WO2011079553A1 - 含Al-Zn-Si-Mg-RE-Ti-Ni的热浸镀铸铝合金及其制备方法 - Google Patents
含Al-Zn-Si-Mg-RE-Ti-Ni的热浸镀铸铝合金及其制备方法 Download PDFInfo
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- WO2011079553A1 WO2011079553A1 PCT/CN2010/071482 CN2010071482W WO2011079553A1 WO 2011079553 A1 WO2011079553 A1 WO 2011079553A1 CN 2010071482 W CN2010071482 W CN 2010071482W WO 2011079553 A1 WO2011079553 A1 WO 2011079553A1
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- aluminum alloy
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- cast aluminum
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- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/12—Aluminium or alloys based thereon
-
- 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
-
- 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
-
- 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
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
-
- 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
- C22C21/10—Alloys based on aluminium with zinc as the next major constituent
-
- 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
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0036—Matrix based on Al, Mg, Be or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0042—Matrix based on low melting metals, Pb, Sn, In, Zn, Cd or alloys thereof
Definitions
- the invention relates to a hot dip-plated cast aluminum alloy containing Al-Zn-Si-Mg-RE-Ti-Ni and a preparation method thereof, in particular to an Al-Zn-containing alloy for anti-corrosion treatment of marine weather engineering parts.
- the present invention provides a hot dip-plated cast aluminum alloy suitable for anti-corrosion treatment of marine weather resistant engineering parts and a manufacturing method thereof.
- the invention provides a hot dip-plated cast aluminum alloy for anti-corrosion treatment of marine weather engineering parts, wherein the cast aluminum alloy is composed of Al, Zn, Si, Mg, RE, Ti, Ni and nano oxide particle reinforcing agent.
- the nano oxide particle reinforcing agent is selected from one or two of Ti0 2 and Ce0 2 , and the total mass percentage of each component is: Zn : 35-58%, Si: 0.3-4.0%, Mg : 0.1-5.0 %, RE: 0.02-1.0%, Ti: 0.01-0.5%, Ni: 0.1-3.0%, total content of nano-oxide particle enhancer: 0.01 ⁇ 1.0%, balance A1 and unavoidable impurities.
- RE is any one or more of rare earth elements.
- the specific surface area of the further preferred nano-oxide particles of the present invention is greater than the calculated value of the above formula:
- the Ti0 2 has an average particle diameter of 15 to 60 nm.
- the specific surface area of the Ti0 2 is 20 to 90 m 2 /g.
- the average particle diameter of the Ce0 2 is 25 to 70 nm.
- the specific surface area of the Ce0 2 is 10 to 80 m 2 /g.
- the nano oxide particle reinforcing agent is TiO ⁇ B Ce0 2 , 110 2 and . 60 2 mass ratio is 1: (1 ⁇ 3). More preferably, the mass ratio of Ti0 2 to Ce0 2 is 1:2.
- the percentage of each component in the total mass percentage is: Zn: 41-51%, Si: 1-3.2%, Mg: 1.8-4%, RE: 0.05-0.8%, Ti: 0.05-0.35%, Ni: 1.5-2.6%, total content of nano-oxide particle enhancer: 0 ⁇ 05 ⁇ 0 ⁇ 8%.
- the present invention also provides a method for manufacturing the hot dip-plated cast aluminum alloy according to the mass percentage of Al, Zn, Si, Mg, RE, Ti, Ni, nano oxide particle reinforcing agent, first in vacuum or In the atmosphere protection furnace, heat the A1 to 700 ⁇ 750 °C, stir evenly, add Si; then heat up to 800 ⁇ 840 °C and add RE; then heat to 830 °C ⁇ 850 °C and add Zn; Heating and heating to 850 ° C ⁇ 880 ° C, then adding Ni and Ti; after cooling to 750 ⁇ 700 ° C, adding Mg and nano oxide particle enhancer; then reducing the temperature to 700 ⁇ 650 ° C after stirring evenly After 10 to 35 minutes, it is cast or die-cast into ingots.
