CN1584101A - Preparation for iron-aluminium intermetallic compound coating on iron-steel surface and thermal treating method - Google Patents
Preparation for iron-aluminium intermetallic compound coating on iron-steel surface and thermal treating method Download PDFInfo
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- CN1584101A CN1584101A CN 200410020758 CN200410020758A CN1584101A CN 1584101 A CN1584101 A CN 1584101A CN 200410020758 CN200410020758 CN 200410020758 CN 200410020758 A CN200410020758 A CN 200410020758A CN 1584101 A CN1584101 A CN 1584101A
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Abstract
A iron-aluminum intermetallic compound coating with iron-steel surface preparation and thermal treating method are disclosed. It is prepared by: 1) clearing greasy dirt and rusting layer of work piece surface; 2) treating the cleared work piece by penetrating agent solution; 3) immersing work piece with fluxing agent solid slat adhering on surface into fused iron-aluminum alloy smelt to form iron-aluminum compound layer; 4) adjusting iron-aluminum compound layer composition and tissue structure by thermal dispersing treating and finishing base material final treating to obtain required intensity. The penetrating agent solution consists of NaCl 20-40wt%, KCl 20-40wt%, MnCl2 10-40wt%, CeCl3 10-20wt%. It achieves no impurity and long life.
Description
Technical field
The present invention relates to a kind of metal surface properties modification and handle, especially relate to method in structural part surface preparation intermetallic Fe-Al compound coatings such as carbon steel, steel alloy, stainless steels.
Background technology
Intermetallic Fe-Al compound (Iron Aluminide, be called for short iron aluminide) has excellent resistance to high temperature oxidation and heat and corrosion resistant performance, and density is low, specific tenacity is high, with low cost, therefore have a lot of performance advantages as high-temperature structural material.From the thirties in 20th century, it just receives the concern of material educational circles.Yet this material drops in batches and uses since over half a century, and its major obstacle has: the room temperature fragility that (1) is serious, and the unit elongation of the iron aluminide for preparing with usual way under the normal temperature is lower than 4%, and impact value is lower than 10J/cm
2(2) when temperature surpassed 600 ℃, the intensity and the creep-resistant property of compound suddenly descended, and had limited its range of application as high-temperature structural material.Enter after the eighties, owing to overcoming Ni
3Obtained important breakthrough on the room temperature fragility of Al, material educational circles in various countries' all steps up its investment in the research of iron aluminide, and makes significant progress, and finds can significantly improve its temperature-room type plasticity by adding the composite alloying of rare earth element and chromium element.By alloying and adding Al such as Mo, W, Nb
2O
3, TiC, TiB
2Deng the particle phase, can further improve its mechanical behavior under high temperature, make iron aluminide progressively enter the practicability stage.But because the fusing point of iron and aluminium differs about 800 ℃, density is also different, metal and crucible reaction are strong, this has just brought difficulty to melting, and hardness height, processing difficulties produces that this class part work efficiency is low, cost is high in batches, thus be difficult to make this class material as a whole material in industrial large scale application.
Yet, apply the iron aluminide coating on the iron surface, can avoid the shortcoming that iron aluminide melting and machine-shaping difficulty and hot strength descend, can give full play to excellent performance such as its high temperature resistance sulfuration, oxidation again, it is widely applied in industrial acquisition.Occurred several different methods at present,, cladding laser surfaces synthetic as pack aluminizing, hot-dip aluminizing using, spraying (slip) Diffusional aluminizing, self propagating high temperature etc. wherein have only pack aluminizing and hot-dip aluminizing using to realize industrial production.
The pack aluminizing method is that steel components is packed into after with pulverous aluminizing medium embedding in the watertight chest, be heated to 800～1050 ℃ of insulations 2～8 hours then, the aluminium atom is infiltrated the steel part surface, thereby form the iron aluminide coating of 0.1～0.3mm, come out of the stove at last with the case air cooling to room temperature.Its advantage is that equipment is simple, and is easy to operate, is particularly suitable for the processing of component of machine.Shortcoming is the cost height, and production efficiency is low, is not suitable as the method that structured material is produced in enormous quantities.
