CN1226468C - Rare earth chromium composite electroplating layer and preparing method and use thereof - Google Patents
Rare earth chromium composite electroplating layer and preparing method and use thereof Download PDFInfo
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- CN1226468C CN1226468C CN 03135654 CN03135654A CN1226468C CN 1226468 C CN1226468 C CN 1226468C CN 03135654 CN03135654 CN 03135654 CN 03135654 A CN03135654 A CN 03135654A CN 1226468 C CN1226468 C CN 1226468C
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Abstract
The present invention relates to a rare earth chromium composite electroplating layer, a preparing method and use thereof, which belongs to the technical field of electroplating. The electroplating layer is composed of a mixed rare earth chromium base phase and a second phase of mixed rare earth sulfate and carbonate. An electroplating process is composed of an electroplating prior period, a middle period and a later period. The electroplating time of each period is 4 hours. Each period carries out the alternate operation of an inverse phase and a positive phase. The operating time of the positive phase in three periods is respectively 30 minutes, 40 minutes and 50 minutes; the operating time of the inverse phase of the electroplating prior period is 1 minute, and the operating time of the rest inverse phases is 3 minutes. The thickness of the rare earth chromium electroplating layer is from 0.3mm to 0.4mm; electroplating solution is 140 to 170 g/l of CrO3, 1.5 to 2.0 g/l of H2SO4, 2 to 2.5 g/l of a soluble rare earth additive with main mixed rare earth oxide, and 3 to 3.5 g/l of an insoluble mixed rare earth salt additive with main sulfate and carbonate, the rest is water; the temperature of the electroplating solution is from 47 DEG C to 54 DEG C; current density is from 25 to 30 A/dm<+2>. The electroplating layer is applied to an anti-abrasion coating of a hydraulic turbine and has the advantages of good anti-abrasion performance of an electroplating member, high hardness, etc.
Description
Technical field:
The present invention relates to a kind of preparation method of rare earth chromium composite galvanized coating, belong to the electroplating technology field.
Background technology:
Water turbine is harming the abundant development and use of hydropower resources because of combined action (the being called for short abrasion) early failure that is subjected to cavitation corrosion and sand erosion is an international difficult scientific problems.Present water turbine is many to be made by stainless steel, damage (different according to each power station water quality and operating mode more for a long time because of its erosion resistance is undesirable, portion water turbine flow passage part energy non-stop run 1-2, portion water turbine flow passage part only can non-stop run 3-6 month), need change flow passage part continually, cause the loss of hydropower resources and generator operation cost to increase.For overcoming this difficult problem, domestic and international research person has all carried out more tackling key problem research, for example Japanese publication use the plasma spray method, on the water turbine steel of base metal, produce (Cr
3C
2-Co) hard-surface coating, and done the anti-cavitation corrosion and the resisting silt abrasion test of coating
[1]Switzerland scholar Akarimi and CVerdon also made the abrasion test of (WC-Co) thermally sprayed coating in the silt medium in testing laboratory
[2,3], and point out that this type coating is suitable for water turbine and water pump.Because of above-mentioned two classes with the cobalt to be that the coating of base (Co accounts for 45-65%) is worth very expensive (coated powder 500-600 unit/kg), in the anti-erosion performance of China's this type coating of unmanned research and the application in water turbine, there is not domestic any power station to be ready to adopt the water turbine of this class band expensive coatings yet.But the report of more spraying NiCr powdered alloy as water turbine anti scuffing coating arranged in China
[4,5]The NiCr alloy coat can make the anti-erosion performance of water turbine increase, but the amplitude that improves is little, and because of not solving the thermal distortion problem behind the NiCr spray coating alloy, therefore, its anti scuffing coating as water turbine still is unwilling to adopt in most power stations.
Reference:
[1] pine forest one, gloomy Tian Yifu et al: " Japan Patent 3-146297 (1994)
[2]A.Karimi，Ch-Verden et al：“wear”186-187(1995)480-486
[3]C.Verden.A.Karimi et al：“Materials Science and Engineering”A 248(1998)11-24.