- the heating rate during the heating process is 10 to 40 ° C / min, and the cooling rate during the cooling process is 20 to 60 ° C / min.
- the invention provides a hot dip-plated cast aluminum alloy resistant to marine weather corrosion, wherein A1 is a metal resistant to atmospheric corrosion, and A1 forms a dense oxide film on the surface in the air quickly, and has rapid self-repair damage. Capability; Zn has a low electrode potential and, as a sacrificial anode, imparts sufficient resistance to electrochemical corrosion of steel. However, if the zinc content is too high, the toughness and hardness of the coating will be reduced, thereby reducing the coating resistance to the atmosphere. Corrosion and airflow erosion resistance.
- the present invention greatly refines the grain of the coating by adding a certain amount of nano-oxide particle reinforcing agent, improves the toughness of the coating, and improves the corrosion resistance and electrochemical corrosion of the coating.
- the performance of the coating layer can be more significantly improved, in addition to the nano-oxide particle reinforcing agent.
- the particle size adopts the numerical range of the invention, and the wear resistance of the coating layer can be greatly improved, and the specific surface area of the nano oxide particle reinforcing agent adopts the numerical range of the invention, so that the degree of aggregation of the alloy can be greatly improved, thereby being more remarkable. Improve the anti-scour performance of alloy coatings.
- microalloying elements such as Mg, Ti, Ni, etc.
- the addition of these microalloying elements can further refine the grains, further improving the toughness and corrosion resistance of the coating, wherein Mg can improve the affinity of the alloy. Corrosion resistance and increase the room temperature strength of the alloy, while Ti strengthens the strengthening phase in the coating and solid solution to the alloy. M not only further solidifies the alloy, but also further improves the alloy. Toughness and stability.
- the cast aluminum alloy produced by the invention can be used as a coating to impart sufficient corrosion resistance and erosion resistance under marine climatic conditions.
- the present invention also provides a method for adding hot dip alloying elements by using multiple temperature sections.
- the nano oxide particle reinforcing agent and various elements can be dispersed with the increase of temperature. Properties, thereby improving the uniformity of the coating composition and significantly increasing the bonding strength of the coating to the substrate.
- the invention adopts a part of the temperature section to add a part of the hot dip coating alloy element, and then reduces the temperature to a certain temperature, then adds the nano oxide particle reinforcing agent, and finally cools and keeps the temperature for a certain time, thus overcoming the above defects.
- a coating with uniform composition and good toughness was obtained.
- the coating has significantly improved resistance to atmospheric corrosion, electrochemical corrosion, and airflow erosion, and the strength, hardness, and erosion resistance of the coating are also significantly improved.
- the layer is firmly bonded to the substrate and is perfectly suited for extreme environments such as the ocean.
- the production process of the present invention is simplified, and a coating having uniform composition and good toughness can be obtained.
- the main components of the alloy such as aluminum and zinc, are rich in alloying elements in nature. Therefore, the material cost is low, and it is environmentally friendly and energy-saving.
- the alloy of the invention is used as a plating layer, and the thickness can be adjusted in a wide range, which is suitable for the processing of various size parts.
- the hot dip-plated cast aluminum alloy for anti-corrosion treatment of marine weather engineering parts provided by the present invention, wherein the cast aluminum alloy is
- the nano oxide particle reinforcing agent is selected from one or two of Ti0 2 and Ce0 2 , and each component accounts for The mass percentage is: Zn: 35-58%, Si: 0.3-4.0%, Mg : 0.1-5.0%, RE: 0.02-1.0%, Ti: 0.01-0.5%, Ni: 0.1-3.0%, nano-oxide particles
- the total content of the reinforcing agent is 0.01-1.0%, and the balance is A1 and unavoidable impurities, and the impurities which are impossible to avoid are usually impurity elements such as Fe, Mn, Pb, Sn, Cd which cannot be completely removed.
