CN103014612B - Method for performing high-speed aluminizing on slurry without protective atmosphere or protective layer under atmospheric conditions - Google Patents
Method for performing high-speed aluminizing on slurry without protective atmosphere or protective layer under atmospheric conditions Download PDFInfo
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- CN103014612B CN103014612B CN201210475696.4A CN201210475696A CN103014612B CN 103014612 B CN103014612 B CN 103014612B CN 201210475696 A CN201210475696 A CN 201210475696A CN 103014612 B CN103014612 B CN 103014612B
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Abstract
The invention discloses a method for performing high-speed aluminizing on slurry without protective atmosphere or a protective layer under atmospheric conditions. A workpiece surface for precipitating aluminized slurry does not need the protective atmosphere or the protective layer and is directly heated so as to form an aluminium-rich layer with a certain thickness on a workpiece surface layer. The technology is carried out according to the following steps: removing surface oil, derusting by sandblast, performing surface cleaning, precipitating aluminized slurry, drying, heating and performing aftertreatment; and precipitating the aluminized slurry on the workpiece surface through the technologies of spraying, performing brush coating, performing dip coating and the like. The induction heating frequency is between 50Hz-1MHz; and the current density is higher than 5A/cm<2>, the frequency is 0-1MHz, the heating temperature is higher than 300 DEG C, the heating time is longer than 10 seconds, and the heating rate is higher than 2 DEG C/s. The method has the beneficial effects that the problems of low efficiency and high cost which are caused by the protective atmosphere or the protective layer which is required by a current slurry aluminizing technology are eliminated, and the problems of complicated hardware aluminizing processes, high technological difficulty and especially difficult realization in ultra long pipeline inner walls are solved.
Description
Technical field
The present invention relates to technical field of surface coating, particularly the slip high speed aluminizing method of unprotect atmosphere or protective layer under a kind of atmospheric condition.
Background technology
For improving the efficiency of efficiency of energy utilization particularly thermal power generation, super (super-) critical generating set in a large number should in fuel-burning power plant, and in boiler tubing, high-temperature high-pressure steam etching problem is more and more severeer.Pipe material is mostly the high temperature steel of the various trade mark, due to usually containing more alloying element chromium, is oxidized and can forms chromic oxide protective membrane in air.But, in high-temperature water vapor, alloy surface but easily forms the volatile products such as the oxyhydroxide containing chromium [see document: M.P.Brady et al., The development of alumina-forming austenitic stainlesssteels for high-temperature structural use, JOM,, and oxide film is easy to peel off 60,12 (2008)].Peeling off of oxide skin not only makes trommel, also can pile up in pipeline and block vapour passage, causes overvoltage and booster, can cause the erosion corrosion of turbine blade simultaneously, greatly reduce the operation life of equipment.Researchist finds the stability of aluminum oxide in water vapor far above chromic oxide [see document: P.Steinmetz et al., Volatility of CommonProtective Oxides in High-Temperature Water Vapor:CurrentUnderstanding and Unanswered Questions, Mat.Sci.Forum, 461 – 464, 765 (2004)], therefore, people exploring always be adapted to Boiler Steam environment and the alloy with aluminum oxide Forming ability [see document: Y.Yamamoto et al., Creep-Resistant, Al
2o
3-Forming Austenitic Stainless Steels, Science, 316,433 (2007)] or surface-coating technology.
