CN105734371A - Novel high-strength corrosion-resistant aluminum alloy pipeline - Google Patents

Novel high-strength corrosion-resistant aluminum alloy pipeline Download PDF

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CN105734371A
CN105734371A CN201610220242.0A CN201610220242A CN105734371A CN 105734371 A CN105734371 A CN 105734371A CN 201610220242 A CN201610220242 A CN 201610220242A CN 105734371 A CN105734371 A CN 105734371A
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aluminium alloy
aluminum
alloy pipeline
pipeline
alloy
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董超超
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/12—Alloys based on aluminium with copper as the next major constituent
    • C22C21/16—Alloys based on aluminium with copper as the next major constituent with magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/026—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/12—Alloys based on aluminium with copper as the next major constituent
    • C22C21/14—Alloys based on aluminium with copper as the next major constituent with silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/057—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with copper as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L9/00—Rigid pipes
    • F16L9/02—Rigid pipes of metal

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)

Abstract

The invention discloses a novel high-strength corrosion-resistant aluminum alloy pipeline. The novel high-strength corrosion-resistant aluminum alloy pipeline is composed of, by weight, 0.2% of Mg, 2.0% of Si, 4.0% of Cu, 0.2% of Mn, 0.2% of Fe, 0.1% of Zr, 0.1% of Er, 0.01% of Cr, 0.01% of Ni, 0.1% of Ti, and the balance Al. The aluminum alloy pipeline is obtained through the steps that (1) smelting is conducted; (2) refining modifying agents are added, that is, the three metal refining modifying agents of Al-5Ti-B, Al-1OSr and Re are added; (3) a cast ingot is formed through 2-h standing at 100 MPa; (4) five-pass hot rolling is conducted, and three-pass cold rolling is conducted under ultrasonic vibration; (5) C laser and V laser are used for modification; and (6) surface treatment is conducted with an octadecyltrichlorosilane solution, and a finished product is obtained. Many measures are used for modifying and treating materials of the aluminum alloy pipeline, the aluminum alloy pipeline is made to maintain the integrity of an oxidation film under severe working condition of corrosion, failures of metal are avoided, and the requirement of current industrial development is met.

Description

Novel high-strength anticorodal aluminium alloy pipeline
Technical field
The present invention relates to pipeline field, particularly relate to novel high-strength anticorodal aluminium alloy pipeline.
Background technology
Aluminium alloy is a most widely used class non-ferrous metal structural material in industry, Aeronautics and Astronautics, automobile, machine-building, Boats and ships and chemical industry are widely applied, is divided into 1000 series, 2000 series, 3000 series ... 9000 series.Relevant In technology, 6000 series alloys mainly contain magnesium and two kinds of elements of silicon, have, low melting point, corrosion resistance, heat-resisting, wear-resisting, Easily coating and the advantage such as processability is good, but, 6000 series alloys seldom have steel strength and mouldability so that aluminum conjunction Gold cannot replace the steel weight with alleviator equipment completely, reduces energy resource consumption and pollutant emission.And along with aluminium alloy The development of application, it is desirable to aluminium alloy and can apply different field and environment, and therefore requirement corrosion proof to aluminium alloy is more and more higher. Although aluminium alloy its surface under natural environment can generate layer oxide film to resist corrosion, but aluminum alloy surface in natural environment The thickness of oxidation film about 4nm generated, loose porous and structure is the most uneven, corrodes under severe operating conditions or from oxide-film Hole, or occur from the fray of oxide-film, cause metal failure, it is impossible to meet the requirement of current industrial development.
Summary of the invention
For the problems referred to above, it is an object of the invention to provide novel high-strength anticorodal aluminium alloy pipeline, solve aluminium alloy and do not have Steel strength and the technical problem of mouldability.
For solve above-mentioned technical problem, the technical solution used in the present invention is novel high-strength anticorodal aluminium alloy pipeline, described outside Shell includes Mg0.2%, Si 2.0%, Cu4.0%, Mn0.2%, Fe0.2%, Zr0.1%, Er0.1%, Cr0.01% by weight percentage, Ni0.01%, Ti0.1%, Al surplus.
Novel high-strength anticorodal aluminium alloy pipeline preparation method, described aluminium alloy pipeline is the shell being made up of following steps:
(1) heating furnace used in pre-hot smelting at 300 DEG C and fine aluminium 1～2h；(2) fine aluminium after preheating is at decompression state Lower smelting temperature be the heating furnace of 750 DEG C is completely melt after add monocrystal silicon granule, add in aluminum bronze after monocrystal silicon particles fuse Between alloy, aluminum manganese intermediate alloy, aluminium chromium hardener, aluminum nickel intermediate alloy, ferro-aluminum intermediate alloy, aluminium zirconium hardener and A small amount of rare earth element er, and be incubated a period of time and be completely melt to intermediate alloy, after being sufficiently stirred for, heating furnace is heated up, add aluminum Titanium intermediate alloy is completely melt to aluminum titanium intermediate alloy, is cooled to 750 DEG C, skims, and adds pure magnesium, protects under conditions of vacuum Temperature 30～40min；(4) tri-kinds of metal fining modifiers of Al-5Ti-B, Al-lOSr and RE are added, the weight hundred that three adds Proportion by subtraction ratio is 8:1:3；(5) add refining agent fully to react, degasification, slagging-off,；(6) melted pouring metal melt is to Preheated to the crucible of about 300 DEG C stands under conditions of 100MPa 2h, form ingot casting；(7) described ingot casting cuts into conjunction Carrying out the homogenizing annealing of 12 hours after suitable size under conditions of 550 DEG C, stove is cooled to room temperature；(8) described ingot casting is warming up to It is incubated 3 hours after 420 DEG C, carries out the hot rolling of five passages, after each passage hot rolling is complete, be incubated half an hour at 530 DEG C；(9) heat Carrying out the cold rolling of three passages after rolling, aluminium alloy one end is relatively fixed and connects ultrasonic vibration apparatus, and the other end enters in milling train, Excited frequency is 12kHz, aluminium alloy supersonic vibration pressurized extend, cold rolling after carry out 2 hours moving back at 240 DEG C to alloy Fire processes, and obtains certain thickness aluminum alloy plate materials；(10) aluminum alloy plate materials is carried out halfhour solution treatment at 540 DEG C, Then shrend；(11) aluminum alloy plate materials carries out the artificial aging of 5 hours at 180 DEG C；(12) by equal for mixed-powder C and V The even surface being applied in aluminum alloy plate materials, uses crossing current continuous wave Cq laser instrument that aluminum alloy plate materials carries out laser treatment modified, makes Obtain and while aluminum alloy sheet material surface forms nanoscale impression, mixed-powder C and V melted the surface being covered in aluminum alloy plate materials, Using argon to protect in processing procedure, its laser process parameter area is: laser power 1.7kw, sweep speed 13mn/s, Beam spot diameter, is 4mm.(13) configuration hydrochloric acid volume is the hydrochloric acid solution of 2:1 with deionized water volume ratio, with ethanol as solute The octadecyl trichlorosilane alkane solution of configuration 5mM, puts into process 2min in hydrochloric acid solution by the aluminium alloy obtained, use after having processed Sample, to remove unnecessary hydrochloric acid, is positioned over octadecyl trichlorosilane alkane solution by a large amount of deionized water rinsing aluminum alloy surface subsequently Middle immersion 12h, the sample of preparation is dried 30min at 80 DEG C；(14) molding.
Beneficial effects of the present invention:
1, the ratio of each element weight percent of Reasonable adjustment so that formed in aluminium alloy pipeline and keep peak aging strengthening ability Mg2Si phase, increases its elongation percentage while strengthening aluminium alloy pipeline intensity.Add the Cu element of proper proportion, when reducing nature The effect adverse effect to material property, forms Mg more tiny, more2Si phase (acicular beta " phase), avoid adding Cu unit simultaneously Aluminium alloy pipeline corrosion stability is reduced after element.Add trace Mn and Cr, disperse phase can be produced, suppress alloy recrystallization, improve alloy Intensity, increases Alloy Anti intercrystalline corrosion ability, improves alloy property.Appropriate rare earth element adds in aluminium alloy pipeline, can subtract Gas less or in elimination fusion-casting process and objectionable impurities, increase mobility, crystal grain thinning, accelerated ag(e)ing process, and in right amount Rare earth element and other elements cooperate and can effectively improve mechanical property and the corrosive nature of alloy.
