CN108360028A - It is a kind of to prepare Ni/ZrO using dipulse2The method of binary gradient functional material - Google Patents

It is a kind of to prepare Ni/ZrO using dipulse2The method of binary gradient functional material Download PDF

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CN108360028A
CN108360028A CN201810156833.5A CN201810156833A CN108360028A CN 108360028 A CN108360028 A CN 108360028A CN 201810156833 A CN201810156833 A CN 201810156833A CN 108360028 A CN108360028 A CN 108360028A
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zro
base material
functional material
binary gradient
copper base
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CN108360028B (en
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葛文
李佳梅
靳帆
靳一帆
周玉杰
周飞杨
梅思雨
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China University of Geosciences
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces

Abstract

The invention discloses a kind of Ni/ZrO is prepared using dipulse2Copper base material is pre-processed to obtain the copper sheet for waiting for coating by the method for binary gradient functional material, including prepare electrolyte, and by one face closure；Using copper sheet as cathode, for nickel plate as anode, cathode connects dual-pulse power supply with anode, and is put into coating bath, and the one side that the copper sheet is not closed out is opposite with nickel plate, and the electrolyte that step S1 is prepared is added in coating bath, and electrolyte temperature is 40 DEG C, pH=4 ± 0.1；Start dual-pulse power supply, if electro-deposition；Post-processing is to get to Ni/ZrO2Binary gradient functional material.Preparation method of the present invention is easy, at low cost, pollution is small, is suitable for enlargement, large-scale production；Ni/ZrO produced by the present invention2Binary gradient functional material is smooth, anti-corrosion, crystal grain is small, surface is uniform, fine and close.

Description

It is a kind of to prepare Ni/ZrO using dipulse2The method of binary gradient functional material
Technical field
The present invention relates to technical field of function materials more particularly to a kind of utilization dipulse to prepare Ni/ZrO2Binary gradient The method of functional material.
Background technology
The phenomenon that metal erosion is spontaneous, generally existing in nature.The corrosion of metal material is widely present in each neck Domain, caused loss is very big, and especially in damp and hot marine environment, steel is vulnerable to salt fog, and the erosions such as tide occur Serious electrochemical corrosion not only results in huge economic loss, it is easier to cause safety accident, due to aviation, the energy, boat Flourishing for the modern sciences industrial technology such as sea, constantly improves the rigors of materials'use under particular surroundings.Commonly Ceramics, metal and composite material mechanical strength, heat resistance, durability and service life be all difficult to meet the requirements, functionally gradient material Material comes into being.
Currently, the preparation method of functionally graded material mainly has vapour deposition process (PVD, CVD), plasma spraying method, powder Last metallurgy method, Self-propagating high-temperature synthesis method and electrodeposition process etc., but each method have the shortcomings that it is inevitable.Gas Phase sedimentation can prepare large-sized sample, but synthesis rate is relatively low, and the material thickness prepared is relatively low and to equipment It is more demanding；Physical vaporous deposition deposition rate is relatively low, and the distribution of material can not continuous control；Powder metallurgy legal system Standby temperature is high, not only consumes energy, but also there are uneven, uppity defects for the structure of matter and composition gradient；Self- propagating is high Warm combustion synthesis method is a kind of high method of production efficiency height, small investment, product purity, but its preparation condition is complicated, temperature compared with It is high, easily splash, in addition, many preparation methods all because cost is excessively high or pollution too again etc. reasons can not all carry out enlargement, The production of scale, functionally graded material are still difficult to generally come into people’s lives.
Invention content
In view of this, the embodiment provides a kind of utilizations smooth, anti-corrosion, crystal grain is small, surface is uniform, fine and close Dipulse prepares Ni/ZrO2The method of binary gradient functional material.
The embodiment of the present invention offer is a kind of to prepare Ni/ZrO using dipulse2The method of binary gradient functional material, packet Include following steps：
S1. electrolyte is prepared, NiSO is selected4·6H2O and NiCl2·6H2O as main salt ionic electrolytes, NaCl and Na2SO4As supporting electrolyte, H3BO3With HCOONa as buffer, saccharin adds ZrO as additive2；
S2. Copper base material is pre-processed to obtain the copper sheet for waiting for coating, and by one face closure；
S3. using step S2 treated copper sheets as cathode, for nickel plate as anode, cathode connects dipulse electricity with anode Source, and be put into coating bath, the one side that the copper sheet is not closed out is opposite with nickel plate, and the electrolysis that step S1 is prepared is added in coating bath Liquid, electrolyte temperature are 40 DEG C, pH=4 ± 0.1；
S4. start dual-pulse power supply, the parameter for setting dual-pulse power supply carries out electro-deposition, and plating is stirred in electrodeposition process Liquid；
S5. the copper sheet after electro-deposition is post-processed to get to Ni/ZrO2Binary gradient functional material.