Because austenitic steel has the mechanical behavior under high temperature more excellent than ferritic steel, thus the latter is being replaced, particularly in high pressure steam section by the former gradually.Developing the material with aluminum oxide Forming ability will to retain premised on austenite phase.And aluminium is strong ferrite former, the aluminium of content ~ about 4wt% just may cause the disappearance of austenite phase.And will reach there is aluminum oxide Forming ability, the aluminium in alloy will reach finite concentration.Thus in alloy development, first this contradiction will be dissolved, relatively successfully report from U.S.'s Oak Ridge National Laboratory [see document: M.P.Brady et al., Composition, Microstructure, and WaterVapor Effects on Internal/External Oxidation of Alumina-FormingAustenitic Stainless Steels, Oxid.Met., 72,311 (2009)].They add a large amount of nickel and carry out stable austenite phase in developed alloy, find that the aluminium of 2wt% just can make this alloy form continuous aluminium oxide film in 800 ° of C air.Under moisture vapor condition, just there is significantly local tuberculation corrosion in 800 ° of C cyclic oxidation 1600h alloy surfaces, is much better than common high temperature steel.But for the requirement of tens thousand of hours life, this alloy is still difficult to meet the demands.In surface-coating technology, it is preferred that both aluminising.After investigator carries out traditional pack cementation aluminizing process to seamless steel tube for boiler material, find that the anti-steam oxidation ability of alloy improves greatly, oxidation 32000h does not find obviously to peel off with local oxidative phenomena [see document: A.Ag ü ero et al., Long exposure steam oxidation testing and mechanical properties ofslurry aluminide coatings for steam turbine components, Surf.Coat.Technol., 200,1219 (2005)].This is because alloy surface defines intermetallic Fe-Al compound phase, has aluminum oxide Forming ability, and thus anti-steam oxidation ability is excellent.Tradition embedding alumetizing process needs high temperature (>800 ° of C) long-time (a few hours) heating, and this can cause the problems such as the grain growth of matrix alloy and reduce base material mechanical property.In addition, Fe2Al5 or the FeAl intermetallic compounds layer generated is more crisp, and often containing the penetrating crack of some amount in coating, this phenomenon also has report in most literature, thus there is larger potential safety hazard in process under arms.Coating cracking and reason thereof are that the thermal expansivity of FeAl intermetallic compound is much higher than matrix (FeAl: ~ 20 × 10
-6/ ° C, stainless steel: <18 × 10
-6/ ° C) [see document: high petrel etc., FeAl intermetallic compound present Research, material Leader, 22,68 (2008)], cause there is larger tension stress in coating, what this factor caused should be more difficult elimination, and thus this cracking of coating is also difficult to overcome.According to reported in literature, after high temperature steel aluminising pack cementation aluminizing, although anti-steam oxidation ability is largely increased, but under the cyclic oxidation condition colded and heat succeed each other, it is serious [see document: A.Ag ü ero et al. that penetrating crack in coating causes breakdown of coating, matrix to be oxidized, Cyclic oxidation and mechanical behaviour ofslurry aluminide coatings for steam turbine components, Surf.Coat.Technol., 201,6253 (2007)].
Continue to bring out out the aluminizing technology that some are novel in recent years, comprise and utilize nanotechnology with the problem solving matrix grain and grow up and adopt electric current to help the method etc. of oozing.Research shows to utilize making Nano surface technology effectively can improve the spread coefficient of element, low temperature can be realized and ooze some elements, as nitriding temperature after shot blasting on surface nanometer can be down to 300 ° of C [see document: W.P.Tong et al. by 500 ° of more than C, Nitriding Iron at Lower Temperatures, Science, 299,686 (2003)].Can predict, adopt this technique aluminising, be expected to the problem eliminating matrix alloy grain growth.But according to pack cementation aluminizing technique, this aluminized coating will still be intermetallic compound, still there is serious brittleness problems.In addition because Heating temperature is lower, obtain certain thickness infiltration layer, its soaking time must reach several hours, and thus efficiency is lower.In addition, for the boiler tubing that internal diameter is less, will do the process of shot-peening nanometer to its inwall, be also technically a kind of challenge.Electric current helps the method for oozing then greatly can improve rate of diffusion, it is reported, apply direct current to sample in pack cementation process, alloying layer thickness does not add more than galvanic ten times [see document: straight China etc., DC electric field is on the impact of powder method aluminising, material heat treatment journal, 29,154 (2008)], the infiltration layer of time acquisition same thickness that thus can be shorter, matrix grain is grown up and can be inhibited, and production efficiency is also higher.