2, under decompression state, smelting aluminium alloy pipeline can be effectively reduced smelting temperature, saves resource.Simultaneously in order to keep heater Interior pressure, heater needs to pour into a certain amount of noble gas while discharging gas, and first noble gas is passed directly into gold Belong in liquation, form bubble, drive the impurity in molten metal to move up, jointly discharge with gas, go the removal of impurity, additionally Noble gas forces the harmful gas produced in fusion process to be discharged therewith, and the gas preventing oxygen etc. to have oxidizing property enters and adds Oxidized metal liquation in hot device.
3, three kinds of fining modifiers have positive role to aluminium alloy pipeline, but have some limitations when being single use, as It is individually added into Sr and makees Metamorphism treatment, the tendency aggravation of alloy air-breathing, drop low-alloyed compactness, be easily formed serious columanar structure, Causing mechanical property to decline on the contrary, rare earth easily aoxidizes, and modification effect is held time short etc.；And the antidamping of Al-5Ti-B fining agent Performance is the most unsatisfactory, and is easily poisoned by Zr atom and lose the ability of crystal grain thinning, it is impossible to give full play to it each Advantage.And triplicity is used and can give full play to respective advantage while overcoming the defect itself having.
4, melted pouring metal melt is to having been warmed up standing under conditions of 100MPa 2h to the crucible of about 300 DEG C, Can prevent from metal liquid process of setting is formed the ingot casting of open structure, thus affect the intensity of aluminium alloy pipeline, simultaneously at high pressure Under conditions of advantageously form the ingot casting of compact texture, strengthen the intensity of aluminium alloy pipeline.
5, aluminium alloy pipeline supersonic vibration pressurized at the vibrating amplitude extends, and can reduce the frictional force being subject in the operation of rolling, thus Reduce the frictional force impact on aluminium alloy pipeline plate surface, cold rolling relative to static state, aluminium alloy pipeline table that supersonic vibration is cold rolling Face is more smooth, is conducive to carrying out the operation of next step.
6, by mixed-powder C and V uniform application in the surface of aluminium alloy pipeline sheet material, crossing current continuous wave Cq laser instrument pair is used It is modified that aluminium alloy pipeline sheet material carries out laser treatment, while effectively enabling aluminum alloy to duct board surface formation nanoscale impression Mixed-powder C and V melts the surface being covered in aluminium alloy pipeline sheet material, and aluminium alloy pipeline plate surface is formed nano level recessed Hole, increases the surface area of aluminium alloy pipeline sheet material, and the octadecyl trichlorosilane alkane making next step while improving frictional force is molten Liquid is easier to enter aluminium alloy pipeline plate surface, forms the micro structure of different morphologies on aluminium alloy pipeline surface, then on surface Upper self assembly possesses the silane film of anticorrosion antiwear performance, thus changes the surface nature of aluminium alloy pipeline sheet material, and aluminium alloy pipeline The C-V overlay film that plate surface is formed can be effectively improved aluminium alloy pipeline sheet material antioxygenic property at high temperature, changes aluminium alloy The surface nature of duct board.
Detailed description of the invention
The invention will be further described with the following Examples.
Embodiment one
Novel high-strength anticorodal aluminium alloy pipeline, includes Mg0.2%, Si 2.0%, Cu4.0%, Mn0.2% by weight percentage, Fe0.2%, Zr0.1%, Er0.1%, Cr0.01%, Ni0.01%, Ti0.1%, Al surplus.
Novel high-strength anticorodal aluminium alloy pipeline preparation method, described aluminium alloy pipeline is the shell being made up of following steps:
(1) heating furnace used in pre-hot smelting at 300 DEG C and fine aluminium 1～2h；(2) fine aluminium after preheating is at decompression state Lower smelting temperature be the heating furnace of 750 DEG C is completely melt after add monocrystal silicon granule, add in aluminum bronze after monocrystal silicon particles fuse Between alloy, aluminum manganese intermediate alloy, aluminium chromium hardener, aluminum nickel intermediate alloy, ferro-aluminum intermediate alloy, aluminium zirconium hardener and A small amount of rare earth element er, and be incubated a period of time and be completely melt to intermediate alloy, after being sufficiently stirred for, heating furnace is heated up, add aluminum Titanium intermediate alloy is completely melt to aluminum titanium intermediate alloy, is cooled to 750 DEG C, skims, and adds pure magnesium, protects under conditions of vacuum Temperature 30～40min；(4) tri-kinds of metal fining modifiers of Al-5Ti-B, Al-lOSr and RE are added, the weight hundred that three adds Proportion by subtraction ratio is 8:1:3；(5) add refining agent fully to react, degasification, slagging-off,；(6) melted pouring metal melt is to Preheated to the crucible of about 300 DEG C stands under conditions of 100MPa 2h, form ingot casting；(7) described ingot casting cuts into conjunction Carrying out the homogenizing annealing of 12 hours after suitable size under conditions of 550 DEG C, stove is cooled to room temperature；(8) described ingot casting is warming up to It is incubated 3 hours after 420 DEG C, carries out the hot rolling of five passages, after each passage hot rolling is complete, be incubated half an hour at 530 DEG C；(9) heat Carrying out the cold rolling of three passages after rolling, aluminium alloy one end is relatively fixed and connects ultrasonic vibration apparatus, and the other end enters in milling train, Excited frequency is 12kHz, aluminium alloy supersonic vibration pressurized extend, cold rolling after carry out 2 hours moving back at 240 DEG C to alloy Fire processes, and obtains certain thickness aluminum alloy plate materials；(10) aluminum alloy plate materials is carried out halfhour solution treatment at 540 DEG C, Then shrend；(11) aluminum alloy plate materials carries out the artificial aging of 5 hours at 180 DEG C；(12) by equal for mixed-powder C and V The even surface being applied in aluminum alloy plate materials, uses crossing current continuous wave Cq laser instrument that aluminum alloy plate materials carries out laser treatment modified, makes Obtain and while aluminum alloy sheet material surface forms nanoscale impression, mixed-powder C and V melted the surface being covered in aluminum alloy plate materials, Using argon to protect in processing procedure, its laser process parameter area is: laser power 1.7kw, sweep speed 13mn/s, Beam spot diameter, is 4mm.(13) configuration hydrochloric acid volume is the hydrochloric acid solution of 2:1 with deionized water volume ratio, with ethanol as solute The octadecyl trichlorosilane alkane solution of configuration 5mM, puts into process 2min in hydrochloric acid solution by the aluminium alloy obtained, use after having processed Sample, to remove unnecessary hydrochloric acid, is positioned over octadecyl trichlorosilane alkane solution by a large amount of deionized water rinsing aluminum alloy surface subsequently Middle immersion 12h, the sample of preparation is dried 30min at 80 DEG C；(14) molding.
The tensile strength of aluminium alloy pipeline sheet material, yield strength, percentage elongation and the Brinell hardness made be respectively 398.4MPa, 325.8MPa, 20%, 112HB.
The ratio of each element weight percent of Reasonable adjustment so that formed in aluminium alloy pipeline and keep peak aging strengthening ability Mg2Si phase, increases its elongation percentage while strengthening aluminium alloy pipeline intensity.Add the Cu element of proper proportion, reduce natrual ageing Adverse effect to material property, forms Mg more tiny, more2Si phase (acicular beta " phase), avoid adding Cu element simultaneously Rear reduction aluminium alloy pipeline corrosion stability.Add trace Mn and Cr, disperse phase can be produced, suppress alloy recrystallization, improve alloy strong Degree, increases Alloy Anti intercrystalline corrosion ability, improves alloy property.Appropriate rare earth element adds in aluminium alloy pipeline, can reduce Or the gas in elimination fusion-casting process and objectionable impurities, increase mobility, crystal grain thinning, accelerated ag(e)ing process, and appropriate Rare earth element and other elements cooperate and can effectively improve mechanical property and the corrosive nature of alloy.
