CN101899598A - Hot dip coating cast aluminium alloy and preparation method thereof - Google Patents
Hot dip coating cast aluminium alloy and preparation method thereof Download PDFInfo
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- CN101899598A CN101899598A CN 201010268475 CN201010268475A CN101899598A CN 101899598 A CN101899598 A CN 101899598A CN 201010268475 CN201010268475 CN 201010268475 CN 201010268475 A CN201010268475 A CN 201010268475A CN 101899598 A CN101899598 A CN 101899598A
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Abstract
The invention relates to a hot dip coating cast aluminium alloy used for antiseptic treatment of various marine climate-resistant engineering components and a preparation method thereof, wherein the cast aluminium alloy is composed of metal of Al, Zn, Si and the like, nanometer oxide particle intensifier and unavoidable impurities; and the nano oxide particle intensifier is selected from one or two of TiO2 and CeO2. The cast aluminium alloy prepared by the invention can be used as a coating which enables the engineering components to have full decay resistance and scour corrosion resistance.
Description
Technical field
The present invention relates to multiple hot dip coating cast aluminium alloy and preparation method thereof, especially relate to hot dip coating cast aluminium alloy and manufacture method thereof that multiple marine climate resistant engineering component rotproofing is used.
Background technology
Along with rapid development of science and technology, the engineer equipment that is applied in coastal waters and the ocean is more and more, but its service condition press ISO 9225 environmental evaluation standards generally＞the C5 level, belong to extreme environment.Described ambient atmosphere is rainy, high temperature, many salt fogs and high wind stream, and exposed part will be subjected to intensive atomospheric corrosion, galvanic corrosion and the comprehensive action of airflow scouring erosive, and the work-ing life of various steel construction is far below general landlocked outdoor environment.
For example, current wind energy has day by day become the renewable clear energy sources that technology is the most ripe, possess the scale development condition most.But because wind power generating set is to utilize wind power generation, and in shoreline, offshore ocean, have abundant wind resource, thus the construction of wind energy turbine set significant proportion is arranged is that addressing is in inshore or offshore ocean.But the wind power plant of under the oceanic climate condition, being on active service since the external member of unit such as cabin, hood, pylon etc. directly be exposed in the extreme corrosion atmosphere, adopt conventional safeguard procedures, often only several months just produce serious corrosion, therefore, press for the corrosion-resistant problem of the coating that the engineering component rotproofing that solves marine climate resistant uses at present.
Summary of the invention
At these problems in the prior art, the invention provides multiple hot dip process cast aluminium alloy and the manufacture method thereof that the marine climate resistant engineering component rotproofing is used that be suitable for.
At first, the hot dip coating cast aluminium alloy that a kind of marine climate resistant engineering component rotproofing provided by the invention is used, wherein said cast aluminium alloy is made up of Al, Zn, Si, RE and nano-oxide particles toughener, and described nano-oxide particles toughener is selected from TiO
2, CeO
2In one or both, each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, RE:0.02～1.0%, the content that the nano-oxide particles toughener is total: 0.01～1.0%, surplus is Al and unavoidable impurities.
Moreover, the hot dip coating cast aluminium alloy that a kind of marine climate resistant engineering component rotproofing provided by the invention is used, wherein said cast aluminium alloy is made up of Al, Zn, Si, Mg, RE and nano-oxide particles toughener, and described nano-oxide particles toughener is selected from TiO
2, CeO
2In one or both, each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, Mg:0.1～5.0%, RE:0.02～1.0%, the content that the nano-oxide particles toughener is total: 0.01～1.0%, surplus is Al and unavoidable impurities.
Moreover, the hot dip coating cast aluminium alloy that a kind of marine climate resistant engineering component rotproofing provided by the invention is used, wherein said cast aluminium alloy is made up of Al, Zn, Si, RE, Ni and nano-oxide particles toughener, and described nano-oxide particles toughener is selected from TiO
2, CeO
2In one or both, each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, RE:0.02～1.0%, Ni:0.1～3.0%, the content that the nano-oxide particles toughener is total: 0.01～1.0%, surplus is Al and unavoidable impurities.
Moreover, the hot dip coating cast aluminium alloy that a kind of marine climate resistant engineering component rotproofing provided by the invention is used, wherein said cast aluminium alloy is made up of Al, Zn, Si, RE, Ti and nano-oxide particles toughener, and described nano-oxide particles toughener is selected from TiO
2, CeO
2In one or both, each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, RE:0.02～1.0%, Ti:0.01～0.5%, the content that the nano-oxide particles toughener is total: 0.01～1.0%, surplus is Al and unavoidable impurities.
Moreover, the hot dip coating cast aluminium alloy that a kind of marine climate resistant engineering component rotproofing provided by the invention is used, wherein said cast aluminium alloy is made up of Al, Zn, Si, Mg, RE, Ni and nano-oxide particles toughener, and described nano-oxide particles toughener is selected from TiO
2, CeO
2In one or both, each composition accounts for total mass per-cent: Zn:35～58%, Si:0.3～4.0%, Mg:0.1～5.0%, RE:0.02～1.0%, Ni:0.1～3.0%, the content that the nano-oxide particles toughener is total: 0.01～1.0%, surplus is Al and unavoidable impurities.
