CN103243356A - Preparation method of iron-nickel-cobalt-molybdenum alloy foil by electrodeposition - Google Patents

Abstract

The invention belongs to the field of electrolytic deposition of metal materials, and relates to a preparation method of iron-nickel-cobalt-molybdenum alloy foil. It is characterized by the use of electrodeposition method, the electrolyte is an acidic sulfate-chloride-sodium molybdate aqueous solution system, and buffers, complexing agents, brighteners and auxiliary agents are added at the same time, and carbon and titanium plates are used as anode and cathode materials respectively. ; The process parameters of electrodeposition are: temperature 50~70℃, pH 3.0~4.5, current density 1.0~10.0A/dm ² , distance between cathode and anode 2~3cm, electrodeposition time 60min. Place the cathode and anode in the electrolyte, pass a direct current for a certain period of time, deposit the iron-nickel-cobalt-molybdenum alloy on the cathode, then take out the cathode plate and rinse it, and dry the iron-nickel-cobalt-molybdenum alloy formed on its surface. The molybdenum alloy layer is peeled off to become iron-nickel-cobalt-molybdenum alloy foil. The composition of the alloy foil is easy to control, the thickness is uniform, the surface is bright, the shape is not fragile and the shape is not distorted. Compared with the calendering method, it has low cost and excellent physical and chemical properties.

Description

A kind of electrodeposition preparation method of iron-nickel-cobalt-molybdenum alloy foil

technical field

The invention relates to an electrodeposition preparation method of an iron-nickel-cobalt-molybdenum alloy foil, more precisely, an electrodeposition method is used to prepare iron-nickel-cobalt-molybdenum in an acidic sulfate-chloride-sodium molybdate aqueous solution Process method of alloy foil. the

Background technique

The outermost electrons of iron group metals have d orbitals that are not full or half full of electrons, and molybdenum elements have paired d electrons. When iron, nickel and cobalt form alloys with molybdenum, empty d can be reduced by molybdenum. Increase the number of states, increase the width of the energy band, form a more suitable new outermost electronic arrangement, and have better mechanical properties, electrical properties and soft magnetic properties. the

As a special profile, metal and alloy foils have been widely used in many fields of industry. The industrial preparation of metal and alloy foils generally adopts the traditional method of mechanical calendering. The production process requires multiple processes such as melting, casting, forging, and repeated rolling to form foil. The process is complicated, the cost is high, it is difficult to obtain a thickness of micron level, and the thickness is uneven, the width is limited, it is difficult to produce large-scale, and it is easy to produce holes. and other defects. the

The metal foil prepared by electrodeposition has the advantages of one-time production, simple process, low cost, uniform and controllable thickness, fine structure, etc., and can avoid defects such as holes and coarse grains that are easy to occur in the forging and rolling process. In terms of technology, it is easy to control the chemical composition of materials by changing parameters, electrolyte composition and other conditions, and it is easy to realize large-scale production, with high productivity and good economy, and relatively low equipment investment. Therefore, the electrodeposition method is the development trend of preparing alloy foils. At present, electrodeposition has been used to prepare printed circuit boards, waveguide materials, heat exchangers, micro-sensors, microcomputers, battery nets, electric razor nets, food filters, magnetic shielding materials, soft magnetic materials, etc. the

At present, in the prior art, the US patent document US P6428672 introduces a device and method for manufacturing continuous nickel-iron alloy thin foils using an electrolytic deposition process. Chinese patent document CN1288979A introduces a process of electrodepositing permalloy thin film and its implementation equipment. Chinese patent document CN1793433A introduces a preparation method of electrodepositing Invar alloy foil in a sulfate system with low metal salt concentration. the

