CN100464010C

CN100464010C - Ni-P-W alpha aluminium oxide composite electroplating formula and its technology

Info

Publication number: CN100464010C
Application number: CNB2005101183975A
Authority: CN
Inventors: 刘峥; 范峰
Original assignee: Guilin University of Technology
Current assignee: Guilin University of Technology
Priority date: 2005-11-01
Filing date: 2005-11-01
Publication date: 2009-02-25
Anticipated expiration: 2025-11-01
Also published as: CN1786293A

Abstract

The invention discloses a Ni-P-W-alpha-Al2O3 composite plating formula and technique. The formula components includes: nickel sulfate, nickel chloride, secondary phosphorous acid, sodium tungstate, boric acid and alpha-Al2O3. Preparing composite bath includes the following steps: grinding micron Al2O3 and 0.08-0.12g/L C12H25NaO3S to put into bath; fast mechanical stirring; the average grain diameter of the ground micron Al2O3 is less than 2micron; nmAl2O3 can directly be put into bath; it can be dispersed by supersonic wave; dissolving NiSO4 and NiCl2 in distilled water; adding H3BO3 and NaH2PO2 solution; transferring to Na2WO4 solution. The composite plating can reduce Ni-P-W alloy plating internal stress and crack. Compared with the Ni-P-W plating, the Ni-P-W-alpha-Al2O3 composite plating has high hardness, wear resistance, and high temperature antioxygenic property.

Description

Ni-P-W-α-Al 2O 3Composite electroplating formula and technology

Technical field

The present invention relates to the composite electrodeposition research field, is composite deposite preparation prescription and technology, particularly the Ni-P-W-α-Al of codeposition material with the multicomponent alloy ₂O ₃Composite electroplating formula and technology.

Background technology

Composite deposite is to utilize the metal electrodeposition method that a kind of or several insoluble solia particles are mixed in the middle of the metal plating and the special coating that forms equably.Since nineteen twenty, Germany scientist obtained first composite deposite, so far, composite plating process and application thereof had obtained great development.The prepared by electrodeposition composite deposite is mainly used in the hardness that improves material at first, wear-resisting, corrosion resisting property, then just be further used for preparing electrocatalysis and light active material at present, and the development and use aspect fields such as energy storage, and from early stage be matrix metal mainly with monometallics such as nickel, copper, cobalts, with SiC, SiO ₂, Al ₂O ₃, Cr ₃C ₂Deng the composite plating of refractory ceramics powder, develop into the various alloys that can satisfy the specific function needs, multiple particulate composite depositing process as inclusion; Occurred again in recent years with metal oxide, conductive polymers is as the composite deposite of matrix.Simultaneously, except that the aqueous solution deposition composite deposite, can also from non-aqueous solution, deposit composite deposite.In addition, by adopting the periodic reverse electric current, the composite deposite, the particularly composite deposite that is mingled with nano particle that is obtained by nanotechnology that pulsed current etc. obtain has the more excellent performance of composite deposite that obtains down than galvanic current, thereby further widened the range of application of composite deposite.The Ni-P-W alloy layer has higher hardness, wear-resisting preferably, corrosion resisting property, Chinese scholars has been carried out extensive studies to the technology and the performance of deposit N i-P-W alloy, but, the internal stress of this alloy layer is higher, if the too thick meeting of coating cracks, thereby influenced its practical application.Ni-P-W-α-Al ₂O ₃Compound plating technology and prescription do not appear in the newspapers.

Summary of the invention

The purpose of this invention is to provide a kind ofly, utilized α-Al at steel surface ₂O ₃Prescription and technology with Ni-P-W alloy codeposition formation composite deposite.