Under decompression state, smelting aluminium alloy pipeline can be effectively reduced smelting temperature, saves resource.In simultaneously in order to keep heater Pressure, heater needs to pour into a certain amount of noble gas discharging while gas, and first noble gas is passed directly into metal In liquation, form bubble, drive the impurity in molten metal to move up, jointly discharge with gas, go the removal of impurity, the most lazy Property gas force in fusion process produce harmful gas discharge therewith, prevent oxygen etc. have oxidizing property gas enter heating Oxidized metal liquation in device.
Three kinds of fining modifiers have positive role to aluminium alloy pipeline, but have some limitations when being single use, such as list Solely add Sr and make Metamorphism treatment, the tendency aggravation of alloy air-breathing, drop low-alloyed compactness, be easily formed serious columanar structure, lead Causing mechanical property to decline on the contrary, rare earth easily aoxidizes, and modification effect is held time short etc.；And the fade resistance of Al-5Ti-B fining agent Can be the most unsatisfactory, and easily poisoned by Zr atom and lose the ability of crystal grain thinning, it is impossible to give full play to it respective Advantage.And triplicity is used and can give full play to respective advantage while overcoming the defect itself having.Can by form Know, relative to single use fining modifier, use simultaneously three kinds of fining modifiers can strengthen aluminium alloy pipeline tensile strength, Yield strength, percentage elongation and Brinell hardness, after wherein in table, data are interpolation fining modifier and without aluminum after fining modifier The comparison in various performance indications of the alloy pipeline, uses the tensile strength of the aluminium alloy pipeline of three kinds of fining modifiers to increase simultaneously 6.892%, yield strength adds 5.974%, percentage elongation add 18.0% and Brinell hardness add 9.821%.
Melted pouring metal melt, to having been warmed up standing under conditions of 100MPa 2h to the crucible of about 300 DEG C, can be prevented Metal liquid process of setting is only formed the ingot casting of open structure, thus affects the intensity of aluminium alloy pipeline sheet material, simultaneously at high pressure Under conditions of advantageously form the ingot casting of compact texture, strengthen the intensity of aluminium alloy pipeline.
Aluminium alloy pipeline supersonic vibration pressurized at the vibrating amplitude extends, and can reduce the frictional force being subject in the operation of rolling, thus drop The low-frictional force impact on aluminium alloy pipeline plate surface, cold rolling relative to static state, aluminium alloy pipeline surface that supersonic vibration is cold rolling More smooth, be conducive to carrying out the operation of next step.
By mixed-powder C and V uniform application in the surface of aluminium alloy pipeline sheet material, use crossing current continuous wave Cq laser instrument that aluminum is closed It is modified that gold duct board carries out laser treatment, and can effectively enable aluminum alloy to will be mixed while duct board surface forms nanoscale impression Closing powder C and V and melt the surface being covered in aluminium alloy pipeline sheet material, aluminium alloy pipeline plate surface forms nano level pit, Increase the surface area of aluminium alloy pipeline sheet material, while improving frictional force, make the octadecyl trichlorosilane alkane solution of next step more It is easily accessible aluminium alloy pipeline plate surface, forms the micro structure of different morphologies on aluminium alloy pipeline surface, the most certainly Assemble the silane film possessing anticorrosion antiwear performance, thus change the surface nature of aluminium alloy pipeline sheet material, and aluminium alloy pipeline sheet material The C-V overlay film that surface is formed can be effectively improved aluminium alloy pipeline sheet material antioxygenic property at high temperature, changes aluminium alloy pipeline The surface nature of sheet material.
In order to measure aluminium alloy pipeline Surface Creation film layer corrosion resisting property in saline solution, use Tafel curve and electrochemical impedance Spectrum evaluates the antiseptic property of thin film, and before carrying out electro-chemical test, all samples all soaks a period of time in NaCl solution, Electrochemical impedance spectroscopy and Plan Curve stably measure afterwards at open circuit point position (OCP), obtain the corrosion of aluminium alloy pipeline sheet material Current potential (Ecorr) and corrosion electric current density (Icorr) numerical value, it is considered that the tendency of the highest sample etches of corrosion potential is the least, And the corrosion rate of corrosion electric current density the least expression sample is the least, corrosion resisting property is the best.Measure the aluminium alloy pipeline sheet material obtained Corrosion potential (Ecorr) it is-545.8mV, the corrosion electric current density (I of aluminium alloy pipeline sheet materialcorr) it is 1.421 μ Acm-2, and Untreated aluminium alloy pipeline is-1057mV, the corrosion electric current density (I of undressed aluminium alloy pipelinecorr) it is 4.303μAcm-2, it follows that the aluminium alloy pipeline sheet material corrosion resistance of the present invention is compared to untreated aluminium-alloy pipe Road has promoted.
Embodiment two
Novel high-strength anticorodal aluminium alloy pipeline, includes Mg0.6%, Si3.5%, Cu6.0%, Mn0.3% by weight percentage, Fe0.3%, Zr0.5%, Er0.5%, Cr0.02%, Ni0.02%, Ti0.2%, Al surplus.
Novel high-strength anticorodal aluminium alloy pipeline preparation method, described aluminium alloy pipeline is the shell being made up of following steps:
(1) heating furnace used in 320 times pre-hot smeltings and fine aluminium 1～2h；(2) the fine aluminium melting under a reduced pressure after preheating Temperature be the heating furnace of 750 DEG C is completely melt after add monocrystal silicon granule, add after monocrystal silicon particles fuse aluminum bronze intermediate alloy, Aluminum manganese intermediate alloy, aluminium chromium hardener, aluminum nickel intermediate alloy, ferro-aluminum intermediate alloy, aluminium zirconium hardener and a small amount of rare earth Element erbium, and be incubated a period of time and be completely melt to intermediate alloy, after being sufficiently stirred for, heating furnace is heated up, add and close in the middle of aluminum titanium Gold is completely melt to aluminum titanium intermediate alloy, is cooled to 750 DEG C, skims, adds pure magnesium, is incubated 30～40min under conditions of vacuum； (4) adding tri-kinds of metal fining modifiers of Al-5Ti-B, Al-lOSr and RE, the percentage by weight ratio that three adds is 8:1:3； (5) add refining agent fully to react, degasification, slagging-off,；(6) melted pouring metal melt is to having been warmed up to 300 DEG C of left sides Right crucible stands under conditions of 100MPa 2.5h, forms ingot casting；(7) in 550 DEG C after described ingot casting cuts into suitable dimension Under conditions of carry out the homogenizing annealing of 12 hours, stove is cooled to room temperature；(8) it is incubated 3 hours after described ingot casting is warming up to 420 DEG C, Carry out the hot rolling of five passages, after each passage hot rolling is complete, be incubated half an hour at 530 DEG C；(9) three passages are carried out after hot rolling Cold rolling, aluminium alloy one end is relatively fixed and connects ultrasonic vibration apparatus, and the other end enters in milling train, and excited frequency is 14kHz, Aluminium alloy supersonic vibration pressurized extends, cold rolling after alloy carried out at 240 DEG C the annealing of 2～3 hours, obtain certain The aluminum alloy plate materials of thickness；(10) aluminum alloy plate materials is carried out halfhour solution treatment, then shrend at 540 DEG C；(11) Aluminum alloy plate materials carries out the artificial aging of 5 hours at 180 DEG C；(12) by mixed-powder C and V uniform application in aluminium alloy plate The surface of material, uses crossing current continuous wave Cq laser instrument that aluminum alloy plate materials carries out laser treatment modified so that aluminum alloy sheet material surface While forming nanoscale impression, mixed-powder C and V is melted the surface being covered in aluminum alloy plate materials, processing procedure uses argon Gas is protected, and its laser process parameter area is: laser power 2.0kw, sweep speed 15mn/s, beam spot diameter, is 4mm. (13) configuration hydrochloric acid volume is the hydrochloric acid solution of 2:1 with deionized water volume ratio, the octadecane being solute configuration 5mM with ethanol Base trichlorosilane solution, puts into the aluminium alloy obtained process 2min in hydrochloric acid solution, uses a large amount of deionized water rinsing after having processed Sample, to remove unnecessary hydrochloric acid, is positioned in octadecyl trichlorosilane alkane solution immersion 12h, preparation by aluminum alloy surface subsequently Sample at 80 DEG C be dried 30min；(14) molding.
