CN103436930B - A kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite and its preparation method and application - Google Patents
A kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite and its preparation method and application Download PDFInfo
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Abstract
The present invention discloses a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite and preparation method, the described electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite is by often liter of calculating, containing nickel salt be 10 ~ 400g, be 10 ~ 800g containing molybdenum heteropolyacid salt, complexing agent is 5 ~ 100g, muriate is 10 ~ 300g, rare earth is 0.05 ~ 6g, molybdenum disilicide is 5 ~ 60g, tensio-active agent is 0.01 ~ 0.9g, surplus is water.Its preparation method comprises 4 steps such as preparation of the preparation of rare earths salt, the pre-treatment of molybdenum disilicide particulate, the nickel salt-preparation of molybdenum heteropolyacid salt-complexing agent-muriate-rare-earth salts mixed solution and the electroplate liquid of nickel molybdenum rare earth-molybdenum disilicide composite deposite, and the electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite obtained forms nickel molybdenum rare earth-molybdenum disilicide composite deposite for carrying out plating on plating piece to be plated.
Description
Technical field
The present invention relates to a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite and its preparation method and application.
Background technology
Thermal Barrier Coating Technologies is the unique practicable method increasing substantially metallic high temperature material working temperature at present.Superalloy has nickel-base alloy, molybdenum base alloy, titanium base alloy and niobium-base alloy etc., and nickel-base alloy is conventional superalloy.The thermal barrier coating of current acquisition practical application is mostly bilayer structure, and top layer is ceramic thermal barrier layer, Main Function be heat insulation, anticorrosive, wash away and corrode; Bottom is metal bonding coating, plays a part high temperature oxidation corrosion resistance and improves matrix and ceramic coating physical compatibility.MCrAlY (M:Ni, Co or Ni+Co) is a kind of bonding layer material that current thermal barrier coating generally adopts.Nickel molybdenum coating has good hardness, high temperature resistant, wear resistance, solidity to corrosion, lower hydrogen gas evolution overpotential etc. compared with pure nickel, has a wide range of applications at the numerous areas such as metallurgy, machinery, chemical industry, chlorine industry, oil, electronics.MoSi
2because of its have pottery and metal dual nature, there is good comprehensive mechanical property, high-melting-point, moderate proportion, lower thermal expansivity, good high-temperature oxidation resistance and good electric heating conductivity, solid molybdenum disilicide particulate is mingled with in nickel molybdenum rare earth alloy coating, the thermal expansivity of coating, hardness, wear-resisting, anti-corrosion, self-lubricating etc. can be improved, but still there is no the relevant report of nickel molybdenum rare earth-molybdenum disilicide composite deposite and preparation method thereof at present.
Summary of the invention
An object of the present invention is to provide a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite.
Two of object of the present invention is to provide the preparation method of above-mentioned a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite.
Three of object of the present invention is to provide the application method of above-mentioned a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite.
Technical scheme of the present invention
A kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite, by often liter of calculating, containing nickel salt be 10 ~ 400g, be 10 ~ 800g containing molybdenum heteropolyacid salt, complexing agent is 5 ~ 100g, muriate is 10 ~ 300g, rare earth is 0.05 ~ 6g, molybdenum disilicide is 5 ~ 60g, tensio-active agent is 0.01 ~ 0.9g, surplus is water;
Wherein said nickel salt is the mixture of one or more compositions in nickelous nitrate, nickelous chloride, single nickel salt;
Described contains mixtures that molybdenum heteropolyacid salt is one or more compositions in ammonium molybdate, Sodium orthomolybdate, ammonium phosphomolybdate, molybdic acid;
Described complexing agent is the mixture of one or more compositions in formic acid, acetic acid, Padil, oxyacetic acid, lactic acid, oxalic acid, succinic acid, citric acid, oxysuccinic acid, tartrate;
Described muriate is the mixture of a kind of and two or more composition in ammonium chloride, Repone K, sodium-chlor;
Described rare earth is the mixture of one or more the rare earth composition in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, scandium;
Described tensio-active agent is the mixture of one or more compositions in triton x-100, cetyl trimethylammonium bromide, brocide, polyethylene glycol 6000.
The preparation method of above-mentioned a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite, specifically comprises the steps:
(1), the preparation of rare earths salt
Be dissolved in by rare earth oxide in nitric acid or hydrochloric acid, the concentration being mixed with rare earth is 10 ~ 50g/L rare earths salt;
Its middle rare earth is the mixture of one or more the rare earth oxide composition in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, scandium;
Rare-earth salts is the mixture that rare earth nitrate, rare earth chloride or rare earth nitrate and rare earth chloride form;
(2), the pre-treatment of molybdenum disilicide particulate
By particle diameter be the molybdenum disilicide particulate of 10 μm ~ 10nm first with acetone cleaning, then 0.2 ~ 1h in the hydrochloric acid soln being soaked in 2 ~ 6mol/L, suction filtration, is washed to neutrality, and at 50 ~ 100 DEG C, dry 0.5 ~ 5h, obtains pretreated molybdenum disilicide particulate;
(3), with water by nickel salt, containing molybdenum heteropolyacid salt, complexing agent and muriate dissolve after, add rare earths salt prepared by step (1), be 7.5 ~ 9.0 with aqueous sodium carbonate adjust pH, obtain nickel salt-molybdenum heteropolyacid salt-complexing agent-muriate-rare-earth salts mixed solution, control wherein nickel salt, be respectively 10-400g/L, 10-800g/L, 5-100g/L, 10-300g/L, 0.05-6g/L containing the concentration of molybdenum heteropolyacid salt, complexing agent, muriate, rare earth;
Wherein nickel salt is the mixture of one or more compositions in nickelous nitrate, nickelous chloride, single nickel salt;
Containing one or more the mixture that molybdenum heteropolyacid salt is in ammonium molybdate, Sodium orthomolybdate, ammonium phosphomolybdate, molybdic acid;
Complexing agent is one or more the mixture in formic acid, acetic acid, Padil, oxyacetic acid, lactic acid, oxalic acid, succinic acid, citric acid, oxysuccinic acid, tartrate;
Muriate is one or more the mixture in ammonium chloride, Repone K, sodium-chlor;
(4), by the pretreated molybdenum disilicide particulate of step (1) gained, after the 1-6.5% of the volume of nickel salt-molybdenum heteropolyacid salt-complexing agent-muriate-rare-earth salts mixed solution prepared by step (2) mixes with tensio-active agent, grind in mortar, then nickel salt-molybdenum heteropolyacid salt-complexing agent-muriate-rare-earth salts mixed solution that new container continues the surplus of adding step (2) gained is proceeded to, controlling mixing speed is after 100 ~ 900rpm carries out stirring 4 ~ 12h, with ultrasonication 0.2 ~ 1h, obtain the electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite,
The amount of above-mentioned nickel salt used-molybdenum heteropolyacid salt-complexing agent-muriate-rare-earth salts mixed solution, molybdenum disilicide and tensio-active agent, in nickel salt-molybdenum heteropolyacid salt-complexing agent-muriate-rare-earth salts mixed solution: molybdenum disilicide: tensio-active agent is that the ratio of 1L:5 ~ 60g:0.01 ~ 0.9g calculates;
Described tensio-active agent is one or more the mixture in triton x-100, cetyl trimethylammonium bromide, brocide, polyethylene glycol 6000.
A kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite of above-mentioned gained for carrying out electroplating the method forming nickel molybdenum rare earth-molybdenum disilicide composite deposite on plating piece to be plated, and step is as follows:
The electroplate liquid put into by plating piece to be plated for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite carries out electroplating and as negative electrode, anode is nickel, and electroplating process controls current density 10 ~ 25A/dm
2, bath pH values 7.5 ~ 9.0, electroplating temperature 40 ~ 60 DEG C, mixing speed 100 ~ 600rpm, electroplating time 10 ~ 60min, after plating, plating piece use water rinses, air-dry, must have the plating piece of nickel molybdenum rare earth-molybdenum disilicide composite deposite;
Described plating piece to be plated is nickelalloy plate, nickel plate or Ni-monocrystal plate.
