CN104923775A - Powder core wire for generating anticorrosion metal coating, manufacturing method for powder core wire, and coating method - Google Patents
Powder core wire for generating anticorrosion metal coating, manufacturing method for powder core wire, and coating method Download PDFInfo
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Abstract
The invention provides a powder core wire for generating an anticorrosion metal coating, and the powder core wire comprises a metal component playing a role as a sacrificial anode; a component which plays a role in stabilizing the perforce of a coating; and a component which improves the performance of resistance to stress corrosion and crack of the coating. The powder core wire is advantageous in that a two-layer structure where the external skin of the powder core wire is additionally provided with powder is employed; the components which affect the machining and preparation of wires are set in the mixed powder not in the external skin, thereby solving a problem that a wire in the prior art becomes hard and fragile and is difficult to prepare. In addition, the powder core wire is additionally provided with the component for stabilizing the performance of the coating, and is also provided with elements combined with foreign matters in a metallic matrix, thereby improving the corrosion resistance of the coating.
Description
Technical field
The present invention relates to powder cored filament material for generating corrosion-resistant metal coating and preparation method thereof, method of application.
Background technology
Corrosion refers to the destruction or rotten caused due to material and environment reaction.Corrosion of metal is the spontaneous process of a thermodynamics, and very general, and such as ferrous materials is all easy to produce corrosion under multiple natural environment and industrial environment.Corrosion of metal principle has multiple, and wherein electrochemical corrosion is the most a kind of.For iron and steel, industrial iron and steel is actually alloy, namely also contains graphite, cementite and impurity thereof outside deironing, and their great majority do not have ironwork to sprinkle.When iron and steel is placed in the aqueous solution or moist atmosphere, its surface can form corrosion micro cell, and wherein more active iron becomes anode, and graphite, cementite and impurity thereof then become negative electrode.There is oxidation reaction in the anode of corrosion micro cell, iron and steel is dissolved, Fe=Fe
2++ 2e
-; Then there is reduction reaction in negative electrode, i.e. oxygen uptake corrosion: 2H
2o+O
2+ 4e
-=4OH
-.Due to iron and impurity close contact, above-mentioned corrosion is constantly carried out.This is the most basic principle that iron and steel occurs to corrode in neutral environment, if under sour environment, then reduction reaction negative electrode occurred is gas-evolving electrodes: 2H
++ 2e
-=H
2.
Containing in the environment of hydrogen sulfide, metal erosion mechanism is more more complex, except common electrochemical corrosion, also observes stress corrosion cracking phenomenon.Stress corrosion cracking under wet hydrogen sulfide environment, when referring to that the aqueous phase that aqueous phase or hydrous matter are formed below dew point and hydrogen sulfide coexist, the cracking that metal occurs under medium and foreign side's (containing interior tissue stress and residual stress) act synergistically.According to " HG20581 steel pressure vessels for the chemical industry material selection regulation ", be Stress corrosion by wet hydrogen sulphide environment when meeting the following condition: (1) temperature is less than or equal to (60+2P) DEG C, wherein P is pressure MPa (gauge pressure) simultaneously; (2) hydrogen sulfide sectional pressure is more than or equal to 0.00035MPa; (3) contain liquid phase water in medium or be in below dew-point temperature; (4) pH value is less than in 9 or medium has cyanide to exist.It is generally acknowledged, the cracking that Wet hydrogen sulfide corrosion causes mainly contains 4 kinds of forms: hydrogen blister (HB), hydrogen induced cracking (HIC) (HIC), hydrogen cracking by stress (SOHIC), sulfide-stress cracking (SSCC).
Lpg spherical tank, Spherical Light Hydrocarbon Tanks, Natural Gas Spherical are the equipment that oil and gas industry is conventional.These gas spherical tanks, in the ordinary course of things all inevitably containing a certain amount of hydrogen sulfide gas, thus define in spherical tank inside the environment that Stress corrosion by wet hydrogen sulphide can occur.About hydrogen sulfide content to the distribution statistics that military service spherical tank damages be abroad: hydrogen sulfide content is greater than the ratio of the spherical tank inwall generation crackle of 100ppm more than 73.5%, the ratio of the spherical tank inwall generation crackle of hydrogen sulfide content between 50ppm and 100ppm is more than 26.5%.It should be pointed out that hydrogen sulfide content is lower than 50ppm, only can as an empirical data or the data should paid much attention at present, a large amount of Investigation On Corrosions shows, still can not determine the lower safety limit of the hydrogen sulfide content preventing stress corrosion cracking completely; Have document announcement abroad, the pressure vessel be less than in the aqueous process environment of 50ppm for hydrogen sulfide content is yet found the cracking rate of 17%.