The tensile strength of aluminium alloy pipeline sheet material, yield strength, percentage elongation and the Brinell hardness made be respectively 427.2MPa, 341.8MPa, 16%, 107HB.
Three kinds of fining modifiers have positive role to aluminium alloy pipeline, but have some limitations when being single use, such as list Solely add Sr and make Metamorphism treatment, the tendency aggravation of alloy air-breathing, drop low-alloyed compactness, be easily formed serious columanar structure, lead Causing mechanical property to decline on the contrary, rare earth easily aoxidizes, and modification effect is held time short etc.；And the fade resistance of Al-5Ti-B fining agent Can be the most unsatisfactory, and easily poisoned by Zr atom and lose the ability of crystal grain thinning, it is impossible to give full play to it respective Advantage.And triplicity is used and can give full play to respective advantage while overcoming the defect itself having.Can by form Know, relative to single use fining modifier, use simultaneously three kinds of fining modifiers can strengthen aluminium alloy pipeline tensile strength, Yield strength, percentage elongation and Brinell hardness, after wherein in table, data are interpolation fining modifier and without aluminum after fining modifier The comparison in various performance indications of the alloy pipeline.
The ratio of each element weight percent of Reasonable adjustment so that formed in aluminium alloy pipeline and keep peak aging strengthening ability Mg2Si phase, increases its elongation percentage while strengthening aluminium alloy pipeline intensity.Add the Cu element of proper proportion, reduce natrual ageing Adverse effect to material property, forms Mg more tiny, more2Si phase (acicular beta " phase), avoid adding Cu element simultaneously Rear reduction aluminium alloy pipeline corrosion stability.Add trace Mn and Cr, disperse phase can be produced, suppress alloy recrystallization, improve alloy strong Degree, increases Alloy Anti intercrystalline corrosion ability, improves alloy property.Appropriate rare earth element adds in aluminium alloy pipeline, can reduce Or the gas in elimination fusion-casting process and objectionable impurities, increase mobility, crystal grain thinning, accelerated ag(e)ing process, and appropriate Rare earth element and other elements cooperate and can effectively improve mechanical property and the corrosive nature of alloy.
Under decompression state, smelting aluminium alloy pipeline can be effectively reduced smelting temperature, saves resource.In simultaneously in order to keep heater Pressure, heater needs to pour into a certain amount of noble gas discharging while gas, and first noble gas is passed directly into metal In liquation, form bubble, drive the impurity in molten metal to move up, jointly discharge with gas, go the removal of impurity, the most lazy Property gas force in fusion process produce harmful gas discharge therewith, prevent oxygen etc. have oxidizing property gas enter heating Oxidized metal liquation in device.
Three kinds of fining modifiers have positive role to aluminium alloy pipeline, but have some limitations when being single use, such as list Solely add Sr and make Metamorphism treatment, the tendency aggravation of alloy air-breathing, drop low-alloyed compactness, be easily formed serious columanar structure, lead Causing mechanical property to decline on the contrary, rare earth easily aoxidizes, and modification effect is held time short etc.；And the fade resistance of Al-5Ti-B fining agent Can be the most unsatisfactory, and easily poisoned by Zr atom and lose the ability of crystal grain thinning, it is impossible to give full play to it respective Advantage.And triplicity is used and can give full play to respective advantage while overcoming the defect itself having.Can by form Know, relative to single use fining modifier, use simultaneously three kinds of fining modifiers can strengthen aluminium alloy pipeline tensile strength, Yield strength, percentage elongation and Brinell hardness, after wherein in table, data are interpolation fining modifier and without aluminum after fining modifier The comparison in various performance indications of the alloy pipeline, uses the tensile strength of the aluminium alloy pipeline of three kinds of fining modifiers to increase simultaneously 7.234%, yield strength adds 6.704%, percentage elongation add 20.0% and Brinell hardness add 10.758%.
Melted pouring metal melt, can to having been warmed up standing under conditions of 100MPa 2.5h to the crucible of about 300 DEG C Prevent from metal liquid process of setting is formed the ingot casting of open structure, thus affect the intensity of aluminium alloy pipeline sheet material, simultaneously at height Advantageously form the ingot casting of compact texture under conditions of pressure, strengthen the intensity of aluminium alloy pipeline.
Aluminium alloy pipeline supersonic vibration pressurized at the vibrating amplitude extends, and can reduce the frictional force being subject in the operation of rolling, thus drop The low-frictional force impact on aluminium alloy pipeline plate surface, cold rolling relative to static state, aluminium alloy pipeline surface that supersonic vibration is cold rolling More smooth, be conducive to carrying out the operation of next step.
By mixed-powder C and V uniform application in the surface of aluminium alloy pipeline sheet material, use crossing current continuous wave Cq laser instrument that aluminum is closed It is modified that gold duct board carries out laser treatment, and can effectively enable aluminum alloy to will be mixed while duct board surface forms nanoscale impression Closing powder C and V and melt the surface being covered in aluminium alloy pipeline sheet material, aluminium alloy pipeline plate surface forms nano level pit, Increase the surface area of aluminium alloy pipeline sheet material, while improving frictional force, make the octadecyl trichlorosilane alkane solution of next step more It is easily accessible aluminium alloy pipeline plate surface, forms the micro structure of different morphologies on aluminium alloy pipeline surface, the most certainly Assemble the silane film possessing anticorrosion antiwear performance, thus change the surface nature of aluminium alloy pipeline sheet material, and aluminium alloy pipeline sheet material The C-V overlay film that surface is formed can be effectively improved aluminium alloy pipeline sheet material antioxygenic property at high temperature, changes aluminium alloy pipeline The surface nature of sheet material.
In order to measure aluminium alloy pipeline Surface Creation film layer corrosion resisting property in saline solution, use Tafel curve and electrochemical impedance Spectrum evaluates the antiseptic property of thin film, and before carrying out electro-chemical test, all samples all soaks a period of time in NaCl solution, Electrochemical impedance spectroscopy and Plan Curve stably measure afterwards at open circuit point position (OCP), obtain the corrosion of aluminium alloy pipeline sheet material Current potential (Ecorr) and corrosion electric current density (Icorr) numerical value, it is considered that the tendency of the highest sample etches of corrosion potential is the least, And the corrosion rate of corrosion electric current density the least expression sample is the least, corrosion resisting property is the best.Measure the aluminium alloy pipeline sheet material obtained Corrosion potential (Ecorr) it is-564.2mV, the corrosion electric current density (I of aluminium alloy pipeline sheet materialcorr) it is 1.145 μ Acm-2, and Untreated aluminium alloy pipeline is-1057mV, the corrosion electric current density (I of undressed aluminium alloy pipelinecorr) it is 4.303μAcm-2, it follows that the aluminium alloy pipeline sheet material corrosion resistance of the present invention is compared to untreated aluminium-alloy pipe Road has promoted.
Embodiment three
Novel high-strength anticorodal aluminium alloy pipeline, includes Mg0.6%, Si2.0%, Cu5.0%, Mn0.25% by weight percentage, Fe0.25%, Zr0.3%, Er0.3%, Cr0.015%, Ni0.015%, Ti0.015%, Al surplus.