Further, in the step S1, NiSO4·6H2O is 280g/L, NiCl2·6H2O is 40g/L, H3BO3For 30g/ L, saccharin 0.5g/L, ZrO2Additive amount be 5g/L.
Further, in the step S2, the pretreated specific method of Copper base material is：
S1.1. it is first polished Copper base material with coarse sandpaper, then is polished Copper base material with fine sandpaper, in the same direction It polishes, washs；
S1.2. oil removing, washing are carried out to Copper base material；
S1.3. pickling, washing are carried out to Copper base material；
S1.4. Copper base material is neutralized, is washed；
S1.5. weak etch, washing are carried out to Copper base material.
Further, 70g/L sodium hydroxides, 70g/L sodium carbonate, 30g/L tertiary sodium phosphates, 4mL/L washings are selected in the oil removing Agent OP-10, temperature are 70~90 DEG C, and the time is 20~30min；90% concentrated hydrochloric acid of the pickling selection, 4g/L methenamines, 10% deionized water, temperature are room temperature, time 50s；The neutralisation treatment selects 40g/L sodium carbonate, time 10s described It is 5~10s that the 1.84g/L sulfuric acid of 20mL, time are selected in weak etch.
Further, in the step S4, the parameter of dual-pulse power supply is：Positive duty ratio 10-80%, forward current density 1-2.5A·dm-2, positive period 2-8ms, reversed duty ratio 20-80%, reversal periods 1-4ms, reverse current density be forward direction Current density 1/10, positive working time and reverse operation time be 12ms.
Compared with prior art, preparation method of the present invention is easy, at low cost, pollution is small, is suitable for enlargement, scale metaplasia Production；Ni/ZrO produced by the present invention2Binary gradient functional material is smooth, anti-corrosion, crystal grain is small, surface is uniform, fine and close.
Description of the drawings
Fig. 1 is that the present invention is a kind of preparing Ni/ZrO using dipulse2Equipment therefor in the method for binary gradient functional material A schematic diagram.
Fig. 2 is that the present invention is a kind of preparing Ni/ZrO using dipulse2One flow chart of the method for binary gradient functional material.
Fig. 3 is different forward direction duty ratios in the embodiment of the present invention, forward current density, the positive period, reversed duty ratio, anti- Ni/ZrO is obtained to the period2The XRD spectra of binary gradient functional material.
Fig. 4 is the ZrO of various concentration in the embodiment of the present invention2Electroplate liquid Ni/ZrO is prepared2Binary gradient function material The XRD spectra of material.
Fig. 5 is the organization chart of XRD determining after 400 DEG C of high temperature corrosions in the embodiment of the present invention.
Fig. 6 is the organization chart of XRD determining after 500 DEG C of high temperature corrosions in the embodiment of the present invention.
Fig. 7 is the organization chart of XRD determining after 600 DEG C of high temperature corrosions in the embodiment of the present invention.
Fig. 8 is difference ZrO in the embodiment of the present invention2The Ni/ZrO of additive amount2The Tafel polarization curves of functionally gradient deposit.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention Formula is further described.
Embodiment 1
The embodiment provides a kind of Ni/ZrO is prepared using dipulse2The method of binary gradient functional material.
The present invention uses dipulse electric deposition device, as shown in Figure 1, including electrolytic cell 1, electrolytic cell 1 of glass by being made Cuboid, electrolytic cell 1 has electrolyte in thermostatic water bath 2, cathode electrode 3, anode electricity placed in electrolyte in electrolytic cell 1 Pole 4 and electric mixer 6, cathode electrode 3 and anode electrode 4 connect dual-pulse power supply 5, and electric mixer 6 is located in coating bath 1 Between.Dual-pulse power supply 5 is responsible for providing rectangular wave type dipulse electric current, and electric mixer 6 controls the mixing speed in reaction process, Thermostatic water bath 2 controls the temperature of electrolyte.
