CN102605224B - Aluminum-titanium alloy wire containing Ce and Nd, and manufacturing method thereof - Google Patents
Aluminum-titanium alloy wire containing Ce and Nd, and manufacturing method thereof Download PDFInfo
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Abstract
The invention relates to a multi-element aluminum-titanium alloy wire comprising components of, by weight: 94%-97% of aluminum Al, 0.05%-1% of vanadium V, 2%-5% of titanium Ti, 0.01-0.7% of cerium Ce, and 0.01-0.2% of neodymium Nd, and no more than 1% of trace additive elements. A total amount of the two rare earth elements is 0.02-0.76%. The resistivity of the aluminum-titanium alloy wire is 2.0-6.0muohm*cm. The specific weight of the aluminum-titanium alloy wire is 2.60-2.75g/cm<3>, and the extensibility of the aluminum-titanium alloy wire is 10-25%.
Description
Technical field
The present invention relates to a kind of polynary aluminum titanium alloy silk and manufacture method thereof, especially relate to aluminum titanium alloy material and the manufacture method thereof of a kind of Ce of containing and Nd.
Background technology
As everyone knows, except that the minority precious metal, metallic substance can be with surrounding medium generation chemical reaction and electrochemical reaction and is corroded.Metallic corrosion has become the maximum harm of large-scale steel structure building, has a strong impact on its safe in utilization and life-span.In addition, the metallic surface is subjected to various mechanical effects and the wearing and tearing that cause are also very serious.A large amount of hardwares lost efficacy because of corroding and wearing and tearing, and caused great waste and loss.According to some industrially developed country's statistics, annual steel account for 10% of steel ultimate production because of the loss of corroding and wearing and tearing cause, and the loss amount of money accounts for 2～4% of total value of production in national economy.Therefore, development protecting metallic surface and intensifying technology are the key subjects that various countries generally are concerned about.
In addition, in case hardware is in the corrosive medium, for example, the steel construction piece surface that is in the wet environment is corroded, and corrosion product deliquescence, and the smoother of steel member own make its surface easily sliding, directly threaten the safety of its surperficial object or person body.For example, the walkway in the public works, the freight container platform of ocean-going freighter, Seaborne Aircraft Platform, the deck of seaplane carrier, takeoff runway etc.Therefore, press for exploitation and a kind ofly can provide corrosionproof protection, prolong the work-ing life of steel construction piece, have anti-skidding or sliding functional coating simultaneously again, thereby guarantee the security of the steel construction piece institute's carrying object or the person steel construction piece.
At present, market anti-corrosion method commonly used mainly adopts the method for chemical process and physics thermospray metallic coating.Chemical process mainly is meant and adopts anticorrosive coating coating etc., as coat composed erosion shields such as inorganic or organic varnishes; And be used for the thermospray metallic coating of anticorrosion purpose, Chang Yong metal coating layer material is zinc and saxonia metal wire in the market, its according to chemical composition difference be divided into: pure zinc silk, Zn-Al alloy wire ZnAl
5, Zn-Al alloy wire ZnAl
15Deng, they extensively are used in fields such as antiseptic project, surface treatment, capacitor end surface metal spraying.They mainly contain two to the protection mechanism of ferrous materials: the one, have the buffer action that similarly stops corrosive medium with the paint spraying anticorrosion mechanism; the 2nd, have the anodic protection effect that realizes by the coated material self-sacrifice; therefore; the popularization and application on colliery, port and pier, large-sized civil steel building, bridge, high-speed railway, large ship and other large industrialized projects (as petrochemical industry, electric power, ocean) of thermospray metallic coating and compound coating guard technology thereof has obtained excellent society and economic benefit.
In the above-mentioned thermospray metal coating layer material, pure zinc silk is because of low price, and production method simply and is widely used.Yet its intensity and hardness are low, and tensile strength is low, and when as the anticorrosion with painting material, strength of materials hardness is low, and material is soft partially, flexible distortion.And Zn-Al alloy wire such as ZnAl
5, ZnAl
15Deng because complex manufacturing, production cost and material price are higher, and the purer zinc silk of consumption is few during therefore as the anticorrosion with painting material.