Novel high-strength anticorodal aluminium alloy pipeline preparation method, described aluminium alloy pipeline is the shell being made up of following steps:
(1) heating furnace used in pre-hot smelting at 330 DEG C and fine aluminium 1～2h；(2) fine aluminium after preheating melts under a reduced pressure Refine and add monocrystal silicon granule after the heating furnace that temperature is 750 DEG C is completely melt, add after monocrystal silicon particles fuse and close in the middle of aluminum bronze Gold, aluminum manganese intermediate alloy, aluminium chromium hardener, aluminum nickel intermediate alloy, ferro-aluminum intermediate alloy, aluminium zirconium hardener and a small amount of Rare earth element er, and be incubated a period of time and be completely melt to intermediate alloy, after being sufficiently stirred for, heating furnace is heated up, add in aluminum titanium Between alloy be completely melt to aluminum titanium intermediate alloy, be cooled to 750 DEG C, skim, add pure magnesium, under conditions of vacuum be incubated 30～ 40min；(4) adding tri-kinds of metal fining modifiers of Al-5Ti-B, Al-lOSr and RE, the weight percent that three adds is frequently Example is 8:1:3；(5) add refining agent fully to react, degasification, slagging-off,；(6) melted pouring metal melt is to having been warmed up To the crucibles of about 300 DEG C, under conditions of 100MPa, stand 3h, form ingot casting；(7) described ingot casting cuts into suitable dimension After under conditions of 550 DEG C, carry out the homogenizing annealing of 12 hours, stove is cooled to room temperature；(8) after described ingot casting is warming up to 420 DEG C It is incubated 3 hours, carries out the hot rolling of five passages, after each passage hot rolling is complete, be incubated half an hour at 530 DEG C；(9) hot rolling is laggard Three passages of row cold rolling, aluminium alloy one end is relatively fixed and connects ultrasonic vibration apparatus, and the other end enters in milling train, exciting Frequency is 15kHz, and aluminium alloy supersonic vibration pressurized extends, cold rolling after alloy carried out at 240 DEG C the annealing of 2～3 hours Process, obtain certain thickness aluminum alloy plate materials；(10) aluminum alloy plate materials is carried out halfhour solution treatment at 540 DEG C, Then shrend；(11) aluminum alloy plate materials carries out the artificial aging of 5 hours at 180 DEG C；(12) by equal for mixed-powder C and V The even surface being applied in aluminum alloy plate materials, uses crossing current continuous wave Cq laser instrument that aluminum alloy plate materials carries out laser treatment modified, makes Obtain and while aluminum alloy sheet material surface forms nanoscale impression, mixed-powder C and V melted the surface being covered in aluminum alloy plate materials, Using argon to protect in processing procedure, its laser process parameter area is: laser power 2.1kw, sweep speed 18mm/s, Beam spot diameter, is 4mm.(13) configuration hydrochloric acid volume is the hydrochloric acid solution of 2:1 with deionized water volume ratio, with ethanol as solute The octadecyl trichlorosilane alkane solution of configuration 5mM, puts into process 2min in hydrochloric acid solution by the aluminium alloy obtained, use after having processed Sample, to remove unnecessary hydrochloric acid, is positioned over octadecyl trichlorosilane alkane solution by a large amount of deionized water rinsing aluminum alloy surface subsequently Middle immersion 12h, the sample of preparation is dried 30min at 80 DEG C；(14) molding.
The tensile strength of aluminium alloy pipeline sheet material, yield strength, percentage elongation and the Brinell hardness made be respectively 402.3MPa, 331.2MPa, 18%, 109HB.The ratio of each element weight percent of Reasonable adjustment so that formed in aluminium alloy pipeline and keep The Mg of peak aging strengthening ability2Si phase, increases its elongation percentage while strengthening aluminium alloy pipeline intensity.Add the Cu of proper proportion Element, reduces the natrual ageing adverse effect to material property, forms Mg more tiny, more2Si phase (acicular beta " phase), Reduce aluminium alloy pipeline corrosion stability after avoiding adding Cu element simultaneously.Add trace Mn and Cr, disperse phase can be produced, suppress alloy Recrystallization, improves alloy strength, increases Alloy Anti intercrystalline corrosion ability, improves alloy property.Appropriate rare earth element adds aluminum and closes In gold pipeline, gas in fusion-casting process and objectionable impurities, increase mobility, crystal grain thinning, accelerated ag(e)ing can be reduced or eliminated Process, and appropriate rare earth element and other elements cooperate and can effectively improve mechanical property and the corrosive nature of alloy.
Under decompression state, smelting aluminium alloy pipeline can be effectively reduced smelting temperature, saves resource.In simultaneously in order to keep heater Pressure, heater needs to pour into a certain amount of noble gas discharging while gas, and first noble gas is passed directly into metal In liquation, form bubble, drive the impurity in molten metal to move up, jointly discharge with gas, go the removal of impurity, the most lazy Property gas force in fusion process produce harmful gas discharge therewith, prevent oxygen etc. have oxidizing property gas enter heating Oxidized metal liquation in device.
Three kinds of fining modifiers have positive role to aluminium alloy pipeline, but have some limitations when being single use, such as list Solely add Sr and make Metamorphism treatment, the tendency aggravation of alloy air-breathing, drop low-alloyed compactness, be easily formed serious columanar structure, lead Causing mechanical property to decline on the contrary, rare earth easily aoxidizes, and modification effect is held time short etc.；And the fade resistance of Al-5Ti-B fining agent Can be the most unsatisfactory, and easily poisoned by Zr atom and lose the ability of crystal grain thinning, it is impossible to give full play to it respective Advantage.And triplicity is used and can give full play to respective advantage while overcoming the defect itself having.Can by form Know, relative to single use fining modifier, use simultaneously three kinds of fining modifiers can strengthen aluminium alloy pipeline tensile strength, Yield strength, percentage elongation and Brinell hardness, after wherein in table, data are interpolation fining modifier and without aluminum after fining modifier The comparison in various performance indications of the alloy pipeline, uses the tensile strength of the aluminium alloy pipeline of three kinds of fining modifiers to increase simultaneously 8.126%, yield strength adds 7.237%, percentage elongation add 22.0% and Brinell hardness add 11.594%.
Melted pouring metal melt, to having been warmed up standing under conditions of 100MPa 3h to the crucible of about 300 DEG C, can be prevented Metal liquid process of setting is only formed the ingot casting of open structure, thus affects the intensity of aluminium alloy pipeline sheet material, simultaneously at high pressure Under conditions of advantageously form the ingot casting of compact texture, strengthen the intensity of aluminium alloy pipeline.
Aluminium alloy pipeline supersonic vibration pressurized at the vibrating amplitude extends, and can reduce the frictional force being subject in the operation of rolling, thus drop The low-frictional force impact on aluminium alloy pipeline plate surface, cold rolling relative to static state, aluminium alloy pipeline surface that supersonic vibration is cold rolling More smooth, be conducive to carrying out the operation of next step.
By mixed-powder C and V uniform application in the surface of aluminium alloy pipeline sheet material, use crossing current continuous wave Cq laser instrument that aluminum is closed It is modified that gold duct board carries out laser treatment, and can effectively enable aluminum alloy to will be mixed while duct board surface forms nanoscale impression Closing powder C and V and melt the surface being covered in aluminium alloy pipeline sheet material, aluminium alloy pipeline plate surface forms nano level pit, Increase the surface area of aluminium alloy pipeline sheet material, while improving frictional force, make the octadecyl trichlorosilane alkane solution of next step more It is easily accessible aluminium alloy pipeline plate surface, forms the micro structure of different morphologies on aluminium alloy pipeline surface, the most certainly Assemble the silane film possessing anticorrosion antiwear performance, thus change the surface nature of aluminium alloy pipeline sheet material, and aluminium alloy pipeline sheet material The C-V overlay film that surface is formed can be effectively improved aluminium alloy pipeline sheet material antioxygenic property at high temperature, changes aluminium alloy pipeline The surface nature of sheet material.