- the performance of the coating layer can be more significantly improved, if the nano-oxide particles used are uniform spherical particles.
- the specific surface area and the average particle diameter of the sphere satisfy the following relationship:
- D represents the average particle size
- ⁇ represents the density
- the preferred surface area of the preferred nano-oxide particles of the present invention is larger than the calculated value of this formula.
- the Ti0 2 has an average particle diameter of 15 to 60 nm.
- the specific surface area of the Ti0 2 is 20 to 90 m 2 /g.
- the average particle diameter of the Ce0 2 is 25 to 70 nm.
- the specific surface area of the Ce0 2 is 10 to 80 m 2 /g.
- the core content is to refine the grain of the coating, improve its toughness, improve its various corrosion resistance, and overcome the zinc content by adding a certain amount of nano-alloy particle reinforcement microalloying elements. The purpose of the adverse effects brought about by the high.
- Example 1 by further selecting the appropriate particle size and suitable specific surface area, it is only to make this technology more prominent and more Superior, therefore, although these two parameters are listed at the same time in Tables 1-3 below, they are only as more preferable conditions, and are for giving more detailed technical information about the present invention, and not as The necessary conditions of the present invention are described.
- Example 1
- a hot dip-plated cast aluminum alloy for anti-corrosion treatment of marine weather engineering parts which is composed of Zn, Al, Si, Mg, RE, Ti, Ni and 110 2 nanometer oxide particle reinforcing agents, and each component accounts for the total mass
- the percentages are: Zn: 35-58%, Si: 0.3-4.0%, Mg: 0.1-5.0%, RE: 0.02-1.0%, Ti: 0.01-0.5%, Ni: 0.1-3.0%, Ti0 2: 0.01- 1.0%,
- Table 1 Content of each component in the total weight (3 ⁇ 4>) and related parameters
- a hot dip-plated cast aluminum alloy for anti-corrosion treatment of marine weather engineering parts which is composed of Al, Zn, Si, Mg, RE, Ti, Ni and CeO ⁇ fi rice oxide particle reinforcing agent, and each component constitutes total
- the mass percentages are: Zn: 35-58%, Si: 0.3-4.0%, Mg: 0.1-5.0%, RE: 0.02-1.0%, Ti: 0.01-0.5%, Ni: 0.1-3.0%, Ce0 2: 0.01 -1.0%,
- the hot dip coating alloy is composed of Al, Zn, Si, Mg, RE, Ti, Ni and nano oxide particle reinforcing agents, wherein the nano oxide particles are TiO ⁇ BCe0 2 and 110 2 and . 60 2 ratio is 1: (1 ⁇ 3), by mass percentage: The percentage of each component in total mass is: Zn: 35-58%, Si: 0.3-4.0%, Mg: 0.1-5.0%, RE: 0.02 -1.0%, Ti: 0.01-0.5%, Ni: 0.1-3.0%, total content of nano-oxide particles Ti0 2 and Ce0 2 : 0.01-1.0%, A1: balance, and unavoidable impurities, see specific Table 3 below:
- each component comprises a total mass percentage: Zn: 41-51%, Si: 1-3.2%, Mg : 1.8-4%, RE: 0.05-0.8%, Ti: 0.05-0.35 %, Ni: 1.5-2.6%, total content of nano-oxide particle enhancer: 0.05 ⁇ 0.8%.
- the Zn content is 45%, the Si content is 1.8%, the Mg content is 3.5%, the RE content is 0.6%, the Ti content is 0.25%, and the Ni content is 2. %, the total content of the nano oxide particle reinforcing agent is 0.2%.
- the bulk density of the Ti0 2 does not exceed 3 g/cm 3 .
- Ce0 2 is used, wherein the Ce0 2 has a bulk density of no more than 5 g/cm 3 .
- Ti0 2 and Ce0 2 are used at the same time, it is preferred that the Ti0 2 and .
