CN101215708A - Method for preparing corrosion resistant nickel/chromium plating steel belt - Google Patents
Method for preparing corrosion resistant nickel/chromium plating steel belt Download PDFInfo
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- CN101215708A CN101215708A CNA2008100704447A CN200810070444A CN101215708A CN 101215708 A CN101215708 A CN 101215708A CN A2008100704447 A CNA2008100704447 A CN A2008100704447A CN 200810070444 A CN200810070444 A CN 200810070444A CN 101215708 A CN101215708 A CN 101215708A
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Abstract
A process for preparing corrosion-resisting nickelplate/chrome steel strip relates to a steel strip, which provides a process for preparing corrosion-resisting nickelplate/chrome steel strip which is formed by compactly combining electrodeposition nickel/chrome coat and low-carbon steel strip. The method comprises deoiling cold-rolled low-carbon steel strip, positioning the cold-rolled low-carbon steel strip which is deoiled in a liquid groove, electroplating chrome layer on the cold-rolled low-carbon steel strip which is deoiled, controlling the thickness of the chrome layer in 0.01-1um, positioning the low-carbon steel strip which is plated with chrome in the liquid groove, electroplating nickel layer on the low-carbon steel strip which is plated with chrome, controlling the thickness of the nickel layer in 10-20um, positioning the low-carbon steel strip which is electroplated with nickel layer in the liquid groove, carrying out inactivating treatment, preserving heat of electroplating chrome/nickel layer steel strip which is inactivated, removing hydrogen in the plating layer, carrying out diffusion annealing treatment on the electroplating chrome / nickel layer steel strip which is dehydrogenated, and obtaining corrosion-resisting nickelplate/chrome steel strip.
Description
Technical field
The present invention relates to a kind of steel band, especially relate to a kind of combining closely and form, can be used for the preparation method of the high performance corrosion-proof nickel plating/chromium steel band of industries such as chemical industry, machinery, signal equipment by electronickelling/chromium thickness coating and mild-carbon steel strip.
Background technology
The nickel-clad steel band is widely used in fields such as chemical industry, machinery, building, signal equipment, power tool, and its preparation technology combines closely electric deposition nickel coating and low carbon steel substrate to form.For example, the box hat production technique of existing secondary cell and alkaline primary battery is with plate one deck nickel coating after the mild-carbon steel strip moulding again with rolling.Owing to cleaning reasons such as difficulty, the dark scarce capacity of plating and plating point discharge in the process of rolling nickel plating, present this technology is replaced by another kind of technology gradually, this technology is after the continuous nickel plating of mild-carbon steel strip, diffuse to form nickel/iron diffusion layer by continuous annealing, and effectively control thickness of diffusion layer, control the exposure of the iron on nickel plating surface.
U.S. Pat 5679181 discloses a kind of production technique of corrosion resistance nickel coated steel strips, and this technology makes nickel coating partly or entirely become iron/nickel diffusion layer in the nickel plating of one side at least of cold-rolled steel strip, and the exposure of nickel layer surface iron accounts for 4%～30%.
European patent EP 1111697 discloses a kind of production technique that is used for battery case or surface-treated steel strips and the steel band and the battery of same structure are arranged, this technology is in rare gas element or except that thermal treatment 4～10h in the oxygen atmosphere, at border formation iron/nickel and nickel/bismuth diffusion layer separately at 300～650 ℃.The housing of battery adopts the steel band production that has in iron/nickel diffusion layer, nickel dam, nickel/bismuth diffusion layer, the iron/nickel/bismuth alloy layer at least 1 layer.The battery case of this surface treated steel band production has excellent alkali resistance and keeps the characteristic of enough discharge levels for a long time.
U.S. Pat 4910096 discloses a kind of nickel-plated cold-rolled band of deep diffusion, and this steel band is the nickel dam of galvanic deposit 1～6 μ m on cold-rolled steel strip, plates the cobalt layer of 0.01～1.0 μ m more thereon, and thermal treatment forms the deep diffusion layer under 580～710 ℃ of temperature.The preparation method of this steel band has characteristics such as economy, plasticity-is strong, the coating diffusion is dark, solidity to corrosion is good.
U.S. Pat 5587248 discloses a kind of solidity to corrosion nickel plated steel strip and production technique thereof, and this technology is in the one side nickel plating of cold-rolled steel strip at least, and makes nickel coating partly or entirely form iron/nickel diffusion layer, and the exposure of nickel coating surface iron is not more than 30%.
