CN104294328A - Nickel-molybdenum-aluminum-rare earth coating and preparation method thereof - Google Patents
Nickel-molybdenum-aluminum-rare earth coating and preparation method thereof Download PDFInfo
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- CN104294328A CN104294328A CN201410569544.XA CN201410569544A CN104294328A CN 104294328 A CN104294328 A CN 104294328A CN 201410569544 A CN201410569544 A CN 201410569544A CN 104294328 A CN104294328 A CN 104294328A
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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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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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
- C25D5/18—Electroplating using modulated, pulsed or reversing current
Abstract
The invention discloses a nickel-molybdenum-aluminum-rare earth coating and a preparation method thereof. The nickel-molybdenum-aluminum-rare earth coating is composed of following four elements: nickel, molybdenum, aluminum and rare earth, wherein calculated by mass percent, the contents of nickel, molybdenum, aluminum and rare earth are respectively 72.95-21.57%, 21.33-43.70%, 3.50-16.70% and 2.22-18.02%. The preparation method comprises the steps: adding a nickel salt, a molybdenum compound, an aluminum salt, a rare earth salt, a complexing agent and a chloride in water, and regulating the pH value to 7.5-9.5 to obtain nickel salt-molybdenum compound-aluminum salt-rare earth salt-complexing agent-chloride electroplating liquid; and then, using a plating piece to be plated as a cathode, using nickel as an anode, putting the cathode and the anode in the electroplating liquid to perform pulse electroplating, flushing the plating piece with water after electroplating, and carrying out air drying to obtain the nickel-molybdenum-aluminum-rare earth coating with strong oxidation corrosion resistance on the surface of the plating piece. The oxidation corrosion resistance of the nickel-molybdenum-aluminum-rare earth coating is stronger than that of a nickel-molybdenum coating and a nickel-molybdenum-aluminum coating.
Description
Technical field
The present invention relates to a kind of nickel molybdenum aluminium rare earth coated and preparation method thereof
.
Background technology
Along with the design inlet temperature of aircraft engine to high thrust-weight ratio demand for development aircraft engine improves constantly, be used alone high-temperature structural material technology and can not have met an urgent demand that advanced aero engine develops rapidly.The practicable method increasing substantially aircraft engine working temperature at present adopts Thermal Barrier Coating Technologies.Obtain the thermal barrier coating of practical application and be mostly bilayer structure, ceramic layer due to have heat insulation, anticorrosive, wash away and erosion performance, as the top layer of thermal barrier coating.Because pottery does not mate with the thermal expansivity of high-temperature structural material, need the metal bonding coating playing a part high temperature oxidation corrosion resistance He improve matrix and ceramic coating physical compatibility, metal bonding coating is bottom.
Current thermal barrier coating adopts that nickel coating, nickel molybdenum coating, nickel molybdenum are rare earth coated, nickel molybdenum-molybdenum disilicide composite deposite, nickel molybdenum rare earth-molybdenum disilicide composite deposite as tack coat, but all there is the technical problems such as antioxidant anticorrosive performance is not bery strong in above-mentioned each bonding layer material.
Summary of the invention
An object of the present invention is the technical problems such as the antioxidant anticorrosive performance in order to solve the coating existence such as above-mentioned nickel molybdenum is not bery strong and provides a kind of nickel molybdenum aluminium rare earth coated.Namely in nickel molybdenum coating, add aluminium and rare earth, coating can be made in oxidising process to form Al
2o
3protective oxide film and improve the antioxidant anticorrosive of coating, can solve the technical problems such as the antioxidant anticorrosive performance of nickel molybdenum coating is not bery strong.
The preparation method that two of object of the present invention is to provide above-mentioned a kind of nickel molybdenum aluminium rare earth coated.
Technical scheme of the present invention
A kind of nickel molybdenum aluminium is rare earth coated, elementary composition by nickel, molybdenum, aluminium, rare earth four kinds, calculates by mass percentage, nickel: molybdenum: aluminium: rare earth is 72.95 ~ 21.57%, 21.33 ~ 43.70%, 3.50 ~ 16.70%, 2.22 ~ 18.02%.