Beneficial effect of the present invention
A kind of nickel molybdenum rare earth-molybdenum disilicide composite deposite of the present invention, owing to being mingled with solid molybdenum disilicide particulate in nickel molybdenum rare earth alloy coating, molybdenum disilicide because of its have pottery and metal dual nature, there is good comprehensive mechanical property, high-melting-point, lower thermal expansivity, good high-temperature oxidation resistance and good electric heating conductivity, the hardness of nickel molybdenum rare earth-molybdenum disilicide composite deposite significantly improves, thermal expansivity declines, its hardness is 812.5-901.2HV, and thermal expansivity is 12.2 × 10
-6k
-1~ 5.5 × 10
-6k
-1scope.
Embodiment
Below by specific embodiment, the present invention is set forth further, but do not limit the present invention.
The microhardness of nickel molybdenum-molybdenum disilicide composite deposite is measured with Wo Baite surveying instrument (Shanghai) Co., Ltd. 401MVDTM micro Vickers, measuring method sees reference document: Liu Xiaozhen, Wang Gang, Song Lingling, Li Xin, Zhu Xuqian. the preparation of chromium-lanthanum coating and spectrum property thereof. spectroscopy and spectroscopic analysis .2011,31 (7): 1964-1967.
Measure the thermal expansivity of nickel molybdenum-molybdenum disilicide composite deposite with German Nai Chi scientific instrument company limited DIL402C thermal dilatometer, measuring method is shown in the working instructions of DIL402C thermal dilatometer.
embodiment 1
A kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite, by often liter of calculating, containing nickel salt be 10g, be 10g containing molybdenum heteropolyacid salt, complexing agent is 5g, muriate is 10g, rare earth is 0.05g, molybdenum disilicide is 5g, tensio-active agent is 0.01g, surplus is water;
Wherein said nickel salt is nickelous nitrate;
Described is Sodium orthomolybdate containing molybdenum heteropolyacid salt;
Described complexing agent is formic acid, oxalic acid calculates in mass ratio, i.e. formic acid: oxalic acid is the mixture of 2:3 composition;
Described muriate is ammonium chloride;
Described tensio-active agent to be molecular weight be 6000 polyoxyethylene glycol;
Described rare earth is lanthanum.
The preparation method of a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite of above-mentioned gained, specifically comprises the steps:
(1), take 2.3456g lanthanum trioxide in 100mL small beaker, under agitation add the hydrochloric acid that 12mL mass concentration is 37%, heating, make it dissolve, after its cooling, move in the volumetric flask of 100mL, be diluted with water to scale, obtain the rare earths salt that rare earth metal la concn is 20g/L;
(2), the pre-treatment of molybdenum disilicide particulate
Taking particle diameter is that 10 μm of molybdenum disilicide particulate 5g are in the beaker of 100mL, add 10mL acetone, stir 5min, suction filtration, by molybdenum disilicide particulate in the beaker of 100mL, add 2mol/L hydrochloric acid soln 10mL, soak 0.2h, suction filtration, is washed to neutrality, dry 5h in 50 DEG C of baking ovens, obtains pretreated molybdenum disilicide particulate;
(3), the preparation of nickelous nitrate-Sodium orthomolybdate-formic acid-oxalic acid-ammonium chloride-Lanthanum trichloride mixing solutions
10g nickelous nitrate, 10g Sodium orthomolybdate, 2g formic acid, 3g oxalic acid, 10g ammonium chloride is added in the beaker of 2L, the la concn adding step (1) gained is the rare earths salt 2.5mL of 20g/L, add 935mL water dissolution nickelous nitrate, Sodium orthomolybdate, formic acid, oxalic acid, ammonium chloride, then be 7.5 by aqueous sodium carbonate regulator solution pH value, move in 1L volumetric flask, be diluted with water to scale, obtain nickelous nitrate-Sodium orthomolybdate-formic acid-oxalic acid-ammonium chloride-Lanthanum trichloride mixing solutions;
(4) the molybdenum disilicide particulate, 5g step (2) processed is in mortar, add the nickelous nitrate-Sodium orthomolybdate-formic acid-oxalic acid-ammonium chloride-Lanthanum trichloride mixed solution of 0.01g tensio-active agent and polyethylene glycol 6000,10mL step (3) gained, grinding 30min, proceed in the there-necked flask of 2L, add the nickelous nitrate-Sodium orthomolybdate-formic acid-oxalic acid-ammonium chloride-Lanthanum trichloride mixed solution of 990mL step (3) gained, controlling mixing speed is after 100rpm carries out stirring 12h, ultrasonication 0.2h, obtains a kind of electroplate liquid for the formation of nickel molybdenum lanthanum-molybdenum disilicide composite deposite.
Be used for by a kind of electroplate liquid for the formation of nickel molybdenum lanthanum-molybdenum disilicide composite deposite of above-mentioned gained treating that nickel plating alloy plate carries out electroplating the method forming nickel molybdenum lanthanum-molybdenum disilicide composite deposite, concrete steps are as follows:
The plating piece to be plated of 80mm × 80mm × 0.5mm is put into above-mentioned gained a kind of electroplate liquid for the formation of nickel molybdenum lanthanum-molybdenum disilicide composite deposite and as negative electrode, anode is that the sheet nickel of 150mm × 100mm × 2mm is electroplated, magnetic agitation in electroplating process, control mixing speed is 100rpm, and current density is 10A/dm
2, bath pH values is 7.5, and temperature is 40 DEG C, and plating time is 10min, takes out plating piece, rinses clean, air-dry, must have the plating piece of nickel molybdenum lanthanum-molybdenum disilicide composite deposite with water;
Described plating piece to be plated is nickelalloy plate.
After testing, its hardness is 812.5HV to nickel molybdenum lanthanum-molybdenum disilicide composite deposite on the plating piece of above-mentioned gained, and its thermal expansivity is 12.2 × 10
-6k
-1.
embodiment 2
A kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite, by often liter of calculating, containing nickel salt be 400g, be 800g containing molybdenum heteropolyacid salt, complexing agent is 100g, muriate is 300g, rare earth is 6g, molybdenum disilicide is 60g, tensio-active agent is 0.9g, surplus is water;
Wherein said nickel salt is nickelous chloride, single nickel salt calculates in mass ratio, i.e. nickelous chloride: single nickel salt is the mixture of the ratio composition of 1:1;
Described is ammonium phosphomolybdate containing molybdenum heteropolyacid salt;
Described complexing agent is citric acid;
Described muriate is Repone K, sodium-chlor calculates in mass ratio, i.e. Repone K: sodium-chlor is the mixture of the ratio composition of 1:1;
Described tensio-active agent is triton x-100, cetyl trimethylammonium bromide calculates in mass ratio, i.e. triton x-100: cetyl trimethylammonium bromide is the mixture of the ratio composition of 4:5;
Described rare earth is the mixture of neodymium, yttrium composition.