[4] Chen Xiaoping: " water conservancy and hydropower technology ", 1996, No.12,33-35
[5] Kang Jinxing, Zhao Wenzhen: " material protection " VOl.35 No.6 (2002) 9-11
[6] Chen Baohua: " electroplating and finish ", 1996 15 (4): 25-29
[7] Qian Daren: " material protection ", 1992 25 (7) 10-13
Summary of the invention:
But because the quality that the dissolved rare earth in the rare earth addition mainly works to accelerate the sedimentation velocity of chromium and improves coating.The rare earth ion of solubility will form [RE (OH) with the part chromium ion in the plating bath
3Cr (OH) CrO
4] complex compound
[6], this complex compound has the effect that improves quality of coating.In addition the rare earth ion of solubility also can with (SO in the plating bath
4)
-2Generate [REO (SO
4)
4(H
2O)
4]
+ 2Complex ion
[7], this kind complex ion has the effect of accelerating electrodeposition rate.The contriver interts anti-phase dissolution process in whole rare earth chromium electroplating process the anti-phase plating of formation cycle after a large amount of experiments.And the plastics acid proof pump placed in the plating tank, forming stronger electroplate liquid " rolls ", force insoluble rare-earth salts particle to be in suspended state, insoluble rare-earth salts particle is clamp-oned in the little hole of the coating that forms in the anti-phase process, formation is by rare earth chromium metal matrix and the mishmetal complex phase coating of dissolved salt second phase composite not, with the water turbine of this coating, performances such as its erosion resistance, hardness not only are better than the stainless steel water turbine, and are better than the conventional single-phase coating of rare earth chromium of electroplating.
Rare earth chromium composite galvanized coating of the present invention is by mishmetal chromium base and mishmetal vitriol and carbonate second phase composite.
The preparation method of rare earth chromium composite galvanized coating is made up of polishing, alkali cleaning, pickling, cycle anti-phase plating rare earth chromium, finishing procedure.Wherein, anti-phase plating rare earth chromium operation is specially the cycle:
This electroplating work procedure is by electroplating early stage, the mid-term of plating, electroplating three stages of later stage and constitute; Triphasic electroplating time is 4 hours, all carries out the alternate operation of anti-phase → positive for several times in each stage; Wherein, the positive operating time of electroplating early stage is 30 minutes, and electroplating the positive operating time in mid-term is 40 minutes, and the positive operating time of electroplating the later stage is 50 minutes, and the operated in anti-phase time, all the other operated in anti-phase times were 3 minutes except that being 1 minute first; After 12 hours plating, the thickness of rare earth chromium coating is 0.3-0.4mm;
The electroplate liquid component is: CrO
3(chromic anhydride): 140-170g/ liter, H
2SO
4: the 1.5-2.0g/ liter, the solvable rare earth addition that market is bought based on mixed rare-earth oxide: the 2-2.5g/ liter, the insoluble mixing rare-earth salts additive that market is bought based on vitriol and carbonate: the 3-3.5g/ liter, all the other are water;
In the electroplating work procedure operating process, bath temperature is: 47-54 ℃, current density is: 25-30 peace/dm
2Be provided with acidproof plastic pump in the coating bath, promote the tumbling motion of electroplate liquid by the rotation of acidproof plastic pump.
By the rare earth chromium composite galvanized coating of method for preparing, as the application of the anti scuffing coating of water turbine.
The microstructure and property of rare earth chromium coating:
Fig. 1 provided cycle anti-phase plating rare earth chromium on the 18-8 stainless steel after 12 hours the micro-enlarged photograph of the coating that obtains, thickness of coating reaches 0.315mm, the A among the figure, B, C three sections are respectively mother metal, electrolytic coating and atmospheric layer.Coating by rare earth chromium base mutually and embedding be distributed in basic particulate state rare-earth salts second phase composite in mutually.As can be seen from Figure 1, coating combines with base material firmly, and the microhardness pressure head of 500 gram loads is beaten on the bonding interface of coating and mother metal, finds the local performance of being out of shape with impression of peeling off, and this explanation coating combines very firm with base material.Once tried out with EP or XRD analysis means the second phase particle of the rare-earth salts in the coating was made the composition Analysis and Identification, but all do not obtain satisfied result, its reason is: mishmetal salt particle second accounts for about 1% of coating cumulative volume mutually, each particle is again the compound polymerization body of mishmetal (8 kinds of elements) in addition, specifically decompose each rare earth element, its content has been lower than the sensitivity (about 0.3%) of analytical instrument.Rare-earth salts second phase that in the rare earth chromium coating, forms, remove and have second reinforcement mutually, improve outside the effect of coating strength and hardness, more important role is to have improved the anti-cavitation corrosion of coating and the ability of resisting silt abrasion, and table 1 has provided cycle anti-phase plating rare earth chromium and the chromed hardened micro-hardness testing result of common electrical.