U.S. Pat 5335841 discloses a kind of production technique with excellent corrosion resistance internal surface welded tube, this technology applies double-deck tungsten coating at least on the one side of steel band, the first layer is nickel or brill or its alloy, and the second layer uses the metal or alloy that relative the first layer melting point metal will be low.Steel band is processed into the pipe postheat treatment makes welded tube not have exposed steel matrix.This welded tube has excellent solidity to corrosion and practicality.
Japanese Patent JP3104855 discloses a kind of DIFFUSION TREATMENT nickel steel band and production technique, and this technology is at the diffusion layer of the two-sided formation nickel of steel band, and the diffusion layer nickel of a nickel is controlled at 2～10g/m
2Scope in, the diffusion layer nickel of another side nickel is 2g/m
2In the two-layer deposited nickel layer that powers on of nickel diffusion layer, correspondingly control one side is at 2～10g/m again
2Scope in, another side is 2g/m
2The heating upper surface makes nickel ooze the people to form diffusion layer, in addition on this basis can also be in two-sided continuation nickel plating, thus be easy to make upper and lower surface to form the nickel diffusion layer of different mass.This technology can satisfy the difference that the surfaces externally and internally corrosion resisting property requires.
Chinese patent CN1600904A discloses a kind of nickel-plated deeply-draw steel strip and production method thereof, continuous electro-deposition nickel 1～2 μ m nickel on steel band, and by thermal treatment and laser thermal shock processing, make nickel coating form iron/nickel diffusion layer, and control dew iron rate makes the anticorrosion steel band of desired size then by finishing procedure in 3%.This steel band has excellent solidity to corrosion and practicality.
Though present many research work have obtained certain progress to nickel plating technology, annealing process, pulse laser impact process, improving nickel coating performance and corrosion resistance nature in varying degrees.But existing technology mainly is the galvanic deposit that concentrates on the nickel flash plating, and is easy of cover light exposes matrix in some processes processes such as degree of depth roll compacting, deep-draw like this; And because the interfacial stress of thick coating and matrix is excessive or because thermal treatment process is inappropriate, coating shedding, skin effect phenomenon appear in thick coating easily.The diffusion layer of existing nickel-clad steel band mainly is Fe-Ni or Fe-Ni-C diffusion layer, and it is higher to reveal the iron rate, reduce antiseptic property easily, and thermal treatment process is improper, is forming phase boundary at the interface easily, and this is extremely harmful for the engineering materials interface mechanical characteristic.In addition, can not form matching relationship preferably aspect unit elongation, tensile strength, the hardness.The deficiency of these nickel-clad steel bands, range of application is little in a lot of fields to make it.
Summary of the invention
The object of the present invention is to provide a kind of by the combine closely preparation method of corrosion-resistant nickel plating/chromium steel band of forming of electric deposition nickel/chromiumcoating and mild-carbon steel strip.
The present invention includes following steps:
1) with the oil removing of cold-rolled low carbon steel band;
2) the cold-rolled low carbon steel band after the oil removing is placed in the solution tank, electrodeposited chromium layers on the cold-rolled low carbon steel band after the oil removing, the gauge control of chromium layer is at 0.01～1 μ m;
3) mild-carbon steel strip after the chromium plating is placed in the solution tank, electroless nickel layer on the mild-carbon steel strip after the chromium plating, the gauge control of nickel dam is at 10～20 μ m;
4) mild-carbon steel strip behind the electroless nickel layer is placed in the solution tank, carry out Passivation Treatment;
5) with the electrodeposited chromium after the Passivation Treatment/nickel dam steel band insulation, remove the hydrogen in the de-plating;
6) electrodeposited chromium after the dehydrogenation/nickel dam steel band diffusion annealing is handled, obtained corrosion-resistant nickel plating/chromium steel band.
In step 1), described oil removing is that the alkali cleaning oil removing is or/and electrolytic degreasing, the alkali cleaning oil removing is that the cold-rolled low carbon steel band is placed the solution tank electrochemical deoiling, remove the grease of cold-rolled low carbon steel belt surface, the solution composition of electrochemical deoiling is preferably sodium hydroxide 50～60g/L, yellow soda ash 35～40g/L, sodium phosphate 25～30g/L, 70～80 ℃ of solution temperatures, current density 4～7A/dm
2, degreasing time 5～10min.Electrolytic degreasing is that the cold-rolled low carbon steel band is placed the solution tank electrochemical degreasing, further remove the grease of remained on surface, the solution composition of electrolytic degreasing is preferably sodium hydroxide 50～60g/L, yellow soda ash 35～40g/L, sodium phosphate 40～45g/L, water glass 3～4g/L, 55～65 ℃ of solution temperatures, current density 4～6A/dm
2, degreasing time 3～6min.