The hot-dip aluminizing using method is that iron and steel is immersed in the molten aluminium alloy, adheres to the composite bed that aluminium alloy layer is formed earlier on steel surface forms by iron aluminide layer and compound layer, again through DIFFUSION TREATMENT, all changes the surfaces of aluminum alloy layer into compound layer.Hot-dip aluminizing using method cost in the whole bag of tricks is minimum.Following 2 kinds of hot-dip aluminizing using technology of present domestic existence: method (abbreviation zinc chloride process) that zinc that provides in the promptly general thermal treatment handbook and hydrochloric acid reaction product are made penetration-assisting agent and the method (abbreviation deactivation method) of making penetration-assisting agent with the chromic anhydride aqueous solution.
Zinc chloride process is with adding the ZnCl that 4～5 kilograms of Zn reactions generate in concentration 33% hydrochloric acid per ton
2The aqueous solution of forming with residue hydrochloric acid is as plating assistant agent, steel part flooded in plating assistant agent 4～5 minutes, help the plating back dry under 200～250 ℃ of temperature, then immersed in 780～800 ℃ the aluminium liquid 10～30 minutes, DIFFUSION TREATMENT 4～6 hours under 850～1000 ℃ of temperature then, the air cooling of coming out of the stove below the last furnace cooling to 600 ℃ can obtain the thick coating of 0.3～0.4mm.This method hot-dip aluminizing using coating is oozed a little because of the plating assistant agent weak effect always has little leakage, though little in the influence of high temperature oxidation applications, be not suitable for the sulfide corrosion situation.
Deactivation method is that steel part was handled 4～5 minutes in 1～3% chromic anhydride aqueous solution (or adding a small amount of potassium permanganate and inferior sodium nitrate therein) penetration-assisting agent, water flushing (producing hexavalent chromium polluted) is proposed, then dry down at 100～120 ℃, immersed 730～760 ℃ of aluminium liquid then 5～30 minutes, DIFFUSION TREATMENT 3～5 hours under 850～1000 ℃ of temperature afterwards, the air cooling of coming out of the stove below the last furnace cooling to 600 ℃ can obtain the thick coating of 0.1～0.3mm.This method causes the requirement of per pass operation all very strict because Passivation Treatment is wayward, and processing condition are extremely narrow, industrial production is difficult to accomplish unanimity really, product scrap rate height differs with batch quality product, occurs quality problems such as aluminide coating comes off in the application often.And, say and to be eliminated from environmental angle because when washing produces the sexavalence lattice pollutes.
In above-mentioned aluminide coating industrial process, all there is the problem that the matrix steel annealing is made strength degradation, can not be used for quenched and tempered steel.Can make coating produce the crackle that deeply reaches matrix and heat-treat again after the aluminising, come off too early when causing using, cause work-ing life short.
Summary of the invention
The objective of the invention is to overcome the weak point of above-mentioned prior art, a kind of iron aluminide coating process of easy enforcement newly is provided, reach the thickness that improves aluminide coating, improve temperature-room type plasticity, prolong its work-ing life.
