CN102534709B - Method for generating nickel-ferroboron composition plating layer on surface of cold-roll steel sheet and thermal treatment - Google Patents

Method for generating nickel-ferroboron composition plating layer on surface of cold-roll steel sheet and thermal treatment Download PDF

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Publication number
CN102534709B
CN102534709B CN201210089904.7A CN201210089904A CN102534709B CN 102534709 B CN102534709 B CN 102534709B CN 201210089904 A CN201210089904 A CN 201210089904A CN 102534709 B CN102534709 B CN 102534709B
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ferro
cold
nickel
steel sheet
boron
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CN102534709A (en
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钟庆东
张磊
蒋继波
朱振宇
罗检
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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Abstract

The invention relates to a method for generating a nickel-ferroboron composition plating layer on the surface of a cold-roll steel sheet and thermal treatment, which belongs to the technical field of metal surface alloying and is characterized in that a plating liquid raw material comprises nickel sulfate (NiSO4), 6 hydrogen oxide (6H2O), nickel chloride (NiCl2), 6 hydrogen oxide (6H2O), boracic acid (H3BO3), cetyl trimethyl ammonium bromide, saccharin, ascorbic acid, sodium citrate and ferroboron powder. A treatment method mainly comprises first generating a nickel-ferroboron composition plating layer on the surface of the cold-roll steel sheet and then performing middle and low temperature thermal treatment in a gas protection furnace. A composite plating layer after treatment has the advantages of being strong in corrosion resistance, high in hardness and abrasion resistance, simple in preparation process and suitable for industrialized production and application.