In step 2) in, the solution composition of described electrodeposited chromium layers is preferably anhydrous chromic acid acid anhydride 750～800g/L, hydrochloric acid 30～40ml/L, cathode current density 15～25A/dm
2, 35～45 ℃ of bath temperatures, immersion plating time 30s～3min.
In step 3), the solution composition of described electroless nickel layer is preferably nickel sulfamic acid 700～800g/L, nickelous chloride 6～8g/L, boric acid 35～45g/L, pH4～6,45～55 ℃ of bath temperatures, cathode current density 4～7A/dm
2, immersion plating time 10～20min.
In step 4), the solution composition of described passivation is preferably potassium bichromate 12～17g/L, sodium hydroxide 2.5～3.5g/L, yellow soda ash 1.5～2.5g/L, current density 1.3～1.8A/dm
2, pH8～9.
In step 5), described insulation preferably is incubated under 120～150 ℃ of vacuum conditions, in order to remove the hydrogen of the coating that is incorporated in electrolytic degreasing and continuous electro-deposition chromium/nickel coating process, prevents to occur hydrogen embrittlement or foaming in heat treatment process.
In step 6), the vacuum tube furnace that can adopt built-in quartz glass tube is handled in described diffusion annealing, uses the poly-light material of aluminum oxide of vacuum forming low heat capacity to stop that hot-fluid impacts, the middle argon gas that feeds in the stove; Diffusion annealing is handled and is comprised thermal pretreatment, diffusion heat treatments and quenching heat treatment, the soaking time section that diffusion annealing is handled is divided into warm up time, diffusion time and quick cooling time, its diffusion temperature is to adopt 900～1300 ℃ of the recrystallization temperatures of chromium/nickel coating and iron matrix element formation single phase solid solution, make the dew iron rate of steel strip surface be not more than 1% for the suitable time of the control diffusion layer degree of depth diffusion time.Described thermal pretreatment is that above-mentioned electronickelling/chromium layer steel band placed vacuum tube furnace, begins to heat up under argon shield atmosphere, and heat-up rate is 5～10 ℃/min, and temperature is risen to 900～1300 ℃.Described diffusion heat treatments is with the electronickelling/chromium layer steel band constant temperature thermal treatment 0.5～2h through thermal pretreatment, by the phase mutual diffusion of siderochrome nickel three constituent elements, forms the single-phase continuous solid solution of being predicted on the siderochrome nickel ternary phase diagrams.Described quenching heat treatment is that the electronickelling after diffusion heat treatments/chromium layer steel band cooled off fast by feeding liquid nitrogen, to keep the diffusion heat treatments single-phase continuous solid solution structure of nickel chromium triangle coating/substrate afterwards.
After obtaining corrosion-resistant nickel plating/chromium steel band, preferably carry out finishing and handle, can adopt 2 roller finishing mills, the nickel plating/chromium layer steel band after handling through diffusion annealing carried out the cold rolling required thickness that is processed into, effectively control its cold rolling reduction.
The present invention is by adding thin chromiumcoating as diffusion impervious layer between nickel plating thickness coating and matrix, in the thermal treatment engineering, can effectively stop the diffusion of iron, and, increased antiseptic property doubly owing to formed the preservative coat of the class stainless steel structure of chromium content 20%～30% in the diffusion layer.Adopt the suitable heat treatment temperature to make chromium/nickel coating and matrix form the gradient material of single-phase unlimited solid solution, greatly improved interface binding power.Control the suitable diffusion heat treatments time and control thickness of diffusion layer, make that revealing the iron rate levels off to 0.This external coating (EC) also has surface-brightening, than low porosity, than the feature of high-mechanical property.
Description of drawings
Fig. 1 is the section one side metallograph of sample 3 after the abrasion of grinding wheel test on soft steel-nickel/chromium.
Fig. 2 is the section opposite side SEM figure of sample 3 after the abrasion of grinding wheel test on soft steel-nickel/chromium.In Fig. 2, the part that arrow is represented is the interface.
Fig. 3 is 700 ℃ of thermal treatment XRD results.In Fig. 3, X-coordinate is diffraction angle 2Theta/Degree, and ordinate zou is diffraction relative intensity Intensity, and curve heat treatment time from top to bottom is 4,3,2,1h, diffraction peak be respectively α mutually with γ mutually.