The microhardness of table 1 cycle anti-phase plating rare earth chromium (containing rare-earth salts second phase) and conventional durionise
| The coating kind | HV mean value | The HV fluctuation range |
| Durionise | 846 | 802-913 |
| Cycle anti-phase plating rare earth chromium | 1054 | 1012--1105 |
Hardness from table as seen, by the rare earth chromium coating that contains rare-earth salts second phase that anti-phase plating of cycle forms, the conventional durionise high approximately 200 of its hardness ratio is spent.
Make the blade (40 * 30 * 6mm) of analog Small turbine machine with the 18-8 stainless steel, part vanes is wherein crossed conventional durionise and cycle anti-phase plating rare earth chromium, partly vanes is crossed ion nitriding surface hardening processing in addition, various blades are installed in the rotating shaft of analog Small turbine machine, husky at water than being continuous operation after 300 hours in the medium of 6: 4 (weight), take off blade, on analytical balance, measure the loss of weight of each test piece, and calculating the unit surface relative weight loss of each blade, the gained result is as shown in Figure 2.From the abrasion test result of Fig. 2 as can be seen, the 18-8 stainless steel is through cycle anti-phase plating rare earth chromium, after formation contains the composite deposite of rare-earth salts second phase, its erosion resistance (inverse of relative weight loss) improves about 28 times than mother metal stainless steel, improves about 12 times than 18-8 stainless steel through 520 ° of ion nitriding coatings.Improve about 5.2 times than 18-8 stainless steel through conventional durionise coating.The 18-8 stainless steel is behind cycle anti-phase plating rare earth chromium, the reason that its erosion resistance significantly improves is that cycle anti-phase plating rare earth chromium all improves the hardness of material and erosion resistance significantly, and the 18-8 stainless steel is after ion nitriding, though its hardness increases considerably (reaching more than the HV1200), but because of its erosion resistance descends to some extent, therefore the amplitude that erosion resistance is improved is little.Stainless steel is behind cycle anti-phase plating rare earth chromium, and the performance of coating also obtains remarkable improvement, and surface smoothness reaches more than 9 grades, and to big tabular water turbine member, its thickness of coating is still even, and fringing effect also obtains obvious improvement.In addition, the electroplating current efficient of cycle anti-phase plating rare earth chromium is also brought up to more than 30%, far above the current efficiency (17% ±) of conventional durionise.
The present invention compared with prior art, have technology rationally, performances such as the erosion resistance of plating piece, hardness not only are better than the stainless steel water turbine, and are better than the conventional advantage such as the single-phase coating of rare earth chromium of electroplating.
Description of drawings:
Fig. 1 is for containing 150 times of amplification displaing micro pictures of the rare earth chromium coating of rare-earth salts second phase with anti-phase plating acquisition of cycle, A, B, C are respectively base material, coating and atmospheric layer among the figure.
Fig. 2 is four kinds of differing materials are made abrasion test on analog Small turbine machine relative weight loss result, and wherein 1 is the 18-8 stainless steel, 2 be the 18-8 steel through 520 ℃ of ion nitridings, 3 be the 18-8 steel through conventional durionise, 4 is that the 18-8 steel is through cycle anti-phase plating rare earth chromium.
Fig. 3 is through the water turbine wearing plate, facing plate of cycle anti-phase plating rare earth chromium (φ 2m) photo.
Fig. 4 is through the water turbine nozzle needle head of cycle anti-phase plating rare earth chromium and retaining ring (heavy 75kg) photo thereof.
Embodiment:
Embodiment 1: Yunnan Province is carried out the plating of rare earth chromium with nozzle needle head of the impulse turbine of gift river power plant and Yuanjiang River Talc plate power plant (heavy 65kg) and retaining ring (heavy 17kg).