"Electrodeposion of thin films of nickel-iron" (Journal of the Electrochemical Society, 1993, 140 (3): 669?674), "Regression Orthogonal Design of Ni-Fe Alloy Foil Process by Electrolysis" (Journal of the Electrochemical Society, 2000 ,36 (7): 723?727), "Research on Process and Properties of Electrodeposited Fe-Ni Alloy Foil" (Electroplating and Finishing, 2006, 28(1): 5-9), "Bright Microcrystalline Nickel-Fe Alloy Foil Electrodeposition" (Journal of Central South University (Natural Science Edition), 2006, 37(2): 263-268), "Preparation, Microstructure and Corrosion Resistance of Invar Alloy Foil Electrodeposition" (Journal of Central South University (Natural Science Edition), Edition), 2006, 37(2): 263-268), "Research on Invar Alloy Foil Electrodeposition Process" (Materials Herald, 2004, 12, 18(12): 91-94), "Electrodeposition of Fe, Ni Morphology and Magnetic Properties of Alloy-Based Foil" (Journal of Nonferrous Metals of China, 2004, 14(2): 273?279) introduces the preparation of Fe-Ni, Fe-Co, Fe-Ni-Co and other iron by electrodeposition method. Process method of group metal alloy foil. the

Chinese patent document CN1641072A and "Orthogonal Design of Electrodeposition Preparation of Fe-Ni-Cr Nanocrystalline Alloy Foil" (Journal of Central South University (Natural Science Edition). 2005, 36(6): 938? 943) introduced the preparation of electrodeposition Iron-nickel-chromium nanocrystalline alloy foil with excellent resistance and magnetic properties, high tensile strength and elongation, and good corrosion resistance. "Preparation of Nanocrystalline Fe-Ni-Mo Alloy Foil by Electrodeposition" (Mining and Metallurgy Engineering, 2006, 26(4): 46-49) introduced the process and method of preparing iron group metal ternary alloy foil. the

The literature discloses the process and method of preparing iron group metal binary and ternary alloy foils by electrodeposition, but there is no report on the process and method of electrodepositing iron group metal quaternary alloy foils. The quaternary alloy foil formed by iron group elements and molybdenum has a more suitable new outermost electron arrangement, so it will have special magnetic properties, high catalytic activity and excellent corrosion resistance, which will undoubtedly open up its industrial application. It has high practical value and prospect in the field of application. the

Contents of the invention

The purpose of the present invention is to provide a process and electrolyte for preparing iron-nickel-cobalt-molybdenum alloy foil by electrodeposition, which is convenient and practical, simple in process and low in cost. Iron-nickel-cobalt-molybdenum alloy foil with special magnetic properties, high catalytic activity and excellent corrosion resistance. the

The purpose of the present invention is achieved by adopting the following technical solutions:

1. The present invention adopts an acidic (citric acid-chloride type) sulfate-chloride-sodium molybdate aqueous electrolyte, and adds stabilizers, buffers, complexing agents, brighteners and auxiliary agents. The specific components of the electrolyte are:

NiSO ₄ 6H ₂ O 80~140 g/L, NiCl ₂ 6H ₂ O 40 g/L, FeSO ₄ 7H ₂ O 5~25 g/L, CoSO ₄ 7H ₂ O 5 ~25 g/L, Na ₂ MoO ₄ 2H ₂ O 4 ~12 g/L, trisodium citrate 95~155 g/L, stabilizer 30 g/L, buffer 30 g/L, saccharin 3 g/L, additive 0.02 g/L L.

① The main salt is sulfate and sodium molybdate. the

② The stabilizer (compounding agent) is citrate, such as trisodium citrate, or pyrophosphate. The complexing agent is any one of citrate series and potassium sodium tartrate. the

Trisodium citrate mainly plays a coordination role in the electrolyte, and cooperates with the metal ions in the electrolyte to promote the reduction discharge of sodium molybdate induced by iron group metals. Trisodium citrate can significantly increase the activation polarization, which is beneficial to obtain a dense coating. Trisodium citrate can also improve the dispersibility of the electrolyte. If the trisodium citrate content is not enough, the matching effect will be reduced, and the stability of the plating solution will decrease, but if the trisodium citrate is too much, the deposition efficiency will be reduced. Citric acid can also maintain the stability of the pH value of the electrolyte. the