Fig. 4 is 950 ℃ of thermal treatment XRD results.In Fig. 4, X-coordinate is diffraction angle 2Theta/Degree, and ordinate zou is diffraction relative intensity Intensity, and curve heat treatment time from top to bottom is 4h, 3h, and 2h, 1h, diffraction peak is the γ phase.
Fig. 5 is sample 2 surperficial metallographs.In Fig. 5, scale is 50 μ m.
Fig. 6 is sample 5 surperficial metallographs.In Fig. 6, scale is 100 μ m.
Fig. 7 is the section SEM figure of soft steel-nickel/chromium sample 4 behind abrasion of grinding wheel test and polish etch.In Fig. 7, the scope that double-headed arrow is represented is a diffusion layer.
Fig. 8 is 950 ℃ of thermal treatment 0.5h diffusion layer composition one distance Curve figure.In Fig. 8, X-coordinate is distance D istance/ μ m, and ordinate zou is elemental composition Concentrantion.Article 3, curve corresponds respectively to Fe, Ni and Cr, and the left side of diffusion impervious layer (0.5 μ mCr) is the Ni coating, the right side is a soft steel.
Embodiment
Embodiment 1
1) with the oil removing of cold-rolled low carbon steel band: oil removing is the alkali cleaning oil removing, the alkali cleaning oil removing is that the cold-rolled low carbon steel band is placed the solution tank electrochemical deoiling, remove the grease of cold-rolled low carbon steel belt surface, the solution composition of electrochemical deoiling is sodium hydroxide 50g/L, yellow soda ash 35g/L, sodium phosphate 25g/L, 70 ℃ of solution temperatures, current density 4A/dm
2, degreasing time 5min.
2) the cold-rolled low carbon steel band after the oil removing is placed in the solution tank, electrodeposited chromium layers on the cold-rolled low carbon steel band after the oil removing, the gauge control of chromium layer is at 0.01～1 μ m: the solution composition of electrodeposited chromium layers is anhydrous chromic acid acid anhydride 750g/L, hydrochloric acid 30ml/L, cathode current density 15A/dm
2, 35 ℃ of bath temperatures, immersion plating time 30s.
3) mild-carbon steel strip after the chromium plating is placed in the solution tank, electroless nickel layer on the mild-carbon steel strip after the chromium plating, the gauge control of nickel dam is at 10～20 μ m: the solution composition of electroless nickel layer is nickel sulfamic acid 700g/L, nickelous chloride 6g/L, boric acid 35g/L, pH4,45 ℃ of bath temperatures, cathode current density 4A/dm
2, immersion plating time 10min.
4) mild-carbon steel strip behind the electroless nickel layer is placed in the solution tank, carry out Passivation Treatment: the solution composition of passivation is potassium bichromate 12g/L, sodium hydroxide 2.5g/L, yellow soda ash 1.5g/L, current density 1.3A/dm
2, pH8: insulation is to be incubated under 120 ℃ of vacuum conditions, in order to remove the hydrogen of the coating that is incorporated in electrolytic degreasing and continuous electro-deposition chromium/nickel coating process, prevents to occur hydrogen embrittlement or foaming in heat treatment process.
5) with the electrodeposited chromium after the Passivation Treatment/nickel dam steel band insulation, remove the hydrogen in the de-plating;
6) electrodeposited chromium after the dehydrogenation/nickel dam steel band diffusion annealing is handled, obtain corrosion-resistant nickel plating/chromium steel band, the vacuum tube furnace that adopts built-in quartz glass tube is handled in diffusion annealing, uses the poly-light material of aluminum oxide of vacuum forming low heat capacity to stop that hot-fluid impacts, the middle argon gas that feeds in the stove; Diffusion annealing is handled and is comprised thermal pretreatment, diffusion heat treatments and quenching heat treatment, the soaking time section that diffusion annealing is handled is divided into warm up time, diffusion time and quick cooling time, its diffusion temperature is to adopt 900～1300 ℃ of the recrystallization temperatures of chromium/nickel coating and iron matrix element formation single phase solid solution, make the dew iron rate of steel strip surface be not more than 1% for the suitable time of the control diffusion layer degree of depth diffusion time.Thermal pretreatment is that above-mentioned electronickelling/chromium layer steel band placed vacuum tube furnace, begins to heat up under argon shield atmosphere, and heat-up rate is 5～10 ℃/min, and temperature is risen to 900 ℃.Diffusion heat treatments is with the electronickelling/chromium layer steel band constant temperature thermal treatment 0.5～2h through thermal pretreatment, by the phase mutual diffusion of siderochrome nickel three constituent elements, forms the single-phase continuous solid solution of being predicted on the siderochrome nickel ternary phase diagrams.