Moreover, the hot dip coating cast aluminium alloy that a kind of marine climate resistant engineering component rotproofing provided by the invention is used, wherein said cast aluminium alloy is made up of Al, Zn, Si, Mg, RE, Ti and nano-oxide particles toughener, and described nano-oxide particles toughener is selected from TiO
2, CeO
2In one or both, each composition accounts for total mass per-cent: Zn:35～58%, Si:0.3～4.0%, Mg:0.1～5.0%, RE:0.02～1.0%, Ti:0.01～0.5%, the content that the nano-oxide particles toughener is total: 0.01～1.0%, surplus is Al and unavoidable impurities.
Moreover, the hot dip coating cast aluminium alloy that a kind of marine climate resistant engineering component rotproofing provided by the invention is used, wherein said cast aluminium alloy is made up of Al, Zn, Si, RE, Ti, Ni and nano-oxide particles toughener, and described nano-oxide particles toughener is selected from TiO
2, CeO
2In one or both, each composition accounts for total mass per-cent: Zn:35～58%, Si:0.3～4.0%, RE:0.02～1.0%, Ti:0.01～0.5%, Ni:0.1～3.0%, the content that the nano-oxide particles toughener is total: 0.01～1.0%, surplus is Al and unavoidable impurities.
Wherein, RE be rare earth element any or several.
Preferably, if the nano-oxide particles that adopts is uniform spherical particles, then spheroid specific surface area and median size satisfy following relational expression:
Wherein D represents median size;
ρ represents density.
If the nano-oxide particles that adopts is more complex-shaped than general spherical particles, the performance of coating, effect can be desirable more, and therefore, the specific surface area of the further preferred nano-oxide particles of the present invention is greater than above-mentioned formula calculated value:
Preferably, nano-oxide particles adopts TiO
2The time, described TiO
2Median size be 15～60nm.
Preferably, nano-oxide particles adopts TiO
2The time, described TiO
2Specific surface area be 20～90m
2/ g.
Preferably, nano-oxide particles adopts CeO
2The time, described CeO
2Median size be 25～70nm.
Preferably, nano-oxide particles adopts CeO
2The time, described CeO
2Specific surface area be 10～80m
2/ g.
Preferably, the nano-oxide particles toughener is TiO
2And CeO
2The time, TiO
2And CeO
2Mass ratio is 1: (1～3).
Preferred, TiO wherein
2And CeO
2Mass ratio is 1: 2.
Preferably, wherein each composition accounts for total mass per-cent and is: Zn:41～51%, Si:1～3.2%, Mg:1.8～4%, RE:0.05～0.8%, Ni:1.5～2.6%, Ti:0.05～0.35%, the content that the nano-oxide particles toughener is total: 0.05～0.8%.
In addition, the present invention also provides a kind of method of making described hot dip coating cast aluminium alloy, gets the raw materials ready according to the mass percent of Al, Zn, Si, RE and nano-oxide particles toughener, in vacuum or atmosphere protection stove Al heat temperature raising to 700～750 ℃ is dissolved earlier, stir, add Si; Add RE after being warming up to 800～840 ℃ then; Reheat adds Zn after being warming up to 830 ℃～850 ℃; After being cooled to 750～700 ℃, add the nano-oxide particles toughener; Temperature being reduced to 700～650 ℃ leaves standstill after 10～35 minutes casting or is cast into ingot again after stirring.
The present invention also provides a kind of method of making described hot dip coating cast aluminium alloy, mass percent according to Al, Zn, Si, Mg, RE and nano-oxide particles toughener is got the raw materials ready, in vacuum or atmosphere protection stove, Al heat temperature raising to 700～750 ℃ are dissolved earlier, stir, add Si; Add RE after being warming up to 800～840 ℃ then; Reheat adds Zn after being warming up to 830 ℃～850 ℃; After being cooled to 750～700 ℃, add Mg and nano-oxide particles toughener; Temperature being reduced to 700～650 ℃ leaves standstill after 10～35 minutes casting or is cast into ingot again after stirring.
The present invention also provides a kind of method of making described hot dip coating cast aluminium alloy, mass percent according to Al, Zn, Si, RE, Ni, nano-oxide particles toughener is got the raw materials ready, in vacuum or atmosphere protection stove, Al heat temperature raising to 700～750 ℃ are dissolved earlier, stir, add Si; Add RE after being warming up to 800～840 ℃ then; Reheat adds Zn after being warming up to 830 ℃～850 ℃; Reheat adds Ni after being warming up to 850 ℃～880 ℃; After being cooled to 750～700 ℃, add the nano-oxide particles toughener; Temperature being reduced to 700～650 ℃ leaves standstill after 10～35 minutes casting or is cast into ingot again after stirring.
The present invention also provides a kind of method of making described hot dip coating cast aluminium alloy, mass percent according to Al, Zn, Si, RE, Ti, nano-oxide particles toughener is got the raw materials ready, in vacuum or atmosphere protection stove, Al heat temperature raising to 700～750 ℃ are dissolved earlier, stir, add Si; Add RE after being warming up to 800～840 ℃ then; Reheat adds Zn after being warming up to 830 ℃～850 ℃; Reheat adds Ti after being warming up to 850 ℃～880 ℃; After being cooled to 750～700 ℃, add the nano-oxide particles toughener; Temperature being reduced to 700～650 ℃ leaves standstill after 10～35 minutes casting or is cast into ingot again after stirring.