As can be seen here, sulfide-stress cracking has become liquefied petroleum gas (LPG) spherical tank and the ubiquitous threat of other Spherical Light Hydrocarbon Tanks.In use, the corrosion failure caused because of storage medium environment is recurrent to LPG spherical tank, can produce etch pit, ditch grain even corrosion cracking, makes the mechanical property deterioration of steel, causes spherical tank to lose efficacy.LPG spherical tank has the features such as inflammable, explosive, once its consequence that has an accident is very serious due to storage medium.
Organic coating or corrosion-resistant metallic material can be used for the spherical tank corrosion under control hydrogen-sulfide environmental; although wherein organic coating has certain protected effect; but its service life is shorter; generally be no more than 1-2; the spherical tank of corrosion-resistant metallic material spherical tank or corrosion-resistant metallic material inside liner is adopted to have good protected effect for hydrogen sulfide splitting; but due to high cost, there is no the precedent of commercial Application so far.
Metal coating is a kind of important corrosion control means, and application spraying technology spray metal coating can prevent hydrogen sulfide splitting effectively, has good protected effect and the advantage of economy concurrently.Metal coating can be divided into cathodic coating and anode coating, its prevent corrode principle be: (1), for cathodic metal coating, because its corrosion resistance is better than metallic matrix, thus serves effect corrosive environment and metallic matrix isolated; (2) for positive polarity metal coating, it serves effect corrosive environment and metallic matrix isolated on the one hand, on the other hand because coating is positive polarity, prior to metallic matrix corrosion, thus serves the protective effect of sacrificial anode character; (3) no matter cathodic coating or anode coating, can carry out Seal treatment, namely applies at metal coating surface the protection that one or more layers organic coating provides extra again, especially can provide protection to the porosity defects place of metal coating.
Comparatively speaking, the application of positive polarity metal coating is more extensive, this is because metal coating is in coating procedure, the formation of coating porosity can not be avoided completely, for anode coating, if when there is coating porosity and Seal treatment inefficacy, steel substrate is negative electrode, anode coating preferentially corrodes and plays the effect of sacrificial anode, avoids the corrosion of steel substrate.But for cathodic coating; if when there is coating porosity and Seal treatment inefficacy; in the corrosion cell formed; steel substrate is anode; although the existence of cathodic coating can protect coated steel substrate, the corrosion of the steel substrate at coating porosity place greatly can be accelerated.
Conventional positive polarity metal coating comprises: aluminized coating, spelter coating, zinc-aluminum alloy coating.Adopt thermal spraying allumen layer to be one of effective ways of corrosion of steel structure protection, but the weak part of Aluminum Coating is to adopt organic coating to carry out Seal treatment to suppress the corrosion of Aluminum Coating hole place steel construction matrix.Grant number be disclose in the utility model patent " preventing the spherical tank of stress corrosion cracking " of CN201568725U a kind of for preventing the zinc-aluminum alloy coating of spherical tank generation stress corrosion cracking.Grant number be disclose in the utility model patent " a kind of anticorrosion spherical tank " of CN202081163U a kind of for preventing the zn-al-re alloy coating of spherical tank generation stress corrosion cracking.These two kinds of alloy coats are all using allumen as main component, all do not add magnesium elements.
Along with the progress of technology, one of ordinary skill in the art propose zinc-aluminium-magnesium alloy coating system, and adding of magnesium makes the closed performance of this coating system and anticorrosion ability be improved.But, still there is shortcoming in this coating system: first, for this alloy coat system, only have after confining bed breakage, magnesium elements runs into corrosive substance and preferentially corrodes, the corrosion product magnesia formed just can be filled up the hole in conjunction alloy coat thus play sealing process, the hysteresis quality in this life period and uncertainty; In addition, the sprayed on material that the spraying process of this coating system the most often uses is solid silk material, because generally solid silk material preparation cost is low, its thermal spraying apparatus also has cost advantage usually, but the manufacture of solid silk material has to pass through the technical process such as melting and drawing, if in Zn-Al alloy, the content of aluminium element is more than 15%, the content of magnesium elements more than 0.5%, then Zn-Al alloy by hardening, become fragile and be difficult to make a material.