1) with the oil removing of cold-rolled low carbon steel band: oil removing is an electrolytic degreasing, electrolytic degreasing is that the cold-rolled low carbon steel band is placed the solution tank electrochemical degreasing, further remove the grease of remained on surface, the solution composition of electrolytic degreasing is preferably sodium hydroxide 60g/L, yellow soda ash 40g/L, sodium phosphate 45g/L, water glass 4g/L, 65 ℃ of solution temperatures, current density 6A/dm
2, degreasing time 6min.
2) the cold-rolled low carbon steel band after the oil removing is placed in the solution tank, electrodeposited chromium layers on the cold-rolled low carbon steel band after the oil removing, the gauge control of chromium layer is at 0.01～1 μ m: the solution composition of electrodeposited chromium layers is anhydrous chromic acid acid anhydride 800g/L, hydrochloric acid 40ml/L, cathode current density 25A/dm
2, 45 ℃ of bath temperatures, immersion plating time 3min.
3) mild-carbon steel strip after the chromium plating is placed in the solution tank, electroless nickel layer on the mild-carbon steel strip after the chromium plating, the gauge control of nickel dam is at 10～20 μ m; The solution composition of electroless nickel layer is nickel sulfamic acid 800g/L, nickelous chloride 8g/L, boric acid 45g/L, pH4.5,55 ℃ of bath temperatures, cathode current density 7A/dm
2, immersion plating time 20min.
4) mild-carbon steel strip behind the electroless nickel layer is placed in the solution tank, carry out Passivation Treatment; The solution composition of passivation is potassium bichromate 17g/L, sodium hydroxide 3.5g/L, yellow soda ash 2.5g/L, current density 1.8A/dm
2, pH is 9.
5) with the electrodeposited chromium after the Passivation Treatment/nickel dam steel band insulation, remove the hydrogen in the de-plating; Insulation is to be incubated under 150 ℃ of vacuum conditions, in order to remove the hydrogen of the coating that is incorporated in electrolytic degreasing and continuous electro-deposition chromium/nickel coating process, prevents to occur hydrogen embrittlement or foaming in heat treatment process.
6) electrodeposited chromium after the dehydrogenation/nickel dam steel band diffusion annealing is handled, obtained corrosion-resistant nickel plating/chromium steel band.The vacuum tube furnace that can adopt built-in quartz glass tube is handled in diffusion annealing, uses the poly-light material of aluminum oxide of vacuum forming low heat capacity to stop that hot-fluid impacts, the middle argon gas that feeds in the stove; Diffusion annealing is handled and is comprised thermal pretreatment, diffusion heat treatments and quenching heat treatment, the soaking time section that diffusion annealing is handled is divided into warm up time, diffusion time and quick cooling time, its diffusion temperature is to adopt 900～1300 ℃ of the recrystallization temperatures of chromium/nickel coating and iron matrix element formation single phase solid solution, make the dew iron rate of steel strip surface be not more than 1% for the suitable time of the control diffusion layer degree of depth diffusion time.Thermal pretreatment is that above-mentioned electronickelling/chromium layer steel band placed vacuum tube furnace, begins to heat up under argon shield atmosphere, and heat-up rate is 5～10 ℃/min, and temperature is risen to 1300 ℃.Diffusion heat treatments is with the electronickelling/chromium layer steel band constant temperature thermal treatment 0.5～2h through thermal pretreatment, by the phase mutual diffusion of siderochrome nickel three constituent elements, forms the single-phase continuous solid solution of being predicted on the siderochrome nickel ternary phase diagrams.
Embodiment 3
Base band adopts common common Q 235 soft steel on the market, and thickness is 0.3mm, Chemical Composition: C 0.14～0.22%, and Mn0.30～0.65%, Si 0.3%, and S 0.050%, and P 0.045%.