The present invention also provides a kind of method of making described hot dip coating cast aluminium alloy, mass percent according to Al, Zn, Si, Mg, RE, Ni and nano-oxide particles toughener is got the raw materials ready, in vacuum or atmosphere protection stove, Al heat temperature raising to 700～750 ℃ are dissolved earlier, stir, add Si; Add RE after being warming up to 800～840 ℃ then; Reheat adds Zn after being warming up to 830 ℃～850 ℃; Reheat adds Ni after being warming up to 850 ℃～880 ℃; After being cooled to 750～700 ℃, add Mg and nano-oxide particles toughener; Temperature being reduced to 700～650 ℃ leaves standstill after 10～35 minutes casting or is cast into ingot again after stirring.
The present invention also provides a kind of method of making described hot dip coating cast aluminium alloy, mass percent according to Al, Zn, Si, Mg, RE, Ti, nano-oxide particles toughener is got the raw materials ready, in vacuum or atmosphere protection stove, Al heat temperature raising to 700～750 ℃ are dissolved earlier, stir, add Si; Add RE after being warming up to 800～840 ℃ then; Reheat adds Zn after being warming up to 830 ℃～850 ℃; Reheat adds Ti after being warming up to 850 ℃～880 ℃; After being cooled to 750～700 ℃, add Mg and nano-oxide particles toughener; Temperature being reduced to 700～650 ℃ leaves standstill after 10～35 minutes casting or is cast into ingot again after stirring.
The present invention also provides a kind of method of making described hot dip coating cast aluminium alloy, mass percent according to Al, Zn, Si, RE, Ti, Ni, nano-oxide particles toughener is got the raw materials ready, in vacuum or atmosphere protection stove, Al heat temperature raising to 700～750 ℃ are dissolved earlier, stir, add Si; Add RE after being warming up to 800～840 ℃ then; Reheat adds Zn after being warming up to 830 ℃～850 ℃; Reheat adds Ni and Ti after being warming up to 850 ℃～880 ℃; After being cooled to 750～700 ℃, add the nano-oxide particles toughener; Temperature being reduced to 700～650 ℃ leaves standstill after 10～35 minutes casting or is cast into ingot again after stirring.
Preferably, the temperature rise rate in the described heat-processed is 10～40 ℃/minute, and the rate of temperature fall in the described temperature-fall period is 20～60 ℃/minute.
Anti-oceanic climate corrosive hot dip coating cast aluminium alloy provided by the invention, wherein Al is weather-resistant metal, the very fast oxide film that forms one deck densification on the surface of Al meeting in air, and have the ability of the damage of selfreparing fast; Zn has low electropotential, as sacrificial anode, can give the sufficient electrochemically resistant of iron and steel and learn corrosive power.
If yet the too high levels of zinc, the toughness of coating and hardness all can decrease, thereby have reduced coating opposing atomospheric corrosion and airflow scouring erosional competency.In order to overcome this problem, the present invention is by adding certain amount of nano oxide particle toughener, greatly refinement the crystal grain of coating, improved the toughness of coating, coating opposing atomospheric corrosion, galvanic corrosion and airflow scouring erosive ability have been improved, and significantly improved intensity, the hardness of coating, thereby give coating better scour resistance.
Further, after testing repeatedly in a large number, screening, by selecting the particle diameter and the specific surface area of suitable nano-oxide particles toughener, can improve the performance of coating more significantly, in addition, the particle diameter of nano-oxide particles toughener adopts numerical range of the present invention, the fastness to rubbing of coating is improved greatly, and the specific surface area of nano-oxide particles toughener adopts numerical range of the present invention, the concentration class of alloy is improved greatly, thereby improve the scour resistance of alloy coat more significantly.
On this basis, also by adding microalloy elements such as Mg, Ni, Ti, the adding of these microalloy elements is crystal grain thinning more, further improve the obdurability and the erosion resistance of coating, wherein Mg can improve avidity, erosion resistance and the raising alloy at room temperature intensity of alloy, and Ni not only can further play the solid solution effect to alloy, can also further improve the toughness and the stability of alloy, Ti has then strengthened the strengthening phase in the coating, and alloy is played the solid solution effect.
In sum, adopt the cast aluminium alloy making coatings that the present invention produced, can under the oceanic climate condition, give its abundant corrosion resistance nature and antiscour erosion performance.
On the other hand, the present invention also provides a kind of method that adopts many temperature sections to add the alloy for hot-dip element, adopt this method, raising along with temperature, can help improving the dispersiveness of nano-oxide particles toughener and various elements, thereby improved the homogeneity of coated component, improved coating and high base strength significantly.
Yet if add all elements when melt temperature is too high, coating easily forms high alumina fragility phase, is unfavorable for bearing contact fine motion load.For this reason, the present invention adopts earlier many temperature sections to add part alloy for hot-dip elements, adds the nano-oxide particles toughener again after temperature being reduced to certain temperature again, lower the temperature again at last and be incubated certain hour, so just overcome above-mentioned defective, it is even to have obtained composition, and toughness is coating preferably.
In sum, the present invention compared with prior art, coating opposing atomospheric corrosion, galvanic corrosion and airflow scouring erosional competency significantly improve, and the intensity of coating, hardness, scour resistance is also all significantly improved, coating and matrix bond are firm in addition, are applicable to exceedingly odious environment such as ocean fully.On the other hand, production technique of the present invention is simplified, and it is even to obtain composition, and toughness is coating preferably.And elements such as the major ingredient aluminium in the alloy, zinc all are that nature is contained abundant alloying element, therefore, and lower cost for material, and environmental protection, energy-conservation.Adopt alloy of the present invention to make coating, the thickness adjustable range is wide, is fit to the processing of various size part.