In fact, another major cause of the less employing of Zn-Al alloy wire stretches easily broken exactly when producing filament and is difficult to carry out.Because raising along with aluminium content, because because of the increase of component gap causes that segregation phenomena increases, be difficult to guarantee its homogeneous microstructure, resistance to deformation increases, so aluminium content is high more, it is difficult more to be drawn into silk, thereby high aluminium content and drawing difficulty be the main difficult problem of a preparation material, and more the development of the Zn-Al alloy wire of high aluminium content does not appear in the newspapers yet.
At this problem, the someone proposes, and rare earth element can significantly improve the physical and mechanical property of alloy in metal field, and rare earth element has obtained extensive concern in the research in corrosion prevention field with using.As Chinese patent CN1718836A, the rare earth cerium (Ce) that accounts for a material gross weight 0.05-0.3% is joined in Mg, the Al metal, make a kind of anticorrosive wire material sprayed with rare-earth aluminum-magnesium alloy, be used for the especially long-effective corrosion of hydro project gate of steel construction, obtained positive protection effect, but what it adopted is to add single rare earth elemental cerium (Ce), thereby has influenced the further raising of silk material barrier propterty, is unfavorable for applying.And experiment shows, adopts the similar techniques scheme, and near down in limited time, for example when less than 0.08% the time, the rare earth role is extremely small as content of rare earth; And when greater than 0.1% the time, it is not obvious again that rare earth rises to the continuation of zinc alloy intensity, and therefore, this technology is used very limited, also fails in the Zn-Al alloy wire of effective use heat metallize coating.
In addition, just more do not appear in the newspapers about preparing not only protection against corrosion but also possessing hot spray wire anti-skidding or not sliding functional coating in the prior art.
So still need a kind of low price on the market and have higher-strength replace traditional zinc silk be used to make the anticorrosion with painting engineering and have simultaneously anti-skidding again or the hot spray wire of sliding function not.
Summary of the invention
Deficiency at zinc silk in the market requirement and the prior art or zinc-aluminium silk exist the object of the present invention is to provide a kind of polynary thermal spraying aluminum titanium alloy wire and manufacture method thereof, and this material is sprayed at the surface of steel, has obtained good anticorrosion and skidproof effect.
The invention provides a kind of polynary aluminum titanium alloy silk, by weight percentage, its component is: aluminium Al:94%-97%; Vanadium V:0.05%-1%; Titanium Ti:2%-5%; Cerium Ce:0.01-0.7%, neodymium Nd:0.01-0.2%, the total amount of these two kinds of rare earth elements: 0.02-0.76%, total amount is no more than 1% trace additives, the resistivity of described aluminum titanium alloy silk is 2.0-6.0 μ Ω cm, and the proportion of described aluminum titanium alloy silk is 2.60-2.75g/cm
3, the unit elongation 10～25% of described aluminum titanium alloy silk.
Preferably, the total amount of wherein said two kinds of rare earth elements: 0.33-0.65%, the resistivity of described aluminum titanium alloy silk is 3.0-5.0 μ Ω cm, the proportion of described aluminum titanium alloy silk is 2.64-2.70g/cm
3, the unit elongation 15-18% of described aluminum titanium alloy silk.
Preferably, the diameter of wherein said aluminum titanium alloy silk is 1.5-4.0mm, and the tensile strength of described aluminum titanium alloy silk after 180-280 ℃ of annealing reached repeatedly drawing in 1.5-3 hour is 75-115Mpa.
Preferably, the mass ratio of wherein said two kinds of rare earth elements is Ce/Nd=2/1～9/1.
Preferably, wherein the mass ratio of each composition is:
V/Ti＝1/40～1/5，
The total amount of V/ rare earth element=1/1～2/1,
The total amount of Ti/ rare earth element=5/1～25/1.
Preferably, the composition of each component is respectively by weight percentage in the wherein said trace additives: Fe＜0.01%, Pb＜0.005%, Cd＜0.002%, Sn＜0.001%.