At first prepare electroplate liquid, the electroplate liquid component is: CrO
3(chromic anhydride): 140g/ liter, H
2SO
4: the 1.5g/ liter, the solvable rare earth addition based on mixed rare-earth oxide that Inner Mongol institute buys: the 2g/ liter, the insoluble mixing rare-earth salts additive based on vitriol and carbonate that Inner Mongol institute buys: the 3g/ liter, all the other are water.
This electroplating technology is made up of polishing, alkali cleaning, pickling, cycle anti-phase plating rare earth chromium, finishing procedure.Wherein, polishing, alkali cleaning, pickling, finishing procedure all carry out according to a conventional method.Cycle anti-phase plating rare earth chromium operation is by electroplating early stage, the mid-term of plating, electroplating three stages of later stage and constitute; Triphasic electroplating time is 4 hours, all carries out the alternate operation of anti-phase → positive for several times in each stage.Be specially: the only one minute first time anti-phase (be that workpiece connects positive pole, lead electrode connects negative pole), it mainly acts on is the passivation layer dissolving that makes the stainless steel surface conduction bad, makes workpiece expose newborn activatory surface.In phase (workpiece connects negative pole, and lead anode connects positive pole), the quick electrodeposition of rare earth chromium on workpiece takes place mainly at first positive.In second and later reversed epoch (3min), except taking place to remove the effect of surface passivation layer, the main uneven dissolution that coating also takes place to have formed makes coating surface form some spot corrosion pit holes., except that the galvanic deposit that rare earth chromium takes place, insoluble mishmetal salt suspension particle also took place enter the process that has formed little hole in reversed epoch in the phase at second and later positive.Enter the rare-earth salts suspended particle in the little hole of coating, will by positive subsequently in the phase rare earth chromium metallographic phase of fast deposition cover, form reinforcement second phase in the coating.Through 12 hours electroplating process, plating piece reached the rare earth chromium coating of 0.3mm.Test shows, galvanized early stage, the electrodeposition rate of (preceding 4 hours) rare earth chromium was very fast, therefore the positive operating time in this stage is 30 minutes, in galvanized mid-term (the 5th to 8 hour), electrodeposition rate is slack-off to some extent, therefore the positive operating time should be 40 minutes, and is slower to (the 9th to 12 hour) electrodeposition rate of galvanized later stage, thus the positive operating time also corresponding prolonging by 50 minutes.In this electroplating work procedure operating process, bath temperature is: 47 ℃, current density is: 25 peace/dm
2Be provided with acidproof plastic pump in the coating bath, promote the tumbling motion of electroplate liquid by the motion of acidproof plastic pump.
Obtained mishmetal chromium base and mishmetal vitriol and carbonate second rare earth chromium composite galvanized coating mutually behind said process, the implementation result of this electrolytic coating sees Table 2.
Embodiment 2: to the plating of the wearing plate, facing plate (φ 2m) of hydroelectric power plant at the bottom of the Yuanjiang River river.
At first prepare electroplate liquid, the electroplate liquid component is: CrO
3(chromic anhydride): 158g/ liter, H
2SO
4: the 1.75g/ liter, the solvable rare earth addition based on mixed rare-earth oxide that Inner Mongol institute buys: the 2.25g/ liter, the insoluble mixing rare-earth salts additive based on vitriol and carbonate that Inner Mongol institute buys: the 3.25g/ liter, all the other are water.
Electroplating work procedure is substantially with embodiment 1, and difference is: bath temperature is 50 ℃, and current density is: 28 peace/dm
2The rare earth chromium coating of plating piece reaches 0.35mm.
Obtained mishmetal chromium base and mishmetal vitriol and carbonate second rare earth chromium composite galvanized coating mutually behind said process, the implementation result of this electrolytic coating sees Table 2.
Embodiment 3: the francis turbine runner to hydroelectric power plant, born dam, Qujing is electroplated.
At first prepare electroplate liquid, the electroplate liquid component is: CrO
3(chromic anhydride): 170g/ liter, H
2SO
4: the 2.0g/ liter, the solvable rare earth addition based on mixed rare-earth oxide that Inner Mongol institute buys: the 2.5g/ liter, the insoluble mixing rare-earth salts additive based on vitriol and carbonate that Inner Mongol institute buys: the 3.5g/ liter, all the other are water.
