho phosphorous acid sodium solution, citric acid solution, citric acid three sodium solution, Metabisulfite solution；Then the citric acid solution joined, citric acid three sodium solution and glacial acetic acid are mixed, be uniformly mixing to obtain network Mixture solution；Again enveloping agent solution is mixed homogeneously with nickel sulfate solution, obtain solution A；The most successively by cerous nitrate, sulfur Acid sodium solution addition solution A stirs, obtains solution B.The most under fast stirring, ortho phosphorous acid sodium solution is added Enter in solution B, finally with 15% weak ammonia, the pH value of solution B is regulated to 3.0-4.0, obtain plating solution A-1.
Preferably in scheme, described base material is ink knife, and length substrate is 35.0cm.
The length being typically based on brush plating sample during brush plating finally controls the thickness of institute's plating coating to control the time.
Beneficial effects of the present invention
The material of the present invention can not only substantially increase the hardness of coating, and can improve wear-and corrosion-resistant material the most to a great extent The wearability of material.
The current efficiency of the present invention is high, alloy deposition accelerates, and inorganic particle is adsorbed onto by force the time captured by mechanism and contracts from producing Short, the most buried granule is reduced by external impact and the probability fallen off, and is more beneficial for inorganic particle at alloy substrate In deposition.
The defects such as the crystal boundary of wear-and corrosion-resistant material that obtains, dislocation, omission reduce, and the corrosion resistance of coating and bond strength improve. Largely improve the overall performance of the material of the present invention.
Instant component is reasonable, preparation technology is simple, effectively improves the second phase insoluble particles and disperses uneven in the plating solution Problem, promotes that the decrystallized of Ni-P alloy, the defect such as crystal boundary, dislocation, omission reduce, and corrosion resistance increase compensate for The defect that corrosion resistance reduces is caused due to the interpolation of nano-particle.Case hardness and the anti-wear performance of the material obtained are all Excellent, be suitable to industrialized production, expand its application.
Accompanying drawing explanation
Fig. 1 is the example of the process chart of multilamellar Ni-P-Cu-Ce/B4C composite deposite Brush Plating.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail rather than limits the invention, the essence of the present invention In god and claims, any amendment that the present invention is made or change, both fall within protection scope of the present invention.
Embodiment 1
According to the volume of plating solution A-1 required in the component of plating solution A-1 and concentration requirement and actual production process spend respectively from Sub-water dissolution 240g nickel sulfate, 15g sodium hypophosphite, 20g citric acid, 20g trisodium citrate, 18g sodium sulfate, 0.1g Sodium lauryl sulphate, 25g cerous nitrate, join and take 20ml glacial acetic acid；Then by the citric acid solution joined, trisodium citrate Solution and glacial acetic acid stirring 6min obtain enveloping agent solution；Enveloping agent solution is mixed homogeneously with nickel sulfate solution 10min again, Obtain solution A；The most successively cerous nitrate, metabisulfite solution are added stirring 5min in solution A, obtain solution B.Afterwards Under fast stirring, ortho phosphorous acid sodium solution is slowly added in solution B, stirs 20min.Finally adjust by pH adjusting agent Joint pH value of solution=3.0, constant volume 1L.Wherein pH adjusting agent is 15% weak ammonia, and preparation obtains plating solution A-1.
B4C nanometer powder (particle diameter is 50nm) is through the NH of 10wt%4F solution roughening 20min, 10g/L SnCl2With Sensitization 3min and at 0.5g/L PdC in 4g/L HCl solutionl2After 22ml/L HCl activating solution activates 3min, centrifugal Separating and dry, insert modification liquid and carry out Cu cladding, modification liquid component is: copper sulfate 10g/L, formaldehyde 25ml/L, winestone Acid potassium sodium 25g/L, A, a` mono-bipyridyl 10mg/L, nickel potassium cyanide 50mg/L, sodium hydroxide 7g/L, pH are 12.5, dress Carrying capacity is 2dm2/ L, temperature is 40 DEG C, after stirring reaction, solid-liquid separation, obtain being coated with the B4C granule of Cu；Described The particle diameter of the B4C granule of cladding Cu is 100nm.
Carry out surface of the work pretreatment on ink knife surface, first dip the manual oil removing in acetone wipe substrate surface with absorbent cotton, Time is 20s；The clean oil removing of electricity, using positive connection, regulation voltage is 12V, dips the clean liquid of electricity by plated pen and wipes base material Wiping, wiping speed is 60mm/s, and the time is 30s.After having brushed, clean with deionized water；Activating solution activates: soak by plated pen Dipping in No. 1 activating solution and base material carries out wiping, regulation voltage is 12V, uses opposition method, and brush plating speed is 90mm/s, the time For 30s；Need to regulate voltage 12V during No. 3 activating solution activation, use opposition method, brush plating speed is 90mm/s, and the time is 90s.