1) with the oil removing of cold-rolled low carbon steel band; Oil removing is alkali cleaning and electrolytic degreasing, and the alkali cleaning oil removing is that the cold-rolled low carbon steel band is placed solution tank, removes the grease of cold-rolled low carbon steel belt surface, the solution composition of electrochemical deoiling is sodium hydroxide 60g/L, yellow soda ash 40g/L, sodium phosphate 30g/L, 75 ℃ of solution temperatures, current density 5A/dm
2, degreasing time 5min.Electrolytic degreasing is that the cold-rolled low carbon steel band is placed the solution tank electrochemical degreasing, further removes the grease of remained on surface, and the solution composition of electrolytic degreasing is sodium hydroxide 50g/L, yellow soda ash 40g/L, sodium phosphate 40g/L, water glass 4g/L, 60 ℃ of solution temperatures, current density 6A/dm
2, degreasing time 6min.
2) the cold-rolled low carbon steel band after the oil removing is placed in the solution tank, electrodeposited chromium layers on the cold-rolled low carbon steel band after the oil removing, the gauge control of chromium layer is at 0.01～1 μ m; The solution composition of electrodeposited chromium layers is anhydrous chromic acid acid anhydride 800g/L, hydrochloric acid 36ml/L, cathode current density 20A/dm
2, 40 ℃ of bath temperatures, immersion plating time 30s.
3) mild-carbon steel strip after the chromium plating is placed in the solution tank, electroless nickel layer on the mild-carbon steel strip after the chromium plating, the gauge control of nickel dam is at 10～20 μ m; The solution composition of electroless nickel layer is nickel sulfamic acid 750g/L, nickelous chloride 7g/L, boric acid 40g/L, pH4.5,50 ℃ of bath temperatures, cathode current density 5A/dm
2, immersion plating time 10min.
4) mild-carbon steel strip behind the electroless nickel layer is placed in the solution tank, carry out Passivation Treatment; The solution composition of passivation is potassium bichromate 15g/L, sodium hydroxide 3g/L, yellow soda ash 2g/L, current density 1.5A/dm
2, pH8.8.
5) with the electrodeposited chromium after the Passivation Treatment/nickel dam steel band insulation, remove the hydrogen in the de-plating; Insulation is to be incubated 24h under 120 ℃ of vacuum conditions, in order to remove the hydrogen of the coating that is incorporated in electrolytic degreasing and continuous electro-deposition chromium/nickel coating process, prevents to occur hydrogen embrittlement or foaming in heat treatment process.
6) electrodeposited chromium after the dehydrogenation/nickel dam steel band diffusion annealing is handled, got corrosion-resistant nickel plating/chromium steel band.The vacuum tube furnace that adopts built-in quartz glass tube is handled in diffusion annealing, uses the poly-light material of aluminum oxide of vacuum forming low heat capacity to stop that hot-fluid impacts, the middle argon gas that feeds in the stove; Diffusion annealing is handled and is comprised thermal pretreatment, diffusion heat treatments and quenching heat treatment, the soaking time section that diffusion annealing is handled is divided into warm up time, diffusion time and quick cooling time, its diffusion temperature is to adopt 900～1300 ℃ of the recrystallization temperatures of chromium/nickel coating and iron matrix element formation single phase solid solution, make the dew iron rate of steel strip surface be not more than 1% for the suitable time of the control diffusion layer degree of depth diffusion time.Thermal pretreatment is that above-mentioned electronickelling/chromium layer steel band placed vacuum tube furnace, begins to heat up under argon shield atmosphere, and heat-up rate is 5～10 ℃/min, and temperature is risen to 700 ℃ and 950 ℃.Diffusion heat treatments is with the electronickelling/chromium layer steel band constant temperature thermal treatment 0.5～2h through thermal pretreatment, by the phase mutual diffusion of siderochrome nickel three constituent elements, forms the single-phase continuous solid solution of being predicted on the siderochrome nickel ternary phase diagrams.Quenching heat treatment is that the electronickelling after diffusion heat treatments/chromium layer steel band cooled off fast by feeding liquid nitrogen, to keep the diffusion heat treatments single-phase continuous solid solution structure of nickel chromium triangle coating/substrate afterwards.
After obtaining corrosion-resistant nickel plating/chromium steel band, preferably carry out finishing and handle, can adopt 2 roller finishing mills, the nickel plating/chromium layer steel band after handling through diffusion annealing carried out the cold rolling required thickness that is processed into, effectively control its cold rolling reduction.