The preparation method that above-mentioned a kind of nickel molybdenum aluminium is rare earth coated, specifically comprises the steps:
(1), by rare earth oxide be dissolved in acid, obtain rare-earth salts;
Described rare earth oxide is one or more the mixture in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, scandium rare earth oxide;
Described acid is nitric acid or hydrochloric acid;
(2) in water, add rare-earth salts, complexing agent, the muriate of nickel salt, molybdenum compound, aluminium salt, step (1) gained, be 7.5 ~ 9.5 by sodium carbonate solution regulator solution pH value, make nickel salt-molybdenum compound-aluminium salt-rare-earth salts-complexing agent-muriate electroplate liquid;
Wherein nickel salt is the mixture of one or more compositions in nickelous chloride, nickelous nitrate, single nickel salt;
Molybdenum compound is the mixture of one or more compositions in molybdenum pentachloride, ammonium molybdate, ammonium phosphomolybdate, Sodium orthomolybdate;
Aluminium salt is the mixture that aluminum chloride, Tai-Ace S 150 or aluminum chloride and Tai-Ace S 150 form;
Complexing agent is the mixture of one or more compositions in oxyacetic acid, Padil, oxalic acid, citric acid, tartrate, lactic acid, succinic acid, oxysuccinic acid;
Muriate is one or more the chloride mix in sodium-chlor, ammonium chloride, Repone K;
In described nickel salt-molybdenum compound-aluminium salt-rare-earth salts-complexing agent-muriate electroplate liquid, nickel salt, molybdenum compound, aluminium salt, rare-earth salts rare earth elements, complexing agent, muriatic concentration are respectively 5 ~ 400g/L, 5 ~ 800g/L, 5 ~ 350g/L, 0.06 ~ 10g/L, 1 ~ 100g/L, 5 ~ 300g/L;
(3), using plating piece to be plated as negative electrode, anode is nickel, nickel salt-molybdenum compound-aluminium salt-rare-earth salts-complexing agent-muriate the electroplate liquid putting into step (1) gained carries out pulse plating, and setting pulse frequency 2000 ~ 5000Hz in pulse plating process, dutycycle are 0.5 ~ 0.9, current density 10 ~ 25A/dm
2, temperature 40 ~ 60 DEG C, rotating speed 100 ~ 600rpm, time 10 ~ 60min, after plating, rinse plating piece use water, air-dry, namely obtains one deck nickel molybdenum aluminium rare earth coated on the surface of plating piece.
Beneficial effect of the present invention
Nickel molybdenum aluminium of the present invention is rare earth coated, owing to adding aluminium and rare earth in nickel molybdenum coating, coating can be made in oxidising process to form Al
2o
3protective oxide film and improve the antioxidant anticorrosive of coating, thus the antioxidant anticorrosive making the nickel molybdenum aluminium that obtains rare earth coated is all stronger than the antioxidant anticorrosive of nickel molybdenum coating and nickel molybdenum aluminium coat.
Further, because general plating in aqueous can not get the coating containing aluminium, the present invention adopts the pulse power, and adds rare earth element in the plating solution, the rare earth element added is not only and forms the rare earth coated source providing rare earth of nickel molybdenum aluminium, and rare earth element is also as the application of plating promotor.Obtain further by experimental verification, when plating solution middle-weight rare earths salt concn is low, when being namely only 0.01 ~ 0.05g/L, rare earth element only does the application of plating promotor, namely when adding rare earth element in the plating solution as plating promotor, adopt the pulse power, can only electroplate in aqueous and obtain a kind of nickel molybdenum aluminium coat; When only having plating solution middle-weight rare earths salt concn to reach 0.06 ~ 10g/L, rare earth element could not be only and form the rare earth coated source providing rare earth of nickel molybdenum aluminium, but also as the application of plating promotor, at this moment electroplates that just to obtain nickel molybdenum aluminium rare earth coated in aqueous.
The Bruker AXS Microanalysis GmbH energy spectrometer mensuration nickel rare earth coated middle aluminium of molybdenum aluminium and content of rare earth is adopted to be respectively 3.5 ~ 16.7% and 2.22 ~ 18.02%.
Embodiment
Below by specific embodiment, the present invention is set forth further, but do not limit the present invention.
The specification of various raw materials used in various embodiments of the present invention and the information of manufacturer, be commercially available.
embodiment 1
A kind of nickel molybdenum aluminium is rare earth coated, elementary composition by nickel, molybdenum, aluminium, rare earth four kinds, calculates by mass percentage, nickel: molybdenum: aluminium: rare earth is 72.95%:21.33 %:3.50%:2.22%.
The preparation method that above-mentioned a kind of nickel molybdenum aluminium is rare earth coated, specifically comprises the steps:
(1), by 0.5856g rare earth oxide be dissolved in 6mL acid, heating, makes it dissolve, and after its cooling, moves in the volumetric flask of 50mL, is diluted with water to scale, obtain the rare earths salt that cerium concentration is 10g/L;
Described rare earth oxide is cerium oxide;
Described acid is concentrated nitric acid;
(2), add in 980mL water 5g nickel salt, 5g molybdenum compound, 5g aluminium salt, 6mL step (1) gained cerium concentration be the rare earths salt of 10g/L, 1g complexing agent, 5g muriate, be 7.5 by sodium carbonate solution regulator solution pH value, add water and be settled to 1L, obtain nickel salt-molybdenum compound-aluminium salt-rare-earth salts-complexing agent-muriate electroplate liquid and nickelous chloride-molybdenum pentachloride-aluminum chloride-cerous nitrate-oxalic acid-sodium-chlor electroplate liquid;
Wherein nickel salt is nickelous chloride;
Molybdenum compound is molybdenum pentachloride;
Aluminium salt is aluminum chloride;
Complexing agent is oxalic acid;
Muriate is sodium-chlor;
In described nickel salt-molybdenum compound-aluminium salt-rare-earth salts-complexing agent-muriate electroplate liquid, nickel salt, molybdenum compound, aluminium salt, rare-earth salts rare earth elements cerium, complexing agent, muriatic concentration are respectively 5g/L, 5g/L, 5g/L, 0.06g/L, 1g/L, 5g/L;
(3) treat that nickel plating alloy plate is as negative electrode, using plating piece 100mm × 100mm × 0.5mm to be plated, anode is the sheet nickel of 150mm × 150mm × 2mm, nickel salt-molybdenum compound-aluminium salt-rare-earth salts-complexing agent-muriate the electroplate liquid putting into step (1) gained carries out pulse plating, and setting pulse frequency 2000Hz in pulse plating process, dutycycle are 0.5, current density 10A/dm
2, temperature 40 DEG C, rotating speed 100rpm, time 60min, after plating, rinse plating piece use water, air-dry, namely obtains the rare earth coated i.e. nickel molybdenum aluminium cerium coating of one deck nickel molybdenum aluminium on the surface of plating piece.