Embodiment
The hot dip coating cast aluminium alloy that marine climate resistant engineering component rotproofing provided by the invention is used, wherein said cast aluminium alloy is made up of with nano-oxide particles toughener and unavoidable impurities Al, Zn, Si etc., wherein this impurity that can not the avoid impurity element that can't thoroughly remove such as Fe, Mn, Pb, Sn, Cd normally.
Further, after testing repeatedly in a large number, screening, by selecting the particle diameter and the specific surface area of suitable nano-oxide particles toughener, can improve the performance of coating more significantly, if the nano-oxide particles that adopts is uniform spherical particles, then spheroid specific surface area and median size satisfy following relational expression:
Wherein D represents median size;
ρ represents density.
Further, if the nano-oxide particles that adopts is more complex-shaped than general spherical particles, the performance of coating, effect can be desirable more, and therefore, the specific surface area of the preferred nano-oxide particles of the present invention is greater than this formula calculated value.
Below, associative list 1-21 provides some preferred embodiments of each composition mass percent of the present invention, 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.
And of particular note, although listed file names with the particle diameter of nano-oxide particles toughener, the correlation values of specific surface area among the table 1-21, these two conditions are described as essential features.For the present invention, the content of core is by adding crystal grain that certain amount of nano oxide particle toughener microalloy element reaches the refinement coating, improve its toughness, improve its various corrosion resistances, overcoming the dysgenic purpose that the zinc too high levels is brought.And on this basis, by the suitable particle diameter of further selection, suitable specific surface area all is in order to make this technique effect more outstanding, more superior, therefore, although these two parameters that all list file names with among the following table 1-21, but all be as preferred condition, all be in order providing in more detail, and described as prerequisite of the present invention about technical intelligence of the present invention.
Embodiment 1:
The hot dip coating cast aluminium alloy that a kind of marine climate resistant engineering component rotproofing is used, it is by Zn, Al, Si, RE and TiO
2The nano-oxide particles toughener is formed, and each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, RE:0.02～1.0%, TiO
2: 0.01～1.0%, Al: surplus, and unavoidable impurities, concrete mass percentage content and correlation parameter see the following form 1:
Table 1: each composition accounts for the mass percentage content (%) and the correlation parameter of gross weight
Embodiment 2:
The hot dip coating cast aluminium alloy that a kind of marine climate resistant engineering component rotproofing is used, it is by Al, Zn, Si, RE and CeO
2The nano-oxide particles toughener is formed, and each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, RE:0.02～1.0%, CeO
2: 0.01～1.0%, Al: surplus, and unavoidable impurities, concrete sees the following form 2:
Table 2: each composition accounts for the mass percentage content (%) and the correlation parameter of gross weight
Embodiment 3:
Described alloy for hot-dip is made up of Al, Zn, Si, RE and nano-oxide particles toughener, and wherein nano-oxide particles is TiO
2And CeO
2, and TiO
2And CeO
2Ratio is 1: (1～3), by mass percentage: each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, RE:0.02～1.0%, nano-oxide particles TiO
2And CeO
2Total content: 0.01～1.0%, Al: surplus, and unavoidable impurities, concrete sees the following form 3:
Table 3: each composition accounts for the mass percentage content (%) and the correlation parameter of gross weight
Embodiment 4:
The hot dip coating cast aluminium alloy that a kind of marine climate resistant engineering component rotproofing is used, it is by Zn, Al, Si, Mg, RE and TiO
2The nano-oxide particles toughener is formed, and each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, Mg:0.1～5.0%, RE:0.02～1.0%, TiO
2: 0.01～1.0%, Al: surplus, and unavoidable impurities, concrete mass percentage content and correlation parameter see the following form 4:
Table 4: each composition accounts for the mass percentage content (%) and the correlation parameter of gross weight
Embodiment 5:
The hot dip coating cast aluminium alloy that a kind of marine climate resistant engineering component rotproofing is used, it is by Al, Zn, Si, Mg, RE and CeO
2The nano-oxide particles toughener is formed, and each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, Mg:0.1～5.0%, RE:0.02～1.0%, CeO
2: 0.01～1.0%, Al: surplus, and unavoidable impurities, concrete sees the following form 5:
Table 5: each composition accounts for the mass percentage content (%) and the correlation parameter of gross weight
Embodiment 6:
Described alloy for hot-dip is made up of Al, Zn, Si, Mg, RE and nano-oxide particles toughener, and wherein nano-oxide particles is TiO
2And CeO
2, and TiO
2And CeO
2Ratio is 1: (1～3), by mass percentage: each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, Mg:0.1～5.0%, RE:0.02～1.0%, nano-oxide particles TiO