Description

At surface of cold-rolled steel plate generating nickel-ferro-boron composite deposite heat-treating methods
Technical field
The present invention relates to one and prepare nickel-ferro-boron composite deposite in common surface of cold-rolled steel plate, and carry out the method for thermodiffusion intensive treatment, belong to Alloying on Metal Planes technical field.
Background technology
The method that tradition is prepared boron-containing alloy layer in surface of cold-rolled steel plate is mainly to utilize boriding process, has the molten-salt growth method of solid process and non-electrolysis-type.The medium that pack boriding uses has the filler of boron supplying agent, energizer and adjusting activity, holding workpieces etc., is mainly used in complex geometry, comprises the part with aperture, screw thread and blind hole, and its defect is that boron supplying agent is as B 4the expensive raw material price such as C, cost is very high.Salt bath boronising is mainly divided into following two kinds: (1), taking borax as base, adds the salt bath of 5%-15% chlorate; (2) add boron taking chlorate as base or add again the salt bath of SiC.Mainly for the treatment of the simple part of geometrical shape, its defect is, after the method boronising, need to do quench hot processing, to improve matrix strength, has a lot of salt crust on the workpiece after boronising, is difficult to remove clean.
Ferro-boron powder has very high hardness, in the solution such as acid, alkali, neutrality, all has good corrosion resistance nature.Ferro-boron is commonly used in STEELMAKING PRODUCTION, and as strong reductor and boron additive, its market value is very cheap.The maximum effect of boron in steel is only to need denier can significantly improve hardening capacity, thereby replaces a large amount of alloying elements, and it also can improve mechanical property, cold deformation performance, welding property and the high-temperature behavior etc. of steel in addition.According to GB5682-87 standard, China's ferro-boron is divided into low-carbon (LC) and middle carbon two classes, and totally 8 trades mark, are widely used in the different steel grades such as structural alloy steel, spring steel, Hi-Stren steel, high temperature steel, stainless steel.
Composite electrodeposition technique is on the basis of traditional electrical depositing process, add micron or nano level powder codeposition, thereby prepare there is high rigidity, the composite deposite of the excellent properties such as corrosion-resistant, self-lubricating, obtained application at numerous areas such as aviation, machinery, electronics.The powder that composite electrodeposition uses is very extensive, comprises SiC, Al 2o 3, TiO 2, BN, B 4c etc.
Inspection information is found, the composite electrodeposition of ferro-boron powder never people was studied, the present invention is exactly by composite electrodeposition technique, prepare a kind of nickel-ferro-boron composite deposite in surface of cold-rolled steel plate, then by middle low-temperature heat treatment, thereby obtain the composite deposite with strong corrosion resistant performance, high rigidity and wear resistance. ?
Summary of the invention
Object of the present invention, generates a kind of nickel-ferro-boron composite deposite with strong corrosion resistant performance, high rigidity and wear resistance in surface of cold-rolled steel plate exactly, and its technique is simple, is suitable for industrialized production.
One of the present invention is at surface of cold-rolled steel plate generating nickel-ferro-boron composite deposite heat-treating methods, and the technical scheme of employing, is characterized in that comprising following technological process and step:
A. electroplate liquid formulation: NiSO 4.6H 2o 200-250g/L; NiCl 2.6H 2o 35-45g/L; H 3bO 335-40g/L; Cetyl trimethylammonium bromide 0.1-0.3g/L; Asccharin 2-5g/L; Xitix 3-5g/L; Trisodium Citrate 40-50g/L; Ferro-boron powder 3-25g/L.Each raw material is analytical pure except ferro-boron powder above, and ferro-boron powder is the industrial raw material that market is bought, the about 0.5-2 μ of particle diameter m;
B. by above formula, first take NiSO 4.6H 2o, NiCl 2.6H 2o, cetyl trimethylammonium bromide, asccharin, xitix, add distilled water mixed dissolution in beaker; Take Trisodium Citrate, after dissolving completely, slowly add in the mixing solutions first preparing; Take again ferro-boron powder, H 3bO 3, successively add above solution, treat H 3bO 3after dissolving completely, the hydrochloric acid that dropping volume ratio is 1:1, adjusts pH value to 3.1-3.4;
C. by ultrasonic above plating solution dispersion 30min, re-use electric mixer and stir, rotating speed is set to 200-400 turn/min, by plating solution heating in water bath to 40-50 DEG C;
D. to cold-rolled steel sheet polish, activation treatment, concrete operations are: successively use No. 1, No. 4, No. 6 abrasive paper for metallograph to polish to mirror status the cold-rolled steel sheet of 10mm × 10mm × 1.5mm, then put into mass percent and be 3% sulphuric acid soln and activate 30 seconds, taking-up is selected 3-9A/dm after cleaning with distilled water 2current density put into immediately plating solution and electroplate; After electroplating 15-30min, take out, after cleaning with distilled water, naturally dry; Finally generating nickel-ferro-boron composite deposite on steel plate;
E. the cold-rolled steel sheet that is coated with above nickel-ferro-boron composite deposite is put into gas shield stove, heat-treat, shielding gas is hydrogen or argon gas, and thermal treatment temp is set to 400-800 DEG C.
The present invention prepares nickel-ferro-boron composite deposite and carries out heat treated technology, and forefathers had not studied use, and industrial ferro-boron powder is cheap, the composite deposite making, have strong corrosion resistant, very high hardness and wear resistance, its technique is simple, is easy to drop into suitability for industrialized production and uses.
Embodiment
Now specific embodiment of the invention is described in down:
embodiment 1