In the electrolyte containing Fe ²⁺ ions and MoO ₄ ^2?, Fe ²⁺ is easily oxidized to Fe ³⁺ with reductive properties, while MoO ₄ ^2- can also be reduced to low-valent compounds with oxidative properties, so the two coexist at the same time In the electrolyte, it will interact and cause the instability of Fe ²⁺ and MoO ₄ ^2- , thereby reducing the apparent quality of the alloy foil and increasing the internal stress of the alloy foil. Therefore, it is particularly important to enhance the stability of Fe ²⁺ and MoO ₄ ^2- in the electrolyte and to choose a suitable stabilizer. For this reason, we use LGLA as a stabilizer (compound stabilizer and additive). LGLA is reductive and can reduce uncomplexed Fe ³⁺ . Due to its weak reducing ability, it cannot reduce MoO ₄ ^2- . LGLA is a polyhydroxy aldehyde compound, and its main function is to enhance the stability of Fe ²⁺ and MoO ₄ ²⁺ in the electrolyte. Stabilizer LGLA has reductivity and can reduce uncoordinated Fe ³⁺ , but its reducing performance is weak and cannot reduce MoO ₄ ^2? .

③The function of the additive is mainly used in conjunction with C ₄ H ₄ O ₆ KNa·4H ₂ O, which can enhance the effect of C ₄ H ₄ O ₆ KNa·4H ₂ O in complexing metal ions

④The electrolyte containing sulfate can obtain alloy foil with low stress, but the deposition rate is also slow. Chloride can increase the conductivity of the solution and have a significant impact on the cathode. The efficiency of the cathode can be increased by increasing the conductivity of the electrolyte and improving the dispersion ability of the electrolyte. So we properly add chloride ions in the electrolyte.

Cl ^ˉ is an anode active agent, which has a significant activation effect on both cathodic and anodic processes. Cl ^ˉin the electrolyte can increase the conductivity of the solution, improve the uniformity of the electrolyte, and increase the deposition rate. If the content of chloride ions is too high, the brittleness of the alloy foil will be increased. Cl ^ˉcan also create an ion bridge between the electrode surface and the discharged ions, and play a role in depolarization, making it easy to discharge Ni ²⁺ and Fe ²⁺ on the electrode.

⑤ The buffer is either boric acid or oxalic acid. the

⑥The brightener is any one or the sum of any two or more of saccharin, thiourea, and butynediol. the

Saccharin is not only a primary brightener, but also a stress reliever, which can make the deposit layer crystallize finely, brighten uniformly, reduce the internal stress of the deposit layer, and improve the flexibility of the alloy foil. the

The use of the additive in conjunction with the primary brightener reduces the stress of the deposited layer, refines the crystal grains, and improves the brightness of the deposited layer at a low current density. the

The brightener in the electrolyte can reduce the brittleness of the electrodeposited layer, which is beneficial to the improvement of the brightness of the electrodeposited layer in the low current density area. At the same time, the auxiliary agent and the brightener can not only obtain a deposited layer with good flatness and controlled internal stress, but also have the effect of refining grains, compacting the structure, and brightening the deposited layer. the

the

⑦ The auxiliary additive is any one of sodium benzenesulfinate, sodium ethylhexylsulfonate, sodium lauryl sulfate, and succinic acid, or the sum of any two or more of them.

the

2. The process parameters of electrodeposition are:

Current density 1.5~5 A/dm ² ,

Temperature 20~45℃,

pH value 3.5~5.5,

Deposition time 60~100 min,

The cathode substrate is a titanium plate, and the anode is a high-density carbon plate or a combined anode of soluble iron and nickel. The anode and cathode are placed facing each other, and the anode and cathode are separated by a desired distance. The distance between the cathode and the cathode is generally 2~3 cm.