Adopt Bruker AXS Microanalysis GmbH energy spectrometer to measure nickel, molybdenum, aluminium, cerium content in the nickel molybdenum aluminium cerium coating of above-mentioned gained, calculate by mass percentage and be respectively 72.95%, 21.33%, 3.50%, 2.22%.
By the above-mentioned plating piece constant temperature oxidation 48h in the air atmosphere of 1100 DEG C being coated with nickel molybdenum aluminium cerium coating, natural stove is chilled to room temperature subsequently, measure the quality before plating piece oxidation and the quality after oxidation respectively with BS224S type electronics Libra, the rear quality of this plating piece oxidation must increase to 0.025mg/cm
2.
embodiment 2
A kind of nickel molybdenum aluminium is rare earth coated, elementary composition by nickel, molybdenum, aluminium, rare earth four kinds, calculates by mass percentage, nickel: molybdenum: aluminium: rare earth is 21.57%:43.70 %:16.70%:18.03%.
The preparation method that above-mentioned a kind of nickel molybdenum aluminium is rare earth coated, specifically comprises the steps:
(1), by 6.3500g yttrium oxide in 100mL small beaker, the hydrochloric acid that 30mL mass concentration is 37% is under agitation added, heating, make it dissolve, after its cooling, move in the volumetric flask of 100mL, be diluted with water to scale, in this solution, yttrium concentration is the rare-earth salts aqueous acid 1 of 50g/L;
By 5.7175g Erbium trioxide in 100mL small beaker, under agitation add the hydrochloric acid that 25mL mass concentration is 37%, heating, make it dissolve, after its cooling, move in the volumetric flask of 100mL, be diluted with water to scale, in this solution, erbium concentration is the rare-earth salts aqueous acid 2 of 50g/L;
(2) in 785mL water, add 400g nickel salt, rare-earth salts aqueous acid 1 that 800g molybdenum compound, 350g aluminium salt, 100mL yttrium concentration are 50g/L and 100mL erbium concentration is 50g/L rare-earth salts aqueous acid 2,100g complexing agent, 300g muriate, be 9.5 by sodium carbonate solution regulator solution pH value, add water and be settled to 1L, obtain nickel salt-molybdenum compound-aluminium salt-rare-earth salts-complexing agent-muriate electroplate liquid and nickelous nitrate-nickelous chloride-ammonium molybdate-Tai-Ace S 150-Yttrium trichloride-Erbium trichloride-tartrate-ammonium chloride-potassium chloride electroplate liquid;
Wherein nickel salt is nickelous nitrate and single nickel salt is the mixture of 1:1 composition in mass ratio;
Molybdenum compound is ammonium molybdate;
Aluminium salt is Tai-Ace S 150;
Complexing agent is tartrate;
Muriate is ammonium chloride and Repone K is the mixture of 1:1 composition in mass ratio;
In described nickel salt-molybdenum compound-aluminium salt-rare-earth salts-complexing agent-muriate electroplate liquid, nickel salt, molybdenum compound, aluminium salt, rare-earth salts rare earth elements yttrium and erbium, complexing agent, muriatic concentration are respectively 400g/L, 800g/L, 350g/L, 10g/L, 100g/L, 300g/L;
(3) treat that nickel-plated sheet is as negative electrode, using plating piece 100mm × 100mm × 0.5mm to be plated, anode is the sheet nickel of 150mm × 150mm × 2mm, nickelous nitrate-nickelous chloride-ammonium molybdate-Tai-Ace S 150-Yttrium trichloride-Erbium trichloride-tartrate-ammonium chloride-potassium chloride electroplate liquid the electroplate liquid putting into step (1) gained carries out pulse plating, and setting pulse frequency 5000Hz in pulse plating process, dutycycle are 0.9, current density 25A/dm
2, temperature 60 C, rotating speed 600rpm, time 40min, after plating, rinse plating piece use water, air-dry, namely obtains the rare earth coated i.e. nickel molybdenum aluminium yttrium erbium coating of one deck nickel molybdenum aluminium on the surface of plating piece.
