CN102703840B - Block ternary nickel-tungsten-phosphorus amorphous alloy and preparation method thereof - Google Patents
Block ternary nickel-tungsten-phosphorus amorphous alloy and preparation method thereof Download PDFInfo
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- CN102703840B CN102703840B CN 201210165230 CN201210165230A CN102703840B CN 102703840 B CN102703840 B CN 102703840B CN 201210165230 CN201210165230 CN 201210165230 CN 201210165230 A CN201210165230 A CN 201210165230A CN 102703840 B CN102703840 B CN 102703840B
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Abstract
The invention relates to a block ternary nickel-tungsten-phosphorus amorphous alloy and a preparation method thereof; chemical composition of the alloy is Ni100-x-yWxPy, wherein x, y are mass fractions, x is equal to 11-14%, and y is equal to 15-18%; the preparation method of the alloy deposits the amorphous alloy on moulds with a jet electro-deposition method, utilizes activated nickel plates with purity of 99.9% as soluble anode to provide nickel ions, designs stainless steel base plates with different shapes according to shapes of amorphous products as insoluble cathode, fixes the stainless steel base plates on electro-deposition moulds, and prepares the block ternary nickel-tungsten-phosphorus amorphous alloy with three-dimensional scale, block, plating thickness which reach millimeter level through different plating solution components and plating processes.
Description
Technical field
The present invention relates to a kind of metallic substance and preparation method thereof, particularly a kind of amorphous alloy and preparation method thereof.
Background technology
The Ni-W-P non-crystaline amorphous metal has the performance of many excellences: excellent solidity to corrosion is applied to the corrosion-resistant finishes of oil field well casing; Good friction and wear behavior, high rigidity and physical strength are widely used in mechanical transmission component; Have good catalytic hydrogen evolution activity, long-term electrolysis stability and higher thermostability and solidity to corrosion, be used for electrocatalytic hydrogen evolution and photoelectrocatalysis liberation of hydrogen; Ultra-fine Ni-W-P non-crystaline amorphous metal has the effect of high activated catalyst, is widely used in chemical field.At present, the preparation of Ni-W-P non-crystaline amorphous metal has three kinds of methods usually: get rid of band method, electroless plating method and electrodip process.Aspect geomery, the sample of these three kinds of method preparations is all very thin, all is micron dimension, rests on filament, band and pellicular stage, can't obtain having the bulk amorphous alloys of three dimension scale.Getting rid of the band method needs pre-melt Ni-W-P mother alloy, and nonmetal P highly volatile, and depart from the composition range that amorphous forms, be difficult to form non-crystaline amorphous metal.As for electroless plating method and electrodip process, because coating directly is deposited on substrate surface, this traditional depositional mode, do not have the constraint of mechanical force, current density is little, and the result causes the prolongation along with depositing time, craze of coating or and strippable substrate, therefore can only make thin-film material.With the non-crystaline amorphous metal of these method preparations, the geomery of non-crystaline amorphous metal is restricted, and makes many good characteristics of amorphous alloy material be difficult in actual applications give full play to.
Summary of the invention
The object of the present invention is to provide a kind of prepare speed fast, have block nickel ternary-tungsten-phosphorus non-crystalline alloy of three dimension scale bulk and preparation method thereof.The present invention adopts custom-designed injection galvanic deposit mould and different solution composition and plating technics, obtains block nickel ternary-tungsten-phosphorus non-crystalline alloy that a kind of thickness of coating reaches millimeter magnitude.
Technical scheme of the present invention is as follows:
One, nickel ternary-tungsten of the present invention-phosphorus non-crystalline alloy, its chemical ingredients are Ni
100-x-yW
xP
y, wherein x, y are massfraction, x=11 ~ 14%, y=15 ~ 18%, and thickness of coating reaches the block of millimeter magnitude.
