CN102703840A - Block ternary nickel-tungsten-phosphorus amorphous alloy and preparation method thereof - Google Patents

Abstract

A bulk ternary nickel-tungsten-phosphorus amorphous alloy, the chemical composition of which is Ni _100-xy W _x P _y , wherein x and y are mass fractions, x=11~14%, y=15~18%; The preparation method mainly adopts the spray electrodeposition method to deposit the amorphous alloy on the mold, uses the activated nickel plate with a purity of 99.9% as the soluble anode to provide nickel ions, and designs different shapes of stainless steel substrates according to the shape of the amorphous product as the insoluble cathode. Fix it on the above-mentioned electrodeposition mold, and prepare a bulk ternary nickel-tungsten-phosphorus amorphous alloy with a three-dimensional scale, a large block, and a thickness of the plating layer on the order of millimeters through different plating solution components and plating processes.

Description

Bulk ternary nickel-tungsten-phosphorus amorphous alloy and preparation method thereof

technical field

The invention relates to a metal material and a preparation method thereof, in particular to an amorphous alloy and a preparation method thereof.

Background technique

Ni-W-P amorphous alloy has many excellent properties: excellent corrosion resistance, corrosion-resistant coating applied to oilfield well pipes; good friction and wear properties, high hardness and mechanical strength, widely used in mechanical transmission parts; excellent Catalytic hydrogen evolution activity, long-term electrolytic stability, high thermal stability and corrosion resistance, used for electrocatalytic hydrogen evolution and photocatalytic hydrogen evolution; ultrafine Ni-W-P amorphous alloy has the function of highly active catalyst and is widely used in chemical industry field. At present, there are usually three methods for the preparation of Ni-W-P amorphous alloys: the stripping method, the electroless plating method and the electrodeposition method. In terms of shape and size, the samples prepared by these three methods are very thin, all of which are in the order of microns, staying at the stage of filaments, strips and films, and it is impossible to obtain bulk amorphous alloys with three-dimensional dimensions. The belt throwing method requires pre-melted metal Ni-W-P master alloy, while the non-metallic P is extremely volatile and deviates from the composition range of amorphous formation, making it difficult to form amorphous alloys. As for the electroless plating method and the electrodeposition method, since the coating is directly deposited on the surface of the substrate, this traditional deposition method has no mechanical constraints and a low current density. As a result, the coating cracks or peels off from the substrate as the deposition time prolongs. Therefore, only thin film materials can be produced. The shape and size of amorphous alloys prepared by these methods are limited, making it difficult to fully exert many excellent properties of amorphous alloy materials in practical applications.

Contents of the invention

The object of the present invention is to provide a block ternary nickel-tungsten-phosphorus amorphous alloy with fast preparation speed and large three-dimensional scale and a preparation method thereof. The invention adopts a specially designed spray electrodeposition mold, different plating solution components and plating processes to obtain a block ternary nickel-tungsten-phosphorus amorphous alloy with a thickness of a millimeter order.

The technical scheme of the present invention is as follows:

1. The ternary nickel-tungsten-phosphorus amorphous alloy of the present invention has a chemical composition of Ni _100-xy W _x P _y , where x and y are mass fractions, x=11~14%, y=15~18% , a block with a coating thickness of the order of millimeters.

Two, the preparation method of the present invention is specifically as follows:

1. Prepare the spray electrodeposition mold of the above-mentioned bulk ternary nickel-tungsten-phosphorus amorphous alloy:

The upper mold and the lower mold of the mold are made of polyvinyl chloride plates, and the upper and lower molds have the same shape. An inner cavity is arranged in the middle of the upper mold, and a deposition cavity is arranged in the middle of the lower mold, and the inner cavity of the upper mold is smaller than the deposition cavity of the lower mold. The shape of the stainless steel substrate corresponds to the shape of the amorphous product, and its size is larger than that of the inner cavity of the upper mold and smaller than that of the deposition cavity of the lower mold. The thickness of the stainless steel substrate is the same as the depth of the deposition cavity of the lower mold, and placed in the deposition cavity of the lower mold. One end of the above-mentioned stainless steel substrate is connected with a copper conductive strip provided with insulating varnish, and the other end of the copper conductive strip extends out of the lower mold. The above stainless steel base plate, lower mold and copper conductive strips are connected by plastic bolts. The upper and lower molds are combined by fastening bolts to form a whole spray electrodeposition mold.