Adopt Bruker AXS Microanalysis GmbH energy spectrometer to measure nickel, molybdenum, aluminium, yttrium, erbium content in the nickel molybdenum aluminium yttrium erbium coating of above-mentioned gained, calculate by mass percentage and be respectively 21.57%, 43.70 %, 16.70%, 8.91%, 9.12%.
By the above-mentioned plating piece constant temperature oxidation 48h in the air atmosphere of 1100 DEG C being coated with nickel molybdenum aluminium yttrium erbium coating, natural stove is chilled to room temperature subsequently, measure the quality before plating piece oxidation and the quality after oxidation respectively with BS224S type electronics Libra, the rear quality of this plating piece oxidation must increase to 0.03mg/cm
2.
embodiment 3
A kind of nickel molybdenum aluminium is rare earth coated, elementary composition by nickel, molybdenum, aluminium, rare earth four kinds, calculates by mass percentage, nickel: molybdenum: aluminium: rare earth is 30.82%:40.27%:13.90%:15.01%.
The preparation method that above-mentioned a kind of nickel molybdenum aluminium is rare earth coated, specifically comprises the steps:
(1), by 2.8688g dysprosium oxide in 50mL small beaker, under agitation add 15mL concentrated nitric acid, heating, makes it dissolve, and after its cooling, moves in the volumetric flask of 100mL, is diluted with water to scale, obtain the rare earth nitrate aqueous solution 1 that dysprosium concentration is 25g/L;
By 2.8816g gadolinium sesquioxide in 50mL small beaker, under agitation add 15mL concentrated nitric acid, heating, makes it dissolve, and after its cooling, moves in the volumetric flask of 100mL, is diluted with water to scale, obtain the rare earth nitrate aqueous solution 2 that gadolinium concentration is 25g/L;
(2) in 780mL water, add 200g nickel salt, rare earth nitrate aqueous solution 2,50g complexing agent, 150g muriate that rare earth nitrate aqueous solution 1 that 400g molybdenum compound, 175g aluminium salt, 100mL dysprosium concentration are 25g/L and 100mL gadolinium concentration are 25g/L, be 8.5 by sodium carbonate solution regulator solution pH value, adding water is settled to 1L and obtains nickel salt-molybdenum compound-aluminium salt-rare-earth salts-complexing agent-muriate electroplate liquid and nickelous chloride-nickelous nitrate-molybdenum pentachloride-ammonium molybdate-aluminum chloride-Tai-Ace S 150-Dysprosium trinitrate-Gadolinium trinitrate-lactic acid-oxalic acid-ammonium chloride-sodium-chlor electroplate liquid;
Wherein nickel salt is nickelous chloride and nickelous nitrate is the mixture of 3:1 composition in mass ratio;
Molybdenum compound is molybdenum pentachloride and ammonium molybdate is the mixture of 1:1 composition in mass ratio;
Aluminium salt is aluminum chloride and Tai-Ace S 150 is the mixture that 4:3 forms;
Complexing agent is oxalic acid and ammonium lacate mass ratio is the mixture that 5:3 forms;
Muriate is that sodium-chlor and ammonium chloride are in mass ratio for 2:1 composition is from mixture;
In described nickel salt-molybdenum compound-aluminium salt-rare-earth salts-complexing agent-muriate electroplate liquid, nickel salt, molybdenum compound, aluminium salt, rare-earth salts rare earth elements dysprosium and gadolinium, complexing agent, muriatic concentration are respectively 200g/L, 400g/L, 175g/L, 5g/L, 50g/L, 150g/L;
(3), using the Ni-monocrystal plate to be plated of plating piece 100mm × 100mm × 0.5mm to be plated as negative electrode, anode is the sheet nickel of 150mm × 150mm × 2mm, nickelous chloride-nickelous nitrate-molybdenum pentachloride-ammonium molybdate-aluminum chloride-Tai-Ace S 150-Dysprosium trinitrate-Gadolinium trinitrate-lactic acid-oxalic acid-ammonium chloride-sodium-chlor the electroplate liquid putting into step (1) gained carries out pulse plating, and setting pulse frequency 3500Hz in pulse plating process, dutycycle are 0.7, current density 17.8A/dm
2, temperature 60 C, rotating speed 550rpm, time 35min, after plating, rinse plating piece use water, air-dry, namely obtains the rare earth coated i.e. nickel molybdenum aluminium dysprosium gadolinium coating of one deck nickel molybdenum aluminium on the surface of plating piece.
Adopt Bruker AXS Microanalysis GmbH energy spectrometer to measure nickel, molybdenum, aluminium, dysprosium, gadolinium concentrations in the nickel molybdenum aluminium gadolinium coating of above-mentioned gained, calculate by mass percentage, be respectively 30.82%, 40.27%, 13.90%, 5.23%, 9.78%.