Grant number is disclose a kind of Zn-Al alloy wire material for being prepared metal coating by thermal spraying mode in the patent of invention " rare earth modified modification anode type zinc-aluminum alloy wire material used for hot spraying " of CN103205666A.In this Zn-Al alloy wire, the content of aluminium is greater than 90%, and the content of magnesium is 0.5%-1.5%.Grant number is disclose a kind of thermal spraying alloy wire material for the preparation of zn-al-re alloy coating in the patent of invention " preventing alloying sacrificial anode film and the method for making thereof of stress corrosion cracking " of CN101928944A, in this material, the content of aluminium is 14%-16%, and the content of magnesium is 0.5%-1.0%.Grant number is disclose a kind of aluminium-magnesium rare earth alloy silk material for thermal spraying in the patent of invention " a kind of rare earth-aluminium-magnesium alloy wire for thermal spraying " of CN102352475A, and in this material, the content of aluminium is more than 95%, and the content of magnesium is 1%-5%.In the coating of above-mentioned 3 patents of invention pure magnesium elements to add played sealing effect comparatively limited, and aluminium content in alloy wire all close to or far away higher than 15%, content of magnesium all reaches or considerably beyond 0.5%, make that alloy is hardening to become fragile, have difficulties in the technical process preparing silk material, make the quality of a material there is unstable situation.
In view of these shortcomings of the prior art, thus this area still needs to provide silk material that can improve above-mentioned shortcoming and preparation method thereof.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of and can generate powder cored filament material of corrosion-resistant metal coating and preparation method thereof.
Compared with powder cored filament material of the prior art, the invention has the advantages that: adopt powder cored filament material crust to add the two-layer structure of powder, and by affect silk material processing preparation composition be arranged in mixed-powder instead of crust, avoid silk material of the prior art hardening, become fragile and be difficult to prepare problem.In addition, the composition of stable coatings performance in powder cored filament material of the present invention, is added, and the element be combined with the field trash of metallic matrix, thus improve the corrosion resistance of formed coating.
In an aspect, the invention provides a kind of powder cored filament material for generating corrosion-resistant metal coating, described powder cored filament material comprises the metal ingredient playing sacrificial anode effect; Play the composition of stable coatings performance; Improve the composition of coating anticorrosion stress-resistant cracking performance.
In above-mentioned powder cored filament material, according to the percentage by weight accounting for whole powder cored filament material, the described metal ingredient playing sacrificial anode effect accounts for 88%-98% (preferred 91%-94%), the described composition playing stable coatings performance accounts for 1% ~ 8% (preferred 4.5%-7.5%), and the percentage by weight of the composition of described raising coating anticorrosion stress-resistant cracking performance accounts for 0.5%-5% (preferred 0.9%-1.8%).
In above-mentioned powder cored filament material, described powder cored filament material comprises crust and the double-layer structure by the coated mixed-powder of crust.
In above-mentioned powder cored filament material, play in the composition of the metal ingredient of sacrificial anode effect, the composition playing stable coatings performance, raising coating anticorrosion stress-resistant cracking performance described, not affecting a composition for material processing preparation is arranged in described crust, and all the other compositions are coated by described crust with mixed-powder form.
In above-mentioned powder cored filament material, described in play sacrificial anode effect metal ingredient be zinc, aluminium, magnesium, according to the percentage by weight accounting for whole powder cored filament material, the content of three kinds of elements is: the magnesium of the zinc of 65%-75%, the aluminium of 6%-12%, 6%-15%.
In above-mentioned powder cored filament material, zinc and aluminium are arranged in described crust, and magnesium is present in described mixed-powder.
In above-mentioned powder cored filament material, the weight content preparing the impurity in raw material of described crust should meet Fe≤0.035%, Cu≤0.025%, C≤0.02%.
In above-mentioned powder cored filament material, described in play stable coatings performance composition be metal oxide.
In above-mentioned powder cored filament material, described metal oxide is present in described mixed-powder.
In above-mentioned powder cored filament material, the size of described metal oxide particle is 300-500 order.
In above-mentioned powder cored filament material, the size of described metal oxide particle is 300-450 order.
In above-mentioned powder cored filament material, the size of described metal oxide particle is 350-500 order.
In above-mentioned powder cored filament material, described metal oxide is one or more the mixture in following metal oxide: the oxide of the oxide of zinc, the oxide of aluminium, magnesium, the oxide of potassium, the oxide of calcium.
In above-mentioned powder cored filament material, if with oxide integrally for 100%, then the ratio between these metal oxides can be any one in following situation: 100% magnesia; 50%-80% magnesia, 20%-50% zinc oxide; 50%-80% magnesia, 20%-50% aluminium oxide; Or 50%-80% magnesia; 10%-25% zinc oxide; 10%-25% aluminium oxide.
In above-mentioned powder cored filament material, the composition of described raising coating anticorrosion stress-resistant cracking performance comprises rare earth element.