But at present the technical study of oozing is helped to electric current, one be this in conjunction with pack cementation aluminizing technique [see document: Z.Zhou et al., A novel powder aluminizing technologyassisted by direct current field at low temperatures, Surf.Coat.Technol., 203,23 (2008); Recklessly wait quietly, the method for accelerating solid power calorizing by DC electric field, the patent No. 200810018925 (2008); Ding Zhimin etc. adopt Electricity Contact Heating method to obtain the method for aluminized coating at steel pipe internal-surface, China Patent No. 200410054890 (2007)].Although infiltration layer growth velocity obtains and significantly promotes, but electric current helps the pack cementation aluminizing oozed to there is the problems such as infiltration layer is crisp equally [see document: Wei Xingzhao etc., the direct electro heating Fast Aluminizing research of steel, metal heat treatmet, (7) 19 (1995)].Another kind is [see document: Ding Qingru in conjunction with thermospray or Paste aluminising technique, ultralong steel tube thermospray induction alumetizing process, chemical industry corrosion and protection, (4) 5 (1997)], this method not only can high speed aluminising, the iron-based solid solution layer of rich aluminium can also be obtained, thus eliminate pack cementation aluminizing formation brittlement phase and the hot infiltration layer problem of Cracking mating imbalance and cause.But the electric current of report helps bleed slurry alumetizing process that inert atmosphere, vacuum or anti oxidation layer need be used to protect the slip of workpiece surface deposition not oxidized [see document: appoint talented; the main characteristic research of slip induction alumetizing process and infiltration layer; oil Refining Technologies and engineering; 33; 33 (2003)]; this reduces production efficiency, add cost.
Summary of the invention
The object of the invention is to need protective atmosphere or protective layer and the problem causing poor efficiency high cost to solve current Paste aluminising technique; and band large-scale metal component aluminising complex procedures; technology difficulty is large; particularly be difficult to the problem realized in inner wall of super-long pipeline, spy provides the slip high speed aluminizing method of unprotect atmosphere or protective layer under a kind of atmospheric condition.
The invention provides the slip high speed aluminizing method of unprotect atmosphere or protective layer under a kind of atmospheric condition, it is characterized in that: the workpiece surface of deposition aluminising slip, without the need to protective atmosphere and protective layer, directly to its heating, thus obtain certain thickness rich aluminium lamination at workpiece surface; .
Technique 1. surface degreasing, 2. derusting by sandblast, 3. clean surface as follows, 4. deposits aluminising slip, 5. dries, 6. heat, 7. aftertreatment;
Aluminising slip passes through the process deposits such as spraying, brushing and dipping in workpiece surface, deposit thickness 0.01-2mm;
Type of heating used is
induction heating,
workpiece direct-electrifying heats,
coordinate external heat source heating, wherein type of heating must contain
one of them,
for optional type of heating.
Induction heating frequency is 50Hz-1MHz; Direct-electrifying heating can be direct current, pulse, interchange or its combination, current density >5A/cm
2, frequency 0-1MHz, Heating temperature >300 ° C, time >10s, heating rate >2 ° C/s.
The present invention helps on the basis of alumetizing process at electric current, uses novel aluminising slip to coordinate suitable type of heating, achieves the high speed aluminising without the need to protective atmosphere or protective layer under atmospheric condition.Present method technique is simple, efficiency is high, cost is low, can be used for the alitizing of various hot metal component particularly large-scale component, and for the preparation of the anti-steam oxidation coating of the larger large-sized boiler inner-walls of duct of difficulty, also scene local aluminising can be carried out to large-scale workpiece.
Advantage of the present invention:
The slip high speed aluminizing method of unprotect atmosphere or protective layer under the atmospheric condition that the present invention specifically proposes; eliminate current Paste aluminising technique and need protective atmosphere or protective layer and the problem causing poor efficiency high cost; band large-scale metal component aluminising complex procedures can be solved; technology difficulty is large, is particularly difficult to the problem realized in inner wall of super-long pipeline.Present method cost is lower simultaneously, and is suitable for large-scale production.
Accompanying drawing explanation
Below in conjunction with drawings and the embodiments, the present invention is further detailed explanation:
Fig. 1 is with the infiltration layer cross-sectional scans electron micrograph that aluminizing method of the present invention obtains on high temperature steel TP347H, induction heating ~ 900 ° C, 20min.
Embodiment
Embodiment 1
Present embodiments provide the slip high speed aluminizing method of unprotect atmosphere or protective layer under a kind of atmospheric condition.