- the average bulk density of 60 2 is 0.6 to 4.5 g/cm 3 .
- the present invention also provides a method for manufacturing the hot dip coating alloy according to the mass percentage of Al, Zn, Si, Mg, RE, Ti, Ni, nano oxide particle reinforcing agent, first in vacuum or In the atmosphere protection furnace, heat the A1 to 700 ⁇ 750 °C, stir evenly, add Si; then heat up to 800 ⁇ 840 °C and add RE; then heat to 830 °C ⁇ 850 °C and add Zn; Heating and heating to 850 ° C ⁇ 880 ° C, then adding Ni and Ti; after cooling to 750 ⁇ 700 ° C, adding Mg and nano oxide particle enhancer; then reducing the temperature to 700 ⁇ 650 ° C after stirring evenly After 10 to 35 minutes, it is cast or die-cast into ingots.
- the A1 is heated and heated to 720-750 ° C in a vacuum or atmosphere protection furnace, and stirred.
- Uniform add Si; then heat to 820 ⁇ 840 ° C and then add RE; then heat to 840 ° C ⁇ 850 ° C and then add Zn; then heat to 860 ° C ⁇ 880 ° C after adding Ni and Ti; After cooling to 730 ⁇ 700 °C, add Mg and nano oxide particle enhancer; then lower the temperature to 690 ⁇ 650 °C, stir it evenly, let it stand for 10 ⁇ 30 minutes, then cast or die-cast into ingot.
- the Mg and the nano oxide particle reinforcing agent are added after cooling to 720 to 700 ° C; and finally the temperature is lowered to 690 to 660 ° C for 22 to 28 minutes.
- the Mg and the nano-oxide particle reinforcing agent are added after cooling to 71 CTC; and finally the temperature is lowered to 680 ° C for 25 minutes.
- the heating rate during the heating is 10 to 40 ° C / min
- the cooling rate during the cooling is 20 to 60 ° C / min.
- the heating rate during the heating process is 20 to 30 ° C / min
- the cooling rate during the cooling process It is 30 ⁇ 50 °C / min.
- the key component of a near-shore wind turbine was treated with conventional coating protection and produced significant corrosion in just a few months.
- the hot-dip alloy of the present invention is used as a plating material to form a 150 ⁇ thick plating coating, and then coated with a 20 ⁇ thick aliphatic polyurethane coating.
- the accelerated corrosion simulation test results show that the durability in the seawater splash zone environment can exceed 20 years. .
- connection bolt size: M36xl000m, material 40CrNiMo
- connection bolt size: M36xl000m, material 40CrNiMo
- the hot-dip alloy of the present invention is used as a plating material to form a ⁇ thick-permeation coating, and then coated with a 15 ⁇ thick polysiloxane, and the accelerated corrosion simulation test results show that the durability in the seawater splash zone environment can exceed 20 years. .