In above-mentioned powder cored filament material, described rare earth element is present in described mixed-powder.
In above-mentioned powder cored filament material, described rare earth element can be the combination of any one rare earth element or any multiple rare earth element in lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc) and yttrium (Y).
In above-mentioned powder cored filament material, described powder cored filament material also comprises and improves the corrosion proof composition of metallic matrix.
In above-mentioned powder cored filament material, the described percentage by weight improving the corrosion proof composition of metallic matrix can be 0.1%-1.5% (preferred 0.2%-1.1%).
In above-mentioned powder cored filament material, the described corrosion proof composition of metallic matrix that improves is present in described mixed-powder
In above-mentioned powder cored filament material, the described corrosion proof composition of metallic matrix that improves comprises manganese, titanium, niobium or molybdenum.
In in another, the invention provides a kind of method preparing above-mentioned powder cored filament material, described method mainly comprises: prepare crust; Make mixed-powder; With the coated mixed-powder of crust to form powder cored filament material.
In said method, the described step preparing crust comprises following operation: prepare burden according to the design mix of crust and ratio, the simple metal wherein for preparing burden can be powder, silk material or ingot; In smelting furnace, the described simple metal preparing material is fused into molten condition; The alloy of described melting is poured in crystallizer, and pulls out cakey alloy-steel casting from the other end of crystallizer; Utilize milling train that described alloy-steel casting is rolled into alloy strip; After treating the cooling of described hot rolled alloy band, surface treatment is carried out to remove the oxide skin on surface to described alloy strip; Straightener is aligned described surface treated alloy strip, with obtain thickness evenly and thickness range for 0.1mm-2.0mm, width range is the alloy strip of 2.5-15mm; Removing surface is carried out to the described alloy strip through aligning, to remove dust on surface or impurity; Finally carry out service check to described alloy strip, described service check content comprises metallographic structure and observes.
In said method, the preparation process of described making mixed-powder comprises carries out batching and fully mixing according to the powdered ingredients designed and ratio.
In said method, described powder is kept at dry environment before combination, or dries 2 hours or the longer time at 100-120 DEG C in an inert atmosphere.
In said method, described coated step comprises: described crust is rolled into U-shaped; Described mixed-powder is sent in inert gas environment in described U-shaped crust; The described U-shaped crust of powder filler is rolled into circle and seals; To described sealing, the U-shaped crust of powder filler carry out drawing tube reducing, finally form powder cored filament material.
In said method, the diameter of described powder cored filament material can be 1.2 millimeters-5 millimeters.
Accompanying drawing explanation
Fig. 1 shows the structure of powder cored filament material of the present invention;
The photo of the coating that Fig. 2 is formed for the silk material of the present invention of welds in spherical tanks district thermal spraying described in the embodiment of the present invention; With
The coating that Fig. 3 is formed for spherical tank water outlet thermal spraying silk material of the present invention described in the embodiment of the present invention photo.
Detailed description of the invention
Describe the present invention below in conjunction with accompanying drawing and specific embodiment.Although one of ordinary skill in the art it is appreciated that these embodiments give ad hoc structure, composition and step etc., but they are only the typicalness explanations made the present invention, be not intended to limit to some extent scope of the present invention, the present invention is only subject to the restriction of appended claims.In this article, as nothing particularly points out, percentage composition all refers to percentage by weight.
There is following relation in powder cored filament material of the present invention and its coating composition formed: if overall for object with powder cored filament material; then after each elements melt, the process sprayed on protected metallic matrix is a physical process; when not considering that process dissipates; in raw meal core-wire material, the composition of each element should be consistent with the composition of the coating that ratio and its are formed and ratio, therefore this description first to it form the composition of coating and ratio is described.
metal-metallic oxide coating
The metal-metallic oxide coating that powder cored filament material of the present invention is formed comprises:
(1) play the metal ingredient of sacrificial anode effect, as zinc, aluminium, magnesium, potassium or calcium etc., its content is in the coating 88%-98%, is preferably 91%-94%.These compositions are more active relative to metallic matrix, are preferentially corroded in corrosive environment, become the sacrificial anode of metallic matrix, avoid the corrosion of environment to matrix.These compositions can exist with the form of simple metal, but conduct more preferably embodiment, the form of the alloy that these compositions form with various metals exists, as zinc-containing alloy, acieral etc.Wherein said zinc-containing alloy can be zinc-aluminium, zinc-magnesium, zinc-aluminum-magnesium, zinc-aluminium silicon, zinc-aluminum-magnesium silicon etc.Wherein zinc accounts for 60%-80% in coating 2.As an example, described coating contains zinc, the aluminium of 6%-12%, the magnesium of 6%-15% of 65%-75%.One of ordinary skill in the art also can according to circumstances select other alloys, as acieral, and such as magnalium, zinc silicon, aluminium silicon etc.
