CN1706992A - Prepn process of solid surface in micron and nanometer structure - Google Patents
Prepn process of solid surface in micron and nanometer structure Download PDFInfo
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- CN1706992A CN1706992A CN 200410046344 CN200410046344A CN1706992A CN 1706992 A CN1706992 A CN 1706992A CN 200410046344 CN200410046344 CN 200410046344 CN 200410046344 A CN200410046344 A CN 200410046344A CN 1706992 A CN1706992 A CN 1706992A
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Abstract
The present invention is preparation process of solid surface in micron and nanometer structure. The preparation process includes chemical corrosion step of corroding anode porous alumina film with alkali solution in controlled proper time, and subsequent drying to obtain solid surface in micron and nanometer structure. The process of the present invention is simple, convenient and easy in operation and adopts cheap and available instrument and chemicals.
Description
Technical field
The invention belongs to the solid surface field of preparation micron and nanostructure, particularly have the preparation method of the solid surface of micron and nanostructure.
Background technology
Wetting property is a key character of solid surface, and hydrophobic performance conduct a kind of manifestation mode wherein has very important potential using value, has caused scientific research personnel's extensive concern and has obtained bigger achievement.Usually, the method that improves solid hydrophobic surface mainly contains two kinds: the one, modify solid surface with material such as fluorochemicals with low surface energy; The 2nd, the degree of roughness of increase solid surface.At present, the existing report of many methods of preparation uneven surface, as: plasma polymerization, microwave plasma CVD, phase separation method, anonizing, melting and solidification method etc., but most preparation process complexity is not easy to operate.
This type of bibliographical information has " physical chemistry " magazine 1996,100, the article of delivering on 19512～19517 " by the super hydrophobic surface of irregular tile structure generation " (S.Shibuich, T.Onda, N.Satoh, K.Tsujii.Super water-repellent surfaces resulting from fractal structure.J.Phys.Chem.B), used method is that the curing of the positive ketene dimer of fusion alkyl (AKD) has prepared irregular tile structure; " physical chemistry B " magazine 2002,106, the article of delivering on the 9274-9276 " ultra-hydrophobicity of the cellular carbon nanotube of big area " (S.H.Li, H.J.Li, X.B.Wang, et al..super-hydrophobicity of large-area honeycomb-like aligned carbon nanotubes.J.Phys.Chem.) used method is that chemical vapor deposition prepares array carbon nano tube, prepares cellular carbon nanotube structure then, above preparation process complexity." bright wrong that " magazine 2000,16,7777～7782 articles of delivering " super hydrophobic surface; appearance and size is to infiltrating influence " (D. ner, T.J.McCarthy.Ultrahydrophobic surfaces.Effects of topography length scales on wettability.Langmuir.) are discussed and are only only limited to micron-scale." applied chemistry " magazine 2002,114, the article of delivering on 1269～1271 " array polyacrylonitrile nano fiber super hydrophobic surface " (L.Feng, S.H.Li, H.J.Li, er a1..Angew.Chem.) and " applied chemistry " magazine 2003, " hydrophilic polymer prepares super hydrophobic surface " (L.Feng, the Y.L.Song that delivers on 115,824～826, J.Zhai, et al..Angew.Chem.) discusses and only only limit to nano-scale.
Summary of the invention
The objective of the invention is to overcome the defective for preparation method complexity when having micron order and nanoscale solids uneven surface, provide a kind of preparation to have the simple and easy method of the solid surface of micron and nanostructure.
The present invention is starting material with the porous alumina in different apertures, by the method for chemical corrosion, prepare have the micron and nanophase bonded configuration of surface structure.
Preparation method of the present invention is simple, easy handling, used instrument and medicine are cheap and easy to get, the micron of preparing and the aperture of the micron order hole in the nanophase bonded configuration of surface structure are 0.5～60 μ m, micron order hole wall thickness is 0.5～2 μ m, the micron order hole wall is that the nano aperture structure of 50～500nm and nano thread structure that width is 20～500nm are formed by the aperture, has constituted thus and has realized the super-hydrophobic ideal surfaced morphological structure of solid surface.
Preparation method with solid surface of micron and nanostructure of the present invention may further comprise the steps:
(1) under the room temperature, being starting material with the anode multiaperture pellumina, is the strong base solution corrosive film of 1～6mol/L with concentration, and etching time is 1～60 minute;
(2) the anode multiaperture pellumina after step (1) corrosion is cleaned up with deionized water, then at normal temperatures, under the infrared lamp, carry out drying in baking oven or the vacuum drying oven, obtain having the solid surface of micron and nanostructure after the drying.