(1) electroplate liquid formulation: NiSO 4.6H 2o 220g/L; NiCl 2.6H 2o 40g/L; H 3bO 335g/L; Cetyl trimethylammonium bromide 0.2g/L; Asccharin 4g/L; Xitix 5g/L; Trisodium Citrate 45g/L; Ferro-boron powder 10g/L.Each raw material is analytical pure except ferro-boron powder above, and ferro-boron powder is the industrial raw material that market is bought, particle diameter approximately 1 μ m.
(2) by above formula, first take NiSO 4.6H 2o, NiCl 2.6H 2o, cetyl trimethylammonium bromide, asccharin, xitix, add distilled water mixed dissolution in beaker; Take Trisodium Citrate, after dissolving completely, slowly add in the mixing solutions first preparing; Take again ferro-boron powder, H 3bO 3, successively add above solution, treat H 3bO 3after dissolving completely, the hydrochloric acid that dropping volume ratio is 1:1, adjusts pH value to 3.2.
(3) by ultrasonic above plating solution dispersion 30min, re-use electric mixer and stir, rotating speed is set to 300 turn/min, by plating solution heating in water bath to 40 DEG C.
(4) to cold-rolled steel sheet polish, activation treatment, concrete operations are: successively use No. 1, No. 4, No. 6 abrasive paper for metallograph to polish to mirror status the cold-rolled steel sheet of 10mm × 10mm × 1.5mm, then put into mass percent and be 3% sulphuric acid soln and activate 30 seconds, taking-up is selected 5A/dm after cleaning with distilled water 2current density put into immediately plating solution and electroplate; After electroplating 20min, take out, after cleaning with distilled water, naturally dry.
(5) cold-rolled steel sheet that is coated with above nickel-ferro-boron composite deposite is put into gas shield stove, heat-treat, shielding gas is hydrogen, and thermal treatment temp is set to 600 DEG C.
Nickel-ferro-boron composite deposite after thermal treatment is carried out to electrochemistry, hardness, wearability test, and the results are shown in Table 1.
embodiment 2
(1) electroplate liquid formulation: NiSO 4.6H 2o 240g/L; NiCl 2.6H 2o 40g/L; H 3bO 335g/L; Cetyl trimethylammonium bromide 0.2g/L; Asccharin 4g/L; Xitix 5g/L; Trisodium Citrate 45g/L; Ferro-boron powder 15g/L.Each raw material is analytical pure except ferro-boron powder above, and ferro-boron powder is the industrial raw material that market is bought, particle diameter approximately 1 μ m.
(2) by above formula, first take NiSO 4.6H 2o, NiCl 2.6H 2o, cetyl trimethylammonium bromide, asccharin, xitix, add distilled water mixed dissolution in beaker; Take Trisodium Citrate, after dissolving completely, slowly add in the mixing solutions first preparing; Take again ferro-boron powder, H 3bO 3, successively add above solution, treat H 3bO 3after dissolving completely, the hydrochloric acid that dropping volume ratio is 1:1, adjusts pH value to 3.2.
(3) by ultrasonic above plating solution dispersion 30min, re-use electric mixer and stir, rotating speed is set to 300 turn/min, by plating solution heating in water bath to 40 DEG C.
(4) to cold-rolled steel sheet polish, activation treatment, concrete operations are: successively use No. 1, No. 4, No. 6 abrasive paper for metallograph to polish to mirror status the cold-rolled steel sheet of 10mm × 10mm × 1.5mm, then put into mass percent and be 3% sulphuric acid soln and activate 30 seconds, taking-up is selected 5A/dm after cleaning with distilled water 2current density put into immediately plating solution and electroplate; After electroplating 20min, take out, after cleaning with distilled water, naturally dry.
(5) cold-rolled steel sheet that is coated with above nickel-ferro-boron composite deposite is put into gas shield stove, heat-treat, shielding gas is hydrogen, and thermal treatment temp is set to 600 DEG C.
Nickel-ferro-boron composite deposite after thermal treatment is carried out to electrochemistry, hardness, wearability test, and the results are shown in Table 1.
embodiment 3
(1) electroplate liquid formulation: NiSO 4.6H 2o 240g/L; NiCl 2.6H 2o 40g/L; H 3bO 337g/L; Cetyl trimethylammonium bromide 0.2g/L; Asccharin 5g/L; Xitix 5g/L; Trisodium Citrate 45g/L; Ferro-boron powder 20g/L.Each raw material is analytical pure except ferro-boron powder above, and ferro-boron powder is the industrial raw material that market is bought, particle diameter approximately 1 μ m.
(2) by above formula, first take NiSO 4.6H 2o, NiCl 2.6H 2o, cetyl trimethylammonium bromide, asccharin, xitix, add distilled water mixed dissolution in beaker; Take Trisodium Citrate, after dissolving completely, slowly add in the mixing solutions first preparing; Take again ferro-boron powder, H 3bO 3, successively add above solution, treat H 3bO 3after dissolving completely, the hydrochloric acid that dropping volume ratio is 1:1, adjusts pH value to 3.2.
(3) by ultrasonic above plating solution dispersion 30min, re-use electric mixer and stir, rotating speed is set to 300 turn/min, by plating solution heating in water bath to 40 DEG C.
(4) to cold-rolled steel sheet polish, activation treatment, concrete operations are: successively use No. 1, No. 4, No. 6 abrasive paper for metallograph to polish to mirror status the cold-rolled steel sheet of 10mm × 10mm × 1.5mm, then put into mass percent and be 3% sulphuric acid soln and activate 30 seconds, taking-up is selected 5A/dm after cleaning with distilled water 2current density put into immediately plating solution and electroplate; After electroplating 20min, take out, after cleaning with distilled water, naturally dry.
(5) cold-rolled steel sheet that is coated with above nickel-ferro-boron composite deposite is put into gas shield stove, heat-treat, shielding gas is hydrogen, and thermal treatment temp is set to 600 DEG C.
Nickel-ferro-boron composite deposite after thermal treatment is carried out to electrochemistry, hardness, wearability test, and the results are shown in Table 1.
Nickel-ferro-boron composite deposite the performance test results after table 1 thermal treatment:
? Embodiment 1 Embodiment 2 Embodiment 3
Electrochemical impedance (/cm 2） 8700 10000 11500
Hardness (HV) 820 860 910
Rubbing factor 0.13 0.16 0.14
Examples prove, utilizes nickel-ferro-boron composite deposite prepared by the technology of the present invention to have very strong erosion resistance, and its hardness is very high, and wear resisting property excellence is suitable for suitability for industrialized production application.