Two, preparation method of the present invention is specific as follows:
1, the injection galvanic deposit mould of preparation above-mentioned block nickel ternary-tungsten-phosphorus non-crystalline alloy:
The upper die and lower die of this mould are made of polyvinyl chloride panel, and upper and lower die topography is identical.Be provided with inner chamber in the middle of the patrix, be provided with deposit cavity in the middle of the counterdie, the mold inner chamber is less than the deposit cavity of bed die.The shape of stainless steel substrate is corresponding with the shape of amorphous product, and size is greater than the patrix inner cavity size, less than bed die deposit cavity geomery.The thickness of stainless steel substrate is identical with the bed die deposit cavity degree of depth, and places among the deposit cavity of bed die.One end of above-mentioned stainless steel substrate links to each other with the copper conduction bands of peripheral hardware insullac, and the other end of these copper conduction bands stretches out outside the bed die.By plastic bolt above-mentioned stainless steel substrate, bed die and copper conduction bands are connected.Upper and lower mould is combined into as a whole injection galvanic deposit mould by holding bolt.
The working face of above-mentioned stainless steel substrate is used 400# successively, 600#, and 800#, the 1000# liquid honing is removed machining marks, cleans the back and immerses 70 ~ 80 ℃, mass concentration 15 ~ 20%NaCO
3In the solution, oil removing 2 ~ 5min takes out with pure water and cleans; The hydrochloric acid soln of putting into mass concentration 5 ~ 10% then activates 1 ~ 2min, takes out and uses the pure water cleaned standby seam.
2, the electroplate liquid of preparation above-mentioned block nickel ternary-tungsten-phosphorus non-crystalline alloy:
Electroplate liquid is to be solvent with water, contains single nickel salt 100-130g, nickelous chloride 10-20g, sodium wolframate 190-220g, inferior sodium phosphate 40-50g, Trisodium Citrate 210-230g, asccharin 4-6g in every liter of this solution.
In the plating bath, single nickel salt is main salt, provides plating required Ni
2+Nickelous chloride is except Ni is provided
2+Provide Cl simultaneously outward,
-Prevent anode passivation; Inferior sodium phosphate is the main source of P in the coating; Sodium wolframate is the main source of W in the coating; Trisodium Citrate is pH value buffer reagent, regulates bath pH value, and the pH value is very little to coating P content influence within the specific limits.
3, the coating bath of preparation above-mentioned block nickel ternary-tungsten-phosphorus non-crystalline alloy is installed:
The stainless steel substrate that is fixed on the above-mentioned galvanic deposit mould is linked to each other with dc power cathode by the copper conduction bands on the mould as insoluble negative plate, purity is linked to each other with dc power anode as the soluble anode that nickel ion is provided for 99.9% activated ni plate, and they are put into the coating bath that above-mentioned plating bath is housed.The impeller pump two ends link to each other with two non-metallic pipes that insert plating baths respectively, and the pipeline that links to each other with the impeller pump liquid outlet is provided with control valve and under meter, and the exit end of this pipeline is towards galvanic deposit upper mould inner chamber.In coating bath, also be provided with well heater and temperature regulating device.
4, preparation above-mentioned block nickel ternary-tungsten-phosphorus non-crystalline alloy: at first open well heater and temperature regulating device in the coating bath, the plating bath bath temperature is transferred to 50-60 ℃.Open impeller pump again, the flow velocity by under meter and control valve adjusting plating bath makes plating bath reach the jet velocity of 100-200m/s; By regulating voltage, make current density reach 200-300A/dm
2At any time by adding the 5%(massfraction) sodium hydroxide and 10%(massfraction) hydrochloric acid adjusting plating bath pH, the pH value 4.4 ~ 4.6 of strict control plating bath is to guarantee quality of coating.After coating reached desired size, the galvanic deposit mould was taken out in outage, and the water flushing splits each part, peels off nickel-tungsten-phosphorus non-crystalline alloy from stainless steel substrate.