(2) composition of stable coatings performance is played, as the oxide of metal, be one or more the mixture in the oxide of the oxide of magnesium, the oxide of zinc, the oxide of aluminium, the oxide of potassium, calcium especially, its content is in the coating 1% ~ 8%, is preferably 4.5%-7.5%.These oxides can hole in seal coat 1, and generate corrosion product again compared with seal coat hole with passive wait metal, adding these oxides in advance can improve sealing effect.The mechanism of action of the oxide pre-set is: contact with the molten drop of melting in spraying process, and the molten drop be melted infiltrates, thus reduce the porosity of metal coating, when corrosive medium attack metal coating, oxide generally can not be further oxided, and the metal of positive polarity such as zinc, aluminium and magnesium are preferentially corroded, the oxide infiltrated owing to being once melted metal is combined with metal in close, the corrosion product that the metal be corroded is produced can along oxide fine particle to outgrowth, therefore described oxide fine particle has fixed bed effect, its starting point produced as corrosion product, corrosion product is fixed on alloy coat, slow down or prevent corrosion further to occur and development.Preferably, these metal oxides are evenly present in metal coating with the form of disperse, the research of the present inventor shows, the effect of this reduction metal coating porosity of oxide and the granularity acting on oxide fine particle of fixed bed are more than 300 orders, such as when 300 order ~ 500 object, effectiveness comparison effectively in other words effectiveness comparison is obvious.In addition, between the oxide be pre-existing in, or between oxide and corrosion of metal product, interaction can be produced, thus improve the protected effect of coating further, such as, metal oxide can improve the passivation effect of aluminium in metal coating, combine with aluminium element and form the oxide-film of spinel structure, oxide-film due to spinel structure has good corrosion resistance, therefore the protective effect of aluminium is improved, and aluminium and described metal oxide have the self sealing capability of reinforcement, be combined the resistance of the works of the zinc oxide magnesium oxide generated with the corrosion product of zinc larger for magnesia for another example, hinder the process of the generation of hydrogen sulfide corrosion.(3) composition of coating anticorrosion stress-resistant cracking performance is improved, as the combination of any one rare earth element or any multiple rare earth element in (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc) and yttrium (Y), the percentage by weight of described rare earth element can be 0.5%-5%.The rare earth element contained in coating and sulphur generation strong reaction, generate stable sulfide ReS or Re
2s
3, reduce or eliminate the corrosion to steel substrate, and loose FeS rusty scale can not be generated.In addition, rare earth element can increase alloy activity, and has extremely strong trapped electrons ability, hydrogen ion effectively can be stoped to be transformed into absorption hydrogen and to form stress corrosion cracking (SCC), inherently greatly reduce the probability of spherical tank generation stress corrosion.
(4) improve the corrosion proof composition of metallic matrix, as manganese, titanium, niobium, nitrogen or molybdenum, its content is in the coating 0.6%-1.0%.In thermal spray process, the manganese of fusing can be combined with the field trash of matrix surface, thus improve metallic matrix corrosion resistance, in addition manganese element and S unit have strong combination and are inclined to, stable sulfide M nS can be generated, and MnS and magnesia meet, class amorphous state bond can be generated, greatly reduce or eliminate the corrosion of hydrogen sulfide to steel substrate.
for the preparation of the powder cored filament material of above-mentioned coating
Fig. 1 shows the structure of the raw meal core-wire material for the preparation of above-mentioned coating, and described powder cored filament material comprises crust 1 and is covered by the mixed-powder 2 in described crust.
The metal ingredient playing sacrificial anode effect included by powder cored filament material, play stable coatings performance composition, improve coating anticorrosion stress-resistant cracking performance composition, improve in the corrosion proof composition of metallic matrix, not affecting a composition for material processing preparation is arranged in alloy strip crust, and all the other compositions are coated by alloy strip crust with mixed-powder form.The present invention adopt this powder cored filament material crust add in the two-layer structure of powder, by affect silk material processing preparation composition be arranged in mixed-powder instead of crust, avoid silk material of the prior art hardening, become fragile and be difficult to preparation problem.In addition, the composition of stable coatings performance in powder cored filament material of the present invention, is added, and the element be combined with the field trash of metallic matrix, thus improve the corrosion resistance of formed coating.