Described strong base solution comprises: sodium hydroxide, potassium hydroxide or their mixing solutions.
The aperture of the anode multiaperture pellumina that the present invention is used is 5～500nm, preferred 100～200nm; Temperature when carrying out drying in baking oven or vacuum drying oven is approximately about 40～100 ℃.
The inventive method is simple and convenient, operation easily, and used instrument and medicine are cheap and easy to get.
Description of drawings
Fig. 1. the stereoscan photograph of the embodiment of the invention 1.
Fig. 2. the stereoscan photograph of the embodiment of the invention 2.
Fig. 3. the stereoscan photograph of the embodiment of the invention 3.
Fig. 4. the stereoscan photograph of the embodiment of the invention 5.
Embodiment
Embodiment 1
(1) preparation potassium hydroxide solution, concentration is 3mol/L.
(2) getting the anode multiaperture pellumina that the aperture is 2nm (Britain Whatman company produces, and commodity are called Anapore) is material, carries out chemical corrosion with alkaline solution, and the time is 5 minutes, and temperature is 18.5 ℃.
(3) drying: drying is 3 hours in baking oven, and temperature is 80 ℃.
Measuring this sample micron order hole wall thickness through SEM is 1～2 μ m, and the aperture of micron order hole is 3 μ m, and the micron order hole wall is that the nano aperture of 200nm and nano wire that width is 50～300nm are formed by the aperture.See accompanying drawing 1.
Embodiment 2
(1) preparation potassium hydroxide solution, concentration is 3mol/L.
(2) porous alumina (Britain Whatman company produce, commodity are called Anapore) of taking the 200nm aperture is a material, carries out chemical corrosion with alkaline solution, and the time is 7 minutes, and temperature is 20.5 ℃.
(3) drying: drying is 3 hours in baking oven, and temperature is 80 ℃.
Measuring this sample micron order hole wall thickness through SEM is 1 μ m, and the on average about 16 μ m in the aperture of micron order hole, micron order hole wall are that the nano aperture of 200nm and nano wire that width is 50～300nm are formed by the aperture.See accompanying drawing 2.
Embodiment 3
(1) preparation sodium hydroxide solution, concentration is 3mol/L.
(2) porous alumina (Britain Whatman company produce, commodity are called Anapore) of taking the 200nm aperture is a material, carries out chemical corrosion with alkaline solution, and the time is 4 minutes, and temperature is 19.5 ℃.
(3) drying: drying is 3 hours in baking oven, and temperature is 80 ℃.
Measuring this sample micron order hole wall thickness through SEM is 1～2 μ m, and the about 2 μ m in the aperture of micron order hole, micron order hole wall are that the nano aperture of 200nm and nano wire that width is 50～300nm are formed by the aperture.See accompanying drawing 3.
Embodiment 4
(1) preparation sodium hydroxide solution, concentration is 3mol/L.
(2) porous alumina (Britain Whatman company produce, commodity are called Anapore) of taking the 200nm aperture is a material, carries out chemical corrosion with alkaline solution, and the time is 5 minutes, and temperature is 20 ℃.
(3) drying: drying is 3 hours in baking oven, and temperature is 80 ℃.
Measuring this sample micron order hole wall thickness through SEM is 1 μ m, and the about 1 μ m in the aperture of micron order hole, micron order hole wall are that the nano aperture of 200nm and nano wire that width is 50～300nm are formed by the aperture.SEM figure is similar to Fig. 3, and size has difference slightly.
Embodiment 5
(1) preparation sodium hydroxide solution, concentration is 3mol/L.
(2) porous alumina (Britain Whatman company produce, commodity are called Anapore) of taking the 200nm aperture is a material, carries out chemical corrosion with alkaline solution, and the time is 5 minutes, and temperature is 19.5 ℃.
(3) drying: drying is 3 hours under infrared lamp, and temperature is 40 ℃.
Measuring this sample micron order hole wall thickness through SEM is 0.5 μ m, and the on average about 2 μ m in the aperture of micron order hole, micron order hole wall are that the nano aperture of 200nm and nano wire that width is 50～300nm are formed by the aperture.See accompanying drawing 4.