By the above-mentioned plating piece constant temperature oxidation 48h in the air atmosphere of 1100 DEG C being coated with nickel molybdenum aluminium dysprosium gadolinium coating, natural stove is chilled to room temperature subsequently, measure the quality before plating piece oxidation and the quality after oxidation respectively with BS224S type electronics Libra, the rear quality of this plating piece oxidation must increase to 0.02mg/cm
2.
embodiment 4 (comparative examples of embodiment 3)
A kind of nickel molybdenum coating, elementary composition by nickel, molybdenum two kinds, calculate by mass percentage, nickel: molybdenum is 67.73%:32.27%.
The preparation method of above-mentioned a kind of nickel molybdenum coating, specifically comprises the steps:
(1) in 990mL water, add 200g nickel salt, 400g molybdenum compound, 175g aluminium salt, 50g complexing agent, 150g muriate, be 8.5 by sodium carbonate solution regulator solution pH value, adding water is settled to 1L and obtains nickel salt-molybdenum compound-aluminium salt-complexing agent-muriate electroplate liquid and nickelous chloride-nickelous nitrate-molybdenum pentachloride-ammonium molybdate-aluminum chloride-Tai-Ace S 150-lactic acid-oxalic acid-ammonium chloride-sodium-chlor electroplate liquid; Wherein nickel salt is nickelous chloride and nickelous nitrate is the mixture of 3:1 composition in mass ratio;
Molybdenum compound is molybdenum pentachloride and ammonium molybdate is the mixture of 1:1 composition in mass ratio;
Aluminium salt is aluminum chloride and Tai-Ace S 150 is the mixture that 4:3 forms;
Complexing agent is oxalic acid and ammonium lacate mass ratio is the mixture that 5:3 forms;
Muriate is that sodium-chlor and ammonium chloride are in mass ratio for 2:1 composition is from mixture;
In described nickel salt-molybdenum compound-aluminium salt-complexing agent-muriate electroplate liquid, nickel salt, molybdenum compound, aluminium salt, complexing agent, muriatic concentration are respectively 200g/L, 400g/L, 175g/L, 50g/L, 150g/L;
(2), using the Ni-monocrystal plate to be plated of plating piece 100mm × 100mm × 0.5mm to be plated as negative electrode, anode is the sheet nickel of 150mm × 150mm × 2mm, nickelous chloride-nickelous nitrate-molybdenum pentachloride-ammonium molybdate-aluminum chloride-Tai-Ace S 150-lactic acid-oxalic acid-ammonium chloride-sodium-chlor the electroplate liquid putting into step (1) gained is electroplated, and controls current density 17.8A/dm in electroplating process
2, temperature 60 C, rotating speed 550rpm, time 35min, after plating, rinse plating piece use water, air-dry, namely obtains one deck on the surface of plating piece
coating.
Adopt Bruker AXS Microanalysis GmbH energy spectrometer to measure nickel in the coating of above-mentioned gained, molybdenum, aluminium content, aluminium do not detected in coating, nickel, molybdenum content, calculate by mass percentage and be respectively 67.73%, 32.27%.
By the above-mentioned plating piece constant temperature oxidation 48h in the air atmosphere of 1100 DEG C being coated with nickel molybdenum coating, natural stove is chilled to room temperature subsequently, measure the quality before plating piece oxidation and the quality after oxidation respectively with BS224S type electronics Libra, the rear quality of this plating piece oxidation must increase to 0.415mg/cm
2.
embodiment 5 (comparative examples of embodiment 4)
A kind of nickel molybdenum aluminium coat, elementary composition by nickel, molybdenum, three kinds, aluminium, calculate by mass percentage, nickel: molybdenum: aluminium is 55.50%:36.92%:7.58%.
The preparation method of above-mentioned a kind of nickel molybdenum aluminium coat, specifically comprises the steps:
(1), by 2.8688g dysprosium oxide in 50mL small beaker, under agitation add 15mL concentrated nitric acid, heating, makes it dissolve, and after its cooling, moves in the volumetric flask of 100mL, is diluted with water to scale, obtain the rare earth nitrate aqueous solution 1 that dysprosium concentration is 25g/L;
By 2.8816g gadolinium sesquioxide in 50mL small beaker, under agitation add 15mL concentrated nitric acid, heating, makes it dissolve, and after its cooling, moves in the volumetric flask of 100mL, is diluted with water to scale, obtain the rare earth nitrate aqueous solution 2 that gadolinium concentration is 25g/L;
(2) in 780mL water, add 200g nickel salt, rare earth nitrate aqueous solution 2,50g complexing agent, 150g muriate that rare earth nitrate aqueous solution 1 that 400g molybdenum compound, 175g aluminium salt, 1mL dysprosium concentration are 25g/L and 1mL gadolinium concentration are 25g/L, be 8.5 by sodium carbonate solution regulator solution pH value, adding water is settled to 1L and obtains nickel salt-molybdenum compound-aluminium salt-rare-earth salts-complexing agent-muriate electroplate liquid and nickelous chloride-nickelous nitrate-molybdenum pentachloride-ammonium molybdate-aluminum chloride-Tai-Ace S 150-Dysprosium trinitrate-Gadolinium trinitrate-lactic acid-oxalic acid-ammonium chloride-sodium-chlor electroplate liquid;
Wherein nickel salt is nickelous chloride and nickelous nitrate is the mixture of 3:1 composition in mass ratio;
Molybdenum compound is molybdenum pentachloride and ammonium molybdate is the mixture of 1:1 composition in mass ratio;
Aluminium salt is aluminum chloride and Tai-Ace S 150 is the mixture that 4:3 forms;