The preparation method of above-mentioned a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite, specifically comprises the steps:
(1), take 3.4992g Neodymium trioxide in 100mL small beaker, under agitation add 30mL concentrated nitric acid, heating, make it dissolve, after its cooling, move in the volumetric flask of 100mL, be diluted with water to scale, obtain the rare earths salt that rare earth metal neodymium concentration is 30g/L;
Take 3.8100g yttrium oxide in 100mL small beaker, under agitation add 30mL concentrated nitric acid, heating, makes it dissolve, and after its cooling, move in the volumetric flask of 100mL, be diluted with water to scale, obtaining rare earth metal yttrium concentration is the rare earths salt of 30g/L;
(2), the pre-treatment of molybdenum disilicide particulate
Taking particle diameter is that 10nm molybdenum disilicide particulate 60g is in the beaker of 200mL, add 50mL acetone, stir 5min, suction filtration, by molybdenum disilicide particulate in the beaker of 200mL, add 6mol/L hydrochloric acid soln 50mL, soak 1h, suction filtration, is washed to neutrality, dry 0.5h in 100 DEG C of baking ovens, obtains pretreated molybdenum disilicide particulate;
(3), the preparation of single nickel salt-nickelous chloride-ammonium phosphomolybdate-citric acid-Repone K-sodium-chlor-neodymium nitrate-Yttrium trinitrate mixed solution
200g single nickel salt, 200g nickelous chloride, 800g ammonium phosphomolybdate, 50g citric acid, 50g Repone K is added in the beaker of 2L, 50g sodium-chlor, the neodymium concentration adding step (1) gained be 30g/L rare earths salt 100mL and the yttrium concentration of step (1) gained be 30g/L rare earths salt 100mL, add 780mL water and stirring and dissolving, be 9.0 by aqueous sodium carbonate regulator solution pH value, move in 1L volumetric flask, be diluted with water to scale, obtain single nickel salt-nickelous chloride-ammonium phosphomolybdate-citric acid-Repone K-sodium-chlor-neodymium nitrate-Yttrium trinitrate mixed solution;
(4), by molybdenum disilicide particulate after pretreatment for 60g step (2) in mortar, add tensio-active agent and 0.5g cetyl trimethylammonium bromide and 0.4g triton x-100, single nickel salt-nickelous chloride-ammonium phosphomolybdate-citric acid-Repone K-sodium-chlor-neodymium nitrate-Yttrium trinitrate the mixed solution of 60mL step (3) gained, grinding 60min, proceed in the there-necked flask of 2L, add the single nickel salt-nickelous chloride-ammonium phosphomolybdate-citric acid-Repone K-sodium-chlor-neodymium nitrate-Yttrium trinitrate mixed solution of 940mL step (3) gained again, controlling mixing speed is after 900rpm carries out stirring 4h, ultrasonication 1h, obtain the electroplate liquid for the formation of nickel molybdenum neodymium yttrium-molybdenum disilicide composite deposite.
The electroplate liquid for the formation of nickel molybdenum neodymium yttrium-molybdenum disilicide composite deposite of above-mentioned gained is proceeded in the beaker of 2L, the plating piece to be plated of 80mm × 80mm × 0.5mm to be put into wherein and as negative electrode, anode is that the sheet nickel of 150mm × 100mm × 2mm is electroplated, magnetic agitation in electroplating process, control mixing speed is 600rpm, and current density is 25A/dm
2, bath pH values is 9.0, and temperature is 60 DEG C, and plating time is 60min, takes out plating piece, rinses clean, air-dry, must have the plating piece of nickel molybdenum neodymium yttrium-molybdenum disilicide composite deposite with water;
Described plating piece to be plated is nickel plate.
After testing, its hardness is 897HV to nickel molybdenum neodymium yttrium-molybdenum disilicide composite deposite on the plating piece of above-mentioned gained, and its thermal expansivity is 5.5 × 10
-6k
-1.
embodiment 3
A kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite, by often liter of calculating, containing nickel salt be 200g, be 400g containing molybdenum heteropolyacid salt, complexing agent is 52.5g, muriate is 155g, rare earth is 3g, molybdenum disilicide is 32.5g, tensio-active agent is 0.455g, surplus is water;
Wherein said nickel salt is that nickelous nitrate and nickelous chloride calculate in mass ratio, i.e. nickelous nitrate: nickelous chloride is the mixture of the ratio composition of 3:1;
Described is that ammonium molybdate and molybdic acid calculate in mass ratio containing molybdenum heteropolyacid salt, i.e. ammonium molybdate: molybdic acid is the mixture of the ratio composition of 1:1;
Described complexing agent is oxalic acid;
Described muriate is ammonium chloride;
Described tensio-active agent is that cetyl trimethylammonium bromide, brocide and polyethylene glycol 6000 calculate in mass ratio, i.e. cetyl trimethylammonium bromide: brocide: polyethylene glycol 6000 is the mixture of the ratio composition of 2:5:1;
Described rare earth is erbium.
The preparation method of above-mentioned a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite, specifically comprises the steps:
(1), take 5.7175g Erbium trioxide in 100mL small beaker, under agitation add 30mL concentrated nitric acid, heating, make it dissolve, after its cooling, move in the volumetric flask of 100mL, be diluted with water to scale, obtain the rare earths salt that rare earth element erbium concentration is 50g/L;
(2), the pre-treatment of molybdenum disilicide particulate
Taking particle diameter is that 1 μm of molybdenum disilicide particulate 32.5g is in the beaker of 200mL, add 35mL acetone, stir 5min, suction filtration, by molybdenum disilicide particulate in the beaker of 200mL, add 3.0mol/L hydrochloric acid soln 50mL, soak 0.8h, suction filtration, is washed to neutrality, dry 3.5h in 65 DEG C of baking ovens, obtains pretreated molybdenum disilicide particulate;
(3), in the beaker of 2L, 150g nickelous nitrate, 50g nickelous chloride, 200g ammonium molybdate, 200g molybdic acid, 52.5g oxalic acid, 155g ammonium chloride is added, the erbium concentration adding 60mL step (1) gained is again the rare earths salt of 50g/L, and then add 920mL water stirring and dissolving, be 8.5 with aqueous sodium carbonate adjust pH, move in 1L volumetric flask, be diluted with water to scale, obtain single nickel salt-nickelous chloride-ammonium phosphomolybdate-citric acid-Repone K-sodium-chlor-Erbium trinitrate mixed solution;
(4), 32.5g step (2) molybdenum disilicide particulate after pretreatment is in mortar, add tensio-active agent and 0.1138g cetyl trimethylammonium bromide, 0.2845g polyethylene glycol 6000 and 0.0569g brocide, single nickel salt-nickelous chloride-ammonium molybdate-molybdic acid-oxalic acid-ammonium chloride-Erbium trinitrate the mixed solution of 49mL step (3) gained, grinding 55min, proceed in the there-necked flask of 2L, add the single nickel salt-nickelous chloride-ammonium molybdate-molybdic acid-oxalic acid-ammonium chloride-Erbium trinitrate mixed solution of 935mL step (3) gained, controlling mixing speed is after 700rpm carries out stirring 6h, ultrasonication 0.3h, obtain the electroplate liquid for the formation of nickel molybdenum bait-molybdenum disilicide composite deposite.
The electroplate liquid for the formation of nickel molybdenum bait-molybdenum disilicide composite deposite of above-mentioned gained is proceeded in the beaker of 2L, the plating piece to be plated of 80mm × 80mm × 0.5mm to be put into wherein and as negative electrode, anode is that the sheet nickel of 150mm × 100mm × 2mm is electroplated, magnetic agitation in electroplating process, control mixing speed is 550rpm, and current density is 17.5A/dm
2, bath pH values is 8.5, and temperature is 50 DEG C, and plating time is 35min, takes out plating piece, rinses clean, air-dry, must have the plating piece of nickel molybdenum bait-molybdenum disilicide composite deposite with water;
Described plating piece to be plated is Ni-monocrystal plate.
After testing, its hardness is 835.8HV to nickel molybdenum erbium-molybdenum disilicide composite deposite on the plating piece of above-mentioned gained, and its thermal expansivity is 8.0 × 10
-6k
-1.
embodiment 4
A kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite, by often liter of calculating, containing nickel salt be 100g, be 600g containing molybdenum heteropolyacid salt, complexing agent is 20g, muriate is 300g, rare earth is 0.15g, molybdenum disilicide is 7g, tensio-active agent is 0.4g, surplus is water;
Wherein said nickel salt is nickelous chloride;
Described is that ammonium molybdate and ammonium phosphomolybdate calculate in mass ratio containing molybdenum heteropolyacid salt, i.e. ammonium molybdate: ammonium phosphomolybdate is the mixture of the ratio composition of 1:1;
Described complexing agent is tartrate;
Described muriate is that ammonium chloride and sodium-chlor calculate in mass ratio, i.e. ammonium chloride: sodium-chlor is the mixture of the ratio composition of 1:1;
Described tensio-active agent is brocide;
Described rare earth is samarium.