Embodiment 6
(1) preparation sodium hydroxide solution, concentration is 3mol/L.
(2) porous alumina (Britain Whatman company produce, commodity are called Anapore) of taking the 200nm aperture is a material, carries out chemical corrosion with alkaline solution, and the time is 4 minutes, and temperature is 19.5 ℃.
(3) drying: drying is 3 hours under infrared lamp, and temperature is 40 ℃.
Measuring this sample micron order hole wall thickness through SEM is 0.5～1 μ m, the on average about 2 μ m in the aperture of micron order hole, and the micron order hole wall is about the nano aperture of 200nm by the aperture and nano wire that width is 50～300nm is formed.SEM figure is similar to accompanying drawing 1, and the micron order hole is slightly different.
Embodiment 7
(1) preparation sodium hydroxide solution, concentration is 3mol/L.
(2) porous alumina (Britain Whatman company produce, commodity are called Anapore) of taking the 200nm aperture is a material, carries out chemical corrosion with alkaline solution, and the time is 5 minutes, and temperature is 20 ℃.
(3) drying: infrared lamp dry 1 hour down, temperature is 46 ℃.
Measuring this sample micron order hole wall thickness through SEM is 1 μ m, and about 0.5～1 μ m in the aperture of micron order hole, micron order hole wall are that the nano aperture of 200nm and nano wire that width is 50～300nm are formed by the aperture.SEM figure is similar to accompanying drawing 3, and micrometer grade hole hole footpath is slightly smaller.
Embodiment 8
(1) preparation sodium hydroxide solution, concentration is 3mol/L.
(2) porous alumina (Britain Whatman company produce, commodity are called Anapore) of taking the 200nm aperture is a material, carries out chemical corrosion with alkaline solution, and the time is 6 minutes, and temperature is 20.5 ℃.
(3) drying: drying is 3 hours in baking oven, and temperature is 80 ℃.
Measure this sample micron order hole wall thickness through SEM and be about 1 μ m, the on average about 5 μ m in the aperture of micron order hole, micron order hole wall are that the nano aperture of 200nm and nano wire that width is 50～300nm are formed by the aperture.SEM figure is similar to accompanying drawing 2, and micrometer grade hole hole footpath is slightly smaller.
Embodiment 9
(1) preparation sodium hydroxide solution, concentration is 3mol/L.
(2) porous alumina (Britain Whatman company produce, commodity are called Anapore) of taking the 200nm aperture is a material, carries out chemical corrosion with alkaline solution, and the time is 2 minutes, and temperature is 22.5 ℃.
(3) drying: drying is 1 hour under infrared lamp, and temperature is 46 ℃.
Measure this sample micron order hole wall thickness through SEM and be about 1 μ m, the on average about 1.5 μ m in the aperture of micron order hole, micron order hole wall are that the nano aperture of 200nm and nano wire that width is 50～300nm are formed by the aperture.Images category is similar to accompanying drawing 3.
Embodiment 10
(1) preparation sodium hydroxide solution, concentration is 3mol/L.
(2) porous alumina (Britain Whatman company produce, commodity are called Anapore) of taking the 200nm aperture is a material, carries out chemical corrosion with alkaline solution, and the time is 3 minutes, and temperature is 22.5 ℃.
(3) drying: drying is 1 hour under infrared lamp, and temperature is 46 ℃.
Measure this sample micron order hole wall thickness through SEM and be about 1.5 μ m, the on average about 35 μ m in the aperture of micron order hole, micron order hole wall are that the nano aperture of 200nm and nano wire that width is 50～300nm are formed by the aperture.Images category is similar to accompanying drawing 2, and the micron order hole is slightly larger.
Embodiment 11
(1) preparation sodium hydroxide solution, concentration is 3mol/L.
(2) porous alumina (Britain Whatman company produce, commodity are called Anapore) of taking the 200nm aperture is a material, carries out chemical corrosion with alkaline solution, and the time is 6 minutes, and temperature is 18 ℃.
(3) drying: drying is 3 hours under infrared lamp, and temperature is 40 ℃.
Measure this sample micron order hole wall thickness through SEM and be about 0.2～0.5 μ m, the on average about 3 μ m in the aperture of micron order hole, micron order hole wall are that the nano aperture of 200nm and nano wire that width is 50～300nm are formed by the aperture.Images category is similar to accompanying drawing 2, and the micron order hole is slightly smaller.