Complexing agent is oxalic acid and ammonium lacate mass ratio is the mixture that 5:3 forms;
Muriate is that sodium-chlor and ammonium chloride are in mass ratio for 2:1 composition is from mixture;
In described nickel salt-molybdenum compound-aluminium salt-rare-earth salts-complexing agent-muriate electroplate liquid, nickel salt, molybdenum compound, aluminium salt, rare-earth salts rare earth elements dysprosium and gadolinium, complexing agent, muriatic concentration are respectively 200g/L, 400g/L, 175g/L, 5g/L, 0.05g/L, 150g/L;
(3), using the Ni-monocrystal plate to be plated of plating piece 100mm × 100mm × 0.5mm to be plated as negative electrode, anode is the sheet nickel of 150mm × 150mm × 2mm, nickelous chloride-nickelous nitrate-molybdenum pentachloride-ammonium molybdate-aluminum chloride-Tai-Ace S 150-Dysprosium trinitrate-Gadolinium trinitrate-lactic acid-oxalic acid-ammonium chloride-sodium-chlor the electroplate liquid putting into step (1) gained carries out pulse plating, and setting pulse frequency 3500Hz in pulse plating process, dutycycle are 0.7, current density 17.8A/dm
2, temperature 60 C, rotating speed 550rpm, time 35min, after plating, rinse plating piece use water, air-dry, namely obtains one deck on the surface of plating piece
nickel molybdenum aluminium coat namelynickel molybdenum aluminium coat.
Adopt Bruker AXS Microanalysis GmbH energy spectrometer to measure nickel, molybdenum, aluminium content in the nickel molybdenum aluminium coat of above-mentioned gained, calculate by mass percentage, be respectively 55.50%, 36.92%, 7.58%.
By the above-mentioned plating piece constant temperature oxidation 48h in the air atmosphere of 1100 DEG C being coated with nickel molybdenum aluminium coat, natural stove is chilled to room temperature subsequently, measure the quality before plating piece oxidation and the quality after oxidation respectively with BS224S type electronics Libra, the rear quality of this plating piece oxidation must increase to 0.140mg/cm
2.
embodiment 6 (comparative examples of embodiment 4)
A kind of nickel molybdenum aluminium coat, elementary composition by nickel, molybdenum, three kinds, aluminium, calculate by mass percentage, nickel: molybdenum: aluminium is 58.85%:34.23%:6.92%.
The preparation method of above-mentioned a kind of nickel molybdenum aluminium coat, specifically comprises the steps:
(1), by 2.8688g dysprosium oxide in 50mL small beaker, under agitation add 15mL concentrated nitric acid, heating, makes it dissolve, and after its cooling, moves in the volumetric flask of 100mL, is diluted with water to scale, obtain the rare earth nitrate aqueous solution 1 that dysprosium concentration is 25g/L;
By 2.8816g gadolinium sesquioxide in 50mL small beaker, under agitation add 15mL concentrated nitric acid, heating, makes it dissolve, and after its cooling, moves in the volumetric flask of 100mL, is diluted with water to scale, obtain the rare earth nitrate aqueous solution 2 that gadolinium concentration is 25g/L;
(2) in 780mL water, add 200g nickel salt, rare earth nitrate aqueous solution 2,50g complexing agent, 150g muriate that rare earth nitrate aqueous solution 1 that 400g molybdenum compound, 175g aluminium salt, 0.2mL dysprosium concentration are 25g/L and 0.2mL gadolinium concentration are 25g/L, be 8.5 by sodium carbonate solution regulator solution pH value, adding water is settled to 1L and obtains nickel salt-molybdenum compound-aluminium salt-rare-earth salts-complexing agent-muriate electroplate liquid and nickelous chloride-nickelous nitrate-molybdenum pentachloride-ammonium molybdate-aluminum chloride-Tai-Ace S 150-Dysprosium trinitrate-Gadolinium trinitrate-lactic acid-oxalic acid-ammonium chloride-sodium-chlor electroplate liquid;
Wherein nickel salt is nickelous chloride and nickelous nitrate is the mixture of 3:1 composition in mass ratio;
Molybdenum compound is molybdenum pentachloride and ammonium molybdate is the mixture of 1:1 composition in mass ratio;
Aluminium salt is aluminum chloride and Tai-Ace S 150 is the mixture that 4:3 forms;
Complexing agent is oxalic acid and ammonium lacate mass ratio is the mixture that 5:3 forms;
Muriate is that sodium-chlor and ammonium chloride are in mass ratio for 2:1 composition is from mixture;
In described nickel salt-molybdenum compound-aluminium salt-rare-earth salts-complexing agent-muriate electroplate liquid, nickel salt, molybdenum compound, aluminium salt, rare-earth salts rare earth elements dysprosium and gadolinium, complexing agent, muriatic concentration are respectively 200g/L, 400g/L, 175g/L, 5g/L, 0.01g/L, 150g/L;
(3), using the Ni-monocrystal plate to be plated of plating piece 100mm × 100mm × 0.5mm to be plated as negative electrode, anode is the sheet nickel of 150mm × 150mm × 2mm, nickelous chloride-nickelous nitrate-molybdenum pentachloride-ammonium molybdate-aluminum chloride-Tai-Ace S 150-Dysprosium trinitrate-Gadolinium trinitrate-lactic acid-oxalic acid-ammonium chloride-sodium-chlor the electroplate liquid putting into step (1) gained carries out pulse plating, and setting pulse frequency 3500Hz in pulse plating process, dutycycle are 0.7, current density 17.8A/dm
2, temperature 60 C, rotating speed 550rpm, time 35min, after plating, rinse plating piece use water, air-dry, namely obtains one deck on the surface of plating piece
nickel molybdenum aluminium coat namelynickel molybdenum aluminium coat.