2And CeO
2Total content: 0.01～1.0%, Al: surplus, and unavoidable impurities, concrete sees the following form 6:
Table 6: each composition accounts for the mass percentage content (%) and the correlation parameter of gross weight
Embodiment 7:
The hot dip coating cast aluminium alloy that a kind of marine climate resistant engineering component rotproofing is used, it is by Zn, Al, Si, RE, Ni and TiO
2The nano-oxide particles toughener is formed, and each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, RE:0.02～1.0%, Ni:0.1～3.0%, TiO
2: 0.01～1.0%, Al: surplus, and unavoidable impurities, concrete mass percentage content and correlation parameter see the following form 7:
Table 7: each composition accounts for the mass percentage content (%) and the correlation parameter of gross weight
Embodiment 8:
The hot dip coating cast aluminium alloy that a kind of marine climate resistant engineering component rotproofing is used, it is by Al, Zn, Si, RE, Ni and CeO
2The nano-oxide particles toughener is formed, and each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, RE:0.02～1.0%, Ni:0.1～3.0%, CeO
2: 0.01～1.0%, Al: surplus, and unavoidable impurities, concrete sees the following form 8:
Table 8: each composition accounts for the mass percentage content (%) and the correlation parameter of gross weight
Embodiment 9:
Described alloy for hot-dip is made up of Al, Zn, Si, RE, Ni and nano-oxide particles toughener, and wherein nano-oxide particles is TiO
2And CeO
2, and TiO
2And CeO
2Ratio is 1: (1～3), by mass percentage: each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, RE:0.02～1.0%, Ni:0.1～3.0%, nano-oxide particles TiO
2And CeO
2Total content: 0.01～1.0%, Al: surplus, and unavoidable impurities, concrete sees the following form 9:
Table 9: each composition accounts for the mass percentage content (%) and the correlation parameter of gross weight
Embodiment 10:
The hot dip coating cast aluminium alloy that a kind of marine climate resistant engineering component rotproofing is used, it is by Zn, Al, Si, RE, Ti and TiO
2The nano-oxide particles toughener is formed, and each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, RE:0.02～1.0%, Ti:0.01～0.5%, TiO
2: 0.01～1.0%, Al: surplus, and unavoidable impurities, concrete mass percentage content and correlation parameter see the following form 10:
Table 10: each composition accounts for the mass percentage content (%) and the correlation parameter of gross weight
Embodiment 11:
The hot dip coating cast aluminium alloy that a kind of marine climate resistant engineering component rotproofing is used, it is by Al, Zn, Si, RE, Ti and CeO
2The nano-oxide particles toughener is formed, and each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, RE:0.02～1.0%, Ti:0.01～0.5%, CeO
2: 0.01～1.0%, Al: surplus, and unavoidable impurities, concrete sees the following form 11:
Table 11: each composition accounts for the mass percentage content (%) and the correlation parameter of gross weight
Embodiment 12:
Described alloy for hot-dip is made up of Al, Zn, Si, RE, Ti and nano-oxide particles toughener, and wherein nano-oxide particles is TiO
2And CeO
2, and TiO
2And CeO
2Ratio is 1: (1～3), by mass percentage: each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, RE:0.02～1.0%, Ti:0.01～0.5%, nano-oxide particles TiO
2And CeO
2Total content: 0.01～1.0%, Al: surplus, and unavoidable impurities, concrete sees the following form 12:
Table 12: each composition accounts for the mass percentage content (%) and the correlation parameter of gross weight
Embodiment 13:
The hot dip coating cast aluminium alloy that a kind of marine climate resistant engineering component rotproofing is used, it is by Zn, Al, Si, Mg, RE, Ni and TiO
2The nano-oxide particles toughener is formed, and each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, Mg:0.1～5.0%, RE:0.02～1.0%, Ni:0.1～3.0%, TiO
2: 0.01～1.0%, Al: surplus, and unavoidable impurities, concrete mass percentage content and correlation parameter see the following form 13:
Table 13: each composition accounts for the mass percentage content (%) and the correlation parameter of gross weight
Embodiment 14:
The hot dip coating cast aluminium alloy that a kind of marine climate resistant engineering component rotproofing is used, it is by Al, Zn, Si, Mg, RE, Ni and CeO
2The nano-oxide particles toughener is formed, and each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, Mg:0.1～5.0%, RE:0.02～1.0%, Ni:0.1～3.0%, CeO
2: 0.01～1.0%, Al: surplus, and unavoidable impurities, concrete sees the following form 14:
Table 14: each composition accounts for the mass percentage content (%) and the correlation parameter of gross weight
Embodiment 15:
Described alloy for hot-dip is made up of Al, Zn, Si, Mg, RE, Ni and nano-oxide particles toughener, and wherein nano-oxide particles is TiO
2And CeO
2, and TiO
2And CeO
2Ratio is 1: (1～3), by mass percentage: each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, Mg:0.1～5.0%, RE:0.02～1.0%, Ni:0.1～3.0%, nano-oxide particles TiO
2And CeO
2Total content: 0.01～1.0%, Al: surplus, and unavoidable impurities, concrete sees the following form 15:
Table 15: each composition accounts for the mass percentage content (%) and the correlation parameter of gross weight
Embodiment 16:
The hot dip coating cast aluminium alloy that a kind of marine climate resistant engineering component rotproofing is used, it is by Zn, Al, Si, Mg, RE, Ti and TiO