Embodiment 12
(1) preparation sodium hydroxide solution, concentration is 3mol/L.
(2) porous alumina (Britain Whatman company produce, commodity are called Anapore) of taking the 200nm aperture is a material, carries out chemical corrosion with alkaline solution, and the time is 5 minutes, and temperature is 18.5 ℃.
(3) drying: drying is 3 hours under infrared lamp, and temperature is 40 ℃.
Measure this sample micron order hole wall thickness through SEM and be about 1 μ m, the on average about 1 μ m in the aperture of micron order hole, micron order hole wall are that the nano aperture of 200nm and nano wire that width is 50～300nm are formed by the aperture.Images category is similar to accompanying drawing 3.
Embodiment 13
(1) preparation sodium hydroxide solution, concentration is 3mol/L.
(2) porous alumina (Britain Whatman company produce, commodity are called Anapore) of taking the 200nm aperture is a material, carries out chemical corrosion with alkaline solution, and the time is 3 minutes, and temperature is 22.5 ℃.
(3) drying: drying is 3 hours under infrared lamp, and temperature is 40 ℃.
Measure this sample micron order hole wall thickness through SEM and be about 1.5 μ m, the on average about 5 μ n in the aperture of micron order hole, micron order hole wall are that the nano aperture of 200nm and nano wire that width is 50～300nm are formed by the aperture.Images category is similar to accompanying drawing 2, and the micron order hole is slightly smaller.
Embodiment 14
(1) mixing solutions of preparation sodium hydroxide and potassium hydroxide, concentration is 3mol/L, and equal-volume mixes.The concentration of mixing back sodium hydroxide and potassium hydroxide is 1.5mol/L.
(2) porous alumina (Britain Whatman company produce, commodity are called Anapore) of taking the 200nm aperture is a material, carries out chemical corrosion with alkaline solution, and the time is 4 minutes, and temperature is 22.5 ℃.
(3) drying: drying is 3 hours under infrared lamp, and temperature is 40 ℃.
Measure this sample micron order hole wall thickness through SEM and be about 1.5 μ m, the on average about 50 μ m in the aperture of micron order hole, micron order hole wall are that the nano aperture of 200nm and nano wire that width is 50～300nm are formed by the aperture.Images category is similar to accompanying drawing 2, and the micron order hole is big slightly.
Embodiment 15
(1) mixing solutions of preparation sodium hydroxide and potassium hydroxide, concentration is 3mol/L, and equal-volume mixes.The concentration of mixing back sodium hydroxide and potassium hydroxide is 1.5mol/L.
(2) porous alumina (Britain Whatman company produce, commodity are called Anapore) of taking the 200nm aperture is a material, carries out chemical corrosion with alkaline solution, and the time is 5 minutes, and temperature is 22.5 ℃.
(3) drying: drying is 3 hours under infrared lamp, and temperature is 40 ℃.
Measure this sample micron order hole wall thickness through SEM and be about 1 μ m, the on average about 60 μ m in the aperture of micron order hole, micron order hole wall are that the nano aperture of 200nm and nano wire that width is 50～300nm are formed by the aperture.Images category is similar to accompanying drawing 2, and the micron order hole is big slightly.
Embodiment 16
(1) preparation sodium hydroxide solution, concentration is 3mol/L.
(2) porous alumina (Britain Whatman company produce, commodity are called Anapore) of taking the 200nm aperture is a material, carries out chemical corrosion with alkaline solution, and the time is 7 minutes, and temperature is 19 ℃.
(3) drying: drying is 3 hours in vacuum drying oven, and temperature is 80 ℃.
Measure this sample micron order hole wall thickness through SEM and be about 2 μ m, the on average about 50 μ m in the aperture of micron order hole, micron order hole wall are that the nano aperture of 200nm and nano wire that width is 50～300nm are formed by the aperture.Images category is similar to accompanying drawing 2, and the micron order hole is big slightly.
Embodiment 17
(1) preparation potassium hydroxide solution, concentration is 3mol/L.
(2) porous alumina (Britain Whatman company produce, commodity are called Anapore) of taking the 100nm aperture is a material, carries out chemical corrosion with alkaline solution, and the time is 7 minutes, and temperature is 19 ℃.
(3) drying: drying is 1 hour in vacuum drying oven, and temperature is 60 ℃.