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/127,237 US8974728B2 (en) | 2009-11-19 | 2010-03-31 | Hot-dip cast aluminum alloy containing Al-Zn-Si-Mg-RE-Ti-Ni and preparation method thereof |
AU2010336896A AU2010336896B2 (en) | 2009-11-19 | 2010-03-31 | Hot dip casting aluminum alloy containing Al-Zn-Si-Mg-RE-Ti-Ni and production method thereof |
KR1020117012899A KR101297617B1 (ko) | 2009-11-19 | 2010-03-31 | Al-Zn-Si-Mg-RE-Ti-Ni를 함유한 용융 도금용 알루미늄 주조 합금 및 그의 제조방법 |
EP10840343.7A EP2503017B1 (en) | 2009-11-19 | 2010-03-31 | Hot dip casting aluminium alloy containing Al-Zn-Si-Mg-RE-Ti-Ni and production method thereof |
JP2012538169A JP5651187B2 (ja) | 2009-11-19 | 2010-03-31 | Al−Zn−Si−Mg−RE−Ti−Ni含有の熱溶融めっきアルミ鋳造合金及びその製造方法 |
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CN2009102237684A CN101935789B (zh) | 2009-11-19 | 2009-11-19 | 含Al-Zn-Si-Mg-RE-Ti-Ni的热浸镀铸铝合金及其制备方法 |
CN200910223768.4 | 2009-11-19 |
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US (1) | US8974728B2 (zh) |
EP (1) | EP2503017B1 (zh) |
JP (1) | JP5651187B2 (zh) |
KR (1) | KR101297617B1 (zh) |
CN (1) | CN101935789B (zh) |
AU (1) | AU2010336896B2 (zh) |
WO (1) | WO2011079553A1 (zh) |
Cited By (1)
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US8974728B2 (en) | 2009-11-19 | 2015-03-10 | Jiangsu Linlong New Materials Co., Ltd. | Hot-dip cast aluminum alloy containing Al-Zn-Si-Mg-RE-Ti-Ni and preparation method thereof |
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CN101760716B (zh) * | 2009-12-28 | 2011-09-21 | 江苏麟龙新材料股份有限公司 | 一种在钛合金表面制备抗接触腐蚀涂层的方法 |
CN102650025B (zh) * | 2011-02-23 | 2014-06-25 | 贵州华科铝材料工程技术研究有限公司 | 一种含Mg多组合变质的低锌热浸镀铝合金镀层材料及其制备方法 |
CN102650026B (zh) * | 2011-02-25 | 2014-11-19 | 贵州华科铝材料工程技术研究有限公司 | Be与多组合变质的低锌热浸镀铝合金镀层材料及其制备方法 |
KR101488288B1 (ko) * | 2012-11-20 | 2015-01-30 | 현대자동차주식회사 | 진동감쇠형 알루미늄 합금 |
WO2014168183A1 (ja) * | 2013-04-12 | 2014-10-16 | 本田技研工業株式会社 | 亜鉛合金の製造方法 |
CN103540813B (zh) * | 2013-09-24 | 2016-07-06 | 李露青 | 一种Yb2O3增强的Al-Si-Zn系铝合金的处理方法 |
CN103540878B (zh) * | 2013-09-24 | 2016-07-06 | 李露青 | 一种CeO2增强的Al-Si-Zn系铝合金的处理方法 |
CN103540879B (zh) * | 2013-09-24 | 2016-05-18 | 李露青 | 一种Pr6O11增强的Al-Si-Zn系铝合金的处理方法 |
CN104759399A (zh) * | 2014-01-07 | 2015-07-08 | 无锡新大中薄板有限公司 | 用于海洋工程的植绒铝合金涂层吹花板材的制造方法 |
CN104233018B (zh) * | 2014-08-26 | 2017-02-15 | 盐城市鑫洋电热材料有限公司 | 一种增强铝合金及其制备方法 |
WO2017034486A1 (en) * | 2015-08-24 | 2017-03-02 | Ptt Public Company Limited | Aluminium alloy for sacrificial anode |
CN111349840B (zh) * | 2020-05-12 | 2021-07-06 | 东华理工大学 | 一种低密度、超高比屈服强度Mg-Ni-Ti-Al四元合金及其制备方法 |
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KR20110098727A (ko) | 2011-09-01 |
US20110293467A1 (en) | 2011-12-01 |
CN101935789A (zh) | 2011-01-05 |
EP2503017A1 (en) | 2012-09-26 |
JP2013510943A (ja) | 2013-03-28 |
AU2010336896B2 (en) | 2013-10-10 |
CN101935789B (zh) | 2012-03-07 |
JP5651187B2 (ja) | 2015-01-07 |
EP2503017B1 (en) | 2016-12-14 |
EP2503017A4 (en) | 2015-07-01 |
KR101297617B1 (ko) | 2013-08-19 |
AU2010336896A1 (en) | 2011-08-25 |
US8974728B2 (en) | 2015-03-10 |
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