The preparation method of above-mentioned a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite, specifically comprises the steps:
(1), samarium concentration is the preparation of the solution of 50g/L
Take 2.8991g Samarium trioxide in 100mL small beaker, under agitation add the hydrochloric acid that 15mL mass percent concentration is 37%, heating, make it dissolve, after its cooling, move in the volumetric flask of 50mL, be diluted with water to scale, obtaining rare earth metal samarium concentration is the rare earths salt of 50g/L;
(2), the pre-treatment of molybdenum disilicide particulate
Taking particle diameter is that 2 μm of molybdenum disilicide particulate 7g are in the beaker of 100mL, add 10mL acetone, stir 5min, suction filtration, by molybdenum disilicide particulate in the beaker of 100mL, add 5mol/L hydrochloric acid soln 10mL, soak 0.5h, suction filtration, is washed to neutrality, dry 4h in 60 DEG C of baking ovens, obtains pretreated molybdenum disilicide particulate;
(3), the preparation of nickelous chloride-ammonium phosphomolybdate-ammonium molybdate-tartrate-sodium-chlor-ammonium chloride-samarium trichloride mixed solution
100g nickelous chloride, 300g ammonium phosphomolybdate, 300g ammonium molybdate, 20g tartrate, 150g sodium-chlor, 150g ammonium chloride is added in the beaker of 2L, the samarium concentration adding 3mL step (1) gained is the solution of 50g/L, add 980mL water, stirring and dissolving, be 8.0 by sodium carbonate solution regulator solution pH value, move in 1L volumetric flask, be diluted with water to scale, obtain nickelous chloride-ammonium phosphomolybdate-ammonium molybdate-tartrate-sodium-chlor-ammonium chloride-samarium trichloride mixed solution;
(4), by the pretreated molybdenum disilicide particulate of step (2) of 7g in mortar, add tensio-active agent and 0.4g brocide, add the nickelous chloride-ammonium phosphomolybdate-ammonium molybdate-tartrate-sodium-chlor-ammonium chloride-samarium trichloride mixed solution of 7mL step (3) gained, grinding 55min, proceed in the there-necked flask of 2L, add the nickelous chloride-ammonium phosphomolybdate-ammonium molybdate-tartrate-sodium-chlor-ammonium chloride-samarium trichloride mixed solution of 993mL step (3) gained, controlling mixing speed is after 800rpm carries out stirring 10h, ultrasonication 0.4h, obtain the electroplate liquid for the formation of nickel molybdenum neodymium samarium-molybdenum disilicide composite deposite.
The electroplate liquid of above-mentioned nickel molybdenum neodymium samarium-molybdenum disilicide composite deposite is proceeded in the beaker of 2L, the plating piece to be plated of 80mm × 80mm × 0.5mm to be put into wherein and as negative electrode, anode is that the sheet nickel of 150mm × 100mm × 2mm is electroplated, magnetic agitation in electroplating process, control mixing speed is 200rpm, and current density is 20A/dm
2, bath pH values is 8.6, and temperature is 55 DEG C, and plating time is 20min, takes out plating piece, rinses clean, air-dry, must have the plating piece of nickel molybdenum neodymium samarium-molybdenum disilicide composite deposite with water;
Described plating piece to be plated is Ni-monocrystal plate.
After testing, its hardness is 832.2HV to nickel molybdenum samarium-molybdenum disilicide composite deposite on the plating piece of above-mentioned gained, and its thermal expansivity is 7.1 × 10
-6k
-1.
embodiment 5
A kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite, by often liter of calculating, containing nickel salt be 150g, be 100g containing molybdenum heteropolyacid salt, complexing agent is 75g, muriate is 50g, rare earth is 0.05g, molybdenum disilicide is 45g, tensio-active agent is 0.2g, surplus is water;
Wherein said nickel salt is that nickelous nitrate, nickelous chloride and single nickel salt calculate in mass ratio, i.e. nickelous nitrate: nickelous chloride: single nickel salt is the mixture of the ratio composition of 1:1:1;
Described is ammonium molybdate containing molybdenum heteropolyacid salt;
Described complexing agent is that acetic acid and oxysuccinic acid calculate in mass ratio, i.e. acetic acid: oxysuccinic acid is the mixture of the ratio composition of 1:1;
Described muriate is Repone K;
Described tensio-active agent is that triton x-100 and polyethylene glycol 6000 calculate in mass ratio, i.e. triton x-100: polyethylene glycol 6000 is the mixture of the ratio composition of 1:1;
Described rare earth is lutetium.
The preparation method of above-mentioned a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite, specifically comprises the steps:
(1), take 0.5686g lutecium oxide in 50mL small beaker, under agitation add 3mL concentrated nitric acid, heating, makes it dissolve, and after its cooling, move in the volumetric flask of 50mL, be diluted with water to scale, obtaining rare earth metal lutetium concentration is the rare earths salt of 10g/L;
(2), the pre-treatment of molybdenum disilicide particulate
Taking particle diameter is that 100nm molybdenum disilicide particulate 45g is in the beaker of 200mL, add 50mL acetone, stir 5min, suction filtration, by molybdenum disilicide particulate in the beaker of 200mL, add 2.5mol/L hydrochloric acid soln 50mL, soak 0.3h, suction filtration, is washed to neutrality, dry 3h in 70 DEG C of baking ovens, obtains pretreated molybdenum disilicide particulate;
(3), in the beaker of 2L, 50g nickelous nitrate, 50g nickelous chloride, 50g single nickel salt, 100g ammonium molybdate, 35g acetic acid, 35g oxysuccinic acid, 50g Repone K is added, the lutetium concentration adding 5mL step (1) gained is the rare earths salt of 10g/L, add 980mL water stirring and dissolving, be 8.2 with aqueous sodium carbonate adjust pH, move in 1L volumetric flask, be diluted with water to scale, obtain nickelous nitrate-nickelous chloride-single nickel salt-ammonium molybdate-acetic acid-oxysuccinic acid-Repone K-lutecium nitrate mixed solution;
(4), by molybdenum disilicide particulate after pretreatment for 45g step (2) in mortar, add tensio-active agent and 0.1g polyethylene glycol 6000 and 0.1g triton x-100, nickelous nitrate-nickelous chloride-single nickel salt-ammonium molybdate-acetic acid-oxysuccinic acid-Repone K-lutecium nitrate the mixed solution of 60mL step (3) gained, grinding 55min, proceed in the there-necked flask of 2L, add the nickelous nitrate-nickelous chloride-single nickel salt-ammonium molybdate-acetic acid-oxysuccinic acid-Repone K-lutecium nitrate mixed solution of 940mL step (3) gained, controlling mixing speed is after 200rpm carries out stirring 11h, ultrasonication 0.5h, obtain the electroplate liquid for the formation of nickel molybdenum lutetium-molybdenum disilicide composite deposite.
The electroplate liquid for the formation of nickel molybdenum lutetium-molybdenum disilicide composite deposite of above-mentioned gained is proceeded in the beaker of 2L, the plating piece to be plated of 80mm × 80mm × 0.5mm to be put into wherein and as negative electrode, anode is that the sheet nickel of 150mm × 100mm × 2mm is electroplated, magnetic agitation in electroplating process, control mixing speed is 300rpm, and current density is 19A/dm
2, bath pH values is 8.9, and temperature is 45 DEG C, and plating time is 50min, takes out plating piece, rinses clean, air-dry, must have the plating piece of nickel molybdenum lutetium-molybdenum disilicide composite deposite with water;
Described plating piece to be plated is Ni-monocrystal plate.
After testing, its hardness is 901.2HV to nickel molybdenum lutetium-molybdenum disilicide composite deposite on the plating piece of above-mentioned gained, and its thermal expansivity is 7.7 × 10
-6k
-1.
embodiment 6
A kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite, by often liter of calculating, containing nickel salt be 50g, be 200g containing molybdenum heteropolyacid salt, complexing agent is 60g, muriate is 200g, rare earth is 3g, molybdenum disilicide is 30g, tensio-active agent is 0.5g, surplus is water;
Wherein said nickel salt is nickelous nitrate;
Described is Sodium orthomolybdate containing molybdenum heteropolyacid salt;
Described complexing agent is that Padil and lactic acid peace mass ratio calculate, i.e. Padil: lactic acid is the mixture of the ratio composition of 1:1;
Described muriate is Repone K;
Described tensio-active agent is cetyl trimethylammonium bromide;
Described rare earth is praseodymium.