The anode can be an insoluble anode or a combined soluble anode. The insoluble anode is generally a high-density carbon rod (plate), and the combined soluble anode can be a combination of iron and nickel or a combination of iron, nickel and cobalt. the

If the pH value of the electrolyte is too high, the stability of Fe ²⁺ ions in the plating solution will decrease, and a large amount of complexing agent needs to be added; if the amount of complexing agent is too large, it will be difficult to reduce iron ions, and it will be difficult to increase the iron content in the alloy foil. When the pH value is too low, the reduction deposition of sodium molybdate is very difficult. When the pH value is lower than 4.0, the molybdenum content in the alloy coating is very small. It is more appropriate to control the pH value of the electrolyte at about 4.5~5.0.

In addition, the electrolyte adopts a higher pH value than the above-mentioned sulfate system, which reduces the hydrogen evolution at the cathode and reduces the brittleness and porosity of the deposited layer. the

3. The electrolyte preparation method is as follows: take two-thirds of the volume of deionized water, and heat it to 70-80 ° C, then add boric acid, stir to dissolve, then add metered nickel sulfate, nickel chloride, trisodium citrate, stabilized agent and cobalt sulfate, stirring and dissolving respectively; then slowly adding sodium molybdate, stirring and dissolving at the same time. the

Use the prepared 10% sulfuric acid solution or 10% NaOH to roughly adjust the pH value of the solution to about 5, then control the solution temperature below 30°C, slowly add ferrous sulfate, and stir rapidly to dissolve;

Take another appropriate amount of deionized water, heat it, add saccharin, after the saccharin dissolves, add the additive to dissolve, pour the solution of saccharin and additive into the previously configured electrolyte, and then use 10% sulfuric acid or 10% NaOH solution to adjust the electrolysis The pH value of the solution was adjusted to 5, and finally the electrolyte solution was adjusted to the specified volume with purified water.

4. The process of preparing iron-nickel-cobalt-molybdenum alloy foil by electrodeposition method, the cathode and anode are placed in the electrolyte, and the direct current is passed for a certain period of time to deposit the iron-nickel-cobalt-molybdenum alloy on the cathode, and then Take out the cathode plate, wash it clean, and peel off the iron-nickel-cobalt-molybdenum alloy layer formed on its surface after drying to become iron-nickel-cobalt-molybdenum alloy foil. the

The composition of iron-nickel-cobalt-molybdenum alloy foil is controlled by the concentration of Ni ²⁺ , Fe ²⁺ , Co ²⁺ and MoO ₄ ^2? in the plating solution, current density and other factors, and the thickness is controlled by the electrolysis time.

The area ratio of nickel, iron and titanium in the combined anode is 1.6:1:0.5. the

Compared with prior art, advantage and effect of the present invention are:

1. The process of preparing iron-nickel-cobalt-molybdenum alloy foil by electrodeposition is convenient and practical, the process is simple, the cost is low, the composition is easy to control, the thickness is uniform, the thickness and width can be adjusted, and the surface is bright and smooth.

2. Iron-nickel-cobalt-molybdenum alloy foil has excellent mechanical properties, electrical properties, special magnetic properties, and high catalytic activity.

3. The surface of the alloy foil is relatively smooth, the structure is compact, the particle size is small, and it belongs to nanocrystalline or amorphous crystal. the

4. Fe ²⁺ and MoO ₄ ^2? in the electrolyte have good stability, solving the interaction between Fe ²⁺ and MoO ₄ ^2? in the electrolyte

Fe ²⁺ is easily oxidized to Fe ³⁺ with reductive properties, and MoO ₄ ^2- can also be reduced to low-valent compounds with oxidative properties, so the two coexist in the electrolyte at the same time and will interact to cause Fe ²⁺ and MoO ₄ ^2- The instability,.