Referring to FIG. 2, specifically including following steps：
S1. electrolyte is prepared, NiSO is selected4·6H2O and NiCl2·6H2O as main salt ionic electrolytes, NaCl and Na2SO4As supporting electrolyte, H3BO3With HCOONa as buffer, saccharin adds ZrO as additive2；
Preferably, NiSO4·6H2O is 280g/L, NiCl2·6H2O is 40g/L, H3BO3For 30g/L, dodecyl sulphate Sodium 0.1g/L, saccharin 0.5g/L, ZrO2Additive amount be 0-40g/L, and do not select 0g/L.
S2. Copper base material is pre-processed to obtain the copper sheet for waiting for coating, specially：
S1.1. it is first polished Copper base material with coarse sandpaper, then is polished Copper base material with fine sandpaper, in the same direction It polishes, washs；
S1.2. to Copper base material carry out oil removing, select 70g/L sodium hydroxides, 70g/L sodium carbonate, 30g/L tertiary sodium phosphates, 4mL/L detergent OP-10, temperature are 70~90 DEG C, and the time is 20~30min；Washing；
S1.3. pickling is carried out to Copper base material, selects 90% concentrated hydrochloric acid, 4g/L methenamines, 10% deionized water, temperature For room temperature, time 50s；Washing；
S1.4. Copper base material is neutralized, selects 40g/L sodium carbonate, time 10s, washing；
S1.5. weak etch is carried out to Copper base material, the 1.84g/L sulfuric acid of 20mL, time is selected to be washed for 5~10s.
By a face closure of pretreated copper sheet, i.e., the face paste is lived with adhesive tape；
S3. using step S2 treated copper sheets as cathode, for nickel plate as anode, cathode connects dipulse electricity with anode Source, and be put into coating bath, the one side that the copper sheet is not closed out is opposite with nickel plate, and the electrolysis that step S1 is prepared is added in coating bath Liquid, electrolyte temperature are 40 DEG C by thermostatic water bath control, pH=4 ± 0.1；
S4. start dual-pulse power supply, the parameter for setting dual-pulse power supply carries out electro-deposition, and the parameter of dual-pulse power supply is preferred For：Positive duty ratio 10-80%, forward current density 1-2.5Adm-2, positive period 2-8ms, reversed duty ratio 20-80%, Reversal periods 1-4ms, 1/10 that reverse current density is forward current density, positive working time and reverse operation time is 12ms stirs electroplate liquid in electrodeposition process, and it is 300r/ to control the mixing speed in reaction process by electric mixer 6 min；
S5. the copper sheet after electro-deposition is post-processed to get to Ni/ZrO2Binary gradient functional material.
The orthogonal test of double-pulse parameters is designed, positive duty ratio is chosen, forward current density, the positive period, reversely accounts for Five sky ratio, reversal periods factors, the results are shown in Figure 3, and each factor takes four level value design orthogonal design table L16(45), Progress orthogonal experiment, the factor and level of orthogonal as shown in table 1, double-pulse parameters orthogonal design table shown in table 2, Remaining selection same parameters.
Table 1
Table 2
1, to Ni/ZrO obtained2The structural characterization and corrosion resistance of binary gradient functional material coating are tested, and are prepared Ni/ZrO2Binary gradient functional material coating is face-centred cubic structure (fcc), and main high preferred orientation is (111) and (200) Face, and the orientation advantage in (200) face becomes apparent；The crystallite dimension of its different high preferred orientation is calculated using Scherrer formula, Discuss double-pulse parameters to Ni nanoparticle/ZrO2The influence of binary gradient functional material structure of plating layer, in order to obtain crystal grain ruler Very little smaller crystal grain, best dual-pulse power supply parameter are：Positive duty ratio γ+20%, reversed duty ratio γ -60% is positive Current density, J+1.0A/dm2, reversal periods T-3ms, positive cycle T+4ms；By range analysis, and with Ni/ZrO2Binary ladder The average grain size of functional material coating is spent as judge index, can obtain five parameters pair of Double-pulse Plating Power Source Ni/ZrO2The crystallite dimension of functionally gradient deposit influence sequence be：The positive reversed duty ratio ＞ forward currents of duty ratio ＞ are close Spend the ＞ reversal periods ＞ positive periods.
2, the ZrO of research addition various concentration2Electroplate liquid prepare Ni/ZrO2Functionally gradient deposit sample, remaining selection are same One parameter, as shown in figure 4, using XRD determining sample institutional framework and the changing rule of structure of plating layer is discussed：From reduction From the perspective of composite galvanized coating crystallite dimension, not the higher the better for the compound quantity of nano particle, but (as zirconium oxide adds The increase of amount, Ni/ZrO2The crystallite dimension of functionally gradient deposit is in increased trend after first reducing)；Ni/ZrO2Functionally gradient plates Layer crystal grain is tiny, nanometer ZrO2The features such as even particle distribution each contribute to the raising of corrosion resistance of coating, as shown in table 3.