The preparation method of above-mentioned a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite, specifically comprises the steps:
(1), take 4.6813g Praseodymium trioxide in 100mL small beaker, under agitation add the hydrochloric acid that 15mL mass concentration is 37%, heating, make it dissolve, after its cooling, move in the volumetric flask of 100mL, be diluted with water to scale, obtaining rare earth metal praseodymium concentration is the rare earths salt of 40g/L;
(2), the pre-treatment of molybdenum disilicide particulate
Taking particle diameter is that 4 μm of molybdenum disilicide particulate 30g are in the beaker of 100mL, add 30mL acetone, stir 5min, suction filtration, by molybdenum disilicide particulate in the beaker of 100mL, add 3.5mol/L hydrochloric acid soln 30mL, soak 0.6h, suction filtration, is washed to neutrality, dry 1.5h in 85 DEG C of baking ovens, obtains pretreated molybdenum disilicide particulate;
(3), in the beaker of 2L, 50g nickelous nitrate, 200g Sodium orthomolybdate, 30g Padil, 30g lactic acid, 200g Repone K is added, the praseodymium concentration adding step (1) gained is the rare earths salt 75mL of 40g/L, add 910mL water stirring and dissolving, pH is adjusted to be 7.8 with aqueous sodium carbonate, move in 1L volumetric flask, be diluted with water to scale, obtain nickelous nitrate-Sodium orthomolybdate-Padil-lactic acid-Repone K-praseodymium chloride mixed solution;
(4), by molybdenum disilicide particulate after pretreatment for 30g step (2) in mortar, add tensio-active agent and 0.5g cetyl trimethylammonium bromide, nickelous nitrate-Sodium orthomolybdate-Padil-lactic acid-Repone K-praseodymium chloride the mixed solution of 45mL step (3) gained, grinding 55min, proceed in the there-necked flask of 2L, add the nickelous nitrate-Sodium orthomolybdate-Padil-lactic acid-Repone K-praseodymium chloride mixed solution of 955mL step (3) gained, controlling mixing speed is after 300rpm carries out stirring 5h, ultrasonication 0.6h, obtain the electroplate liquid for the formation of nickel molybdenum praseodymium-molybdenum disilicide composite deposite.
Above-mentioned electroplate liquid is proceeded in the beaker of 2L, the plating piece to be plated of 80mm × 80mm × 0.5mm being put into electroplate liquid is also negative electrode, and anode is that the sheet nickel of 150mm × 100mm × 2mm is electroplated, magnetic agitation in electroplating process, control mixing speed is 400rpm, and current density is 15A/dm
2, bath pH values is 7.8, and temperature is 30 DEG C, and plating time is 30min.Take out plating piece, rinse with water clean, air-dry, the plating piece of nickel molybdenum praseodymium-molybdenum disilicide composite deposite must be had;
Described plating piece to be plated is nickelalloy plate.
After testing, its hardness is 837.9HV to nickel molybdenum praseodymium-molybdenum disilicide composite deposite on the plating piece of above-mentioned gained, and its thermal expansivity is 8.3 × 10
-6k
-1.
embodiment 7
A kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite, by often liter of calculating, containing nickel salt be 250g, be 500g containing molybdenum heteropolyacid salt, complexing agent is 30g, muriate is 300g, rare earth 5g, molybdenum disilicide is 35g, tensio-active agent is 0.4g, and surplus is water;
Wherein said nickel salt is that nickelous nitrate and nickelous chloride calculate in mass ratio, i.e. nickelous nitrate: nickelous chloride is the mixture of the ratio composition of 2:3;
Described is that ammonium molybdate and ammonium phosphomolybdate calculate in mass ratio containing molybdenum heteropolyacid salt, and namely ammonium molybdate, ammonium phosphomolybdate are the mixture of the ratio composition of 3:2;
Described complexing agent is oxysuccinic acid;
Described muriate is that ammonium chloride and Repone K calculate in mass ratio, i.e. ammonium chloride: Repone K is the mixture of the ratio composition of 1:1;
Described tensio-active agent is that triton x-100 and cetyl trimethylammonium bromide calculate in mass ratio, i.e. triton x-100: cetyl trimethylammonium bromide is the mixture of the ratio composition of 1:1;
Described rare earth is that terbium and dysprosium calculate in mass ratio, i.e. terbium: dysprosium is the mixture of the ratio composition of 1:1.
The preparation method of above-mentioned a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite, specifically comprises the steps:
(1), take 2.8775g terbium 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 50mL, is diluted with water to scale, obtain the rare earths salt that rare earth metal Tb concentration is 50g/L;
Take 2.8688g dysprosium oxide in 50mL small beaker, under agitation add 15mL concentrated nitric acid, heating, makes it dissolve, and after its cooling, move in the volumetric flask of 50mL, be diluted with water to scale, obtaining rare earth metal dysprosium concentration is the rare earths salt of 50g/L;
(2), the pre-treatment of molybdenum disilicide particulate
Taking particle diameter is that 80nm molybdenum disilicide particulate 35g is in the beaker of 200mL, add 40mL acetone, stir 5min, suction filtration, by molybdenum disilicide particulate in the beaker of 200mL, add 3mol/L hydrochloric acid soln 50mL, soak 0.8h, suction filtration, is washed to neutrality, dry 3.5h in 65 DEG C of baking ovens, obtains pretreated molybdenum disilicide particulate;
(3), the preparation of nickelous nitrate-nickelous chloride-ammonium molybdate-ammonium phosphomolybdate-oxysuccinic acid-Repone K-ammonium chloride-Terbium trinitrate-Dysprosium trinitrate mixed solution
100g nickelous nitrate, 150g nickelous chloride, 300g ammonium molybdate, 200g ammonium phosphomolybdate, 30g oxysuccinic acid, 150g Repone K, 150g ammonium chloride is added in the beaker of 2L, the terbium concentration adding 50ml step (1) gained is again the rare earths salt of 50g/L and 50mL dysprosium concentration is the rare earths salt of 50g/L, add 885mL water stirring and dissolving again, be after 7.9 with aqueous sodium carbonate adjust pH, move in 1L volumetric flask, be diluted with water to scale, obtain nickelous nitrate-nickelous chloride-ammonium molybdate-ammonium phosphomolybdate-oxysuccinic acid-Repone K-ammonium chloride-Terbium trinitrate-Dysprosium trinitrate mixed solution;
(4), by molybdenum disilicide particulate after pretreatment for 35g step (2) in mortar, add tensio-active agent and 0.2g cetyl trimethylammonium bromide and 0.2g triton x-100, nickelous nitrate-nickelous chloride-ammonium molybdate-ammonium phosphomolybdate-oxysuccinic acid-Repone K-ammonium chloride-Terbium trinitrate-Dysprosium trinitrate the mixed solution of 60mL step (3) gained, grinding 50min, proceed in the there-necked flask of 2L, add the nickelous nitrate-nickelous chloride-ammonium molybdate-ammonium phosphomolybdate-oxysuccinic acid-Repone K-ammonium chloride-Terbium trinitrate-Dysprosium trinitrate mixed solution of 940mL step (3) gained, controlling mixing speed is after 500rpm carries out stirring 8h, ultrasonication 0.8h, obtain the electroplate liquid for the formation of nickel molybdenum terbium dysprosium-molybdenum disilicide composite deposite.
The electroplate liquid for the formation of nickel molybdenum terbium dysprosium-molybdenum disilicide composite deposite of above-mentioned gained is proceeded in the beaker of 2L, the plating piece to be plated of 80mm × 80mm × 0.5mm to be put into wherein and as negative electrode, anode is that the sheet nickel of 150mm × 100mm × 2mm is electroplated, magnetic agitation in electroplating process, control mixing speed is 450rpm, and current density is 22A/dm
2, bath pH values is 7.9, and temperature is 35 DEG C, and plating time is 55min, takes out plating piece, rinses clean, air-dry, must have the plating piece of nickel molybdenum terbium dysprosium-molybdenum disilicide composite deposite with water;
Described plating piece to be plated is nickel plate.