The working surface of the above-mentioned stainless steel substrate is polished _with 400#, 600#, 800#, 1000# water sandpaper in turn to remove the traces of mechanical processing. 2~5min, take it out and wash it with pure water; then put it into a hydrochloric acid solution with a mass concentration of 5~10% for activation for 1~2min, take it out and wash it with pure water for use.

2. Prepare the electroplating solution for the above bulk ternary nickel-tungsten-phosphorus amorphous alloy:

The electroplating solution uses water as a solvent, and each liter of the solution contains 100-130g of nickel sulfate, 10-20g of nickel chloride, 190-220g of sodium tungstate, 40-50g of sodium hypophosphite, 210-230g of sodium citrate, and saccharin 4-6g.

In the plating solution, nickel sulfate is the main salt to provide Ni ²⁺ required for plating; nickel chloride provides Cl ^- in addition to Ni ²⁺ to prevent anode passivation; sodium hypophosphite is the main source of P in the plating layer; Sodium tungstate is the main source of W in the coating; sodium citrate is a pH buffer to adjust the pH of the plating solution, and the pH has little effect on the P content of the coating within a certain range.

3. Install and prepare the plating tank for the above bulk ternary nickel-tungsten-phosphorus amorphous alloy:

The stainless steel substrate fixed on the above-mentioned electrodeposition mold is used as an insoluble cathode plate and connected to the negative pole of the DC power supply through the copper conductive strip on the mold, and the activated nickel plate with a purity of 99.9% is used as a soluble anode for providing nickel ions to the positive pole of the DC power supply. And put them into the plating tank filled with the above-mentioned plating solution. Both ends of the centrifugal pump are respectively connected to two non-metallic pipes inserted into the plating solution, and a control valve and a flow meter are installed on the pipe connected to the liquid outlet of the centrifugal pump, and the outlet end of the pipe faces the inner cavity of the upper mold of the electrodeposition mold . A heater and a temperature control device are also provided in the plating tank.

4. Preparation of the above bulk ternary nickel-tungsten-phosphorus amorphous alloy: first turn on the heater and temperature control device in the plating tank, and adjust the temperature of the plating solution to 50-60°C. Then turn on the centrifugal pump, adjust the flow rate of the plating solution through the flow meter and control valve, so that the spraying speed of the plating solution reaches 100-200m/s; adjust the voltage to make the current density reach 200-300A/dm ² . Adjust the pH of the plating solution by adding 5% (mass fraction) sodium hydroxide and 10% (mass fraction) hydrochloric acid at any time, and strictly control the pH value of the plating solution to 4.4~4.6 to ensure the quality of the coating. When the coating reaches the required size, turn off the power, take out the electrodeposition mold, rinse with water, disassemble each part, and peel off the nickel-tungsten-phosphorus amorphous alloy from the stainless steel substrate.

Compared with the prior art, the present invention has the following advantages:

1. Since the stainless steel plate and polyvinyl chloride plate used in the spray electrodeposition mold of the present invention are very easy to process, the spray electrodeposition mold can be processed according to the desired shape of the bulk amorphous sample.

2. By changing the composition of the plating solution and the plating process, a bulk ternary nickel-tungsten-phosphorus amorphous alloy with the required composition, shape and size can be prepared.

3. It is possible to prepare a bulk ternary nickel-tungsten-phosphorus amorphous alloy with a three-dimensional scale, a large block, and a coating thickness of millimeters.