Table 3
3, different high temperature corrosion temperature (being respectively 400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C) continuous high temperatures are studied After 12h, using the institutional framework after XRD determining its high temperature corrosion, different high temperature corrosion temperature are inquired into Ni/ZrO2Functionally gradient The influence of structure of plating layer, as shown in Fig. 5-7 and table 4-6, table 4 is Ni/ZrO after 400 DEG C of oxidations2The crystalline substance of functionally gradient deposit Particle size, table 5 are Ni/ZrO after 500 DEG C of oxidations2The crystallite dimension of functionally gradient deposit, table 6 are Ni/ZrO after 600 DEG C of oxidations2Work( The crystallite dimension of energy gradient coating.
Table 4
Table 5
Table 6
After 400,500 and 600 DEG C of high-temperature oxydations, coating preferred orientation face is (111) and (200) face, (200) face Orientation advantage becomes apparent.Ni/ZrO after high temperature2The crystallite dimension of functionally gradient deposit is generally than Ni/ZrO under room temperature2Function The crystallite dimension of gradient coating is big, and as temperature increases, Ni/ZrO2The average grain size of functionally gradient deposit gradually increases Greatly；The crystallite dimension ratio Ni/ZrO of nickel coating2The crystallite dimension of functionally gradient deposit is big.With the increasing of zirconium oxide additive amount Add, Ni/ZrO2The crystallite dimension of functionally gradient deposit is in increased trend after first reducing.Passing through 400,500 and 600 DEG C of high temperature After oxidation, be zirconium oxide additive amount be 30g/L when Ni/ZrO2The average grain size of functionally gradient deposit is minimum, is respectively 24.9,25.45 and 26.05nm.Oxidation occurs for nickel coating without apparent high preferred orientation, Ni/ZrO after 700 DEG C of high temperature2Functionally gradient Coating preferred orientation face is (111) and (200) face, and the orientation advantage in (200) face becomes apparent.Nickel coating is by oxygen after 800 DEG C Turn to NiO, Ni/ZrO2Although also there are NiO characteristic peaks in functionally gradient deposit, coating preferred orientation face be still (111) and (200) the orientation advantage in face, (200) face becomes apparent.Average grain size variation is after high temperature with nanometer ZrO2Particle is answered Resultant first reduces and increases afterwards, meets the analysis of nano-particles reinforcement amount in composite galvanized coating at normal temperatures.As nanometer ZrO2Particle Adding too much generates reunion between nano particle, leads to Ni/ZrO2Functionally gradient deposit is loosely organized, high temperature corrosion It can reduce, high-temperature oxydation easily occurs, cause crystallite dimension when crystallite dimension is than room temperature after high temperature big.
4, addition various concentration ZrO is measured using Muffle furnace hot test2Ni/ZrO2The high temperature of functionally gradient deposit is resistance to Corrosion, using the surface topography before SEM observation corrosion of coating and after corrosion：Ni/ZrO before high temperature corrosion2Functionally gradient deposit Planarization is better than pure Ni coating, or even under conditions of amplifying 3000 times, still smooth, no significant defect is pure after high temperature corrosion Nickel coating is increased with temperature, and local pitting occurs first for surface, is finally fully oxidized, short texture, different ZrO2Add The Ni/ZrO of dosage2The Tafel polarization curves of functionally gradient deposit are as shown in Figure 8.
Dipulse electrodeposition process can prepare Ni/ZrO2Binary gradient functional material coating, gradient direction ZrO2Content by 0 progressively increases to 34.99% (mass fraction)；The addition of zirconium oxide can make Ni/ZrO2Coating is more smooth, and corrosion resistance has Larger raising；Under conditions of same process parameter, by the Ni/ZrO prepared by dipulse electro-deposition2Functionally gradient deposit with it is pure Nickel coating is compared, and crystal grain is more tiny, and the more uniform densification of coating surface, corrosion resistance improves a lot.