In order to measure aluminium alloy pipeline Surface Creation film layer corrosion resisting property in saline solution, use Tafel curve and electrochemical impedance Spectrum evaluates the antiseptic property of thin film, and before carrying out electro-chemical test, all samples all soaks a period of time in NaCl solution, Electrochemical impedance spectroscopy and Plan Curve stably measure afterwards at open circuit point position (OCP), obtain the corrosion of aluminium alloy pipeline sheet material Current potential (Ecorr) and corrosion electric current density (Icorr) numerical value, it is considered that the tendency of the highest sample etches of corrosion potential is the least, And the corrosion rate of corrosion electric current density the least expression sample is the least, corrosion resisting property is the best.Measure the aluminium alloy pipeline sheet material obtained Corrosion potential (Ecorr) it is-627.1mV, the corrosion electric current density (I of aluminium alloy pipeline sheet materialcorr) it is 1.298 μ Acm-2, and Untreated aluminium alloy pipeline is-1057mV, the corrosion electric current density (I of undressed aluminium alloy pipelinecorr) it is 4.303μAcm-2, it follows that the aluminium alloy pipeline sheet material corrosion resistance of the present invention is compared to untreated aluminium-alloy pipe Road has promoted.
Embodiment four
Novel high-strength anticorodal aluminium alloy pipeline, includes Mg0.3%, Si 2.5%, Cu4.5%, Mn0.25% by weight percentage, Fe0.2%, Zr0.2%, Er0.2%, Cr0.01%, Ni0.01%, Ti0.1%, Al surplus.
Novel high-strength anticorodal aluminium alloy pipeline preparation method, described aluminium alloy pipeline is the shell being made up of following steps:
(1) heating furnace used in pre-hot smelting at 340 DEG C and fine aluminium 1～2h；(2) fine aluminium after preheating melts under a reduced pressure Refine and add monocrystal silicon granule after the heating furnace that temperature is 750 DEG C is completely melt, add after monocrystal silicon particles fuse and close in the middle of aluminum bronze Gold, aluminum manganese intermediate alloy, aluminium chromium hardener, aluminum nickel intermediate alloy, ferro-aluminum intermediate alloy, aluminium zirconium hardener and a small amount of Rare earth element er, and be incubated a period of time and be completely melt to intermediate alloy, after being sufficiently stirred for, heating furnace is heated up, add in aluminum titanium Between alloy be completely melt to aluminum titanium intermediate alloy, be cooled to 750 DEG C, skim, add pure magnesium, under conditions of vacuum be incubated 30～ 40min；(4) adding tri-kinds of metal fining modifiers of Al-5Ti-B, Al-lOSr and RE, the weight percent that three adds is frequently Example is 8:1:3；(5) add refining agent fully to react, degasification, slagging-off,；(6) melted pouring metal melt is to having been warmed up To the crucibles of about 300 DEG C, under conditions of 100MPa, stand 3.5h, form ingot casting；(7) described ingot casting cuts into suitable chi Carrying out the homogenizing annealing of 12 hours after very little under conditions of 550 DEG C, stove is cooled to room temperature；(8) described ingot casting is warming up to 420 DEG C Rear insulation 3 hours, carries out the hot rolling of five passages, is incubated half an hour at 530 DEG C after each passage hot rolling is complete；(9) after hot rolling Carrying out the cold rolling of three passages, aluminium alloy one end is relatively fixed and connects ultrasonic vibration apparatus, and the other end enters in milling train, swashs Vibration frequency is 16kHz, and aluminium alloy supersonic vibration pressurized extends, cold rolling after alloy carried out at 240 DEG C 2～move back for 3 hours Fire processes, and obtains certain thickness aluminum alloy plate materials；(10) aluminum alloy plate materials is carried out halfhour solution treatment at 540 DEG C, Then shrend；(11) aluminum alloy plate materials carries out the artificial aging of 5 hours at 180 DEG C；(12) by equal for mixed-powder C and V The even surface being applied in aluminum alloy plate materials, uses crossing current continuous wave Cq laser instrument that aluminum alloy plate materials carries out laser treatment modified, makes Obtain and while aluminum alloy sheet material surface forms nanoscale impression, mixed-powder C and V melted the surface being covered in aluminum alloy plate materials, Using argon to protect in processing procedure, its laser process parameter area is: laser power 2.3kw, sweep speed 19mn/s, Beam spot diameter, is 4mm.(13) configuration hydrochloric acid volume is the hydrochloric acid solution of 2:1 with deionized water volume ratio, with ethanol as solute The octadecyl trichlorosilane alkane solution of configuration 5mM, puts into process 2min in hydrochloric acid solution by the aluminium alloy obtained, use after having processed Sample, to remove unnecessary hydrochloric acid, is positioned over octadecyl trichlorosilane alkane solution by a large amount of deionized water rinsing aluminum alloy surface subsequently Middle immersion 12h, the sample of preparation is dried 30min at 80 DEG C；(14) molding.
The tensile strength of aluminium alloy pipeline sheet material, yield strength, percentage elongation and the Brinell hardness made be respectively 412.3MPa, 311.6MPa, 21%, 110HB.The ratio of each element weight percent of Reasonable adjustment so that formed in aluminium alloy pipeline and keep The Mg of peak aging strengthening ability2Si phase, increases its elongation percentage while strengthening aluminium alloy pipeline intensity.Add the Cu of proper proportion Element, reduces the natrual ageing adverse effect to material property, forms Mg more tiny, more2Si phase (acicular beta " phase), Reduce aluminium alloy pipeline corrosion stability after avoiding adding Cu element simultaneously.Add trace Mn and Cr, disperse phase can be produced, suppress alloy Recrystallization, improves alloy strength, increases Alloy Anti intercrystalline corrosion ability, improves alloy property.Appropriate rare earth element adds aluminum and closes In gold pipeline, gas in fusion-casting process and objectionable impurities, increase mobility, crystal grain thinning, accelerated ag(e)ing can be reduced or eliminated Process, and appropriate rare earth element and other elements cooperate and can effectively improve mechanical property and the corrosive nature of alloy.
Under decompression state, smelting aluminium alloy pipeline can be effectively reduced smelting temperature, saves resource.In simultaneously in order to keep heater Pressure, heater needs to pour into a certain amount of noble gas discharging while gas, and first noble gas is passed directly into metal In liquation, form bubble, drive the impurity in molten metal to move up, jointly discharge with gas, go the removal of impurity, the most lazy Property gas force in fusion process produce harmful gas discharge therewith, prevent oxygen etc. have oxidizing property gas enter heating Oxidized metal liquation in device.
Three kinds of fining modifiers have positive role to aluminium alloy pipeline, but have some limitations when being single use, such as list Solely add Sr and make Metamorphism treatment, the tendency aggravation of alloy air-breathing, drop low-alloyed compactness, be easily formed serious columanar structure, lead Causing mechanical property to decline on the contrary, rare earth easily aoxidizes, and modification effect is held time short etc.；And the fade resistance of Al-5Ti-B fining agent Can be the most unsatisfactory, and easily poisoned by Zr atom and lose the ability of crystal grain thinning, it is impossible to give full play to it respective Advantage.And triplicity is used and can give full play to respective advantage while overcoming the defect itself having.Can by form Know, relative to single use fining modifier, use simultaneously three kinds of fining modifiers can strengthen aluminium alloy pipeline tensile strength, Yield strength, percentage elongation and Brinell hardness, after wherein in table, data are interpolation fining modifier and without aluminum after fining modifier The comparison in various performance indications of the alloy pipeline, uses the tensile strength of the aluminium alloy pipeline of three kinds of fining modifiers to increase simultaneously 6.092%, yield strength adds 5.124%, percentage elongation add 15.0% and Brinell hardness add 8.067%.
Melted pouring metal melt, can to having been warmed up standing under conditions of 100MPa 3.5h to the crucible of about 300 DEG C Prevent from metal liquid process of setting is formed the ingot casting of open structure, thus affect the intensity of aluminium alloy pipeline sheet material, simultaneously at height Advantageously form the ingot casting of compact texture under conditions of pressure, strengthen the intensity of aluminium alloy pipeline.
Aluminium alloy pipeline supersonic vibration pressurized at the vibrating amplitude extends, and can reduce the frictional force being subject in the operation of rolling, thus drop The low-frictional force impact on aluminium alloy pipeline plate surface, cold rolling relative to static state, aluminium alloy pipeline surface that supersonic vibration is cold rolling More smooth, be conducive to carrying out the operation of next step.