B4C granule modified for 35g is added in plating solution A-1, carries out ultrasonic vibration 10min, then carry out mechanical agitation 15min, control rotating speed is 200r/min, obtains plating solution A-2.
After base material after activation is cleaned with deionized water, with 12V voltage, use positive connection, dip containing nickel plating bath by plated pen Base material is carried out brush plating, and speed 40mm/s during brush plating, the time is 50s, obtains base material/Ni layer sample (wherein first Ni layer thickness is 0.5 μm), with 11V voltage, use positive connection, dip plating solution A-1 by plated pen and sample is carried out brush plating, During brush plating, speed is 40mm/s, and the time is 3min, obtains (the wherein Ni-P-Ce plating of a base material/Ni layer/Ni-P-Ce sample Layer thickness is 5 μm)；Behind deionized water washed samples surface, with 12V voltage, use positive connection, dip by plated pen and contain Nickel plating bath carries out brush plating to base material, speed 40mm/s during brush plating, and the time is 50s, obtains base material/Ni/Ni-P-Ce/Ni sample (thickness of the most special nickel sandwich of layers is 0.5 μm)；Behind deionized water washed samples surface, with 11V voltage, with plating Pen is dipped plating solution A-2 and sample is carried out brush plating, uses positive connection, and during brush plating, speed is 40mm/s, and the time is 4min, To base material/Ni/Ni-P-Ce/Ni/Ni-P-Ce-B4C (Cu) sample (wherein brush plating Ni-P-Ce-B4C (Cu) thickness is 6 μm).Will Ni/Ni-P-Ce/Ni/Ni-P-Ce-B4C (Cu) the MULTILAYER COMPOSITE coating of preparation is at 400 DEG C, and constant temperature processes 1.5h, takes out sky Cold, prepare final coating sample.
End properties detected value is as follows:
Cross section microhardness is 1053HV, and corrosion current density is 3.85 μ A, and corrosion potential is-213mV.
Embodiment 2
According to the volume of plating solution A-1 required in the component of plating solution A-1 and concentration requirement and actual production process spend respectively from Sub-water dissolution 260g nickel sulfate, 20g sodium hypophosphite, 20g citric acid, 20g trisodium citrate, 18g sodium sulfate, 0.1g Sodium lauryl sulphate, 35g cerous nitrate, join and take 20ml glacial acetic acid；Then by the citric acid solution joined, trisodium citrate Solution and glacial acetic acid stirring 6min obtain enveloping agent solution；Enveloping agent solution is mixed homogeneously with nickel sulfate solution 10min again, Obtain solution A；The most successively cerous nitrate, metabisulfite solution are added stirring 5min in solution A, obtain solution B.Afterwards Under fast stirring, ortho phosphorous acid sodium solution is slowly added in solution B, stirs 20min.Finally adjust by pH adjusting agent Whole pH value of solution=4.0, constant volume 1L.Wherein pH adjusting agent is 15% weak ammonia, and now plating solution A-1 preparation is complete.
B4C powder is through the NH of 0wt%4F solution roughening 25min, 10g/L SnCl2With sensitization 5min in 4g/L HCl solution And at 0.5g/L PdCl2Dry with centrifugation after activation 5min in 22ml/L HCl activating solution, insert modification liquid and carry out copper Cladding, modification liquid component is: copper sulfate 12g/L, formaldehyde 20ml/L, sodium potassium tartrate tetrahydrate 25g/L, A, a` mono-bipyridyl 15mg/L, Nickel potassium cyanide 75mg/L, sodium hydroxide 7g/L, pH are 11, useful load 3dm2/ L, temperature is 50 DEG C, after stirring reaction, Solid-liquid separation, obtains being coated with the B4C granule of Cu；The particle diameter of the B4C granule of the described Cu of being coated with is 200nm.
B4C granule modified for 55g is added in plating solution A-1, carries out ultrasonic vibration 10min, then carry out mechanical agitation 15min, control rotating speed is 250r/min, obtains plating solution A-2.