Detailed ways

    The electrolyte composition and process conditions of electrodeposited Fe-Ni-Co-Mo alloy foil are shown in Table 1:

Table 1 Electrolyte composition and process conditions of electrodeposited Fe-Ni-Co-Mo alloy foil

Example 1 (Influence of Ferrous Sulfate Content on Alloy Foil Composition and Cathode Current Efficiency)

The electrolyte composition is NiSO ₄ ·6H ₂ O 120 g/L, NiCl ₂ ·6H ₂ O 40 g/L, FeSO ₄ ·6H ₂ O 15 g/L, CoSO ₄ ·7H ₂ O 15 g/L, Na ₂ MoO ₄ 2H ₂ O 8 g/L, trisodium citrate 125 g/L, stabilizer 30 g/L, boric acid 30 g/L, saccharin 3 g/L, additive 0.02 g/L. The operating conditions of the process are J = 2 A/dm ² , t = 30 oC, pH = 5.

Experimental results: The components of the iron-nickel-cobalt-molybdenum alloy foil are: Fe 20.2%, Ni 58.4%, Co15.7%, Mo5.7%. the

The iron-nickel-cobalt-molybdenum alloy foil is 50 μm thick, uniform in thickness, smooth and bright, with strong corrosion resistance, grain size in the nanometer range, resistivity of 50~100 μΩ cm, magnetic saturation of 1.25 Tesla, and Tensile strength 794.85MPa, elongation 6.67%. the

the

Example 2 (Influence of Nickel Sulfate Content on Alloy Foil Composition and Cathode Current Efficiency)

The electrolyte composition is NiSO ₄ ·6H ₂ O 100 g/L, NiCl ₂ ·6H ₂ O 40 g/L, FeSO ₄ ·6H ₂ O 10 g/L, CoSO ₄ ·7H ₂ O 15 g/L, Na ₂ MoO ₄ 2H ₂ O 10 g/L, trisodium citrate 110 g/L, stabilizer 30 g/L, boric acid 30 g/L, saccharin 3 g/L, additive 0.02 g/L. The process conditions are J = 5 A/dm ² , t = 30 oC, pH = 5.5

Experimental results: The components of the iron-nickel-cobalt-molybdenum alloy foil are: Fe 23.8%, Ni 36.4%, Co15.6%, Mo24.2%. The surface of the alloy foil is relatively smooth, the structure is compact, and the particles are very small and agglomerated into large particles. The particle size is 3.8nm, belonging to nanocrystal. The X-ray diffraction peaks are broadened, and the alloy structure is between microcrystalline and amorphous crystals.

The resistivity is 50-100 μΩ·cm, the magnetic saturation is 1.25 Tesla, the tensile strength is 794.85MPa, and the elongation is 6.67%. the

the

Example 3

The electrolyte composition is NiSO ₄ 6H ₂ O 70 g/L; NiCl ₂ 6H ₂ O 35 g/L; FeSO ₄ 7H ₂ O 10 g/L; Na ₂ MoO ₄ 2H ₂ O 10 g/L; CoSO ₄ 7H ₂ O 15 g/L; trisodium citrate 125 g/L; stabilizer 30 g/L; boric acid 30 g/L; saccharin 3 g/L; additive 0.02 g/L; 30 oC; pH = 5; J = 2 A/ ^dm2

Experimental results: The components of the iron-nickel-cobalt-molybdenum alloy foil are: Fe 18.2%, Ni 52.4%, Co15.7%, Mo10.0%. The surface of the alloy foil is relatively smooth, the structure is compact, and the particle size is very small and agglomerated into large particles. The X-ray diffraction peak is wide, and the alloy structure is between microcrystalline and amorphous crystal.