Claims (1)

1. at surface of cold-rolled steel plate generating nickel-ferro-boron composite deposite a heat-treating methods, it is characterized in that comprising following technological process and step:
A. design electroplate liquid formulation: NiSO 4.6H 2o 200-250g/L; NiCl 2.6H 2o 35-45g/L; H 3bO 335-40g/L; Cetyl trimethylammonium bromide 0.1-0.3g/L; Asccharin 2-5g/L; Xitix 3-5g/L; Trisodium Citrate 40-50g/L; Ferro-boron powder 10-25g/L;
Each raw material is analytical pure except ferro-boron powder above, and ferro-boron powder is the industrial raw material that market is bought, particle diameter 0.5-2 μ m;
B. by above formula, first take NiSO 4.6H 2o, NiCl 2.6H 2o, cetyl trimethylammonium bromide, asccharin, xitix, add distilled water mixed dissolution in beaker; Take Trisodium Citrate, after dissolving completely, slowly add in the mixing solutions first preparing; Take again ferro-boron powder, H 3bO 3, successively add above solution, treat H 3bO 3after dissolving completely, the hydrochloric acid that dropping volume ratio is 1:1, adjusts pH value to 3.1-3.4;
C. by ultrasonic above plating solution dispersion 30min, re-use electric mixer and stir, rotating speed is set to 200-400 turn/min, by plating solution heating in water bath to 40-50 DEG C;
D. to cold-rolled steel sheet polish, activation treatment, concrete operations are: successively use No. 1, No. 4, No. 6 abrasive paper for metallograph to polish to mirror status the cold-rolled steel sheet of 10mm × 10mm × 1.5mm, then put into mass percent and be 3% sulphuric acid soln and activate 30 seconds, taking-up is selected 3-9A/dm after cleaning with distilled water 2current density put into immediately plating solution and electroplate; After electroplating 15-30min, take out, after cleaning with distilled water, naturally dry; Finally generating nickel-ferro-boron composite deposite on steel plate;
E. the cold-rolled steel sheet that is coated with above nickel-ferro-boron composite deposite is put into gas shield stove, heat-treat, shielding gas is hydrogen or argon gas, and thermal treatment temp is set to 400-800 DEG C.
CN201210089904.7A 2012-03-30 2012-03-30 Method for generating nickel-ferroboron composition plating layer on surface of cold-roll steel sheet and thermal treatment Expired - Fee Related CN102534709B (en)

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