Such as, described in play sacrificial anode effect metal ingredient can be zinc, aluminium, magnesium, wherein zinc and aluminium are arranged in described crust, and described magnesium is present in mixed-powder; The described composition playing stable coatings performance can be metal oxide, and it is present in described mixed-powder; The composition of described raising coating anticorrosion stress-resistant cracking performance can be rare earth element, and it is present in described mixed-powder; The described corrosion proof composition of metallic matrix that improves can be manganese, titanium, niobium, nitrogen or molybdenum, and it is present in described mixed-powder.In addition, in the raw material of described crust, the total content of impurity element should meet Fe≤0.035%, Cu≤0.025%, C≤0.02%.In above-mentioned silk material, magnesium is covered by crust with pulverulence, which avoid Zn-Al alloy wire material of the prior art due to add magnesium elements and hardening, become fragile and be difficult to prepare problem, the magnesium dust simultaneously added and magnesium oxide powder can reduce this material form the porosity of coating, strengthen the sealing effect of metal coating, the elements such as manganese, titanium, niobium, nitrogen or molybdenum be combined with field trash improve this material form the corrosion resistance of coating.
the preparation method of above-mentioned powder cored filament material
Hereafter be described to the preparation method of described powder cored filament material:
The first step, preparation alloy strip crust.Be specially: (1) prepares burden according to the design mix of crust and ratio, simple metal wherein for preparing burden can be powder, silk material or ingot, especially to notice that the impurity content in the raw material for preparing burden should meet Fe≤0.035%, Cu≤0.025%, C≤0.02%; (2) under the smelting temperature of 750-900 DEG C, in smelting furnace, the simple metal preparing material is fused into molten condition; (3) alloy of melting is poured in crystallizer, and pull out cakey alloy-steel casting from the other end of crystallizer; (4) utilize milling train that described alloy-steel casting is rolled into alloy strip; (5), after treating the cooling of described hot rolled alloy band, surface treatment is carried out to remove the oxide skin on surface to described alloy strip; (6) on straightener, described surface treated alloy strip is aligned, with obtain thickness evenly and thickness range for 0.3mm-1.0mm, width range is the alloy strip of 2.5-15mm; (7) removing surface is carried out to the described alloy strip through aligning, to remove dust on surface or impurity; (8) finally the service checks such as metallographic structure observation are carried out to described alloy strip.
Second step, makes mixed-powder.Be specially: being mixed by various powder according to the powdered ingredients of aforementioned powder cored filament material and utilize mixer fully to mix, the powder mixed, is dried 2 hours at the temperature of 100-120 DEG C as in ar gas environment at inert gas.
3rd step, with the coated described powder of crust.Be specially: described alloy strip crust is rolled into U-shaped by (1); (2) described mixed-powder is sent in inert gas is as ar gas environment as described in U-shaped crust; (3) the described U-shaped crust of powder filler is rolled into circle and seals; (4) to described sealing, the U-shaped crust of powder filler carry out drawing tube reducing, final to form diameter be 1.2 millimeters-5 millimeters, preferably 3 millimeters, powder cored filament material.
specific embodiment 1
applied environment
In the present embodiment, the coatings applications formed by powder cored filament material of the present invention is in 3 in-service light-hydrocarbon fuel spherical tanks, and spherical tank volume is 1000 cubic metres, and the internal surface area of each spherical tank is about 484 square metres.These spherical tank active times are all more than 10 years, and in tank, hydrogen sulfide mean concentration is more than 3900ppm, and the safe operation of this situation to spherical tank causes very adverse influence.Annual open tank inspection, all can find on spherical tank inwall that a large amount of length is the micro-crack of 20mm-50mm.In order to eliminate accident potential, alleviating harm, ensureing hydrocarbon spherical tank safety and steady long-term operation, must counter-measure be taked, avoid equipment breakdown to occur.In addition, tank bottom, wallboard and top board to be welded together by welding manner by the installation of these spherical tanks becomes spheroid, therefore on spherical tank matrix, there is weld seam, spherical tank inwall is divided into weld metal zone (within the scope of each 15cm in weld seam both sides) and non-weld metal zone.