After testing, its hardness is 893.9HV to nickel molybdenum terbium dysprosium-molybdenum disilicide composite deposite on the plating piece of above-mentioned gained, and its thermal expansivity is 7.2 × 10
-6k
-1.
embodiment 8
A kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite, by often liter of calculating, containing nickel salt be 300g, be 300g containing molybdenum heteropolyacid salt, complexing agent is 40g, muriate is 300g, rare earth is 2g, molybdenum disilicide is 40g, tensio-active agent is 0.4g, surplus is water;
Wherein said nickel salt is that nickelous nitrate, nickelous chloride and single nickel salt calculate in mass ratio, i.e. nickelous nitrate: nickelous chloride: single nickel salt is the mixture of the ratio composition of 1:1:1;
Described is ammonium molybdate containing molybdenum heteropolyacid salt;
Described complexing agent is that oxyacetic acid and succinic acid calculate in mass ratio, i.e. oxyacetic acid: succinic acid is the mixture of the ratio composition of 3:1;
Described muriate is that ammonium chloride and Repone K calculate in mass ratio, i.e. ammonium chloride: Repone K is the mixture of the ratio composition of 2:1;
Described tensio-active agent is that triton x-100 and cetyl trimethylammonium bromide calculate in mass ratio, i.e. triton x-100: cetyl trimethylammonium bromide is the mixture of the ratio composition of 1:1;
Described rare earth is that cerium and gadolinium calculate in mass ratio, i.e. cerium: gadolinium is the mixture of the ratio composition of 1:1.
The preparation method of above-mentioned a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite, specifically comprises the steps:
(1), take 1.4408g gadolinium sesquioxide in 50mL small beaker, under agitation add 7mL concentrated nitric acid, heating, makes it dissolve, and after its cooling, move in the volumetric flask of 50mL, be diluted with water to scale, obtaining rare earth gadolinium concentration is the rare earths salt of 25g/L;
Take 1.4641g cerium 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 50mL, is diluted with water to scale, obtain the rare earths salt that cerium concentration is 25g/L;
(2), the pre-treatment of molybdenum disilicide particulate
Taking particle diameter is that 500nm molybdenum disilicide particulate 40g is in the beaker of 200mL, add 40mL acetone, stir 5min, suction filtration, by molybdenum disilicide particulate in the beaker of 100mL, add 4.5mol/L hydrochloric acid soln 40mL, soak 0.9h, suction filtration, is washed to neutrality, dry 1h in 90 DEG C of baking ovens, obtains pretreated molybdenum disilicide particulate;
(3), 100g nickelous nitrate is added in the beaker of 2L, 100g nickelous chloride, 100g single nickel salt, 300g ammonium molybdate, 30g oxyacetic acid, 10g succinic acid, 200g Repone K, 100g ammonium chloride, the gadolinium concentration adding 40mL step (1) gained is again the rare earths salt of 25g/L and the cerium concentration of 40mL step (1) gained is the rare earths salt of 25g/L, add 905mL water stirring and dissolving again, be 8.8 with aqueous sodium carbonate adjust pH, move in 1L volumetric flask, be diluted with water to scale, obtain nickelous nitrate-nickelous chloride-single nickel salt-ammonium molybdate-oxyacetic acid-succinic acid-Repone K-ammonium chloride-Gadolinium trinitrate-cerous nitrate mixed solution,
(4), by molybdenum disilicide particulate after pretreatment for 40g step (2) in mortar, add tensio-active agent and 0.2g cetyl trimethylammonium bromide and 0.2g triton x-100, nickelous nitrate-nickelous chloride-single nickel salt-ammonium molybdate-oxyacetic acid-succinic acid-Repone K-ammonium chloride-Gadolinium trinitrate-cerous nitrate the mixed solution of 55mL step (3) gained, grinding 50min, proceed in the there-necked flask of 2L, add the nickelous nitrate-nickelous chloride-single nickel salt-ammonium molybdate-oxyacetic acid-succinic acid-Repone K-ammonium chloride-Gadolinium trinitrate-cerous nitrate mixed solution of 945mL step (3) gained, controlling mixing speed is after 400rpm carries out stirring 7h, ultrasonication 0.7h, obtain the electroplate liquid for the formation of nickel molybdenum gadolinium cerium-molybdenum disilicide composite deposite.
The electroplate liquid for the formation of nickel molybdenum gadolinium cerium-molybdenum disilicide composite deposite of above-mentioned gained is proceeded in the beaker of 2L, the plating piece to be plated of 80mm × 80mm × 0.5mm to be put into wherein and as negative electrode, anode is that the sheet nickel of 150mm × 100mm × 2mm is electroplated, magnetic agitation in electroplating process, control mixing speed is 500rpm, and current density is 12A/dm
2, bath pH values is 8.8, and temperature is 20 DEG C, and plating time is 45min, takes out plating piece, rinses clean, air-dry, must have the plating piece of nickel molybdenum gadolinium cerium-molybdenum disilicide composite deposite with water;
Described plating piece to be plated is nickel plate.
After testing, its hardness is 879.8HV to nickel molybdenum gadolinium cerium-molybdenum disilicide composite deposite on the plating piece of above-mentioned gained, and its thermal expansivity is 8.5 × 10
-6k
-1.
embodiment 9 (example is executed in the contrast of embodiment 8)
The preparation method of above-mentioned a kind of electroplate liquid for the formation of nickel molybdenum coating, specifically comprises the steps:
100g nickelous nitrate, 100g nickelous chloride, 100g single nickel salt, 300g ammonium molybdate, 30g oxyacetic acid, 10g succinic acid, 200g Repone K is added in the beaker of 2L, 100g ammonium chloride, add 985mL water dissolution and form nickelous nitrate-nickelous chloride-single nickel salt-ammonium molybdate-oxyacetic acid-succinic acid-Repone K-ammonium chloride mixed solution, be 8.8 with aqueous sodium carbonate adjust pH, move in 1L volumetric flask, be diluted with water to scale, the obtained electroplate liquid for the formation of nickel molybdenum coating.
The electroplate liquid for the formation of nickel molybdenum coating of above-mentioned gained is proceeded in the beaker of 2L, the plating piece to be plated of 80mm × 80mm × 0.5mm to be put into wherein and as negative electrode, anode is that the sheet nickel of 150mm × 100mm × 2mm is electroplated, magnetic agitation in electroplating process, control mixing speed is 500rpm, and current density is 12A/dm
2, bath pH values is 8.8, and temperature is 20 DEG C, and plating time is 45min, takes out plating piece, rinses clean, air-dry, must have the plating piece of nickel molybdenum coating with water; Described plating piece to be plated is nickel plate.
After testing, its hardness is 553.8HV to nickel molybdenum coating on the plating piece of above-mentioned gained, and its thermal expansivity is 9.3 × 10
-6k
-1.
embodiment 10 (example is executed in the contrast of embodiment 8)
The preparation method of above-mentioned a kind of electroplate liquid for the formation of nickel molybdenum-molybdenum disilicide composite deposite, specifically comprises the steps:
Taking particle diameter is that 500nm molybdenum disilicide particulate 40g is in the beaker of 200mL, add 40mL acetone, stir 5min, suction filtration, by molybdenum disilicide particulate in the beaker of 100mL, add 4.5mol/L hydrochloric acid soln 40mL, soak 0.9h, suction filtration, is washed to neutrality, dry 1h in 90 DEG C of baking ovens, obtains pretreated molybdenum disilicide particulate;
100g nickelous nitrate, 100g nickelous chloride, 100g single nickel salt, 300g ammonium molybdate, 30g oxyacetic acid, 10g succinic acid, 200g Repone K is added in the beaker of 2L, 100g ammonium chloride, add 985mL water dissolution and form nickelous nitrate-nickelous chloride-single nickel salt-ammonium molybdate-oxyacetic acid-succinic acid-Repone K-ammonium chloride mixed solution, be 8.8 with aqueous sodium carbonate adjust pH, move in 1L volumetric flask, be diluted with water to scale, the obtained electroplate liquid for the formation of nickel molybdenum coating.
By the molybdenum disilicide particulate 40g of above-mentioned gained after pretreatment in mortar, 0.2g cetyl trimethylammonium bromide, 0.2g triton x-100, nickelous nitrate-nickelous chloride-single nickel salt-ammonium molybdate-oxyacetic acid-succinic acid-Repone K-ammonium chloride the mixed solution of the above-mentioned gained of 55mL, grinding 50min, proceed in the there-necked flask of 2L, add the nickelous nitrate-nickelous chloride-single nickel salt-ammonium molybdate-oxyacetic acid-succinic acid-Repone K-ammonium chloride mixed solution of the above-mentioned preparation of 945mL, controlling mixing speed is after 400rpm carries out stirring 7h, ultrasonication 0.7h, obtain a kind of electroplate liquid for the formation of nickel molybdenum-molybdenum disilicide composite deposite.