With commercial heat resisting pipe TP347H(1Cr19Ni11Nb) for sample is by present method aluminising, specimen size: external diameter 58mm, wall thickness 5mm, length 40mm.Processing step is surface degreasing 1.: for the sample that greasy dirt is more, first carry out oil removal treatment, can adopt universal process method.2. derusting by sandblast: the less sample of greasy dirt also directly can carry out derusting by sandblast process.This sample without obvious greasy dirt, therefore directly carries out derusting by sandblast process, and sandblasting air pressure used is about 0.5MPa, and sand grains is 250 order glass microballons.After Surface Rust removing, the sand grains of remained on surface must be removed.3. clean surface: cleaning method can rinse with high pressure water or air.4. aluminising slip is deposited: slip adopts patent formulation [see document: Shen Mingli; Zhu Shenglong; Wang Fuhui; a kind of aqueous phosphate alkali aluminising silicon slip of environment-friendly chromium-free ion; Chinese Patent Application No. 2012103340010]; according to slip viscosity adjustment dipping number of times, make the slip thickness of deposition to 0.2mm.5. dry: in 50-80 ° of C air, stop >3min, stop >3min in 100-150 ° of C air and dry the slip deposited.6. heat: adopt
induction heating, frequency is 50kHz, and adjustment electric current makes sample reach 900 ° of C, insulation 20min, air cooling.7. aftertreatment: use the high pressure water flushing of 0.6MPa to wash surperficial remnant off.As shown in Figure 1, visible alloying layer thickness ~ 150 μm, energy spectrum analysis shows its main chemical to the stereoscan photograph of the aluminized coating cross section microstructure obtained thus: Al 8.03, Cr 17.62, Ni 8.91, Si 0.85, Mn 1.02, Fe surplus (wt%).This composition is similar to the FeCrAl electrical heating alloys composition of resistance to high temperature corrosion performance excellence, and the aluminium content in this infiltration layer is higher than the latter.
Embodiment 2
With industrial pure ni be sample by present method aluminising, specimen size: long 15mm, wide 10mm, thick 2mm.Processing step is surface degreasing 1.: adopt the cleaning of alcohol acetone.2. derusting by sandblast: sandblasting air pressure used is about 0.5MPa, sand grains is 250 order glass microballons.3. clean surface: cleaning method can rinse with high pressure water or air.4. aluminising slip is deposited: slip adopts patent formulation [see document: Shen Mingli; Zhu Shenglong; Wang Fuhui; a kind of aqueous phosphate alkali aluminising silicon slip of environment-friendly chromium-free ion; Chinese Patent Application No. 2012103340010]; according to slip viscosity adjustment dipping number of times, make the slip thickness of deposition to 1.5mm.5. dry: in 50-80 ° of C air, stop 5min, stop 5min in 100-150 ° of C air and dry the slip deposited.6. heat: adopt
induction heating, frequency is 200kHz, and adjustment electric current makes sample reach 800 ° of C, insulation 2min, air cooling.7. aftertreatment: use the high pressure water flushing of 0.6MPa to wash surperficial remnant off.Obtain the aluminized coating that can obtain thickness more than 10 μm thus thus.
Embodiment 3
With commercial 304 Stainless Steel Wires for sample is by present method aluminising, specimen size: diameter 0.5mm, length 100mm.Processing step is surface degreasing 1.: adopt the cleaning of acetone alcohol blend.2. derusting by sandblast: because surface is rustless, removes this step from.3. clean surface: this step is removed from equally.4. aluminising slip is deposited: slip adopts patent formulation [see document: Shen Mingli; Zhu Shenglong; Wang Fuhui; a kind of aqueous phosphate alkali aluminising silicon slip of environment-friendly chromium-free ion; Chinese Patent Application No. 2012103340010]; according to slip viscosity adjustment dipping number of times, make the slip thickness of deposition to 0.02mm.5. dry: in 50-80 ° of C air, stop 3min, stop 3min in 100-150 ° of C air and dry the slip deposited.6. heat: adopt
workpiece direct-electrifying heats, and frequency is 50Hz industrial-frequency alternating current, and adjustment electric current makes sample reach 500 ° of C, insulation 10min, air cooling.7. aftertreatment: use the high pressure water flushing of 0.6MPa to wash surperficial remnant off.The aluminized coating of thickness more than 5 μm can be obtained thus.
Below by reference to the accompanying drawings the specific embodiment of the present invention is described; but these explanations can not be understood to limit protection scope of the present invention; protection scope of the present invention is limited by the claims of enclosing, and any change on the claims in the present invention basis is all protection scope of the present invention.