Electroplating work procedure is substantially with embodiment 1, and difference is: bath temperature is 54 ℃, and current density is: 30 peace/dm
2The rare earth chromium coating of plating piece reaches 0.4mm.
Obtained mishmetal chromium base and mishmetal vitriol and carbonate second rare earth chromium composite galvanized coating mutually behind said process, the implementation result of this electrolytic coating sees Table 2.
Table 2
| The power station title | Water mechanism part title and material | The workpiece life-span originally | The life-span of rare earth chromium plated item | Working life improves multiple |
| With gift river (320,000 kw) | 2Cr13 nozzle needle head and retaining ring | About 6 months | ＞30 months | ＞5 |
| Yuanjiang River Talc plate (1.6 ten thousand kw) | 2Cr13 nozzle needle head and retaining ring | About 4 months | ＞24 months | ＞6 |
| At the bottom of the Yuanjiang River river (1.2 ten thousand kw) | 18-8 steel wearing plate, facing plate | About 12 months | ＞36 months | ＞3 |
| Born dam, Qujing (1.2 ten thousand kw) | The 18-8 francis turbine runner | About 12 months | ＞36 months | ＞3 |
From the result of table 2 as seen, electroplating rare earth chromium uses on the water sealing piece of water turbine (as nozzle needle head and retaining ring thereof etc.), to have more outstanding effect, make non-stop run life-span of these members improve that (the minority member improves more than 8 times more than 5 times, syringe needle as Yuanjiang River Talc plate power plant), be applied to non-water sealing pieces such as wearing plate, facing plate, runner, also obtain effect preferably.
Claims (1)
1, a kind of by the preparation method of mishmetal chromium base with the rare earth chromium composite galvanized coating of mishmetal vitriol and carbonate second phase composite, form by polishing, alkali cleaning, pickling, plating, finishing procedure, it is characterized in that electroplating work procedure is a cycle anti-phase plating rare earth chromium operation; Cycle anti-phase plating rare earth chromium operation is specially:
A. this electroplating work procedure is by electroplating early stage, the mid-term of plating, electroplating three stages of later stage and constitute; Triphasic electroplating time is 4 hours, all carries out the alternate operation of for several times anti-phase and positive in each stage; Wherein, the positive operating time of electroplating early stage is 30 minutes, and electroplating the positive operating time in mid-term is 40 minutes, and the positive operating time of electroplating the later stage is 50 minutes, and the operated in anti-phase time, all the other operated in anti-phase times were 3 minutes except that being 1 minute first; After 12 hours plating, the thickness of rare earth chromium coating is 0.3-0.4mm;
B. the electroplate liquid component is: CrO
3: 140-170g/ liter, H
2SO
4: the 1.5-2.0g/ liter, based on the solvable rare earth addition of mixed rare-earth oxide: the 2-2.5g/ liter serves as main insoluble mixing rare-earth salts additive with vitriol and carbonate: the 3-3.5g/ liter, all the other are water;
C. in the electroplating work procedure operating process, bath temperature is: 47-54 ℃, current density is: 25-30 peace/dm
2Be provided with acidproof plastic pump in the coating bath, promote the tumbling motion of electroplate liquid by the rotation of acidproof plastic pump.
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| TWI441961B (en) * | 2012-10-11 | 2014-06-21 | Chang Yi Chen | Hydrophobic conduction appliance with coating chromium carbide ceramic electroplating layer and manufacturing method thereof |
| CN104264205B (en) * | 2014-09-22 | 2018-05-22 | 华东理工大学 | A kind of composite deposite for inhibiting tube coking and its preparation method and application |
| CN104818483A (en) * | 2015-04-13 | 2015-08-05 | 南京理工大学 | Medium carbon CrNiMo steel surface chromium-tantalum gradient coating and preparation method thereof |
| GB2539965A (en) * | 2015-07-03 | 2017-01-04 | Dublin Inst Of Tech | A surface treatment for enhanced resistance to corrosion and synergistic wear and corrosion (tribocorrosion) degradation |
| CN110029379A (en) * | 2019-05-05 | 2019-07-19 | 东莞市康圣精密合金材料有限公司 | Ultra-wide stainless steel materials nickel plating appearance optimization technique |
| CN109957822B (en) * | 2019-05-05 | 2021-06-29 | 东莞市康圣精密合金材料有限公司 | Copper alloy electroplating process |
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