The present invention compared with prior art has following advantage:
1, because stainless steel plate and polyvinyl chloride panel that injection galvanic deposit mould of the present invention uses are very easily processed, can process and spray the galvanic deposit mould according to required bulk amorphous alloy sample shape.
2, by changing solution composition and plating technic, can prepare the block nickel ternary-tungsten-phosphorus non-crystalline alloy of required composition, shape and size.
3, can prepare have three dimension scale, block nickel ternary-tungsten-phosphorus non-crystalline alloy that bulk, thickness of coating reach millimeter magnitude.
Description of drawings
Fig. 1 is that the present invention sprays galvanic deposit mould master and looks the section simplified schematic diagram.
Fig. 2 is that the present invention sprays the electrodeposition technology master and looks the section simplified schematic diagram.
Fig. 3 is the block nickel ternary-tungsten-phosphorus non-crystalline alloy of the embodiment of the invention 1 preparation photo figure in kind.
Embodiment
Embodiment 1
Spraying galvanic deposit mould master in the present invention shown in Figure 1 looks in the section simplified schematic diagram, it is made up of two identical polyvinyl chloride mold 1 and bed dies 3 of profile up and down, the mould intermediate section is not provided with inner chamber and deposit cavity up and down, and the mold inner chamber is less than the deposit cavity of bed die.The shape of stainless steel substrate 2 is corresponding with the shape of amorphous product, and size is greater than the mold inner cavity size, less than bed die deposit cavity geomery.The thickness of stainless steel substrate is identical with the bed die deposit cavity degree of depth, and places among the deposit cavity of bed die.End at above-mentioned stainless steel plate connects the copper conduction bands 4 that insulate with insullac, and the other end of these copper conduction bands stretches out outside the bed die.The working face of above-mentioned stainless steel substrate is used 400# successively, 600#, and 800#, the 1000# liquid honing is removed machining marks, cleans the back and immerses 70 ℃, mass concentration 20%NaCO
3In the solution, oil removing 2min takes out with pure water and cleans; The hydrochloric acid soln of putting into mass concentration 10% then activates 1min, takes out and uses the pure water cleaned standby seam.By 4 * M4 plastic bolt above-mentioned stainless steel substrate, bed die and copper conduction bands are connected.Upper and lower mould is combined into as a whole injection galvanic deposit mould by the uniform holding bolt of 6 * M4.
The preparation electroplate liquid contains single nickel salt 100g, nickelous chloride 20g, sodium wolframate 190g, inferior sodium phosphate 40g, Trisodium Citrate 230g, asccharin 4g in every liter of this solution, all the other are water.
The present invention as shown in Figure 2 sprays the electrodeposition technology master and looks in the section simplified schematic diagram, to be fixed on stainless steel plate on the above-mentioned galvanic deposit mould as insoluble negative plate, be that the activated ni plate of 99.9%, 100 * 100 mm is as soluble anode with purity, and they are put into the coating bath that above-mentioned plating bath is housed, power supply 10 positive and negative electrode are connected with copper conduction bands on the galvanic deposit mould 8 with above-mentioned activated ni plate 9 respectively.Impeller pump 12 1 terminations are inserted the plastics tubing 11 of plating bath, and another termination control valve 13 is provided with under meter 14 at the plastics tubing that connects the control valve the other end.In coating bath 5, also be provided with well heater and temperature regulating device 6.At first open well heater and temperature regulating device in the coating bath, bath temperature is transferred to 50 ℃, open impeller pump again, the flow velocity by under meter and control valve adjusting plating bath makes plating bath reach the jet velocity of 100m/s; By regulating voltage, make current density reach 300A/dm
2At any time by adding the 5%(massfraction) sodium hydroxide and 10%(massfraction) to regulate bath pH value be 4.4 to hydrochloric acid.After coating reached 2 mm, the galvanic deposit mould was taken out in outage, and the water flushing splits each part, separates the Ni74-W11-P15 non-crystaline amorphous metal from stainless steel substrate.As shown in Figure 3, prepared block ternary Ni-W-P non-crystaline amorphous metal smooth surface, thickness reaches 2.1mm.