Embodiment 2
The present embodiment is differed only in embodiment 1, and the parameter of dual-pulse power supply is：Mean Forward Current density 1A/ dm2, positive duty ratio 40%, positive working time 12ms, reversed duty ratio 60%, reverse operation time 12ms, Yu Zeyu are real It is essentially identical to apply example 1
Electron-microscope scanning is carried out to material is made, by Cross Section Morphology it can be seen that the color close to copper sheet is deeper, structure causes It is close；Close to coating surface, color is brighter, and hole is larger more, ZrO2Particle distribution gradually becomes intensive from top to bottom.In conjunction with Scanning electron microscope (SEM) Cross Section Morphology, cross sectional elements distribution map and section A, the result of EDS constituent analyses of B and C points can be sentenced It is disconnected, it can be prepared containing 0~34.99%ZrO by dipulse electrodeposition process2Ni/ZrO2Functionally gradient deposit.
Embodiment 3
The present embodiment is differed only in embodiment 1, ZrO2Additive amount be 5g/L, the parameter of dual-pulse power supply is： Positive duty ratio 10%, forward current density 1Adm-2, positive period 3ms, reversed duty ratio 20%, reversal periods 1ms, it is remaining It is then essentially identical with implementation 1.
Embodiment 4
The present embodiment is differed only in embodiment 1, zirconium oxide additive amount be 30g/L, it is remaining then with 1 basic phase of embodiment Together.
Preparation method of the present invention is easy, at low cost, pollution is small, is suitable for enlargement, large-scale production；It is produced by the present invention Ni/ZrO2Binary gradient functional material is smooth, anti-corrosion, crystal grain is small, surface is uniform, fine and close.
In the absence of conflict, the feature in embodiment and embodiment herein-above set forth can be combined with each other.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.

Claims (5)

1. a kind of preparing Ni/ZrO using dipulse2The method of binary gradient functional material, which is characterized in that include the following steps：
S1. electrolyte is prepared, NiSO is selected4·6H2O and NiCl2·6H2O is as main salt ionic electrolytes, NaCl and Na2SO4Make For supporting electrolyte, H3BO3With HCOONa as buffer, saccharin adds ZrO as additive2；
S2. Copper base material is pre-processed to obtain the copper sheet for waiting for coating, and by one face closure；
S3. using step S2 treated copper sheets as cathode, for nickel plate as anode, cathode connects dual-pulse power supply with anode, and It is put into coating bath, the one side that the copper sheet is not closed out is opposite with nickel plate, and the electrolyte that step S1 is prepared, electricity are added in coating bath It is 40 DEG C to solve liquid temperature, pH=4 ± 0.1；
S4. start dual-pulse power supply, the parameter for setting dual-pulse power supply carries out electro-deposition, and electroplate liquid is stirred in electrodeposition process；
S5. the copper sheet after electro-deposition is post-processed to get to Ni/ZrO2Binary gradient functional material.
2. according to claim 1 prepare Ni/ZrO using dipulse2The method of binary gradient functional material, feature exist In, in the step S1, NiSO4·6H2O is 280g/L, NiCl2·6H2O is 40g/L, H3BO3For 30g/L, saccharin 0.5g/ L, ZrO2Additive amount be 40g/L within.
3. according to claim 1 prepare Ni/ZrO using dipulse2The method of binary gradient functional material, feature exist In in the step S2, the pretreated specific method of Copper base material is：
S1.1. it is first polished Copper base material with coarse sandpaper, then is polished Copper base material with fine sandpaper, carried out in the same direction Polishing, washing；
S1.2. oil removing, washing are carried out to Copper base material；
S1.3. pickling, washing are carried out to Copper base material；
S1.4. Copper base material is neutralized, is washed；
S1.5. weak etch, washing are carried out to Copper base material.
4. according to claim 3 prepare Ni/ZrO using dipulse2The method of binary gradient functional material, feature exist In 70g/L sodium hydroxides, 70g/L sodium carbonate, 30g/L tertiary sodium phosphates, 4mL/L detergent OP-10, temperature are selected in the oil removing It it is 70~90 DEG C, the time is 20~30min；The pickling selects 90% concentrated hydrochloric acid, 4g/L methenamines, 10% deionization Water, temperature are room temperature, time 50s；The neutralisation treatment selects 40g/L sodium carbonate, time 10s, the weak etch to select The 1.84g/L sulfuric acid of 20mL, time are 5~10s.
5. according to claim 1 prepare Ni/ZrO using dipulse2The method of binary gradient functional material, feature exist In in the step S4, the parameter of dual-pulse power supply is：Positive duty ratio 10-80%, forward current density 1-2.5Adm-2、 Positive period 2-8ms, reversed duty ratio 20-80%, reversal periods 1-4ms, 1/ that reverse current density is forward current density 10, positive working time and reverse operation time are 12ms.
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