By mixed-powder C and V uniform application in the surface of aluminium alloy pipeline sheet material, use crossing current continuous wave Cq laser instrument that aluminum is closed It is modified that gold duct board carries out laser treatment, and can effectively enable aluminum alloy to will be mixed while duct board surface forms nanoscale impression Closing powder C and V and melt the surface being covered in aluminium alloy pipeline sheet material, aluminium alloy pipeline plate surface forms nano level pit, Increase the surface area of aluminium alloy pipeline sheet material, while improving frictional force, make the octadecyl trichlorosilane alkane solution of next step more It is easily accessible aluminium alloy pipeline plate surface, forms the micro structure of different morphologies on aluminium alloy pipeline surface, the most certainly Assemble the silane film possessing anticorrosion antiwear performance, thus change the surface nature of aluminium alloy pipeline sheet material, and aluminium alloy pipeline sheet material The C-V overlay film that surface is formed can be effectively improved aluminium alloy pipeline sheet material antioxygenic property at high temperature, changes aluminium alloy pipeline The surface nature of sheet material.
In order to measure aluminium alloy pipeline Surface Creation film layer corrosion resisting property in saline solution, use Tafel curve and electrochemical impedance Spectrum evaluates the antiseptic property of thin film, and before carrying out electro-chemical test, all samples all soaks a period of time in NaCl solution, Electrochemical impedance spectroscopy and Plan Curve stably measure afterwards at open circuit point position (OCP), obtain the corrosion of aluminium alloy pipeline sheet material Current potential (Ecorr) and corrosion electric current density (Icorr) numerical value, it is considered that the tendency of the highest sample etches of corrosion potential is the least, And the corrosion rate of corrosion electric current density the least expression sample is the least, corrosion resisting property is the best.Measure the aluminium alloy pipeline sheet material obtained Corrosion potential (Ecorr) it is-603.2mV, the corrosion electric current density (I of aluminium alloy pipeline sheet materialcorr) it is 1.389 μ Acm-2, and Untreated aluminium alloy pipeline is-1057mV, the corrosion electric current density (I of undressed aluminium alloy pipelinecorr) it is 4.303μAcm-2, it follows that the aluminium alloy pipeline sheet material corrosion resistance of the present invention is compared to untreated aluminium-alloy pipe Road has promoted.
Embodiment five
Novel high-strength anticorodal aluminium alloy pipeline, includes Mg0.5%, Si 2.0～3.5%, Cu5.0% by weight percentage, Mn0.25%, Fe0.3%, Zr0.4%, Er0.4%, Cr0.015%, Ni0.015%, Ti0.015%, Al surplus.
Novel high-strength anticorodal aluminium alloy pipeline preparation method, described aluminium alloy pipeline is the shell being made up of following steps:
(1) heating furnace used in pre-hot smelting at 350 DEG C and fine aluminium 1～2h；(2) fine aluminium after preheating is at decompression state Lower smelting temperature be the heating furnace of 750 DEG C is completely melt after add monocrystal silicon granule, add in aluminum bronze after monocrystal silicon particles fuse Between alloy, aluminum manganese intermediate alloy, aluminium chromium hardener, aluminum nickel intermediate alloy, ferro-aluminum intermediate alloy, aluminium zirconium hardener and A small amount of rare earth element er, and be incubated a period of time and be completely melt to intermediate alloy, after being sufficiently stirred for, heating furnace is heated up, add aluminum Titanium intermediate alloy is completely melt to aluminum titanium intermediate alloy, is cooled to 750 DEG C, skims, and adds pure magnesium, protects under conditions of vacuum Temperature 30～40min；(4) tri-kinds of metal fining modifiers of Al-5Ti-B, Al-lOSr and RE are added, the weight hundred that three adds Proportion by subtraction ratio is 8:1:3；(5) add refining agent fully to react, degasification, slagging-off,；(6) melted pouring metal melt is to Preheated to the crucible of about 300 DEG C stands under conditions of 100MPa 4h, form ingot casting；(7) described ingot casting cuts into conjunction Carrying out the homogenizing annealing of 12 hours after suitable size under conditions of 550 DEG C, stove is cooled to room temperature；(8) described ingot casting is warming up to It is incubated 3 hours after 420 DEG C, carries out the hot rolling of five passages, after each passage hot rolling is complete, be incubated half an hour at 530 DEG C；(9) heat Carrying out the cold rolling of three passages after rolling, aluminium alloy one end is relatively fixed and connects ultrasonic vibration apparatus, and the other end enters in milling train, Excited frequency is 18kHz, aluminium alloy supersonic vibration pressurized extends, cold rolling after alloy carried out at 240 DEG C 2～3 hours Annealing, obtains certain thickness aluminum alloy plate materials；(10) aluminum alloy plate materials is carried out at halfhour solid solution at 540 DEG C Reason, then shrend；(11) aluminum alloy plate materials carries out the artificial aging of 5 hours at 180 DEG C；(12) by mixed-powder C and V Uniform application, in the surface of aluminum alloy plate materials, uses crossing current continuous wave Cq laser instrument that aluminum alloy plate materials carries out laser treatment modified, While making aluminum alloy sheet material surface form nanoscale impression, mixed-powder C and V is melted the surface being covered in aluminum alloy plate materials, Using argon to protect in processing procedure, its laser process parameter area is: laser power 2.5kw, sweep speed 20mm/s, Beam spot diameter, is 4mm.(13) configuration hydrochloric acid volume is the hydrochloric acid solution of 2:1 with deionized water volume ratio, with ethanol as solute The octadecyl trichlorosilane alkane solution of configuration 5mM, puts into process 2min in hydrochloric acid solution by the aluminium alloy obtained, use after having processed Sample, to remove unnecessary hydrochloric acid, is positioned over octadecyl trichlorosilane alkane solution by a large amount of deionized water rinsing aluminum alloy surface subsequently Middle immersion 12h, the sample of preparation is dried 30min at 80 DEG C；(14) molding.
The tensile strength of aluminium alloy pipeline sheet material, yield strength, percentage elongation and the Brinell hardness made be respectively 395.5MPa, 329.1MPa, 21%, 111HB.The ratio of each element weight percent of Reasonable adjustment so that formed in aluminium alloy pipeline and keep The Mg of peak aging strengthening ability2Si phase, increases its elongation percentage while strengthening aluminium alloy pipeline intensity.Add the Cu of proper proportion Element, reduces the natrual ageing adverse effect to material property, forms Mg more tiny, more2Si phase (acicular beta " phase), Reduce aluminium alloy pipeline corrosion stability after avoiding adding Cu element simultaneously.Add trace Mn and Cr, disperse phase can be produced, suppress alloy Recrystallization, improves alloy strength, increases Alloy Anti intercrystalline corrosion ability, improves alloy property.Appropriate rare earth element adds aluminum and closes In gold pipeline, gas in fusion-casting process and objectionable impurities, increase mobility, crystal grain thinning, accelerated ag(e)ing can be reduced or eliminated Process, and appropriate rare earth element and other elements cooperate and can effectively improve mechanical property and the corrosive nature of alloy.
Under decompression state, smelting aluminium alloy pipeline can be effectively reduced smelting temperature, saves resource.In simultaneously in order to keep heater Pressure, heater needs to pour into a certain amount of noble gas discharging while gas, and first noble gas is passed directly into metal In liquation, form bubble, drive the impurity in molten metal to move up, jointly discharge with gas, go the removal of impurity, the most lazy Property gas force in fusion process produce harmful gas discharge therewith, prevent oxygen etc. have oxidizing property gas enter heating Oxidized metal liquation in device.