Description of drawings

Fig. 1 is a schematic diagram of the front section of the spray electrodeposition mold of the present invention.

Fig. 2 is a schematic diagram of the front section of the spray electrodeposition process of the present invention.

Fig. 3 is a photograph of the bulk ternary nickel-tungsten-phosphorus amorphous alloy prepared in Example 1 of the present invention.

Detailed ways

Example 1

In the schematic diagram of the front view of the spray electrodeposition mold of the present invention shown in Figure 1, it is composed of two upper and lower polyvinyl chloride upper molds 1 and lower molds 3 with the same shape, and an inner cavity and a lower mold are respectively arranged in the middle of the upper and lower molds. The deposition cavity, the inner cavity of the upper mold is smaller than the deposition cavity of the lower mold. The shape of the stainless steel substrate 2 corresponds to the shape of the amorphous product, and its size is larger than that of the inner cavity of the upper mold and smaller than that of the deposition cavity of the lower mold. The thickness of the stainless steel substrate is the same as the depth of the deposition cavity of the lower mold, and placed in the deposition cavity of the lower mold. One end of the above-mentioned stainless steel plate is connected with a copper conductive strip 4 insulated with insulating varnish, and the other end of the copper conductive strip stretches out of the lower mold. The working surface of _the above-mentioned stainless steel substrate is polished with 400#, 600#, 800#, 1000# water sandpaper in sequence to remove the traces of mechanical processing. Wash it with pure water; then put it into a 10% hydrochloric acid solution for activation for 1 min, take it out and wash it with pure water for later use. Connect the above-mentioned stainless steel base plate, lower mold and copper conductive strip through 4×M4 plastic bolts. The upper and lower molds are combined by 6×M4 uniformly distributed fastening bolts to form a whole spray electrodeposition mold.

Prepare electroplating solution, each liter of this solution contains nickel sulfate 100g, nickel chloride 20g, sodium tungstate 190g, sodium hypophosphite 40g, sodium citrate 230g, saccharin 4g, and the rest is water.

In the schematic diagram of the front view of the spray electrodeposition process of the present invention as shown in Figure 2, the stainless steel plate fixed on the above-mentioned electrodeposition mold is used as the insoluble cathode plate, and the activated nickel with a purity of 99.9% and 100 × 100 mm is used Plates are used as soluble anodes, and they are put into the plating tank with the above-mentioned plating solution, and the positive and negative poles of the power supply 10 are connected with the copper conductive strips on the above-mentioned activated nickel plate 9 and the electrodeposition mold 8 respectively. One end of the centrifugal pump 12 is connected to a plastic pipe 11 inserted into the plating solution, the other end is connected to a control valve 13, and a flow meter 14 is arranged on the plastic pipe connected to the other end of the control valve. A heater and a temperature control device 6 are also provided in the plating tank 5 . First turn on the heater and temperature control device in the plating tank, adjust the temperature of the plating solution to 50°C, then turn on the centrifugal pump, adjust the flow rate of the plating solution through the flow meter and control valve, so that the spraying speed of the plating solution reaches 100m/s; By adjusting the voltage, the current density can reach 300A/dm ² . Adjust the pH of the plating solution to 4.4 by adding 5% (mass fraction) sodium hydroxide and 10% (mass fraction) hydrochloric acid at any time. When the coating reaches 2 mm, power off, take out the electrodeposition mold, rinse with water, disassemble each part, and peel off the Ni74-W11-P15 amorphous alloy from the stainless steel substrate. As shown in Figure 3, the prepared bulk ternary Ni-WP amorphous alloy has a smooth surface and a thickness of 2.1 mm.