A kind of electroplate liquid for the formation of nickel molybdenum-molybdenum disilicide composite deposite of above-mentioned gained is proceeded in the beaker of 2L, the plating piece to be plated of 80mm × 80mm × 0.5mm to be put into wherein and as negative electrode, anode is that the sheet nickel of 150mm × 100mm × 2mm is electroplated, magnetic agitation in electroplating process, control mixing speed is 500rpm, and current density is 12A/dm
2, bath pH values is 8.8, and temperature is 20 DEG C, and plating time is 45min, takes out plating piece, rinses clean, air-dry, must have the plating piece of nickel molybdenum-molybdenum disilicide composite deposite with water; Described plating piece to be plated is nickel plate.
After testing, its hardness is 725.2HV to nickel molybdenum-molybdenum disilicide composite deposite on the plating piece of above-mentioned gained, and its thermal expansivity is 8.8 × 10
-6k
-1.
Contrasted by the hardness of the nickel molybdenum terbium dysprosium-molybdenum disilicide composite deposite of the nickel molybdenum-molybdenum disilicide composite deposite of above-described embodiment 10, the nickel molybdenum coating of embodiment 9 and embodiment 8 and thermal expansivity, can find out, a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite of the present invention is used for plating piece to carry out electroplating formed nickel molybdenum rare earth-molybdenum disilicide composite deposite, its hardness is significantly improved, and hot thermal expansivity is less.
Foregoing be only the present invention conceive under basic explanation, and according to any equivalent transformation that technical scheme of the present invention is done, all should protection scope of the present invention be belonged to.
Claims (11)
1. the electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite, it is characterized in that by often liter of calculating, containing nickel salt be 10 ~ 400g, containing molybdenum heteropolyacid salt and molybdic acid mixture be 10 ~ 800g, complexing agent is 5 ~ 100g, muriate is 10 ~ 300g, rare earth is 0.05 ~ 6g, molybdenum disilicide is 5 ~ 60g, tensio-active agent is 0.01 ~ 0.9g, surplus is water;
Wherein said nickel salt is the mixture of one or more compositions in nickelous nitrate, nickelous chloride, single nickel salt;
Described contains mixtures that molybdenum heteropolyacid salt is one or more compositions in ammonium molybdate, Sodium orthomolybdate, ammonium phosphomolybdate;
Described complexing agent is the mixture of one or more compositions in formic acid, acetic acid, Padil, oxyacetic acid, lactic acid, oxalic acid, succinic acid, citric acid, oxysuccinic acid, tartrate;
Described muriate is the mixture of one or more compositions in ammonium chloride, Repone K, sodium-chlor;
Described rare earth is the mixture of one or more the rare earth composition in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, scandium;
Described tensio-active agent is the mixture of one or more compositions in triton x-100, cetyl trimethylammonium bromide, brocide, polyethylene glycol 6000.
2. a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite as claimed in claim 1, it is characterized in that by often liter of calculating, containing nickel salt be 10g, be 10g containing molybdenum heteropolyacid salt, complexing agent is 5g, muriate is 10g, rare earth is 0.05g, molybdenum disilicide is 5g, tensio-active agent is 0.01g, surplus is water;
Wherein said nickel salt is nickelous nitrate;
Described is Sodium orthomolybdate containing molybdenum heteropolyacid salt;
Described complexing agent is formic acid, oxalic acid calculates in mass ratio, i.e. formic acid: oxalic acid is the mixture of 2:3 composition;
Described muriate is ammonium chloride;
Described tensio-active agent is in polyethylene glycol 6000;
Described rare earth is lanthanum.
3. a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite as claimed in claim 1, it is characterized in that by often liter of calculating, containing nickel salt be 400g, be 800g containing molybdenum heteropolyacid salt, complexing agent is 100g, muriate is 300g, rare earth is 6g, molybdenum disilicide is 60g, tensio-active agent is 0.9g, surplus is water;
Wherein said nickel salt is nickelous chloride, single nickel salt calculates in mass ratio, i.e. nickelous chloride: single nickel salt is the mixture of the ratio composition of 1:1;
Described is ammonium phosphomolybdate containing molybdenum heteropolyacid salt;
Described complexing agent is citric acid;
Described muriate is Repone K, sodium-chlor calculates in mass ratio, i.e. Repone K: sodium-chlor is the mixture of the ratio composition of 1:1;
Described tensio-active agent is triton x-100, cetyl trimethylammonium bromide calculates in mass ratio, i.e. triton x-100: cetyl trimethylammonium bromide is the mixture of the ratio composition of 4:5;
Described rare earth is the mixture of neodymium, yttrium composition.
4. a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite as claimed in claim 1, it is characterized in that by often liter of calculating, containing nickel salt be 200g, containing the mixture of molybdenum heteropolyacid salt and molybdic acid be 400g, complexing agent is 52.5g, muriate is 155g, rare earth is 3g, molybdenum disilicide is 32.5g, tensio-active agent is 0.455g, surplus is water;
Wherein said nickel salt is that nickelous nitrate and nickelous chloride calculate in mass ratio, i.e. nickelous nitrate: nickelous chloride is the mixture of the ratio composition of 3:1;
The described mixture containing molybdenum heteropolyacid salt and molybdic acid is that ammonium molybdate and molybdic acid calculate in mass ratio, i.e. ammonium molybdate: molybdic acid is the mixture of the ratio composition of 1:1;
Described complexing agent is oxalic acid;
Described muriate is ammonium chloride;
Described tensio-active agent is that cetyl trimethylammonium bromide, brocide and polyethylene glycol 6000 calculate in mass ratio, i.e. cetyl trimethylammonium bromide: brocide: polyethylene glycol 6000 is the mixture of the ratio composition of 2:5:1;
Described rare earth is erbium.
5. a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite as claimed in claim 1, it is characterized in that by often liter of calculating, containing nickel salt be 100g, be 600g containing molybdenum heteropolyacid salt, complexing agent is 20g, muriate is 300g, rare earth is 0.15g, molybdenum disilicide is 7g, tensio-active agent is 0.4g, surplus is water;
Wherein said nickel salt is nickelous chloride;
Described is that ammonium molybdate and ammonium phosphomolybdate calculate in mass ratio containing molybdenum heteropolyacid salt, i.e. ammonium molybdate: ammonium phosphomolybdate is the mixture of the ratio composition of 1:1;
Described complexing agent is tartrate;
Described muriate is that ammonium chloride and sodium-chlor calculate in mass ratio, i.e. ammonium chloride: sodium-chlor is the mixture of the ratio composition of 1:1;
Described tensio-active agent is brocide;
Described rare earth is samarium.
6. a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite as claimed in claim 1, it is characterized in that by often liter of calculating, containing nickel salt be 150g, be 100g containing molybdenum heteropolyacid salt, complexing agent is 75g, muriate is 50g, rare earth is 0.05g,
Molybdenum disilicide is 45g, tensio-active agent is 0.2g, and surplus is water;
Wherein said nickel salt is that nickelous nitrate, nickelous chloride and single nickel salt calculate in mass ratio, i.e. nickelous nitrate: nickelous chloride: single nickel salt is the mixture of the ratio composition of 1:1:1;
Described is ammonium molybdate containing molybdenum heteropolyacid salt;
Described complexing agent is that acetic acid and oxysuccinic acid calculate in mass ratio, i.e. acetic acid: oxysuccinic acid is the mixture of the ratio composition of 1:1;
Described muriate is Repone K;
Described tensio-active agent is that triton x-100 and polyethylene glycol 6000 calculate in mass ratio, i.e. triton x-100: polyethylene glycol 6000 is the mixture of the ratio composition of 1:1;
Described rare earth is lutetium.