On the other hand, the present invention also provides a kind of method for preparing described aluminum titanium alloy silk, weight percent according to described each component of aluminum titanium alloy silk is got the raw materials ready, each component is made aluminum titanium alloy by proportioning in smelting furnace, pour into the aluminum titanium alloy rod by the deep-well forging type again, then, the aluminum titanium alloy rod put into 350～450 ℃ electric furnace 4～8 hours, carrying out homogenizing handles, use extrusion machine again, at 380～420 ℃ of following hot extrusion materials, make material pass through circular die, form the thick line base of diameter 4.5～8mm, with the thick line base in vacuum annealing furnace 180～280 ℃ annealing 1.5～3 hours, carry out drawing again, annealing, and then repeat above drawing successively, the annealed step is up to the silk material of making 1.5～4.0mm.
Preferably, wherein drawing process is as follows: the thick line base of diameter 4.5～8mm is stretched to diameter 4.0mm～7.0mm, and then annealing; Again with the wire stretching of 4.0mm～7.0mm to 3.5mm～6.0mm, and then annealing; At last with wire stretching to 1.5～4.0mm of 3.5mm～6.0mm.
Preferably, the annealing temperature after wherein each drawing is 180～230 ℃, and annealing time is 1.5～3 hours.
Preferably, wherein the drawing speed of each passage is 10～35mm/min, and draft temperature is 20～30 ℃.
Adopt technical scheme of the present invention, obtained the technique effect of highly significant, specific as follows:
Aluminium provides extraordinary passivation, and adding titanium in the aluminium can crystal grain thinning, improves the casting surface quality, and titanium forms the aluminium titanium compound with aluminium simultaneously, forms superfluous, precipitation strength phase, and the intensity of raising alloy is beneficial to moulding.Therefore, the hardness of coating is higher, and the extensibility of wear resistance and spraying particle is better, forms flat particle, and erosion resistance is better.In addition, the adhesivity of coating is stronger, and skidproof effect significantly is improved.
The present invention adopts and adds Ce and two kinds of thuliums of Nd, except crystal grain thinning better, can also eliminate the deleterious effect of ferro element to aluminium alloy better, thereby improve the intensity and the plasticity of aluminium alloy.
And, the present invention is by adding Ce and two kinds of thuliums of Nd, the increase that has overcome the component gap that causes owing to the adding titanium causes the defective that segregation phenomena increases, reduce the surface tension on the new and old two-phase interface better, also between crystal grain and alloy liquid, form surface-active film when accelerating nucleus growth speed better, stop the grain growth that generates, make the alloy structure refinement, guaranteed homogeneous microstructure, resistance to deformation increases.
And the present invention has improved the antioxidant property of thermal spraying material better by adding Ce and two kinds of thuliums of Nd, has suppressed the formation speed of oxide film better, has strengthened the antistripping ability of oxide film better.
And the present invention is by adding Ce and two kinds of thuliums of Nd, and rare earth element can react simultaneously with oxygen, sulphur in alloy liquid, can adsorb in a large number and dissolved hydrogen, more effectively reduces its hazardness, reduces the hydrogen content and the pin hole rate of aluminium greatly.
At last, the present invention is by adding Ce and two kinds of thuliums of Nd, optimized aluminium alloy interior metal crystalline structure better, when having improved the alloy structure corrosion resisting property better, also improved the physical and mechanical properties of alloy greatly, guaranteed the processing and fabricating of silk material and the application in the construction, thoroughly overcome because the high more difficult more defective of silk that is drawn into of aluminium content.
Therefore, the present invention is by adding Ce and two kinds of thuliums of Nd, with respect to adding single rare earth element, influence to zinc alloy intensity is more obvious, and minimum of middle-weight rare earths content of the present invention needs to add the technique effect that 0.02% of total amount promptly can reach expection, this is very important to saving rare day by day rare earth resources, can greatly save production cost; On the other hand, the performance of aluminum titanium alloy silk also can overcome to add the existing defective of single rare earth element in the prior art fully along with the continuation of content of rare earth is risen and improvement more significantly.
Yet, the interpolation of rare earth metal is not The more the better yet, and the present invention is according to the composition of base mateiral, after testing repeatedly in a large number, screening, finally determined the optimum range of two kinds of rare earth element total contents technique effect of the present invention to be improved further by a series of creative works.