prepare powder cored filament material
The powder cored filament material in the present embodiment is prepared according to the previously described method preparing powder cored filament material, herein only to concrete composition, content, technological parameter or condition limit in detail (clipped refer to above in conjunction with powder cored filament material preparation method describe content, repeat no more herein): first, according to zinc 69.9%, aluminium 9.1% (is the percentage by weight accounting for whole powder cored filament material, lower same), ratio batching, batching metal is ingot, in batching ingot, the total content of impurity element should meet Fe≤0.035%, Cu≤0.025%, C≤0.02%.Smelting temperature is 750 DEG C, final formation thickness 1.0mm, the alloy strip crust of width 10mm.Secondly, mixed-powder is prepared according to the ratio at magnesium dust 12.5%, magnesium oxide powder 4.4%, mishmetal powder 3.2%, manganese powder end 0.8%, wherein mishmetal powder is lanthanum, cerium, praseodymium, promethium 4 kinds of rare earth elements carry out being mixed to get according to the ratio of 1: 1: 1: 1, the granular size of magnesium oxide powder is 350 orders, and the powder mixed is dried 2 hours in ar gas environment, at the temperature of 100-120 DEG C.Finally, finally form with the coated described powder of alloy strip crust the powder cored filament material that diameter is 3mm.
prepare metal coating
On spherical tank, the metal coating in the present embodiment is prepared according to the previously described method preparing metal coating, only concrete composition, content, technological parameter or condition are described in detail (clipped refers to above in conjunction with the content that metal coating preparation method describes, and repeats no more herein) herein:
First, because described storage tank once stored the lighter hydrocarbons of hydrogen sulfide content up to 3900ppm, spherical tank inwall has a large amount of micro-crack, therefore first grinding process should be carried out to spherical tank inwall, a large amount of micro-cracks of spherical tank inwall are got rid of, adopts pressure sending type to send sand to carry out derusting by sandblasting to spherical tank inwall afterwards again, sandblasting distance 200-300mm, blasting pressure 0.6-1.0MPa, blast time 10-20s.Derusting by sandblasting rank reaches Sa3 grade standard in GB8923-88 " division of steel surface derusting grade ", namely metal surface is without attachments such as visible grease, dirt, oxide skin, iron rust and painting layers, and any residual vestige should be only the slight color spot of point-like or striated.
Secondly, after stating derusting by sandblasting step on the implementation in 8 hours, be not more than the condition of 85% in relative humidity under, utilize electric arc spraying mode that the powder cored filament material prepared is sprayed to spherical tank on the surface above, the coating layer thickness at described spherical tank mother metal place is on the surface made to reach 180 microns, spray 4 times, the coating layer thickness on weld metal zone reaches 270 microns, sprays 6 times.Described coating and described surface to be protected have good adhesive force, and bond strength is not less than 6MPa.
Again, after stating spraying process on the implementation, in spherical tank surface temperature at least higher than dew-point temperature more than 3 DEG C, and environment temperature be more than or equal to 0 DEG C or relative humidity is less than or equal to 85% when, organic siliconresin class sealer is utilized to implement Seal treatment step as early as possible, to avoid metal coating surface depositing dust, greasy dirt or other foreign material, enclosed layer thickness 100 microns, applies 3 times.
with the Comparative result of prior art
Fig. 2 is for after coating described in embodiment 1 is applied to 2 months upper 3 years of spherical tank, and the photo that open tank inspection photographs, is shown as the weld seam that protruding fillet is spherical tank in photo.Check result shows: the coating layer thickness at mother metal place becomes 162 microns from 180 microns, the coating layer thickness of weld metal zone becomes 236 microns from 270 microns, these coating layer thicknesses still can provide good protection, and any H 2 S stress corrosion crackle does not appear in spherical tank inner wall surface.The original design life-span of alloy coat is 5 years, and according to residue alloy coat thickness, the safety military service alloy coat of 3 years 2 months, estimates safety to be on active service more than 8 years.For prior art, the spherical tank inwall allumen metalloid coating of being on active service more than 3 years, the metal coating of commissure is preferentially corroded, and approach exhaustion, expose the parent metal state with brown corrosion product, and near weld seam, be checked through the stress corrosion cracking (SCC) that length is 2-5mm.
specific embodiment 2
applied environment
In the present embodiment, the coatings applications formed by powder cored filament material of the present invention is in 6 in-service LNG spherical tanks of certain city gas company, and spherical tank volume is 5000 cubic metres, and the internal surface area of each spherical tank is about 1414 square metres.These spherical tank active times are all more than 8 years, and in tank, hydrogen sulfide mean concentration is more than 1500ppm, and in tank, water content is not less than 300ppm simultaneously, and the safe operation of this situation to spherical tank causes very adverse influence.Annual open tank inspection, all can find on spherical tank inwall that a large amount of length is the micro-crack of 10mm-22mm.In the same manner as in Example 1, there is weld seam equally in the spherical tank matrix in the present embodiment, spherical tank inwall is divided into weld metal zone (within the scope of each 15cm in weld seam both sides) and non-weld metal zone.A delivery port is also there is in addition at the inwall bottom surface of storage tank, owing to there is steam in spherical tank during one's term of military service LNG, under gas pressure, steam condenses into connate water at delivery port, in water outlet mouth region (delivery port hole and around the scope of 600mm), the thickness of hot-spraying coating processes according to weld metal zone.