2The nano-oxide particles toughener is formed, and each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, Mg:0.1～5.0%, RE:0.02～1.0%, Ti:0.01～0.5%, TiO
2: 0.01～1.0%, Al: surplus, and unavoidable impurities, concrete mass percentage content and correlation parameter see the following form 16:
Table 16: each composition accounts for the mass percentage content (%) and the correlation parameter of gross weight
Embodiment 17:
The hot dip coating cast aluminium alloy that a kind of marine climate resistant engineering component rotproofing is used, it is by Al, Zn, Si, Mg, RE, Ti and CeO
2The nano-oxide particles toughener is formed, and each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, Mg:0.1～5.0%, RE:0.02～1.0%, Ti:0.01～0.5%, CeO
2: 0.01～1.0%, Al: surplus, and unavoidable impurities, concrete sees the following form 17:
Table 17: each composition accounts for the mass percentage content (%) and the correlation parameter of gross weight
Embodiment 18:
Described alloy for hot-dip is made up of Al, Zn, Si, Mg, RE, Ti and nano-oxide particles toughener, and wherein nano-oxide particles is TiO
2And CeO
2, and TiO
2And CeO
2Ratio is 1: (1～3), by mass percentage: each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, Mg:0.1～5.0%, RE:0.02～1.0%, Ti:0.01～0.5%, nano-oxide particles TiO
2And CeO
2Total content: 0.01～1.0%, Al: surplus, and unavoidable impurities, concrete sees the following form 18:
Table 18: each composition accounts for the mass percentage content (%) and the correlation parameter of gross weight
Embodiment 19:
The hot dip coating cast aluminium alloy that a kind of marine climate resistant engineering component rotproofing is used, it is by Zn, Al, Si, RE, Ti, Ni and TiO
2The nano-oxide particles toughener is formed, and each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, RE:0.02～1.0%, Ti:0.01～0.5%, Ni:0.1～3.0%, TiO
2: 0.01～1.0%, Al: surplus, and unavoidable impurities, concrete mass percentage content and correlation parameter see the following form 19:
Table 19: each composition accounts for the mass percentage content (%) and the correlation parameter of gross weight
Embodiment 20:
The hot dip coating cast aluminium alloy that a kind of marine climate resistant engineering component rotproofing is used, it is by Al, Zn, Si, RE, Ti, Ni and CeO
2The nano-oxide particles toughener is formed, and each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, RE:0.02～1.0%, Ti:0.01～0.5%, Ni:0.1～3.0%, CeO
2: 0.01～1.0%, Al: surplus, and unavoidable impurities, concrete sees the following form 20:
Table 20: each composition accounts for the mass percentage content (%) and the correlation parameter of gross weight
Embodiment 21:
Described alloy for hot-dip is made up of Al, Zn, Si, RE, Ti, Ni and nano-oxide particles toughener, and wherein nano-oxide particles is TiO
2And CeO
2, and TiO
2And CeO
2Ratio is 1: (1～3), by mass percentage: each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, RE:0.02～1.0%, Ti:0.01～0.5%, Ni:0.1～3.0%, nano-oxide particles TiO
2And CeO
2Total content: 0.01～1.0%, Al: surplus, and unavoidable impurities, concrete sees the following form 21:
Table 21: each composition accounts for the mass percentage content (%) and the correlation parameter of gross weight
Among the embodiment 1-21, preferably, wherein each composition accounts for total mass per-cent and is: Zn:41～51%, Si:1～3.2%, Mg:1.8～4%, RE:0.05～0.8%, Ni:1.5～2.6%, Ti:0.05～0.35%, the content that the nano-oxide particles toughener is total: 0.05～0.8%.
Preferred, described Zn content is 45%, and described Si content is 1.8%, and described Mg content is 3.5%, and described RE content is 0.6%, and described Ni content is 2%, and described Ti content is 0.25%, and the total content of nano-oxide particles toughener is 0.2%.
In addition, find also that if the loose density of the nano-oxide particles toughener that the present invention is adopted also can suitably be selected, the then final coating performance that obtains, effect are with even more ideal by a large amount of experiments repeatedly.
If adopt TiO
2, then preferred, wherein said TiO
2Loose density be no more than 3g/cm
3
If adopt CeO
2, then preferred, wherein said CeO
2Loose density be no more than 5g/cm
3
If adopt TiO simultaneously
2And CeO
2, then preferred, wherein said TiO
2And CeO
2Average loose density is 0.6～4.5g/cm
3
In addition, the present invention also provides a kind of method of making described alloy for hot-dip, and is preferred, adds Mg and nano-oxide particles toughener after being cooled to 720～700 ℃; At last temperature is reduced to that 690～660 ℃ of insulations obtained in 22～28 minutes.
Preferred, after being cooled to 710 ℃, add Mg and nano-oxide particles toughener; Last again temperature is reduced to that 680 ℃ of insulations obtained in 25 minutes.
Temperature rise rate in the wherein said heat-processed is 10～40 ℃/minute, and the rate of temperature fall in the described temperature-fall period is 20～60 ℃/minute.
Preferably, the temperature rise rate in the wherein said heat-processed is 20～30 ℃/minute, and the rate of temperature fall in the described temperature-fall period is 30～50 ℃/minute.
Preferred, the temperature rise rate in the wherein said heat-processed is 25 ℃/minute, and the rate of temperature fall in the described temperature-fall period is 40 ℃/minute.