Simultaneously, the contriver also finds, though any two or more rare earth adds the corrosion resistance that all can promote the aluminum titanium alloy silk in the aluminum titanium alloy silk simultaneously in 17 kinds of rare earth elements, but neither all arbitrarily two or more rare earth elements add the technique effect that all can play equal highly significant in the aluminum titanium alloy silk simultaneously to, this with can add the derivation that any two kinds of rare earth elements all can reach identical technique effect in theory and differ greatly.The present invention has finally determined Ce and Nd and optimum range when adding separately by a series of creative works, thereby has made technique effect of the present invention realize optimizing after testing repeatedly in a large number, screening.
Also add the vanadium of certain content in the aluminum titanium alloy silk that the present invention adopts, added the hardness that a certain amount of vanadium can further improve the persistent corrosion resistance of aluminum titanium alloy silk coating and increase coating, especially further improved the non-skid property of coating.
Simultaneously, the present invention comprises according to practical situation or does not comprise such as trace elements such as Fe, and this can improve coating opposing atomospheric corrosion, galvanic corrosion and airflow scouring erosive ability to a certain extent.
Further, the contriver finds by the mass ratio that suitable each formed part is set after testing repeatedly in a large number, screening, and can improve the ability such as anticorrosive of coating more significantly.Wherein, when V/Ti=1/40～1/5, the best results of the hardness of coating and non-skid property due to V and the Ti, when total amount=1/1～2/1 of two kinds of rare earth elements of V/, total amount=5/1～25/1 of two kinds of rare earth elements of Ti/ o'clock, rare earth element does not have obvious influence to the formation of oxide compound, simultaneously can effectively remove wherein unnecessary free oxygen level, the fastness to rubbing of coating is improved greatly, the concentration class of alloy is improved greatly, thereby improve the resistance to corrosion of alloy silk more significantly.
The present invention also provides a kind of method for preparing the aluminum titanium alloy silk, adopt this method, manufacturing process is simple and direct, product cost is moderate, the metal thermal spraying coating silk material that adopts this method to make, have excellent sticking power, good physical mechanical property, solidity to corrosion and not sliding performance, its construction cost appropriateness helps applying.Technical problem such as solved manufacturing cost costliness, barrier propterty deficiency, construction application cost height that present rare earth wire rod exists, be difficult to apply.
In addition, adopt the very tangible technique effect of technical scheme another one of the present invention to be, the resistivity of described aluminum titanium alloy silk is 2.0-6.0 μ Ω cm, and the proportion of described alloy silk is 2.60-2.75g/cm
3The unit elongation 10～25% of described aluminum titanium alloy silk, these excellent performances are more than alloy silk of the prior art far away, the interior microscopic that aluminum titanium alloy silk of the present invention is described is organized very large variation has also been taken place, although these variations can't be described with the structure of aluminum titanium alloy silk or the qualification of composition, but by the improvement of above-mentioned performance perameter, those skilled in the art can clearly be known its qualification effect of being played to aluminum titanium alloy silk of the present invention.
Therefore, aluminum titanium alloy silk of the present invention has that intensity is big, hardness is high, advantages such as low price, and alternative traditional zinc silk is used for the anticorrosion with painting engineering and to anti-skidding field such as particular requirement is arranged.And this rare earth aluminum titanium alloy hot coating has excellent sticking power, good physical mechanical property, corrosion resisting property and non-skid property, pass through experimental test, its average year erosion rate less than or be equivalent to the coatings such as the pseudo-alloy of aluminum titanium alloy, aluminium titanium of thermospray zinc, aluminium low levels, and have non-skid property.Whole silk material process for machining and manufacturing is simple and direct, cost is lower, construction application cost appropriateness.
Adopt aluminum titanium alloy silk of the present invention to do sacrificial anode and be sprayed at the steel and iron member top layer, can make member prolong 5～10 times work-ing life, have skidproof effect simultaneously.Therefore, this technology is widely used in ship deck, public works, walkway, in the facilities such as tunnel frame, has boundless application prospect.
Description of drawings
Fig. 1 diameter is the microtexture of the polynary aluminum titanium alloy silk material of 2.0mm.
Fig. 2 adopts the coating section morphology of electric arc spraying.
Fig. 3 adopts the coatingsurface form of electric arc spraying.