Embodiment 2
The mould that uses is all identical with embodiment 1 with electroplanting device.The working face of stainless steel substrate is used 400# successively, 600#, 800#, the 1000# liquid honing is removed machining marks, cleans the back and immerses 75 ℃, mass concentration 15%NaCO
3In the solution, oil removing 5min takes out with pure water and cleans; The hydrochloric acid soln of putting into mass concentration 8% then activates 1.5min, takes out and uses the pure water cleaned standby seam.The preparation electroplate liquid contains single nickel salt 110g, nickelous chloride 15g, sodium wolframate 200g, inferior sodium phosphate 45g, Trisodium Citrate 220g, asccharin 5g in every liter of this solution, all the other are water.
At first open well heater and temperature regulating device in the coating bath, the plating bath bath temperature is transferred to 55 ℃, open impeller pump again, the flow velocity by control valve adjusting under meter makes plating bath reach the jet velocity of 150m/s; By regulating voltage, make current density reach 260A/dm
2At any time by adding the 5%(massfraction) sodium hydroxide and 10%(massfraction) to regulate bath pH value be 4.5 to hydrochloric acid.After coating reached desired size, the galvanic deposit mould was taken out in outage, and the water flushing splits each part, and Ni71-W13-P16 non-crystaline amorphous metal and matrix on the stainless steel substrate are peeled off, and its thickness reaches 2.0 mm.
Embodiment 3
The mould that uses is all identical with embodiment 1 with electroplanting device.The working face of stainless steel substrate is used 400# successively, 600#, 800#, the 1000# liquid honing is removed machining marks, cleans the back and immerses 80 ℃, mass concentration 17%NaCO
3In the solution, oil removing 4min takes out with pure water and cleans; The hydrochloric acid soln of putting into mass concentration 5% then activates 2min, takes out and uses the pure water cleaned standby seam.The preparation electroplate liquid contains single nickel salt 130g, nickelous chloride 10g, sodium wolframate 220g, inferior sodium phosphate 50g, Trisodium Citrate 210g, asccharin 6g in every liter of this solution, all the other are water.
At first open well heater and temperature regulating device in the coating bath, the plating bath bath temperature is transferred to 60 ℃, open impeller pump again, the flow velocity by control valve adjusting under meter makes plating bath reach the jet velocity of 200m/s; By regulating voltage, make current density reach 200A/dm
2At any time by adding the 5%(massfraction) sodium hydroxide and 10%(massfraction) to regulate bath pH value be 4.6 to hydrochloric acid.After coating reached desired size, the galvanic deposit mould was taken out in outage, and the water flushing splits each part, and Ni68-W14-P18 non-crystaline amorphous metal and matrix on the stainless steel substrate are peeled off, and its alloy thickness reaches 1.9 mm.