In order to illustrate that the different heat treatment processing condition are to Interface composition, boundary strength and thickness of diffusion layer influence, vacuum tube furnace in argon shield atmosphere, adopt respectively temperature be 700 ℃ with 950 ℃ of thermal treatments of sample being carried out the identical time, its interface performance adopts emery wheel rub(bing)test method, by Fig. 1 and Fig. 2 as can be seen, the coating interface binding power that 700 ℃ of thermal treatment obtains is poor, obvious obscission appears through emery wheel friction back, carry out morphology analysis by scanning electron microscope and find that there is sharp interface in the coating section; Drawn by Fig. 2 and Fig. 3: nickel chromium triangle/base band combination that 700 ℃ of thermal treatment obtains is two phase structure at least, and nickel chromium triangle/substrate joint body that 950 ℃ of thermal treatment obtains is a phase structure.Drawn by Fig. 4 and Fig. 5: do not have considerable change before 700 ℃ of thermal treatments obtain coatingsurface crystal grain and handle, hole is many, and is uneven, and is inhomogeneous; It is thick that 950 ℃ of thermal treatment obtains coatingsurface crystal grain, and smooth densification after the coating regrowth is with the naked eye seen to present the silvery white light.Find out by Fig. 7 and Fig. 8: the nickel chromium triangle coating of 10 micron thickness through 950 ℃ of thermal treatment 0.5h after, the coating interface binding power is very strong, any peeling or obscission do not appear, section is through polish etch laggard line scanning Electronic Speculum pattern and energy spectrum analysis, surface as a result: coating and substrate are combined closely, formed the single phase solid solution of infinitely dissolving each other, diffuseing to form chromium content is the Fe-Ni-Cr single phase solid solution diffusion layer of 20%-30%.
According to GB/TT5935-97, ferroxyl test is the result show: 950 ℃ of thermal treatments obtain the thick smooth densification of coatingsurface crystal grain, and porosity is less than hole/cm
2According to GB/T10125-97, the nickel chromium triangle coat-thickness is that 10 microns sample 4 solidity to corrosions reach 8 grades.According to GB/T228-2002, the metallic substance tensile test at room temperature is the surface as a result: sample 4 tensile strength reach 280-450Mpa, and elongation reaches more than 30%.
The present invention is by adopting nickel plating/chromium thick coating, by adding thin chromium layer, cool off fast after the diffusion heat treatments and obtain the high interfacial strength single phase solid solution, form the Fe-Cr-Ni diffusion layer in the diffusion layer, make the nickel/chromium steel band that covers of the present invention have good solidity to corrosion, bonding force and mechanical property, can be used as the multi-usage corrosion protection coating, overcome the deficiencies in the prior art, for example the sheating material of heavy-duty battery has broad application prospects.
Table 1
| Sample (10mm nickel/0.5 μ m chromium) | Thermal treatment | The Fe-Ni-Cr diffusion thickness | Reveal the iron rate | Porosity | Electroplate bonding force | Unit elongation | Tensile strength | |
| Temperature | Time (hour) | (micron) | (％) | (individual/cm2) | (emery wheel test) | (％) | (N/rmm2) | |
| 1 | 700 | 0.5 | 4.5 | 1 | 1.5 | Difference | 27 | 340 |
| 2 | 700 | 1 | 6.3 | 4.5 | 1.6 | Difference | 31 | 367 |
| 3 | 700 | 2 | 8.2 | 9.8 | 3.6 | Difference | 24 | 386 |
| 4 | 950 | 0.5 | 9.5 | 1.5 | 0.5 | Excellent | 37 | 443 |
| 5 | 950 | 1 | 13.5 | 6.8 | 0.3 | Excellent | 34 | 462 |
| 6 | 950 | 2 | 18.1 | 11.5 | 0.4 | Excellent | 36 | 452 |
Claims (10)
1. the preparation method of corrosion-resistant nickel plating/chromium steel band is characterized in that may further comprise the steps:
1) with the oil removing of cold-rolled low carbon steel band;
2) the cold-rolled low carbon steel band after the oil removing is placed in the solution tank, electrodeposited chromium layers on the cold-rolled low carbon steel band after the oil removing, the gauge control of chromium layer is at 0.01～1 μ m;
3) mild-carbon steel strip after the chromium plating is placed in the solution tank, electroless nickel layer on the mild-carbon steel strip after the chromium plating, the gauge control of nickel dam is at 10～20 μ m;
4) mild-carbon steel strip behind the electroless nickel layer is placed in the solution tank, carry out Passivation Treatment;
5) with the electrodeposited chromium after the Passivation Treatment/nickel dam steel band insulation, remove the hydrogen in the de-plating;
6) electrodeposited chromium after the dehydrogenation/nickel dam steel band diffusion annealing is handled, obtained corrosion-resistant nickel plating/chromium steel band.