On steel surface, carry out composite electrodeposition, at first will polish, after the oil removing, chemical rightenning, 5% salt acid dipping, carry out composite plating again the matrix carbon steel.Ni-P-W-α-Al ₂O ₃Composite plating is mainly filled a prescription and mainly is made up of following material: single nickel salt, nickelous chloride, inferior sodium phosphate, sodium wolframate, boric acid, α-Al ₂O ₃Undertaken by following mode during the preparation composite plating bath: 1) μ mAl ₂O ₃With 0.08-0.12g/L tensio-active agent Sodium dodecylbenzene sulfonate C ₁₂H ₂₅NaO ₃S grinds the back together and moves in the plating bath, and mechanical stirring 0.5-1 hour fast, with μ mAl ₂O ₃Fully be suspended in the plating bath.Through the μ mAl after grinding ₂O ₃The particulate median size is determined as less than 2 μ m through laser particle analyzer.If use nmAl ₂O ₃Then directly add in the plating bath, utilize ultrasonic wave nmAl ₂O ₃Be dispersed in the plating bath.2) each component adding mode of composite plating bath is: with NiSO ₄, NiCl ₂Be dissolved in distilled water, add H again ₃BO ₃Solution and NaH ₂PO ₂Solution is transferred to Na at last ₂WO ₄In the solution.

Composite electrodeposition Ni-P-W-α-Al on the carbon steel ₂O ₃Prescription and technology:

NiSO ₄·6H ₂O 235-245g/L

NiCl ₂·6H ₂O 35-45g/L

NaH ₂PO ₂·H ₂O 10-20g/L

Na ₂WO ₄·2H ₂O 3-9g/L

H ₃BO ₃ 25-35g/L

μ mAl ₂O ₃Or nmAl ₂O ₃45-55g/L

Asccharin is a small amount of

Current density 1.5-2.5A/cm ²

Temperature 55-65 ℃

pH 4.5-5.5

Electroplating time 1-1.5h

Utilize above-mentioned prescription and technology, can obtain outward appearance light, smooth, Al ₂O ₃Content is 11.93% composite deposite.With scanning electron microscope, x-ray diffractometer, energy spectrometer, mensuration Ni-P-W, Ni-P-W-nmAl ₂O ₃, Ni-P-W-μ mAl ₂O ₃3 kinds of coating surface morphologies, phase structure, composition and content, the result is as follows:

1) the SEM photo shows the Ni-P-W alloy with laminated crystalline, numerous bag shape thing not of uniform size in its surface arrangement; Add Al ₂O ₃After, because Al ₂O ₃The embedding of particulate, SEM photo show the refinement of the existing institute of bag shape thing, Ni-P-W-nmAl ₂O ₃The performance of composite deposite is more obvious.

2) the XRD figure stave is bright under plated state, and 3 kinds of coating are based on non-crystalline state, and part is crystallization.Through handling in 1 hour 450 ℃ of insulations, the crystalline state trend of 3 kinds of coating strengthens.

3) the EDS collection of illustrative plates shows under plated state, and Ni-P-W coating mainly contains Ni, P, W, C, O element; Ni-P-W-nmAl ₂O ₃Coating mainly contains Ni, P, W, Al, C, O element; Ni-P-W-μ mAl ₂O ₃Coating mainly contains Ni, P, W, Al, C, O element.

4) through the hardness tester test shows, the hardness level of 3 kinds of coating is in proper order: Ni-P-W-nmAl ₂O ₃Coating〉Ni-P-W-μ mAl ₂O ₃Coating〉Ni-P-W coating, after 450 ℃ of insulations were handled in 1 hour, the hardness of 3 kinds of coating was improved, but added Al ₂O ₃Particle, particularly nanometer Al ₂O ₃Hardness improves more remarkable.

5) high temperature oxidation resistance of composite deposite is better than the Ni-P-W alloy layer.The hardness level of 3 kinds of coating is in proper order: Ni-P-W-nmAl ₂O ₃Coating=Ni-P-W-μ mAl ₂O ₃Coating〉Ni-P-W coating.

α-Al that the present invention is higher with hardness ₂O ₃Form composite deposite with Ni-P-W alloy codeposition, reduced its internal stress and crackle, compare the Ni-P-W-α-Al of its acquisition with Ni-P-W coating ₂O ₃Composite deposite has higher hardness and wear resistance and high-temperature oxidation resistance.