Three kinds of fining modifiers have positive role to aluminium alloy pipeline, but have some limitations when being single use, such as list Solely add Sr and make Metamorphism treatment, the tendency aggravation of alloy air-breathing, drop low-alloyed compactness, be easily formed serious columanar structure, lead Causing mechanical property to decline on the contrary, rare earth easily aoxidizes, and modification effect is held time short etc.；And the fade resistance of Al-5Ti-B fining agent Can be the most unsatisfactory, and easily poisoned by Zr atom and lose the ability of crystal grain thinning, it is impossible to give full play to it respective Advantage.And triplicity is used and can give full play to respective advantage while overcoming the defect itself having.Can by form Know, relative to single use fining modifier, use simultaneously three kinds of fining modifiers can strengthen aluminium alloy pipeline tensile strength, Yield strength, percentage elongation and Brinell hardness, after wherein in table, data are interpolation fining modifier and without aluminum after fining modifier The comparison in various performance indications of the alloy pipeline, uses the tensile strength of the aluminium alloy pipeline of three kinds of fining modifiers to increase simultaneously 8.126%, yield strength increases by 7.237%, and percentage elongation increase by 22.0%% and Brinell hardness add 11.594%.
Melted pouring metal melt, to having been warmed up standing under conditions of 100MPa 4h to the crucible of about 300 DEG C, can be prevented Metal liquid process of setting is only formed the ingot casting of open structure, thus affects the intensity of aluminium alloy pipeline sheet material, simultaneously at high pressure Under conditions of advantageously form the ingot casting of compact texture, strengthen the intensity of aluminium alloy pipeline.
Aluminium alloy pipeline supersonic vibration pressurized at the vibrating amplitude extends, and can reduce the frictional force being subject in the operation of rolling, thus drop The low-frictional force impact on aluminium alloy pipeline plate surface, cold rolling relative to static state, aluminium alloy pipeline surface that supersonic vibration is cold rolling More smooth, be conducive to carrying out the operation of next step.
By mixed-powder C and V uniform application in the surface of aluminium alloy pipeline sheet material, use crossing current continuous wave Cq laser instrument that aluminum is closed It is modified that gold duct board carries out laser treatment, and can effectively enable aluminum alloy to will be mixed while duct board surface forms nanoscale impression Closing powder C and V and melt the surface being covered in aluminium alloy pipeline sheet material, aluminium alloy pipeline plate surface forms nano level pit, Increase the surface area of aluminium alloy pipeline sheet material, while improving frictional force, make the octadecyl trichlorosilane alkane solution of next step more It is easily accessible aluminium alloy pipeline plate surface, forms the micro structure of different morphologies on aluminium alloy pipeline surface, the most certainly Assemble the silane film possessing anticorrosion antiwear performance, thus change the surface nature of aluminium alloy pipeline sheet material, and aluminium alloy pipeline sheet material The C-V overlay film that surface is formed can be effectively improved aluminium alloy pipeline sheet material antioxygenic property at high temperature, changes aluminium alloy pipeline The surface nature of sheet material.
In order to measure aluminium alloy pipeline Surface Creation film layer corrosion resisting property in saline solution, use Tafel curve and electrochemical impedance Spectrum evaluates the antiseptic property of thin film, and before carrying out electro-chemical test, all samples all soaks a period of time in NaCl solution, Electrochemical impedance spectroscopy and Plan Curve stably measure afterwards at open circuit point position (OCP), obtain the corrosion of aluminium alloy pipeline sheet material Current potential (Ecorr) and corrosion electric current density (Icorr) numerical value, it is considered that the tendency of the highest sample etches of corrosion potential is the least, And the corrosion rate of corrosion electric current density the least expression sample is the least, corrosion resisting property is the best.Measure the aluminium alloy pipeline sheet material obtained Corrosion potential (Ecorr) it is-541.6mV, the corrosion electric current density (I of aluminium alloy pipeline sheet materialcorr) it is 1.385 μ Acm-2, and Untreated aluminium alloy pipeline is-1057mV, the corrosion electric current density (I of undressed aluminium alloy pipelinecorr) it is 4.303μAcm-2, it follows that the aluminium alloy pipeline sheet material corrosion resistance of the present invention is compared to untreated aluminium-alloy pipe Road has promoted.
Last it should be noted that, above example is only in order to illustrate technical scheme, rather than to scope Restriction, although having made to explain to the present invention with reference to preferred embodiment, it will be understood by those within the art that, Technical scheme can be modified or equivalent, without deviating from the spirit and scope of technical solution of the present invention.

Claims (2)

1. novel high-strength anticorodal aluminium alloy pipeline, it is characterised in that described aluminium alloy pipeline includes Mg0.2% by weight percentage, Si 2.0%, more than Cu4.0%, Mn0.2%, Fe0.2%, Zr0.1%, Er0.1%, Cr0.01%, Ni0.01%, Ti0.1%, Al Amount.
Novel high-strength anticorodal aluminium alloy pipeline the most according to claim 1, it is characterised in that described aluminium alloy pipeline is served as reasons The shell that following steps are made:
(1) heating furnace used in pre-hot smelting at 300 DEG C and fine aluminium 1～2h；(2) fine aluminium after preheating melts under a reduced pressure Refine and add monocrystal silicon granule after the heating furnace that temperature is 750 DEG C is completely melt, add after monocrystal silicon particles fuse and close in the middle of aluminum bronze Gold, aluminum manganese intermediate alloy, aluminium chromium hardener, aluminum nickel intermediate alloy, ferro-aluminum intermediate alloy, aluminium zirconium hardener and a small amount of Rare earth element er, and be incubated a period of time and be completely melt to intermediate alloy, after being sufficiently stirred for, heating furnace is heated up, add in aluminum titanium Between alloy be completely melt to aluminum titanium intermediate alloy, be cooled to 750 DEG C, skim, add pure magnesium, under conditions of vacuum be incubated 30～ 40min；(4) adding tri-kinds of metal fining modifiers of Al-5Ti-B, Al-lOSr and RE, the weight percent that three adds is frequently Example is 8:1:3；(5) add refining agent fully to react, degasification, slagging-off,；(6) melted pouring metal melt is to having been warmed up To the crucibles of about 300 DEG C, under conditions of 100MPa, stand 2h, form ingot casting；(7) described ingot casting cuts into suitable dimension After under conditions of 550 DEG C, carry out the homogenizing annealing of 12 hours, stove is cooled to room temperature；(8) after described ingot casting is warming up to 420 DEG C It is incubated 3 hours, carries out the hot rolling of five passages, after each passage hot rolling is complete, be incubated half an hour at 530 DEG C；(9) hot rolling is laggard Three passages of row cold rolling, aluminium alloy one end is relatively fixed and connects ultrasonic vibration apparatus, and the other end enters in milling train, exciting Frequency is 12kHz, and aluminium alloy supersonic vibration pressurized extends, cold rolling after alloy carried out at 240 DEG C 2 hours annealing treatment Reason, obtains certain thickness aluminum alloy plate materials；(10) aluminum alloy plate materials is carried out halfhour solution treatment at 540 DEG C, so Rear shrend；(11) aluminum alloy plate materials carries out the artificial aging of 5 hours at 180 DEG C；(12) by uniform for mixed-powder C and V It is applied in the surface of aluminum alloy plate materials, uses crossing current continuous wave Cq laser instrument that aluminum alloy plate materials carries out laser treatment modified so that While aluminum alloy sheet material surface formation nanoscale impression, mixed-powder C and V is melted the surface being covered in aluminum alloy plate materials, place Using argon to protect during reason, its laser process parameter area is: laser power 1.7kw, sweep speed 13mn/s, Beam spot diameter, is 4mm.(13) configuration hydrochloric acid volume is the hydrochloric acid solution of 2:1 with deionized water volume ratio, with ethanol as solute The octadecyl trichlorosilane alkane solution of configuration 5mM, puts into process 2min in hydrochloric acid solution by the aluminium alloy obtained, use after having processed Sample, to remove unnecessary hydrochloric acid, is positioned over octadecyl trichlorosilane alkane solution by a large amount of deionized water rinsing aluminum alloy surface subsequently Middle immersion 12h, the sample of preparation is dried 30min at 80 DEG C；(14) molding.
CN201610220242.0A 2016-04-08 2016-04-08 Novel high-strength corrosion-resistant aluminum alloy pipeline Pending CN105734371A (en)

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