The X-ray diffraction analysis of Fe-Ni-Co-Mo alloy foil shows that there is an obvious diffraction peak near 43.5° in the XRD spectrum, and the shape of the diffraction peak is broadened, indicating that the alloy foil has a crystal structure with very fine grains. 5.5 nm, Fe-Ni-Co-Mo alloy foil belongs to nanocrystalline. The phase is a heterogeneous structure of face-centered cubic NiFe solid solution and MoNi ₄ intermetallic compound, and the main diffraction planes of the texture of the face-centered cubic NiFe solid solution are (111), (200), (221), (311) and ( 222) crystal plane, and presents a strong preferred orientation of (111) crystal plane, while the texture of MoNi ₄ intermetallic compound is (121), (310), (002), (240), (312), ( 123) and (242) crystal planes.

There is no cobalt diffraction peak on the diffraction spectrum, which shows that cobalt enters the nickel-iron solid solution by substituting atoms to form a substitutional nickel-iron solid solution. the

It has been tested that the crystal size of the alloy foil is in the nanometer range, the surface is smooth and bright, the thickness is uniform, the corrosion resistance is good, the tensile strength is high, the toughness is good, and the resistivity is about 49μΩ·cm. the

the

Claims (9)

1. the preparation method of an iron-nickel-cobalt-molybdenum alloy foils, adopt electrodip process, electrolytic solution is hydrosulphate-muriate-sodium molybdate aqueous solution system, is anode and cathode with the metal, and places electrolytic solution, pass to the direct current of certain hour, the Fe-Ni-Co-Mo alloy deposition on negative electrode, is taken out negative plate then and rinses well, and drying strips down the Fe-Ni-Co-Mo alloy layer that its surface forms, namely obtain the Fe-Ni-Co-Mo Alloy Foil, it is characterized in that:

Adopt hydrosulphate-muriate-sodium molybdate aqueous solution electrolytic solution, the concrete component of electrolytic solution is:

NiSO ₄6H ₂O 80 ~ 140 g/L, NiCl ₂6H ₂O 40 g/L, FeSO ₄7H ₂O 5 ~ 25 g/L, CoSO ₄7H ₂O 5 ~ 25 g/L, Na ₂MoO ₄2H ₂O 4 ~ 12 g/L, trisodium citrate 95 ~ 155 g/L, stablizer 30 g/L, buffer reagent 30 g/L, asccharin 3 g/L, additive 0.02 g/L.

2. the processing parameter of galvanic deposit is: current density 1.5 ~ 5 A/dm ², 20 ~ 45 ℃ of temperature, pH value 3.5 ~ 5.5, depositing time 60 ~ 100 min, cathode and anode spacing 2 ~ 3 cm.

3. cathode base is the titanium plate, anode employing high-density carbon plate or soluble iron, nickel combined anode.

4. the preparation method of Fe-Ni-Co-Mo Alloy Foil according to claim 1, it is characterized in that buffer reagent be in boric acid, the oxalic acid any.

5. the preparation method of Fe-Ni-Co-Mo Alloy Foil according to claim 1, it is characterized in that complexing agent be in Citrate trianion series, the Seignette salt any.

6. the preparation method of Fe-Ni-Co-Mo Alloy Foil according to claim 1 is characterized in that brightening agent is any or any two above sum in asccharin, thiocarbamide, the butynediol.

7. the preparation method of Fe-Ni-Co-Mo Alloy Foil according to claim 1 is characterized in that auxiliary is any or any two above sum in benzene sulfinic acid sodium salt, ethylhexyl sodium sulfonate, sodium lauryl sulphate, the succsinic acid.

8. the preparation method of Fe-Ni-Co-Mo Alloy Foil according to claim 1, it is characterized in that anode and negative electrode be arranged to mutually towards mode, anode separates the distance of expecting with negative electrode, is generally 2 ~ 3 cm.

9. the preparation method of Fe-Ni-Co-Mo Alloy Foil according to claim 1, it is characterized in that: anode can be insoluble anode or combination soluble anode, insoluble anode is generally high-density carbon-point (plate), and the combination soluble anode can be iron, nickel combination or iron, nickel, cobalt combination.