Carry out surface of the work pretreatment on ink knife surface, first dip the manual oil removing in acetone wipe substrate surface with absorbent cotton 40s；The clean oil removing of electricity, using positive connection, regulation voltage is 12V, dips the clean liquid of electricity by plated pen and base material is carried out wiping, wiping Speed is 80mm/s, and the time is 25s.After having brushed, clean with deionized water；Activating solution activates: dip No. 1 work by plated pen Changing liquid and base material carries out wiping, regulation voltage is 12V, uses opposition method, and brush plating speed is 110mm/s, and the time is 25s； Need to regulate voltage 12V during No. 3 activating solution activation, use opposition method, brush plating speed is 110mm/s, and the time is 70s.
After base material after activation is cleaned with deionized water, with 12V voltage, use positive connection, dip containing nickel plating bath by plated pen Base material is carried out brush plating, and speed 50mm/s during brush plating, the time is 50s, and (the most special nickel is thick to obtain base material/Ni layer sample Degree is 1.0 μm)；, with 11V voltage, use positive connection, dip plating solution A-1 by plated pen and sample is carried out brush plating, during brush plating Speed is 60mm/s, and the time is 3.5min, obtains base material/Ni/Ni-P-Ce sample (wherein Ni-P-Ce thickness of coating is 6 μm)； Behind deionized water washed samples surface, with 12V voltage, use positive connection, dip by plated pen and containing nickel plating bath, base material is carried out Brush plating, speed 60mm/s during brush plating, the time is 70s, and (the most special nickel is sandwich to obtain base material/Ni/Ni-P-Ce/Ni sample The thickness of layer is 1.0 μm)；Behind deionized water washed samples surface, with 11V voltage, dip plating solution A-2 pair by plated pen Sample carries out brush plating, uses positive connection, and during brush plating, speed is 60mm/s, and the time is 4.5min, obtains base material / Ni/Ni-P-Ce/Ni/Ni-P-Ce-B4C (Cu) sample (wherein brush plating Ni-P-Ce-B4C (Cu) thickness is 7.0 μm).Will preparation Ni/Ni-P-Ce/Ni/Ni-P-Ce-B4C (Cu) MULTILAYER COMPOSITE coating at 415 DEG C, constant temperature process 1.0h, take out air cooling, Prepare final coating sample.
End properties detected value is as follows:
Cross section microhardness is 1052HV, and corrosion current density is 3.79 μ A, and corrosion potential is-214mV.
Embodiment 3
Ion is spent respectively according to the volume of plating solution A-1 required in the component of plating solution A and concentration requirement and actual production process Water dissolution 280g nickel sulfate, 25g sodium hypophosphite, 20g citric acid, 20g trisodium citrate, 18g sodium sulfate, 0.1g Sodium lauryl sulphate, 45g cerous nitrate, join and take 20ml glacial acetic acid；Then by the citric acid solution joined, trisodium citrate Solution and glacial acetic acid stirring 6min obtain enveloping agent solution；Enveloping agent solution is mixed homogeneously with nickel sulfate solution 10min again, Obtain solution A；The most successively cerous nitrate, metabisulfite solution are added stirring 5min in solution A, obtain solution B.Afterwards Under fast stirring, ortho phosphorous acid sodium solution is slowly added in solution B, stirs 20min.Finally adjust by pH adjusting agent Whole pH value of solution=5.0, constant volume 1L.Wherein regulator is 15% weak ammonia, and now plating solution A-1 preparation is complete.
B4C powder is roughened sensitization 8min in 30min, 10g/L SnCl2 and 4g/L HCl solution through the NH4F solution of 10% And after activating 8min in 0.5g/L PdCl2 and 22ml/L HCl activating solution, centrifugation is dried, and inserts modification liquid and enters Row copper clad, modification liquid component is: copper sulfate 10g/L, formaldehyde 15ml/L, sodium potassium tartrate tetrahydrate 25g/L, A, a` mono-bipyridyl 20mg/L, nickel potassium cyanide 100mg/L, sodium hydroxide 7g/L, pH11, useful load 4dm2/ L, temperature is 60 DEG C, stirring After reaction, solid-liquid separation, obtain being coated with the B4C granule of Cu；The particle diameter of the B4C granule of the described Cu of being coated with is 200nm.
B4C granule modified for 75g is added in plating solution A-1, carries out ultrasonic vibration 10min, then carry out mechanical agitation 15min, control rotating speed is 300r/min, obtains plating solution A-2.