The technical scheme that realizes the object of the invention is to carry out as follows:
1) adopts degreaser to remove the greasy dirt of workpiece surface, use shot peening again, and then immerse in the dilute hydrochloric acid solution of 10% weight and soaked 5 minutes;
2) by the penetration-assisting agent solution-treated;
3) surface attachment is had the workpiece of penetration-assisting agent solid salt class immerse in the molten aluminium alloy melt, melt temperature is 760～850 ℃, and the hold-time is 5～30 minutes formation iron aluminide layers;
4) Heating temperature is to pass through heat diffusion treatment under 850～1050 ℃, again through cooling, its main points are that to develop a kind of penetration-assisting agent solution be by the potassium chloride (KCl) of 20～40% weight sodium chloride nacls, 20～40% weight, the Manganous chloride tetrahydrate MnCl of 10～40% weight in the present invention afterwards
2Cerium II Chloride CeCl with 10～20% weight
3Form.Workpiece is to be 15～45% weight in concentration, and temperature is to handle in 50～70 ℃ the penetration-assisting agent aqueous solution.This penetration-assisting agent has solved calorized coating and a problem of oozing occurred leaking; The aluminium alloy melt selected for use of the present invention is made up of the aluminium of 92～98% weight, the chromium of 0～3% weight, cerium and other impurity of 0.1～0.5% weight in addition, helps improving the temperature-room type plasticity of aluminum compound coating.
The above-mentioned oil gas that removes adopts the conventional chemical oil removing, promptly adopts commercially available commodity degreaser.The workpiece surface greasy dirt is less, and when not influencing rust cleaning, this operation can be omitted.
Workpiece after penetration-assisting agent is handled immerses in the molten aluminium alloy melt immediately, finally can form the iron aluminide layer of 0.4～0.6mm at workpiece surface.
In addition, according to the performance requriements and the use occasion of workpiece, need carry out different heat diffusion treatment, the heat diffusion treatment Heating temperature is 850～1050 ℃, specifically depends on the kind of body material.Work-piece cools after the processing can adopt that stove is cold, air cooling, oil cooling and water-cooled.By the composition of heat diffusion treatment adjustment iron aluminide layer, weave construction is finished the final thermal treatment of body material simultaneously, with the intensity that obtains to require.
Compared with prior art, the present invention has following advantage and significant benefit:
(1) owing to the present invention is directed to the problem that prior art exists, work out a kind of penetration-assisting agent solution of forming by sodium-chlor, Repone K, Manganous chloride tetrahydrate and Cerium II Chloride, make gained iron aluminide layer not have point of discontinuity, fine and close nothing is mingled with, be combined with basal body interface, solved in the prior art and a problem of oozing to occur leaking;
(2) the present invention also improves the composition of aluminium alloy melt, and having selected for use with aluminium is main component, adds a spot of chromium, cerium and some other inevitable impurity simultaneously and forms, and has greatly improved the temperature-room type plasticity of aluminum compound coating;
(3) in view of the foregoing, again in conjunction with the preferred processing condition of workpiece in immersing aluminium alloy melt, make its workpiece surface form thicker iron aluminide layer, its long service life does not produce cracking or comes off.
The iron aluminide thick coating is the present invention's one big important breakthrough.At present, the work-ing life of aluminide coating is not very good, and it shows as one and is to use in the process floating coat aluminium atom constantly to the matrix diffusion, causes surfaces of aluminum concentration low and lost efficacy, and the 2nd, coating in use comes off.The reason that first phenomenon produces is that coat-thickness is not enough, and the reason that second phenomenon produces for a long time people think always that the high coating of surfaces of aluminum concentration easily produces and come off, in fact this is a presentation, real reason still is due to the coat-thickness deficiency, because the coefficient of expansion of aluminide coating is all greater than matrix, all be in tensile stress state, as long as speed of cooling is fast in the use, nature cracks on the surface, in case crackle arrives matrix, will produce interior oxidation and make coating shedding, therefore, obtaining thick coating is to prolong the aluminide coating key in work-ing life;
(4) processing of iron aluminide coating is combined with the matrix heat treatment phase, keep the original intensity of body material, coating can not ftracture or come off when thermal treatment.