The erosion resistance experimental result
Embodiment 22
Certain inshore wind power generating set vital part " root of blade flange gasket " (size: Φ 2200 * 30mm, material Q345), the former coating protection of routine that adopts is handled, and only promptly produces significant corrosion after the several months.Adopt hot dip alloy of the present invention as coating material, form the thick plating coating of 150 μ m, the thick aliphatic polyurethane coating of application 20 μ m shows that through the accelerated corrosion analog reslt its weather resistance can be above 20 years in seawater splash(spray)zone environment again.
Embodiment 23
Certain inshore wind power generating set vital part " joint bolt " (size: M36 * 1000m, material 40CrNiMo), the former protective coating of routine that adopts is handled, and only promptly produces significant corrosion after the several months.Adopt hot dip alloy of the present invention as coating material, form the thick plating coating of 100 μ m, the thick polysiloxane of application 15 μ m shows that through the accelerated corrosion analog reslt its weather resistance can be above 20 years in seawater splash(spray)zone environment again.
Claims (21)
1. hot dip coating cast aluminium alloy that the marine climate resistant engineering component rotproofing is used, wherein said cast aluminium alloy is made up of Al, Zn, Si, RE and nano-oxide particles toughener, and described nano-oxide particles toughener is selected from TiO
2, CeO
2In one or both, each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, RE:0.02～1.0%, the content that the nano-oxide particles toughener is total: 0.01～1.0%, surplus is Al and unavoidable impurities.
2. hot dip coating cast aluminium alloy that the marine climate resistant engineering component rotproofing is used, wherein said cast aluminium alloy is made up of Al, Zn, Si, Mg, RE and nano-oxide particles toughener, and described nano-oxide particles toughener is selected from TiO
2, CeO
2In one or both, each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, Mg:0.1～5.0%, RE:0.02～1.0%, the content that the nano-oxide particles toughener is total: 0.01～1.0%, surplus is Al and unavoidable impurities.
3. hot dip coating cast aluminium alloy that the marine climate resistant engineering component rotproofing is used, wherein said cast aluminium alloy is made up of Al, Zn, Si, RE, Ni and nano-oxide particles toughener, and described nano-oxide particles toughener is selected from TiO
2, CeO
2In one or both, each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, RE:0.02～1.0%, Ni:0.1～3.0%, the content that the nano-oxide particles toughener is total: 0.01～1.0%, surplus is Al and unavoidable impurities.
4. hot dip coating cast aluminium alloy that the marine climate resistant engineering component rotproofing is used, wherein said cast aluminium alloy is made up of Al, Zn, Si, RE, Ti and nano-oxide particles toughener, and described nano-oxide particles toughener is selected from TiO
2, CeO
2In one or both, each composition accounts for total mass per-cent and is: Zn:35～58%, Si:0.3～4.0%, RE:0.02～1.0%, Ti:0.01～0.5%, the content that the nano-oxide particles toughener is total: 0.01～1.0%, surplus is Al and unavoidable impurities.
5. hot dip coating cast aluminium alloy that the marine climate resistant engineering component rotproofing is used, wherein said cast aluminium alloy is made up of Al, Zn, Si, Mg, RE, Ni and nano-oxide particles toughener, and described nano-oxide particles toughener is selected from TiO
2, CeO
2In one or both, each composition accounts for total mass per-cent: Zn:35～58%, Si:0.3～4.0%, Mg:0.1～5.0%, RE:0.02～1.0%, Ni:0.1～3.0%, the content that the nano-oxide particles toughener is total: 0.01～1.0%, surplus is Al and unavoidable impurities.
6. hot dip coating cast aluminium alloy that the marine climate resistant engineering component rotproofing is used, wherein said cast aluminium alloy is made up of Al, Zn, Si, Mg, RE, Ti and nano-oxide particles toughener, and described nano-oxide particles toughener is selected from TiO
2, CeO
2In one or both, each composition accounts for total mass per-cent: Zn:35～58%, Si:0.3～4.0%, Mg:0.1～5.0%, RE:0.02～1.0%, Ti:0.01～0.5%, the content that the nano-oxide particles toughener is total: 0.01～1.0%, surplus is Al and unavoidable impurities.
7. hot dip coating cast aluminium alloy that the marine climate resistant engineering component rotproofing is used, wherein said cast aluminium alloy is made up of Al, Zn, Si, RE, Ti, Ni and nano-oxide particles toughener, and described nano-oxide particles toughener is selected from TiO
2, CeO
2In one or both, each composition accounts for total mass per-cent: Zn:35～58%, Si:0.3～4.0%, RE:0.02～1.0%, Ti:0.01～0.5%, Ni:0.1～3.0%, the content that the nano-oxide particles toughener is total: 0.01～1.0%, surplus is Al and unavoidable impurities.
8. as each described hot dip coating cast aluminium alloy of claim 1-7, wherein the nano-oxide particles toughener is uniform spherical particles, and the specific surface area of nano-oxide particles toughener and median size satisfy following relational expression:
Wherein D represents median size;
ρ represents density.
9. as each described hot dip coating cast aluminium alloy of claim 1-7, wherein said TiO
2Median size be 15～60nm.
10. as each described hot dip coating cast aluminium alloy of claim 1-7, wherein said TiO
2Specific surface area be 20～90m
2/ g.
11. as each described hot dip coating cast aluminium alloy of claim 1-7, wherein said CeO
2Median size be 25～70nm.
12. as each described hot dip coating cast aluminium alloy of claim 1-7, wherein said CeO
2Specific surface area be 10～80m
2/ g.