Example 2

The mold and electroplating device used are all the same as in Example 1. Grind the working surface of the stainless steel substrate with 400#, 600#, 800#, 1000# water sandpaper in turn to remove the traces of mechanical processing _. Wash it with pure water; then put it into a hydrochloric acid solution with a mass concentration of 8% for activation for 1.5 minutes, take it out and wash it with pure water for use. Prepare electroplating solution, each liter of the solution contains 110g of nickel sulfate, 15g of nickel chloride, 200g of sodium tungstate, 45g of sodium hypophosphite, 220g of sodium citrate, 5g of saccharin, and the rest is water.

First turn on the heater and temperature control device in the plating tank, adjust the temperature of the plating solution to 55°C, then turn on the centrifugal pump, adjust the flow rate of the flowmeter through the control valve, so that the spraying speed of the plating solution reaches 150m/s; The voltage was adjusted so that the current density reached 260A/dm ² . Adjust the pH of the plating solution to 4.5 by adding 5% (mass fraction) sodium hydroxide and 10% (mass fraction) hydrochloric acid at any time. When the coating reaches the required size, turn off the power, take out the electrodeposition mold, rinse with water, disassemble each part, and peel off the Ni71-W13-P16 amorphous alloy on the stainless steel substrate from the substrate, and its thickness reaches 2.0 mm.

Example 3

The mold and electroplating device used are all the same as in Example 1. Grind the working surface of the stainless steel substrate with 400#, 600#, 800#, 1000# water sandpaper in turn to remove the traces of mechanical processing. After cleaning, immerse it in 80°C and 17% NaCO ₃ solution, degrease for 4min, and take it out for use. Wash it with pure water; then put it into a 5% hydrochloric acid solution for activation for 2 minutes, take it out and wash it with pure water for later use. Prepare the electroplating solution, containing 130g of nickel sulfate, 10g of nickel chloride, 220g of sodium tungstate, 50g of sodium hypophosphite, 210g of sodium citrate, 6g of saccharin in each liter of the solution, and the rest is water.

First turn on the heater and temperature control device in the plating tank, adjust the temperature of the plating solution to 60°C, then turn on the centrifugal pump, adjust the flow rate of the flowmeter through the control valve, so that the spraying speed of the plating solution reaches 200m/s; The voltage was adjusted so that the current density reached 200A/dm ² . Adjust the pH of the plating solution to 4.6 by adding 5% (mass fraction) sodium hydroxide and 10% (mass fraction) hydrochloric acid at any time. When the coating reaches the required size, turn off the power, take out the electrodeposition mold, rinse with water, disassemble each part, and peel off the Ni68-W14-P18 amorphous alloy on the stainless steel substrate from the substrate, and the alloy thickness reaches 1.9 mm.

Claims (3)

1. block nickel ternary-tungsten-phosphorus non-crystalline alloy, it is characterized in that: 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.

2. aforesaid right requires the preparation method of 1 described a kind of block nickel ternary-tungsten-phosphorus non-crystalline alloy, it is characterized in that:

(1) the galvanic deposit mould is sprayed in preparation:

This mould is made with polyvinyl chloride panel; And upper and lower die topography is identical, and last mold cavity is less than the deposit cavity of counterdie, and 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 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, through plastic bolt above-mentioned stainless steel substrate, bed die and copper conduction bands is connected, and upper and lower mould is combined into as a whole injection galvanic deposit mould through 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 through 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 valve and under meter, and 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 through under meter and valve adjusting plating bath makes plating bath reach the projection velocity of 100-200m/s; Regulating voltage makes current density reach 200-300A/dm ², at any time through to add massfraction be 5% sodium hydroxide and massfraction is that 10% hydrochloric acid is regulated plating bath pH, the strict pH value 4.4 ~ 4.6 of controlling 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.

3. the preparation method of block nickel ternary-tungsten according to claim 2-phosphorus non-crystalline alloy is characterized in that: the workplace of stainless steel substrate is used 400#, 600# successively; 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; Put into the hydrochloric acid soln activation 1 ~ 2min of mass concentration 5 ~ 10% then, take out and use the pure water cleaned standby seam.

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