Embodiment
Example 1:
No. 20 carbon steel pipes, specification Ф 57 * 2600 * 3.5mm.In 10% hydrochloric acid, eliminated rust 5 minutes washing after the sandblast.Immersing concentration is in the penetration-assisting agent solution of 15% weight, and solution composition (weight percent) is: 20% NaCl+20%KCl+40%MnCl
2+ 20% CeCl
3, handled 2 minutes down for 60 ℃, drench and do.Immerse 760 ℃ of molten aluminum iron alloys, its composition (weight percent) is to be incubated 10 minutes in the 98%Al+2%Fe impurity, propose directly to enter in 930 ℃ the diffusion furnace insulation 2 hours, and proposed naturally cooling in air at last, can obtain the Fe-Al coating of thickness 0.5mm.Be used for replacing the 1Cr18Ni9Ti stainless steel to use down in 850 ℃ at the roasting kiln air preheater.
Example 2:
The N80 oil pipe, specification Ф 57 * 950 * 3.5mm.In 10% hydrochloric acid, eliminated rust 5 minutes washing after the sandblast.Immersing concentration is in the penetration-assisting agent solution of 25% weight, and solution composition (weight percent) is: 30%NaCl+30%KCl+30%MnCl
2+ 10%CeCl
3, handled 2 minutes down for 50 ℃, drench and do.Immerse in 800 ℃ of molten aluminum iron alloys, its composition (weight percent) is a 94%Al+1.5%Cr+0.1%Ce+ impurity, be incubated 20 minutes, insulation is proposed directly to enter in 850 ℃ the diffusion furnace 1 hour, propose at last in water, to cool off, through 600 ℃ of tempering, can obtain the Fe-Al coating of thickness 0.45mm.Be used for the sulfur-bearing oil-gas field and do the well casing use.
Example 3:
The 1Cr18Ni9Ti stainless steel tube, specification Ф 57 * 2980 * 3.5mm.In 10% hydrochloric acid, eliminated rust 5 minutes washing after the sandblast.Immersing concentration is in the penetration-assisting agent solution of 35% weight, and solution composition (weight percent) is: 30%NaCl+35%KCl+20%MnCl
2+ 15%CeCl
3, under 70C, handled 3 minutes.Immerse then in 850 ℃ the aluminium alloy melt, its composition (weight percent) is a 92%Al+3%Cr+0.3%Ce+ impurity, is incubated 6 minutes, proposes to handle 0.5 hour in 1050 ℃ process furnace, propose naturally cooling in air at last, can obtain the aluminide coating of thickness 0.4mm.Be used for using under the 1000C temperature.
Example 4:
The Q235 steel plate, specification 2000 * 750 * 30mm.In 10% hydrochloric acid, eliminated rust 5 minutes washing after the sandblast.Immersing concentration is in the penetration-assisting agent solution of 45% weight, and solution composition (weight percent) is: 40%NaCl+40%KCl+10%MnCl
2+ 10%CeCl
3, handled 3 minutes down at 70 ℃.Immerse then in 800 ℃ the aluminium alloy melt, its composition (weight percent) is a 96%Al+0.5%Ce+ impurity, is incubated 30 minutes, proposes to handle 3 hours in 950 ℃ process furnace, propose naturally cooling in air at last, can obtain the aluminide coating of thickness 0.6mm.Be used for 1000 ℃ and do the use of process furnace base plate below the temperature.
Claims (2)
1, a kind ofly prepare intermetallic Fe-Al compound coating and heat treating method, carry out as follows at steel surface:
1) adopts degreaser to remove the greasy dirt of workpiece surface, use shot peening again, and then immerse in the dilute hydrochloric acid solution of 10% weight and soaked 5 minutes;
2) again by the penetration-assisting agent solution-treated;
3) surface attachment is had the workpiece of penetration-assisting agent solid salt class immerse in the molten aluminium alloy melt, melt temperature is 760～850 ℃, and the hold-time is 5～30 minutes formation iron aluminide layers;
4) be 850～1050 ℃ in Heating temperature and pass through heat diffusion treatment down, again through cooling, it is characterized in that: described penetration-assisting agent solution is by the KCl of the NaCl of 20～40% weight, 20～40% weight, the MnCl of 10～40% weight afterwards
2CeCl with 10～20% weight
3Form, workpiece is to be 15～45% weight in concentration, and temperature is to handle in 50～70 ℃ the penetration-assisting agent aqueous solution; Selected aluminium alloy melt is made up of the aluminium of 92～98% weight, the chromium of 0～3% weight, cerium and other impurity of 0.1～0.5% weight.