prepare powder cored filament material
Compared with embodiment 1, the difference of the present embodiment is: in crust, the composition of each element and proportioning are zinc 67.5%, aluminium 11.4%; In mixed-powder, the composition of each element and proportioning are magnesium 10.7%, magnesia 5.5%, mishmetal 2.2%, manganese 0.9%, wherein mishmetal is lanthanum, cerium, praseodymium, neodymium 4 kinds of rare earth elements carry out being mixed to get according to the ratio of 1: 1: 1: 1, and the granular size of magnesium oxide powder is 400 orders.
prepare metal coating
Compared with embodiment 1, the difference of the present embodiment is: when implementing spraying process, the coating layer thickness at described spherical tank mother metal place is on the surface made to reach 150 microns, spray 3 times, coating layer thickness on weld metal zone reaches 240 microns, spray 5 times, the coating layer thickness in delivery port hole district reaches 240 microns, sprays 5 times.
with the Comparative result of prior art
Fig. 3 for coating described in embodiment 2 be applied to 6 months upper 3 years of spherical tank time, the photo photographed, the circular hole in photo is the apopore of spherical tank.Check result shows: the coating layer thickness at mother metal place becomes 120 microns from 150 microns, the coating layer thickness of weld metal zone becomes 212 microns from 240 microns, the coating layer thickness in delivery port hole district becomes 205 microns from 240 microns, and any H 2 S stress corrosion crackle does not appear in spherical tank inner wall surface.The original design life-span of alloy coat is 5 years, and according to residue alloy coat thickness, the safety military service alloy coat of 3.5 years, estimates safety to be on active service more than 6 years.For prior art, the spherical tank inwall allumen metalloid coating of being on active service more than 3 years, the metal coating of commissure is preferentially corroded, and approach exhaustion, expose the parent metal state with brown corrosion product, and near weld seam, be checked through the stress corrosion cracking (SCC) that length is 2-3mm.At water outlet, the metal coating of spherical tank inwall is not only consumed totally, and there occurs general corrosion, after removing the corrosion product of water outlet, finds the crackle of a large amount of length 3mm-10mm.
The above is only preferred embodiment of the present invention, and be not restriction invention being made to other form, any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the Equivalent embodiments of equivalent variations.But everyly do not depart from technical solution of the present invention content, any simple modification, equivalent variations and the remodeling done above embodiment according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (9)
1., for generating a powder cored filament material for corrosion-resistant metal coating, described powder cored filament material comprises the metal ingredient playing sacrificial anode effect; Play the composition of stable coatings performance; Improve the composition of coating anticorrosion stress-resistant cracking performance.
2. powder cored filament material according to claim 1, wherein according to the percentage by weight accounting for whole powder cored filament material, the described metal ingredient playing sacrificial anode effect accounts for 88%-98%, the described composition playing stable coatings performance accounts for 1% ~ 8%, and the percentage by weight of the composition of described raising coating anticorrosion stress-resistant cracking performance accounts for 0.5%-5%.
3. powder cored filament material according to claim 1 and 2, wherein said powder cored filament material comprises crust and the double-layer structure by the coated mixed-powder of crust.
4. the powder cored filament material according to any one of claim 1-3, wherein play in the composition of the metal ingredient of sacrificial anode effect, the composition playing stable coatings performance, raising coating anticorrosion stress-resistant cracking performance described, not affecting a composition for material processing preparation is arranged in described crust, and all the other compositions are coated by described crust with mixed-powder form.
5. the powder cored filament material according to any one of claim 1-4, the wherein said metal ingredient playing sacrificial anode effect is zinc, aluminium, magnesium, according to the percentage by weight accounting for whole powder cored filament material, the content of three kinds of elements is: the magnesium of the zinc of 65%-75%, the aluminium of 6%-12%, 6%-15%.
6. powder cored filament material according to claim 5, wherein zinc and aluminium are arranged in described crust, and magnesium is present in described mixed-powder.
7. the powder cored filament material according to any one of claim 1-6, the wherein said composition playing stable coatings performance is metal oxide.
8. the powder cored filament material according to any one of claim 1-7, the composition of wherein said raising coating anticorrosion stress-resistant cracking performance comprises rare earth element.
9. prepare a method for the powder cored filament material according to any one of claim 1-8, described method mainly comprises: prepare crust; Make mixed-powder; With the coated mixed-powder of crust to form powder cored filament material.
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