Carry out surface of the work pretreatment on ink knife surface, first dip the manual oil removing in acetone wipe substrate surface with absorbent cotton 60s；The clean oil removing of electricity, using positive connection, regulation voltage is 12V, dips the clean liquid of electricity by plated pen and base material is carried out wiping, wiping Speed is 100mm/s, and the time is 20s.After having brushed, clean with deionized water；Activating solution activates: dip No. 1 by plated pen Activating solution carries out wiping to base material, and regulation voltage is 12V, uses opposition method, and brush plating speed is 130mm/s, and the time is 20s； Need to regulate voltage 12V during No. 3 activating solution activation, use opposition method, brush plating speed is 130mm/s, and the time is 50s.
After base material after activation is cleaned with deionized water, with 12V voltage, use positive connection, dip containing nickel plating bath by plated pen Base material is carried out brush plating, and speed 50mm/s during brush plating, the time is 90s, and (the most special nickel is thick to obtain base material/Ni layer sample Degree is 1.5 μm)；, with 11V voltage, use positive connection, dip plating solution A-1 by plated pen and sample is carried out brush plating, during brush plating Speed is 80mm/s, and the time is 4min, obtains base material/Ni/Ni-P-Ce sample (wherein Ni-P-Ce thickness of coating is 7.0 μm)； Behind deionized water washed samples surface, with 12V voltage, use positive connection, dip by plated pen and containing nickel plating bath, base material is carried out Brush plating, speed 80mm/s during brush plating, the time is 90s, and (the most special nickel is sandwich to obtain base material/Ni/Ni-P-Ce/Ni sample The thickness of layer is 1.5 μm)；Behind deionized water washed samples surface, with 11V voltage, dip plating solution A-2 pair by plated pen Sample carries out brush plating, uses positive connection, and during brush plating, speed is 80mm/s, and the time is 5min, obtains base material / Ni/Ni-P-Ce/Ni/Ni-P-Ce-B4C (Cu) sample (wherein brush plating Ni-P-Ce-B4C (Cu) thickness is 8.0 μm).Will preparation Ni/Ni-P-Ce/Ni/Ni-P-Ce-B4C (Cu) MULTILAYER COMPOSITE coating at 430 DEG C, constant temperature process 0.5h, take out air cooling, Prepare final coating sample.
The performance detected value of product is as follows:
Cross section microhardness is 1033HV, and corrosion current density is 3.87 μ A, and corrosion potential is-201mV.
Comparative example 1
With deionized water dissolving 280g nickel sulfate, 25g sodium hypophosphite, 20g citric acid, 20g trisodium citrate, 18g Sodium sulfate, 0.1g sodium lauryl sulphate, 45g cerous nitrate, join and take 20ml glacial acetic acid；Then by the citric acid solution joined, Citric acid three sodium solution and glacial acetic acid stirring 6min obtain enveloping agent solution；Again enveloping agent solution is mixed with nickel sulfate solution Uniformly 10min, obtains solution A；The most under fast stirring, ortho phosphorous acid sodium solution is slowly added in solution B, stirs Mix 20min.Finally adjust pH value of solution=5.0 with pH meter, constant volume 1L.Wherein regulator is 15% weak ammonia, now plating solution A preparation is complete.
Carry out surface of the work pretreatment on ink knife surface, first dip the manual oil removing in acetone wipe substrate surface with absorbent cotton 60s；The clean oil removing of electricity, using positive connection, regulation voltage is 12V, dips the clean liquid of electricity by plated pen and base material is carried out wiping, wiping Speed is 100mm/s, and the time is 20s.After having brushed, clean with deionized water；Activating solution activates: dip No. 1 by plated pen Activating solution carries out wiping to base material, and regulation voltage is 12V, uses opposition method, and brush plating speed is 130mm/s, and the time is 20s； Need to regulate voltage 12V during No. 3 activating solution activation, use opposition method, brush plating speed is 130mm/s, and the time is 50s.To live After base material after change cleans with deionized water, with 12V voltage, use positive connection, dip containing nickel plating bath, base material to be entered by plated pen Row brush plating, speed 50mm/s during brush plating, the time is 90s, obtains base material/Ni layer sample (the most special nickel thickness is 1.5 μm)；, With 11V voltage, using positive connection, dip plating solution A by plated pen and sample is carried out brush plating, during brush plating, speed is 80mm/s, Time is 4min, obtains base material/Ni/Ni-P sample.By the Ni/Ni-P composite deposite of preparation at 400 DEG C, constant temperature processes 0.5h, takes out air cooling, prepares final coating sample.
End properties detected value is as follows:
Cross section microhardness is 780HV, and corrosion current density is 7.81 μ A, and corrosion potential is-311.8mV.