Embodiment

Ni-P-W-nmAl ₂O ₃Composite electrodeposition plating prescription and technology:

1, substrate pretreated technology and prescription

(1) oil removing

The plating piece surface speckles with greasy dirt, therefore need carry out oil removing to plating piece under 60-80 ℃.The degreasing fluid prescription is as follows:

NaOH 70g/L

Na ₂CO ₃ 40g/L

Na ₃PO ₄·12H ₂O 20g/L

Na ₂SiO ₃ 6g/L

The OP-10 emulsifying agent is a small amount of

(2) chemical rightenning and 5% salt acid dipping

Because the plating piece surface irregularity need carry out chemical rightenning to the plating piece surface and handle about 60 ℃, after polishing finishes, uses 5% salt acid dipping more at normal temperatures.The polishing fluid prescription is as follows:

H ₂SO ₄ 230ml/L

HC1 70ml/L

HNO ₃ 40ml/L

H ₂O 660ml/L

2, the prescription and the processing condition of composite electrodeposition plating basal liquid

NiSO ₄·6H ₂O 240g/L

NiCl ₂·6H ₂O 40g/L

NaH ₂PO ₂·H ₂O 15g/L

Na ₂WO ₄·2H ₂O 6g/L

H ₃BO ₃ 30g/L

μmAl ₂O ₃ 50g/L

Asccharin is a small amount of

Current density 2A/cm ²

60 ℃ of temperature

pH 5.0

Electroplating time 1h

Undertaken by following mode during the preparation composite plating bath: 1) μ mAl ₂O ₃With 0.1g/L tensio-active agent Sodium dodecylbenzene sulfonate C ₁₂H ₂₅NaO ₃S grinds the back together and moves in the plating bath, and mechanical stirring is 1 hour fast, with μ mAl ₂O ₃Fully be suspended in the plating bath.Through the μ mAl after grinding ₂O ₃The particulate median size is determined as 1.6 μ m through laser particle analyzer.2) each component adding mode of composite plating bath is: with NiSO ₄6H ₂O, NiCl ₂6H ₂O is dissolved in distilled water, adds H again ₃BO ₃Solution and NaH ₂PO ₂H ₂O solution is transferred to Na at last ₂WO ₄2H ₂In the O solution.

The concrete operation method of composite plating is as follows: electroplate and carry out in Hull groove or plating tank.The basal liquid that at first adds 200-250mL in groove (contains the Al that disperses or fully suspend ₂O ₃), in coating bath, install mechanical stirrer, control stirring velocity well, and Hull groove or plating tank are placed the constant temperature water temperature, guarantee that in electroplating process, bath temperature is constant.With the nickel plate is anode, and negative electrode adopts soft steel after pre-treatment, carries out continuous current and electroplates the single face plating.

Claims

1. Ni-P-W-α-Al ₂O ₃Composite plating process comprises oil removing, chemical rightenning and salt acid dipping pre-treatment, it is characterized in that pre-treatment after composite plating process as follows:

NiSO ₄·6H ₂O 235-245g/L

NiCl ₂·6H ₂O 35-45g/L

NaH ₂PO ₂·H ₂O 10-20g/L

Na ₂WO ₄·2H ₂O 3-9g/L

H ₃BO ₃ 25-35g/L

μ mAl ₂O ₃Or nmAl ₂O ₃45-55g/L

Asccharin is a small amount of

Current density 1.5-2.5A/cm ²

Temperature 55-65 ℃

pH 4.5-5.5

Electroplating time 1-1.5h.

2. Ni-P-W-α-Al according to claim 1 ₂O ₃Composite plating process, undertaken by following mode when it is characterized in that preparing composite plating bath:

1) μ mAl ₂O ₃With 0.08-0.12g/L tensio-active agent Sodium dodecylbenzene sulfonate C ₁₂H ₂₅NaO ₃S grinds the back together and moves in the plating bath, and quick mechanical stirring is with μ mAl ₂O ₃Fully be suspended in the plating bath; Through the μ mAl after grinding ₂O ₃The particulate median size is determined as less than 2 μ m through laser particle analyzer; If use nmAl ₂O ₃Then directly add in the plating bath, utilize ultrasonic wave nmAl ₂O ₃Be dispersed in the plating bath;

2) each component adding mode of composite plating bath is: with NiSO ₄6H ₂O, NiCl ₂6H ₂O is dissolved in distilled water, adds H again ₃BO ₃Solution and NaH ₂PO ₂H ₂O solution is transferred to Na at last ₂WO ₄2H ₂In the O solution.