Embodiment
Polynary aluminum titanium alloy silk of the present invention, by weight percentage, its component is: aluminium Al:94%-97%; Vanadium V:0.05%-1%; Titanium Ti:2%-5%; Cerium Ce:0.01-0.7%, neodymium Nd:0.01-0.2%, the total amount of these two kinds of rare earth elements: 0.02-0.76%, total amount is no more than 1% trace additives, the resistivity of described aluminum titanium alloy silk is 2.0-6.0 μ Ω cm, and the proportion of described aluminum titanium alloy silk is 2.60-2.75g/cm
3, the unit elongation 10～25% of described aluminum titanium alloy silk.
Of particular note, adopt the very important improvement of technical scheme of the present invention to be herein, the resistivity of described aluminum titanium alloy silk is 2.0-6.0 μ Ω cm, and the proportion of described aluminum titanium alloy silk is 2.60-2.75g/cm
3, the unit elongation 10～25% of described aluminum titanium alloy silk.These excellent performances all are more than the alloy silk under the equal conditions in the prior art far away, the interior microscopic that aluminum titanium alloy silk of the present invention is described is organized very large variation has also been taken place, although these micro-variations can't be described with the structure of aluminum titanium alloy silk and/or the qualification of composition, but by further describing of above-mentioned performance perameter, those skilled in the art can clearly be known its qualification effect of being played to aluminum titanium alloy silk of the present invention.
Provide some preferred embodiments of each composition mass percent of the present invention below in conjunction with table 1, but the content of each composition of the present invention is not limited to listed numerical value in this table, for a person skilled in the art, fully can be in table rationally summarize and reasoning on the basis of listed numerical range.
Table 1: each composition accounts for the mass percentage content (%) and the index of correlation parameter of gross weight
Preferably, wherein the mass ratio of each composition is:
V/Ti=1/20～1/8, total amount=5/4～3/2 of two kinds of rare earth elements of V/, total amount=8/1～15/1 of two kinds of rare earth elements of Ti/.
In addition, the present invention also provides a kind of method for preparing described aluminum titanium alloy silk, weight percent according to described each component of aluminum titanium alloy silk is got the raw materials ready, each component is made aluminum titanium alloy by proportioning in smelting furnace, pour into the aluminum titanium alloy rod by the deep-well forging type again, then, the aluminum titanium alloy rod put into 450～550 ℃ electric furnace 4～8 hours, carrying out homogenizing handles, use extrusion machine again, at 380～420 ℃ of following hot extrusion materials, make material pass through circular die, form the thick line base of diameter 4.5～8mm, with the thick line base in vacuum annealing furnace 180～280 ℃ annealing 1.5～3 hours, carry out drawing again, repeat above annealing then successively, the drawing step is up to the silk material of making 1.5～4.0mm.
Preferably, the thick line base of diameter 4.5～8mm is stretched to diameter 4.0mm～7.0mm, and then annealing; Again with the wire stretching of 4.0mm～7.0mm to 3.5mm～6.0mm, and then annealing; At last with wire stretching to 1.5～4.0mm of 3.5mm～6.0mm.
Preferably, the annealing temperature after wherein each drawing is 180～230 ℃, and annealing time is 1.5～3 hours.
Preferably, wherein the drawing speed of each passage is 10～35mm/min, and draft temperature is 20～30 ℃.
Preferably, wherein polynary aluminum titanium alloy silk is 1.33 * 10 in vacuum tightness
-2In 180-280 ℃ of annealing 1.5-3 hour, 350～500 tons extrusion machine was adopted in extruding in the vacuum oven of Pa.
The described aluminum titanium alloy silk that adopts aforesaid method to obtain, diameter is 1.5-4.0mm, and the tensile strength of described aluminum titanium alloy silk is 75-115Mpa, and concrete performance perameter is as shown in table 2 below:
Table 2: the diameter of aluminum titanium alloy silk and the performance perameter of tensile strength
| Diameter (mm) | Tensile strength (Mpa) |
| 1.5 | 75 |
| 1.8 | 80 |
| 2.0 | 84 |
| 2.2 | 87 |
| 2.5 | 93 |
| 2.8 | 95 |
| 3.0 | 100 |
| 3.3 | 105 |
| 3.8 | 110 |
| 4.0 | 115 |
In sum, the present invention is by to aluminum titanium alloy silk, preparation technology's improvement, can form anti-corrosion, wear resistance good, the coating good with the matrix mechanical bond.The improvement of any adaptation of carrying out on basis of the present invention does not all break away from thought of the present invention, all falls into the scope of protection of the invention.