2, a kind ofly prepare intermetallic Fe-Al compound coating and heat treating method according to claim 1 is described, it is characterized in that workpiece immerses that to form the iron aluminide coat-thickness behind the molten aluminium alloy melt be 0.4～0.6mm at steel surface.
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| CNB2004100207588A CN1323189C (en) | 2004-06-15 | 2004-06-15 | Preparation for iron-aluminium intermetallic compound coating on iron-steel surface and thermal treating method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102021469A (en) * | 2010-11-02 | 2011-04-20 | 山东开泰抛丸机械有限公司 | Powder for strengthening wear resistance of high-chromium iron, preparing method thereof and wear resistant castings |
| CN102021511A (en) * | 2011-01-09 | 2011-04-20 | 南昌航空大学 | Low-temperature powder embedding aluminum-rich penetrating agent for stainless steel |
| CN107815630A (en) * | 2017-10-18 | 2018-03-20 | 三峡大学 | A kind of Q235 alumetized steels and preparation method thereof |
| CN108315684A (en) * | 2018-04-24 | 2018-07-24 | 中国科学院力学研究所 | A kind of aluminizing method of round-link chain |
| CN109321872A (en) * | 2018-11-08 | 2019-02-12 | 中国石油天然气集团有限公司 | A kind of preparation method of graphene enhancement type aluminising oil pipe |
| CN109454535A (en) * | 2018-09-29 | 2019-03-12 | 浙江步丹工贸有限公司 | A kind of the derusting plastic soaking device and its processing technology of small members |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1036411A (en) * | 1988-04-09 | 1989-10-18 | 东北工学院 | Water-soluble plating aid for hot immersion aluminum-plating |
| JPH04333592A (en) * | 1991-05-10 | 1992-11-20 | Kawasaki Steel Corp | Production of al-mn alloy plated steel sheet |
| CN1028247C (en) * | 1992-04-29 | 1995-04-19 | 东南大学 | New hot-dip aluminium plating technology for steels and iron castings |
| JP2000282263A (en) * | 1999-03-30 | 2000-10-10 | Nippon Steel Corp | Hot dip aluminum plated steel sheet excellent in corrosion resistance after working and in edge face |
| US6652991B1 (en) * | 2002-10-09 | 2003-11-25 | The Governors Of The University Of Alberta | Ductile NiAl intermetallic compositions |
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- 2004-06-15 CN CNB2004100207588A patent/CN1323189C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102021469A (en) * | 2010-11-02 | 2011-04-20 | 山东开泰抛丸机械有限公司 | Powder for strengthening wear resistance of high-chromium iron, preparing method thereof and wear resistant castings |
| CN102021511A (en) * | 2011-01-09 | 2011-04-20 | 南昌航空大学 | Low-temperature powder embedding aluminum-rich penetrating agent for stainless steel |
| CN107815630A (en) * | 2017-10-18 | 2018-03-20 | 三峡大学 | A kind of Q235 alumetized steels and preparation method thereof |
| CN108315684A (en) * | 2018-04-24 | 2018-07-24 | 中国科学院力学研究所 | A kind of aluminizing method of round-link chain |
| CN109454535A (en) * | 2018-09-29 | 2019-03-12 | 浙江步丹工贸有限公司 | A kind of the derusting plastic soaking device and its processing technology of small members |
| CN109454535B (en) * | 2018-09-29 | 2024-01-30 | 浙江步丹工贸有限公司 | Rust removal plastic dipping equipment for small-sized components and processing technology thereof |
| CN109321872A (en) * | 2018-11-08 | 2019-02-12 | 中国石油天然气集团有限公司 | A kind of preparation method of graphene enhancement type aluminising oil pipe |
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