2. the preparation method of a kind of corrosion-resistant nickel plating as claimed in claim 1/chromium steel band, it is characterized in that described oil removing is that the alkali cleaning oil removing is or/and electrolytic degreasing, the alkali cleaning oil removing is that the cold-rolled low carbon steel band is placed the solution tank electrochemical deoiling, remove the grease of cold-rolled low carbon steel belt surface, the solution composition of electrochemical deoiling is sodium hydroxide 50～60g/L, yellow soda ash 35～40g/L, sodium phosphate 25～30g/L, 70～80 ℃ of solution temperatures, current density 4～7A/dm
2, degreasing time 5～10min; Electrolytic degreasing is that the cold-rolled low carbon steel band is placed the solution tank electrochemical degreasing, the solution composition of electrolytic degreasing is sodium hydroxide 50～60g/L, yellow soda ash 35～40g/L, sodium phosphate 40～45g/L, water glass 3～4g/L, 55～65 ℃ of solution temperatures, current density 4～6A/dm
2, degreasing time 3～6min.
3. the preparation method of a kind of corrosion-resistant nickel plating as claimed in claim 1/chromium steel band, the solution composition that it is characterized in that electrodeposited chromium layers is anhydrous chromic acid acid anhydride 750～800g/L, hydrochloric acid 30～40ml/L, cathode current density 15～25A/dm
2, 35～45 ℃ of bath temperatures, immersion plating time 30s～3min.
4. the preparation method of a kind of corrosion-resistant nickel plating as claimed in claim 1/chromium steel band, the solution composition that it is characterized in that electroless nickel layer is nickel sulfamic acid 700～800g/L, nickelous chloride 6～8g/L, boric acid 35～45g/L, pH4～6,45～55 ℃ of bath temperatures, cathode current density 4～7A/dm
2, immersion plating time 10～20min.
5. the preparation method of a kind of corrosion-resistant nickel plating as claimed in claim 1/chromium steel band, the solution composition that it is characterized in that passivation is potassium bichromate 12～17g/L, sodium hydroxide 2.5～3.5g/L, yellow soda ash 1.5～2.5g/L, current density 1.3～1.8A/dm
2, pH8～9.
6. the preparation method of a kind of corrosion-resistant nickel plating as claimed in claim 1/chromium steel band is characterized in that insulation is to be incubated under 120～150 ℃ of vacuum conditions.
7. the preparation method of a kind of corrosion-resistant nickel plating as claimed in claim 1/chromium steel band, it is characterized in that the diffusion annealing processing comprises thermal pretreatment, diffusion heat treatments and quenching heat treatment, the soaking time section that diffusion annealing is handled is divided into warm up time, diffusion time and quick cooling time, its diffusion temperature is to adopt 900～1300 ℃ of the recrystallization temperatures of chromium/nickel coating and iron matrix element formation single phase solid solution, make the dew iron rate of steel strip surface be not more than 1% for the suitable time of the control diffusion layer degree of depth diffusion time.
8. the preparation method of a kind of corrosion-resistant nickel plating as claimed in claim 7/chromium steel band; it is characterized in that described thermal pretreatment is that electronickelling/chromium layer steel band placed vacuum tube furnace; under argon shield atmosphere, begin to heat up; heat-up rate is 5～10 ℃/min, and temperature is risen to 900～1300 ℃.
9. the preparation method of a kind of corrosion-resistant nickel plating as claimed in claim 7/chromium steel band, it is characterized in that described diffusion heat treatments is with the electronickelling/chromium layer steel band constant temperature thermal treatment 0.5～2h through thermal pretreatment, by the phase mutual diffusion of siderochrome nickel three constituent elements, form the single-phase continuous solid solution of being predicted on the siderochrome nickel ternary phase diagrams.
10. the preparation method of a kind of corrosion-resistant nickel plating as claimed in claim 7/chromium steel band, it is characterized in that described quenching heat treatment is that the electronickelling after diffusion heat treatments/chromium layer steel band cooled off fast by feeding liquid nitrogen, to keep the diffusion heat treatments single-phase continuous solid solution structure of nickel chromium triangle coating/substrate afterwards.
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| CNA2008100704447A CN101215708A (en) | 2008-01-08 | 2008-01-08 | Method for preparing corrosion resistant nickel/chromium plating steel belt |
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|---|---|---|---|
| CNA2008100704447A CN101215708A (en) | 2008-01-08 | 2008-01-08 | Method for preparing corrosion resistant nickel/chromium plating steel belt |
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