Claims (10)
1. polynary aluminum titanium alloy silk, by weight percentage, its component is: aluminium Al:94%-97%; Vanadium V:0.05%-1%; Titanium Ti:2%-5%; Cerium Ce:0.01-0.7%, neodymium Nd:0.01-0.2%, the total amount of these two kinds of rare earth elements: 0.02-0.76%, total amount is no more than 1% trace additives, the resistivity of described aluminum titanium alloy silk is 2.0-6.0 μ Ω cm, and the proportion of described aluminum titanium alloy silk is 2.60-2.75g/cm
3, the unit elongation 10～25% of described aluminum titanium alloy silk.
2. aluminum titanium alloy silk as claimed in claim 1, the total amount of wherein said two kinds of rare earth elements: 0.33-0.65%, the resistivity of described aluminum titanium alloy silk is 3.0-5.0 μ Ω cm, the proportion of described aluminum titanium alloy silk is 2.64-2.70g/cm
3, the unit elongation 15-18% of described aluminum titanium alloy silk.
3. aluminum titanium alloy silk as claimed in claim 1, the diameter of wherein said aluminum titanium alloy silk are 1.5-4.0mm, and the tensile strength of described aluminum titanium alloy silk after 180-280 ℃ of annealing reached repeatedly drawing in 1.5-3 hour is 75-115MPa.
4. aluminum titanium alloy silk as claimed in claim 1, the mass ratio of wherein said two kinds of rare earth elements are Ce/Nd=2/1～9/1.
5. aluminum titanium alloy silk as claimed in claim 1, wherein the mass ratio of each composition is:
V/Ti＝1/40～1/5，
Total amount=1/1～2/1 of two kinds of rare earth elements of V/,
Total amount=5/1～25/1 of two kinds of rare earth elements of Ti/.
6. as shining the described aluminum titanium alloy silk of claim 1, the composition of each component is respectively by weight percentage in the wherein said trace additives: Fe＜0.01%, Pb＜0.005%, Cd＜0.002%, Sn＜0.001%.
7. method for preparing the described aluminum titanium alloy silk of claim 1, weight percent according to described each component of aluminum titanium alloy silk is got the raw materials ready, each component is made aluminum titanium alloy by proportioning in smelting furnace, pour into the aluminum titanium alloy rod by the deep-well forging type again, then, the aluminum titanium alloy rod put into 350～450 ℃ electric furnace 4～8 hours, carrying out homogenizing handles, use extrusion machine again, at 380～420 ℃ of following hot extrusion materials, make material pass through circular die, form the thick line base of diameter 4.5～8mm,, carry out drawing again 180～280 ℃ of annealing 1.5～3 hours in vacuum annealing furnace of thick line base, annealing, and then repeat above drawing successively, the annealed step is up to the silk material of making 1.5～4.0mm.
8. method as claimed in claim 7, wherein drawing process is as follows: the thick line base of diameter 4.5～8mm is drawn to diameter 4.0mm～7.0mm, and then annealing; Again with the wire drawing of 4.0mm～7.0mm to 3.5mm～6.0mm, and then annealing; At last with wire drawing to 1.5～4.0mm of 3.5mm～6.0mm.
9. method as claimed in claim 8, the annealing temperature after wherein each drawing is 180～230 ℃, annealing time is 1.5～3 hours.
10. method as claimed in claim 8, wherein the drawing speed of each passage is 10～35mm/min, the drawing temperature is 20～30 ℃.
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| CN1718836A (en) * | 2004-07-09 | 2006-01-11 | 上海润实防蚀新材料科技有限公司 | Rare earth aluminium magnesium alloy spray coating corrosion resistant wire material, its preparation method and application |
| CN101906604B (en) * | 2010-07-30 | 2013-01-23 | 江苏中矿大正表面工程技术有限公司 | Rare earth aluminum alloy wire for thermal spraying |
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