Claims (2)
1. the slip high speed aluminizing method of unprotect atmosphere or protective layer under atmospheric condition, is characterized in that: the workpiece surface of deposition aluminising slip, without the need to protective atmosphere and protective layer, directly to its heating, thus obtains certain thickness rich aluminium lamination at workpiece surface;
Technique 1. surface degreasing, 2. derusting by sandblast, 3. clean surface as follows, 4. deposits aluminising slip, 5. dries, 6. heat, 7. aftertreatment;
Aluminising slip passes through spraying, brushing and dipping process deposits in workpiece surface, deposit thickness 0.01-2mm:
Described aluminising slip, without chromium ion, comprises liquid phase and solid phase powder two components; During use by liquid phase and solid phase powder in proportion 1ml:0.25 ~ 2g mix formation slip, require that this slip was deposited on workpiece surface in 10 hours; Liquid phase is colourless transparent liquid, pH value 5 ~ 8, and its composition comprises PO in addition to water
4 3-5 ~ 25mol/L, Mg
2+0.2 ~ 1mol/L, Li
+5 ~ 30mol/L; Add neutrality or weakly alkaline silicon sol in liquid phase, silicon sol add-on is 5% ~ 200% of stoste phase volume; Solid phase comprises aluminium powder, silica flour, aluminum silicon alloy powder or its combination, powder size scope 0.2 ~ 100 μm;
Type of heating used is
induction heating,
workpiece direct-electrifying heats, and wherein type of heating must contain
one of them.
2. according to the slip high speed aluminizing method of unprotect atmosphere or protective layer under atmospheric condition according to claim 1, it is characterized in that: induction heating frequency is 50Hz-1MHz; Direct-electrifying is heated to be direct current, pulse, interchange or its combination, current density >5A/cm
2, frequency 0-1MHz, Heating temperature >300 DEG C, time > 10s, heating rate > 2 DEG C/s.
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| CN103343516B (en) * | 2013-07-08 | 2016-08-10 | 湖北交投四优钢科技有限公司 | A kind of aluminising freeway guardrail and preparation method |
| CN105695930A (en) * | 2016-04-18 | 2016-06-22 | 华能国际电力股份有限公司 | Method for infiltrating aluminum-silicon coating on surface of boiler pipe with large length-diameter ratio |
| CN106893972B (en) * | 2017-03-15 | 2019-01-04 | 常熟理工学院 | A kind of method of induction heating neutral salt bath in surface of low-carbon steel aluminising |
| CN114473171A (en) * | 2021-11-29 | 2022-05-13 | 中国船舶重工集团公司第七二五研究所 | Preparation method of high-temperature-resistant and antioxidant layered composite material |
| CN114351082B (en) * | 2022-01-12 | 2024-01-30 | 彭州航大新材料有限公司 | Nickel-based superalloy local slurry aluminizing process and slurry penetrant |
| CN114657544B (en) * | 2022-03-24 | 2023-10-27 | 彭州航大新材料有限公司 | Cobalt aluminizing process and cobalt aluminizing layer for inner cavity surface of nickel-based superalloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031572A (en) * | 1987-04-14 | 1989-03-08 | 齐鲁石油化工公司胜利炼油厂 | Aluminizing method and equipment with the coating of protection slip and Frequency Induction Heating |
| CN1060116A (en) * | 1990-09-25 | 1992-04-08 | 山东省新材料研究所 | Self-protective paste for induction heating cementation |
| CN1587433A (en) * | 2004-07-30 | 2005-03-02 | 大连交通大学 | Method for obtaining calorization layer on steel pipe inner surface using elecric contact heating method |
-
2012
- 2012-11-21 CN CN201210475696.4A patent/CN103014612B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031572A (en) * | 1987-04-14 | 1989-03-08 | 齐鲁石油化工公司胜利炼油厂 | Aluminizing method and equipment with the coating of protection slip and Frequency Induction Heating |
| CN1060116A (en) * | 1990-09-25 | 1992-04-08 | 山东省新材料研究所 | Self-protective paste for induction heating cementation |
| CN1587433A (en) * | 2004-07-30 | 2005-03-02 | 大连交通大学 | Method for obtaining calorization layer on steel pipe inner surface using elecric contact heating method |
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