Claims (10)

1. the wear-and corrosion-resistant material of band Ni-P-Ce-B4C (Cu) composite deposite, it is characterised in that described wear-and corrosion-resistant material from In to including base material, a Ni coating, Ni-P-Ce coating, the 2nd Ni coating, Ni-P-Ce-B4C (Cu) coating successively outward.
Wear-and corrosion-resistant material the most according to claim 1, it is characterised in that a described Ni coating, the 2nd Ni coating Thickness be 0.5-1.5 μm.
Wear-and corrosion-resistant material the most according to claim 1 and 2, it is characterised in that the thickness of described Ni-P-Ce coating 5.0-7.0μm。
Wear-and corrosion-resistant material the most according to claim 3, it is characterised in that the thickness of described Ni-P-Ce-B4C (Cu) coating For 6.0-8.0 μm.
5. the preparation technology of the wear-and corrosion-resistant material of band Ni-P-Ce-B4C (Cu) wear-and corrosion-resistant composite deposite, it is characterised in that Substrate surface brush plating the oneth Ni coating, Ni-P-Ce coating, the 2nd Ni coating, Ni-P-Ce-B4C (Cu) the most successively Coating.
Preparation technology the most according to claim 5, it is characterised in that comprise the following steps that:
Step one:
Under the conditions of 40-50 DEG C, clean for activation processing rear surface base material is used the brush plating carrying out nickel containing nickel plating bath, obtain base material/ Oneth Ni coating；
Step 2:
Base material/Ni coating sample use water is cleaned, carries out the brush plating of plating solution A-1, obtain a base material/Ni coating/Ni-P-Ce Coating sample, reuses the brush plating carrying out nickel containing nickel plating bath, obtains a base material/Ni coating/Ni-P-Ce coating after cleaning with water / the two Ni coating and the remaining liquid B of plating；Cu is coated with B4C granule add in the remaining liquid B of plating, controls Cu cladding B4C at the remaining liquid of plating In B, concentration is 35-75g/L, carries out ultrasonic disperse, stirring, obtains plating solution A-2, uses plating solution A-2 to implement brush plating subsequently, To a base material/Ni coating/Ni-P-Ce coating/the 2nd Ni coating/Ni-P-Ce-B4C (Cu) coating sample；
Described include following components containing nickel plating bath: six hydration nickel sulfate 320-350g/L, citric acid 60-80g/L, boric acid 15-30g/L, Carboxylic acid, during plating, is 1-3 containing nickel plating bath pH；
Described brush plating liquid A-1 includes following components: nickel sulfate 240g/L-280g/L, sodium hypophosphite 15-25g/L, citric acid 20-30g/L, trisodium citrate 15-25g/L, sodium sulfate 15-20g/L, glacial acetic acid 20-30ml/L, sodium lauryl sulphate 0.1-0.3g/L, cerous nitrate 25-45g/L；
During plating, the pH value of plating solution A-1 controls: 3.0-5.0.
Preparation technology the most according to claim 6, it is characterised in that the granularity of described Cu cladding B4C granule is 100-350nm。
8. according to the preparation technology described in claim 6 or 7, it is characterised in that described Cu cladding B4C granule will be by receiving It is the NH of 8-12wt% that rice B4C powder immerses concentration4In F solution after roughening treatment, solid-liquid separation adds 10-11g/L SnCl2 With sensitization in 4-5g/L HCl solution, solid-liquid separation, add 0.4-0.6g/L PdCl2Activate with in 20-22ml/L HCl activating solution, Add stirring in ortho phosphorous acid sodium water solution after solid-liquid separation, and drying and form suspension, add in modification liquid, after stirring reaction, Solid-liquid separation obtains；
Wherein, modification liquid composition: copper sulfate 7.5g/L-15g/L, formaldehyde 15ml/L-25ml/L, sodium potassium tartrate tetrahydrate 20-30g/L, A, a` One bipyridyl 10mg-20mg/L, nickel potassium cyanide 50mg/L-100mg/L, sodium hydroxide 6-9/L；
The pH of modification liquid is 11.5-12.5, and useful load is 2-4dm2/ L, temperature is 45-60 DEG C.
Preparation technology the most according to claim 6, it is characterised in that when preparing nickel dam, the control brush plating time is 50s-90s；
During preparation Ni-P-Ce coating, the control brush plating time is 3-4min；
During preparation Ni-P-Ce-B4C (Cu) coating, the control brush plating time is 4-5min.
10. according to the preparation technology described in claim 6 or 9, it is characterised in that the plating piece after brush plating being completed exists 400-430 DEG C, after constant temperature processes 0.5h-1.5h, air cooling, obtain finished product.
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