Adopt Bruker AXS Microanalysis GmbH energy spectrometer to measure nickel, molybdenum, aluminium content in the nickel molybdenum aluminium gadolinium coating of above-mentioned gained, calculate by mass percentage, be respectively 58.85%, 34.23%, 6.92%.
By the above-mentioned plating piece constant temperature oxidation 48h in the air atmosphere of 1100 DEG C being coated with nickel molybdenum aluminium coat, natural stove is chilled to room temperature subsequently, measure the quality before plating piece oxidation and the quality after oxidation respectively with BS224S type electronics Libra, the rear quality of this plating piece oxidation must increase to 0.145mg/cm
2.
Further, by the plating piece constant temperature oxidation 48h in the air atmosphere of 1100 DEG C respectively of embodiment 3, embodiment 4, embodiment 5 and embodiment 6, show from the data results of the quality of final plating piece every square centimeter increase, the antioxidant anticorrosive that a kind of nickel molybdenum aluminium of gained of the present invention is rare earth coated is all stronger than the antioxidant anticorrosive of nickel molybdenum coating and nickel molybdenum aluminium coat.
Further, the present invention adopts the pulse power, adds rare earth element in the plating solution, and the rare earth element of interpolation is not only and forms the rare earth coated source providing rare earth of nickel molybdenum aluminium, and rare earth element is also as the application of plating promotor.As can be seen from embodiment 5 and embodiment 6, when plating solution middle-weight rare earths salt concn is low, when being namely only 0.01 ~ 0.05g/L, rare earth element only does the application of plating promotor, namely
whenwhen adding rare earth element in the plating solution as plating promotor, adopt the pulse power, can only electroplate in aqueous and obtain a kind of nickel molybdenum aluminium coat;
Further, can find out when only having plating solution middle-weight rare earths salt concn to reach 0.06 ~ 10g/L from embodiment 1, embodiment 2 and embodiment 3, rare earth element could not be only and form the rare earth coated source providing rare earth of nickel molybdenum aluminium, but also as the application of plating promotor, at this moment electroplate that just to obtain nickel molybdenum aluminium rare earth coated in aqueous.
The above is only the citing of embodiments of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (8)
1. a nickel molybdenum aluminium is rare earth coated, it is characterized in that described nickel molybdenum aluminium is rare earth coated elementary composition by nickel, molybdenum, aluminium, rare earth four kinds, calculate by mass percentage, nickel: molybdenum: aluminium: rare earth is 72.95 ~ 21.57%, 21.33 ~ 43.70%, 3.50 ~ 16.70%, 2.22 ~ 18.02%.
2. nickel molybdenum aluminium as claimed in claim 1 is rare earth coated, it is characterized in that calculating by mass percentage, nickel: molybdenum: aluminium: rare earth is 72.95%:21.33 %:3.50%:2.22%.
3. nickel molybdenum aluminium as claimed in claim 1 is rare earth coated, it is characterized in that calculating by mass percentage, nickel: molybdenum: aluminium: rare earth is 21.57%:43.70 %:16.70%:18.03%.
4. nickel molybdenum aluminium as claimed in claim 1 is rare earth coated, it is characterized in that calculating by mass percentage, nickel: molybdenum: aluminium: rare earth is 30.82%:40.27%:13.90%:15.01%.