Claims (1)
1. the preparation method of block nickel ternary-tungsten-phosphorus non-crystalline alloy, its chemical ingredients is Ni
100-x-yW
xP
y, wherein x, y are massfraction, x=11～14%, y=15～18%, and thickness of coating reaches the block of millimeter magnitude, it is characterized in that:
(1) the galvanic deposit mould is sprayed in preparation:
This mould is made of polyvinyl chloride panel, and on, following die topography is identical, last mold cavity is less than the deposit cavity of counterdie, the shape of stainless steel substrate is corresponding with the shape of amorphous product, and size is greater than the patrix inner cavity size, less than bed die deposit cavity geomery, the thickness of stainless steel substrate is identical with the bed die deposit cavity degree of depth, and place among the deposit cavity of counterdie, one end of above-mentioned stainless steel substrate links to each other with the copper conduction bands of peripheral hardware insullac, the other end of these copper conduction bands stretches out outside the bed die, by plastic bolt with above-mentioned stainless steel substrate, bed die is connected with the copper conduction bands, on, bed die is combined into as a whole injection galvanic deposit mould by holding bolt;
(2) preparation electroplate liquid:
Electroplate liquid is solvent with water, contains single nickel salt 100-130g, nickelous chloride 10-20g, sodium wolframate 190-220g, inferior sodium phosphate 40-50g, Trisodium Citrate 210-230g, asccharin 4-6g in every liter of this solution;
(3) coating bath is installed:
The stainless steel substrate that is fixed on the above-mentioned galvanic deposit mould is linked to each other with dc power cathode by the copper conduction bands on the mould, be that 99.9% activated ni plate links to each other with the direct supply anode is anodal with purity, and they are put into the coating bath that above-mentioned plating bath is housed, the impeller pump two ends link to each other with two non-metallic pipes that insert plating bath respectively, and the pipeline that links to each other with the impeller pump liquid outlet is provided with control valve and under meter, the exit end of this pipeline also is provided with well heater and temperature regulating device towards galvanic deposit upper mould inner chamber in coating bath;
(4) preparation block nickel ternary-tungsten-phosphorus non-crystalline alloy:
At first open well heater and temperature regulating device in the coating bath, temperature of electroplating solution is transferred to 50-60 ℃, open impeller pump again, the flow velocity by under meter and control valve adjusting plating bath makes plating bath reach the jet velocity of 100-200m/s; Regulating voltage makes current density reach 200-300A/dm
2At any time be that 5% sodium hydroxide and massfraction are that 10% hydrochloric acid is regulated plating bath pH by adding massfraction, the pH value 4.4～4.6 of strict control plating bath, after coating reaches desired size, the galvanic deposit mould is taken out in outage, the water flushing, split each part, peel off nickel-tungsten-phosphorus non-crystalline alloy from stainless steel substrate.
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| CN103290436B (en) * | 2013-05-24 | 2015-08-05 | 燕山大学 | A kind of high-meltiing alloy jet-electrodeposited method rapid die-manufacturing method |
| CN104152957A (en) * | 2014-07-24 | 2014-11-19 | 燕山大学 | Ni-Fe-W three-component alloy plating method of crystallizer |
| CN104195606B (en) * | 2014-08-26 | 2017-02-15 | 燕山大学 | Thick nickel-iron-tungsten ternary alloy plating layer and preparation method thereof |
| CN104762644A (en) * | 2015-04-24 | 2015-07-08 | 西峡龙成特种材料有限公司 | Electroplated amorphous-state nickel-tungsten-phosphorous alloy for copper plate of crystallizer for continuous casting and preparation process of amorphous-state nickel-tungsten-phosphorous alloy |
| CN108220825A (en) * | 2016-12-14 | 2018-06-29 | 刘志红 | A kind of Ni based amorphous alloy powders and its preparation process |
| CN108203793A (en) * | 2016-12-16 | 2018-06-26 | 刘志红 | A kind of Ni bases amorphous powder and preparation method |
| CN108977843A (en) * | 2017-05-31 | 2018-12-11 | 刘志红 | A kind of ni-based amorphous alloy catalysis electrode and preparation method thereof |
| CN117779130A (en) * | 2024-02-23 | 2024-03-29 | 昆山一鼎工业科技有限公司 | Wafer electroplated tungsten alloy solution, preparation method and electroplating method |
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| CN101008096A (en) * | 2006-12-29 | 2007-08-01 | 清华大学 | Method for electrodepositing Ni-W-P amorphous film on low carbon steel |
| CN101445946B (en) * | 2008-11-27 | 2011-02-09 | 湖南纳菲尔新材料科技股份有限公司 | Anticorrosive wearable electrodeposit clad layer of Ni-W-P ternary alloy and manufacturing technique and electroplate liquid thereof |
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