7. a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite as claimed in claim 1, is characterized in that by often liter of calculating, containing nickel salt be 50g, be 200g containing molybdenum heteropolyacid salt, complexing agent is 60g, muriate is 200g, rare earth is 3g,
Molybdenum disilicide is 30g, tensio-active agent is 0.5g, and surplus is water;
Wherein said nickel salt is nickelous nitrate;
Described is Sodium orthomolybdate containing molybdenum heteropolyacid salt;
Described complexing agent is that Padil and lactic acid peace mass ratio calculate, i.e. Padil: lactic acid is the mixture of the ratio composition of 1:1;
Described muriate is Repone K;
Described tensio-active agent is cetyl trimethylammonium bromide;
Described rare earth is praseodymium.
8. a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite as claimed in claim 1, it is characterized in that by often liter of calculating, containing nickel salt be 250g, be 500g containing molybdenum heteropolyacid salt, complexing agent is 30g, muriate is 300g, rare earth is 5g, molybdenum disilicide is 35g, tensio-active agent is 0.4g, and surplus is water;
Wherein said nickel salt is that nickelous nitrate and nickelous chloride calculate in mass ratio, i.e. nickelous nitrate: nickelous chloride is the mixture of the ratio composition of 2:3;
Described is that ammonium molybdate and ammonium phosphomolybdate calculate in mass ratio containing molybdenum heteropolyacid salt, and namely ammonium molybdate, ammonium phosphomolybdate are the mixture of the ratio composition of 3:2;
Described complexing agent is oxysuccinic acid;
Described muriate is that ammonium chloride and Repone K calculate in mass ratio, i.e. ammonium chloride: Repone K is the mixture of the ratio composition of 1:1;
Described tensio-active agent is that triton x-100 and cetyl trimethylammonium bromide calculate in mass ratio, i.e. triton x-100: cetyl trimethylammonium bromide is the mixture of the ratio composition of 1:1;
Described rare earth is that terbium and dysprosium calculate in mass ratio, i.e. terbium: dysprosium is the mixture of the ratio composition of 1:1.
9. a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite as claimed in claim 1, it is characterized in that by often liter of calculating, containing nickel salt be 300g, be 300g containing molybdenum heteropolyacid salt, complexing agent is 40g, muriate is 300g, rare earth is 2g, molybdenum disilicide is 40g, tensio-active agent is 0.4g, surplus is water;
Wherein said nickel salt is that nickelous nitrate, nickelous chloride and single nickel salt calculate in mass ratio, i.e. nickelous nitrate: nickelous chloride: single nickel salt is the mixture of the ratio composition of 1:1:1;
Described is ammonium molybdate containing molybdenum heteropolyacid salt;
Described complexing agent is that oxyacetic acid and succinic acid calculate in mass ratio, i.e. oxyacetic acid: succinic acid is the mixture of the ratio composition of 3:1;
Described muriate is that ammonium chloride and Repone K calculate in mass ratio, i.e. ammonium chloride: Repone K is the mixture of the ratio composition of 2:1;
Described tensio-active agent is that triton x-100 and cetyl trimethylammonium bromide calculate in mass ratio, i.e. triton x-100: cetyl trimethylammonium bromide is the mixture of the ratio composition of 1:1;
Described rare earth is that cerium and gadolinium calculate in mass ratio, i.e. cerium: gadolinium is the mixture of the ratio composition of 1:1.
10. the preparation method of a kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite as described in claim as arbitrary in claim 1-9, is characterized in that specifically comprising the steps:
(1) preparation of rare earths salt
Be dissolved in by rare earth oxide in nitric acid or hydrochloric acid, the concentration being mixed with rare earth is 10 ~ 50g/L rare earths salt;
Its middle rare earth is the mixture of one or more the rare earth oxide composition in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, scandium;
Rare-earth salts is the mixture that rare earth nitrate, rare earth chloride or rare earth nitrate and rare earth chloride form;
(2), the pre-treatment of molybdenum disilicide particulate
By particle diameter be the molybdenum disilicide particulate of 10nm ~ 10 μm first with acetone cleaning, then 0.2 ~ 1h in the hydrochloric acid soln being soaked in 2 ~ 6mol/L, suction filtration, is washed to neutrality, and at 50 ~ 100 DEG C, dry 0.5 ~ 5h, obtains pretreated molybdenum disilicide particulate;
(3) with water by nickel salt, containing molybdenum heteropolyacid salt, complexing agent and muriate dissolve after, add rare earths salt prepared by step (1),
Be 7.5 ~ 9.0 with aqueous sodium carbonate adjust pH, obtain nickel salt-molybdenum heteropolyacid salt-complexing agent-muriate-rare-earth salts mixed solution,
Control wherein nickel salt, to be respectively containing the concentration of molybdenum heteropolyacid salt, complexing agent, muriate, rare earth 10-400g/L, 10-800g/L,
5-100g/L、10-300g/L、0.05-6g/L；
(4) by the pretreated molybdenum disilicide particulate of step (1) gained, after the 1-6.5% of the volume of nickel salt-molybdenum heteropolyacid salt-complexing agent-muriate-rare-earth salts mixed solution prepared by step (2) mixes with tensio-active agent, grind in mortar, then nickel salt-molybdenum heteropolyacid salt-complexing agent-muriate-rare-earth salts mixed solution that new container continues the surplus of adding step (2) gained is proceeded to, controlling mixing speed is after 100 ~ 900rpm carries out stirring 4 ~ 12h, with ultrasonication 0.2 ~ 1h, obtain the electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite,
The amount of above-mentioned nickel salt used-molybdenum heteropolyacid salt-complexing agent-muriate-rare-earth salts mixed solution, molybdenum disilicide and tensio-active agent, in nickel salt-molybdenum heteropolyacid salt-complexing agent-muriate-rare-earth salts mixed solution: molybdenum disilicide: tensio-active agent is that the ratio of 1L:5 ~ 60g:0.01 ~ 0.9g calculates.
A kind of electroplate liquid for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite as described in 11. claims as arbitrary in claim 1-9 carries out electroplating the method forming nickel molybdenum rare earth-molybdenum disilicide composite deposite on plating piece to be plated, it is characterized in that step is as follows:
The electroplate liquid put into by plating piece to be plated for the formation of nickel molybdenum rare earth-molybdenum disilicide composite deposite carries out electroplating and as negative electrode, anode is nickel, and electroplating process controls current density 10 ~ 25A/dm
2, bath pH values 7.5 ~ 9.0, electroplating temperature 40 ~ 60 DEG C, mixing speed 100 ~ 600rpm, electroplating time 10 ~ 60min, after plating, plating piece use water rinses, air-dry, must have the plating piece of nickel molybdenum rare earth-molybdenum disilicide composite deposite;
Described plating piece to be plated is nickel plate.
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| CN104294328B (en) * | 2014-10-23 | 2017-02-01 | 上海应用技术学院 | Nickel-molybdenum-aluminum-rare earth coating and preparation method thereof |
| CN104342730B (en) * | 2014-10-23 | 2017-01-18 | 上海应用技术学院 | Nickel-molybdenum-aluminum coating and preparation method thereof |
| CN104342729B (en) * | 2014-10-23 | 2017-01-18 | 上海应用技术学院 | Ni-Mo-Al-rear earth coating and preparation method thereof |
| CN104278301B (en) * | 2014-10-23 | 2016-09-14 | 上海应用技术学院 | A kind of nickel molybdenum aluminium coat and preparation method thereof |
| CN105297115A (en) * | 2015-10-08 | 2016-02-03 | 上海应用技术学院 | Preparation method of nickel molybdenum aluminum rare earth-molybdenum disilicide composite plating layer |
| CN106086958B (en) * | 2016-08-22 | 2017-10-13 | 黄激扬 | A kind of rare earth nickel cobalt tungsten disulfide multicomponent alloy anticorrosion antiwear composite deposite, electroplate liquid and preparation method thereof |
| CN110079840A (en) * | 2019-04-26 | 2019-08-02 | 山东金宝电子股份有限公司 | A kind of surface treatment additive package improving copper foil high-temp antioxidizing performance |
| CN111910214B (en) * | 2020-07-09 | 2021-03-26 | 北方工业大学 | Preparation method of gas-guiding hydrogen evolution material with gradually-expanded pore channel structure |
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