5. the preparation method that a kind of nickel molybdenum aluminium as claimed in claim 1 is rare earth coated, is characterized in that specifically comprising the steps:
(1), by rare earth oxide be dissolved in acid, obtain rare-earth salts;
Described rare earth oxide is one or more the mixture in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, scandium rare earth oxide;
Described acid is nitric acid or hydrochloric acid;
(2) in water, add rare-earth salts, complexing agent, the muriate of nickel salt, molybdenum compound, aluminium salt, step (1) gained, be 7.5 ~ 9.5 by sodium carbonate solution regulator solution pH value, make nickel salt-molybdenum compound-aluminium salt-rare-earth salts-complexing agent-muriate electroplate liquid;
Wherein nickel salt is the mixture of one or more compositions in nickelous chloride, nickelous nitrate, single nickel salt;
Molybdenum compound is the mixture of one or more compositions in molybdenum pentachloride, ammonium molybdate, ammonium phosphomolybdate, Sodium orthomolybdate;
Aluminium salt is the mixture that aluminum chloride, Tai-Ace S 150 or aluminum chloride and Tai-Ace S 150 form;
Complexing agent is the mixture of one or more compositions in oxyacetic acid, Padil, oxalic acid, citric acid, tartrate, lactic acid, succinic acid, oxysuccinic acid;
Muriate is one or more the chloride mix in sodium-chlor, ammonium chloride, Repone K;
In described nickel salt-molybdenum compound-aluminium salt-rare-earth salts-complexing agent-muriate electroplate liquid, nickel salt, molybdenum compound, aluminium salt, rare-earth salts rare earth elements, complexing agent, muriatic concentration are respectively 5 ~ 400g/L, 5 ~ 800g/L, 5 ~ 350g/L, 0.06 ~ 10g/L, 1 ~ 100g/L, 5 ~ 300g/L;
(3), using plating piece to be plated as negative electrode, anode is nickel, nickel salt-molybdenum compound-aluminium salt-rare-earth salts-complexing agent-muriate the electroplate liquid putting into step (1) gained carries out pulse plating, and setting pulse frequency 2000 ~ 5000Hz in pulse plating process, dutycycle are 0.5 ~ 0.9, current density 10 ~ 25A/dm
2, temperature 40 ~ 60 DEG C, rotating speed 100 ~ 600rpm, time 10 ~ 60min, after plating, rinse plating piece use water, air-dry, namely obtains one deck nickel molybdenum aluminium rare earth coated on the surface of plating piece.
6. the preparation method that nickel molybdenum aluminium as claimed in claim 1 is rare earth coated, it is characterized in that the nickel salt described in step (2) is nickelous chloride, molybdenum compound is molybdenum pentachloride, aluminium salt is aluminum chloride, rare-earth salts is cerous nitrate, and complexing agent is oxalic acid, and muriate is sodium-chlor;
In described nickel salt-molybdenum compound-aluminium salt-rare-earth salts-complexing agent-muriate electroplate liquid, nickel salt, molybdenum compound, aluminium salt, rare-earth salts rare earth elements, complexing agent, muriatic concentration are respectively 5g/L, 5g/L, 5g/L, 0.06g/L, 1g/L, 5g/L;
Setting pulse frequency 2000Hz in pulse plating process described in step (3), dutycycle are 0.5, current density 10A/dm
2, temperature 40 DEG C, rotating speed 100rpm, time 60min.
7. the preparation method that nickel molybdenum aluminium as claimed in claim 1 is rare earth coated, it is characterized in that the nickel salt described in step (2) to be nickelous nitrate and single nickel salt be in mass ratio the mixture of 1:1 composition, molybdenum compound is ammonium molybdate, aluminium salt is Tai-Ace S 150, rare-earth salts is the mixture of Yttrium trichloride and Erbium trichloride composition, complexing agent is tartrate, and muriate is ammonium chloride and Repone K is the mixture of 1:1 composition in mass ratio;
In described nickel salt-molybdenum compound-aluminium salt-rare-earth salts-complexing agent-muriate electroplate liquid, nickel salt, molybdenum compound, aluminium salt, rare-earth salts rare earth elements, complexing agent, muriatic concentration are respectively 400g/L, 800g/L, 350g/L, 10g/L, 100g/L, 300g/L;
Setting pulse frequency 5000Hz in pulse plating process described in step (3), dutycycle are 0.9, current density 25A/dm
2, temperature 60 C, rotating speed 600rpm, time 40min.
8. the preparation method that nickel molybdenum aluminium as claimed in claim 1 is rare earth coated, it is characterized in that the nickel salt described in step (2) to be nickelous chloride and nickelous nitrate be in mass ratio the mixture of 3:1 composition, molybdenum compound is molybdenum pentachloride and ammonium molybdate is the mixture of 1:1 composition in mass ratio, aluminium salt is aluminum chloride and Tai-Ace S 150 is the mixture that 4:3 forms, rare-earth salts is the mixture of Dysprosium trinitrate and Gadolinium trinitrate composition, the mixture of complexing agent to be oxalic acid and ammonium lacate mass ratio be 5:3 composition, muriate is that sodium-chlor and ammonium chloride are in mass ratio for 2:1 forms from mixture;
In described nickel salt-molybdenum compound-aluminium salt-rare-earth salts-complexing agent-muriate electroplate liquid, nickel salt, molybdenum compound, aluminium salt, rare-earth salts rare earth elements, complexing agent, muriatic concentration are respectively 200g/L, 400g/L, 175g/L, 5g/L, 50g/L, 150g/L;
Setting pulse frequency 3500Hz in pulse plating process described in step (3), dutycycle are 0.7, current density 17.8A/dm
2, temperature 60 C, rotating speed 550rpm, time 35min
.
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