13. as each described hot dip coating cast aluminium alloy of claim 1-7, wherein the nano-oxide particles toughener is TiO
2And CeO
2, and TiO
2And CeO
2Mass ratio is 1: (1～3).
14. method of making the described hot dip coating cast aluminium alloy of claim 1, mass percent according to Al, Zn, Si, RE and nano-oxide particles toughener is got the raw materials ready, in vacuum or atmosphere protection stove, Al heat temperature raising to 700～750 ℃ are dissolved earlier, stir, add Si; Add RE after being warming up to 800～840 ℃ then; Reheat adds Zn after being warming up to 830 ℃～850 ℃; After being cooled to 750～700 ℃, add the nano-oxide particles toughener; Temperature being reduced to 700～650 ℃ leaves standstill after 10～35 minutes casting or is cast into ingot again after stirring.
15. method of making the described hot dip coating cast aluminium alloy of claim 2, mass percent according to Al, Zn, Si, Mg, RE and nano-oxide particles toughener is got the raw materials ready, in vacuum or atmosphere protection stove, Al heat temperature raising to 700～750 ℃ are dissolved earlier, stir, add Si; Add RE after being warming up to 800～840 ℃ then; Reheat adds Zn after being warming up to 830 ℃～850 ℃; After being cooled to 750～700 ℃, add Mg and nano-oxide particles toughener; Temperature being reduced to 700～650 ℃ leaves standstill after 10～35 minutes casting or is cast into ingot again after stirring.
16. method of making the described hot dip coating cast aluminium alloy of claim 3, mass percent according to Al, Zn, Si, RE, Ni, nano-oxide particles toughener is got the raw materials ready, in vacuum or atmosphere protection stove, Al heat temperature raising to 700～750 ℃ are dissolved earlier, stir, add Si; Add RE after being warming up to 800～840 ℃ then; Reheat adds Zn after being warming up to 830 ℃～850 ℃; Reheat adds Ni after being warming up to 850 ℃～880 ℃; After being cooled to 750～700 ℃, add the nano-oxide particles toughener; Temperature being reduced to 700～650 ℃ leaves standstill after 10～35 minutes casting or is cast into ingot again after stirring.
17. method of making the described hot dip coating cast aluminium alloy of claim 4, mass percent according to Al, Zn, Si, RE, Ti, nano-oxide particles toughener is got the raw materials ready, in vacuum or atmosphere protection stove, Al heat temperature raising to 700～750 ℃ are dissolved earlier, stir, add Si; Add RE after being warming up to 800～840 ℃ then; Reheat adds Zn after being warming up to 830 ℃～850 ℃; Reheat adds Ti after being warming up to 850 ℃～880 ℃; After being cooled to 750～700 ℃, add the nano-oxide particles toughener; Temperature being reduced to 700～650 ℃ leaves standstill after 10～35 minutes casting or is cast into ingot again after stirring.
18. method of making the described hot dip coating cast aluminium alloy of claim 5, mass percent according to Al, Zn, Si, Mg, RE, Ni and nano-oxide particles toughener is got the raw materials ready, in vacuum or atmosphere protection stove, Al heat temperature raising to 700～750 ℃ are dissolved earlier, stir, add Si; Add RE after being warming up to 800～840 ℃ then; Reheat adds Zn after being warming up to 830 ℃～850 ℃; Reheat adds Ni after being warming up to 850 ℃～880 ℃; After being cooled to 750～700 ℃, add Mg and nano-oxide particles toughener; Temperature being reduced to 700～650 ℃ leaves standstill after 10～35 minutes casting or is cast into ingot again after stirring.
19. method of making the described hot dip coating cast aluminium alloy of claim 6, mass percent according to Al, Zn, Si, Mg, RE, Ti, nano-oxide particles toughener is got the raw materials ready, in vacuum or atmosphere protection stove, Al heat temperature raising to 700～750 ℃ are dissolved earlier, stir, add Si; Add RE after being warming up to 800～840 ℃ then; Reheat adds Zn after being warming up to 830 ℃～850 ℃; Reheat adds Ti after being warming up to 850 ℃～880 ℃; After being cooled to 750～700 ℃, add Mg and nano-oxide particles toughener; Temperature being reduced to 700～650 ℃ leaves standstill after 10～35 minutes casting or is cast into ingot again after stirring.
20. method of making the described hot dip coating cast aluminium alloy of claim 7, mass percent according to Al, Zn, Si, RE, Ti, Ni, nano-oxide particles toughener is got the raw materials ready, in vacuum or atmosphere protection stove, Al heat temperature raising to 700～750 ℃ are dissolved earlier, stir, add Si; Add RE after being warming up to 800～840 ℃ then; Reheat adds Zn after being warming up to 830 ℃～850 ℃; Reheat adds Ni and Ti after being warming up to 850 ℃～880 ℃; After being cooled to 750～700 ℃, add the nano-oxide particles toughener; Temperature being reduced to 700～650 ℃ leaves standstill after 10～35 minutes casting or is cast into ingot again after stirring.
21. as each described method of claim 14-20, the temperature rise rate in the described heat-processed is 10～40 ℃/minute, the rate of temperature fall in the described temperature-fall period is 20～60 ℃/minute.
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| CN102312141A (en) | 2012-01-11 |
| CN102312139A (en) | 2012-01-11 |
| CN101899598B (en) | 2012-03-07 |
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