Measure this sample micron order hole wall thickness through SEM and be about 1.5 μ m, the on average about 55 μ m in the aperture of micron order hole, the micron order hole wall is about the nano aperture of 100nm by the aperture and nano wire that width is 30～100nm is formed.Images category is similar to accompanying drawing 2, and the micron order hole is big slightly.
Embodiment 18
(1) preparation potassium hydroxide solution, concentration is 3mol/L.
(2) porous alumina (Britain Whatman company produce, commodity are called Anapore) of taking the 300nm aperture is a material, carries out chemical corrosion with alkaline solution, and the time is 5 minutes, and temperature is 19 ℃.
(3) drying: dry 24 hours at normal temperatures, temperature was 19 ℃.
Measure this sample micron order hole wall thickness through SEM and be about 1 μ m, the on average about 15 μ m in the aperture of micron order hole, the micron order hole wall is about the nano aperture of 300nm by the aperture and nano wire that width is 80～300nm is formed.Images category is similar to accompanying drawing 1, and the micron order hole is big slightly.
Embodiment 19
(1) mixing solutions of preparation sodium hydroxide and potassium hydroxide, concentration is 3mol/L, and equal-volume mixes.The concentration of mixing back sodium hydroxide and potassium hydroxide is 1.5mol/L.
(2) porous alumina (Britain Whatman company produce, commodity are called Anapore) of taking the 500nm aperture is a material, carries out chemical corrosion with alkaline solution, and the time is 4 minutes, and temperature is 20 ℃.
(3) drying: dry 24 hours at normal temperatures, temperature was 20 ℃.
Measure this sample micron order hole wall thickness through SEM and be about 1.5 μ m, the on average about 5 μ m in the aperture of micron order hole, the micron order hole wall is about the nano aperture of 500nm by the aperture and nano wire that width is 100～600nm is formed.Images category is similar to accompanying drawing 1, and the micron order hole is big slightly.
Embodiment 20
(1) preparation sodium hydroxide solution, concentration is 1mol/L.
(2) porous alumina (Britain Whatman company produce, commodity are called Anapore) of taking the 100nm aperture is a material, carries out chemical corrosion with alkaline solution, and the time is 25 minutes, and temperature is 20 ℃.
(3) drying: dry 48 hours at normal temperatures, temperature was 20 ℃.
Measure this sample micron order hole wall thickness through SEM and be about 1.5 μ m, the on average about 2 μ m in the aperture of micron order hole, the micron order hole wall is about the nano aperture of 100nm by the aperture and nano wire that width is 20～100nm is formed.Images category is similar to accompanying drawing 3.
Embodiment 21
(1) preparation sodium hydroxide solution, concentration is 5mol/L.
(2) porous alumina (Britain Whatman company produce, commodity are called Anapore) of taking the 100nm aperture is a material, carries out chemical corrosion with alkaline solution, and the time is 3 minutes, and temperature is 18 ℃.
(3) drying: dry 48 hours at normal temperatures, temperature was 18 ℃.
Measure this sample micron order hole wall thickness through SEM and be about 1.5 μ m, the on average about 5 μ m in the aperture of micron order hole, the micron order hole wall is about the nano aperture of 100nm by the aperture and nano wire that width is 20～100nm is formed.Images category is similar to accompanying drawing 1.
Embodiment 22
(1) preparation potassium hydroxide solution, concentration is 6mol/L.
(2) porous alumina (Britain Whatman company produce, commodity are called Anapore) of taking the 100nm aperture is a material, carries out chemical corrosion with alkaline solution, and the time is 4 minutes, and temperature is 18 ℃.
(3) drying: dry 24 hours at normal temperatures, temperature was 18 ℃.
Measure this sample micron order hole wall thickness through SEM and be about 1 μ m, the on average about 25 μ m in the aperture of micron order hole, the micron order hole wall is about the nano aperture of 100nm by the aperture and nano wire that width is 20～100nm is formed.Images category is similar to accompanying drawing 2.
Claims (5)
1. preparation method with micron and solid surface of nanostructure, it is characterized in that: described method may further comprise the steps:
(1) under the room temperature, being starting material with the anode multiaperture pellumina, is the strong base solution corrosive film of 1～6mol/L with concentration, and etching time is 1～60 minute;
(2) the anode multiaperture pellumina after step (1) corrosion is cleaned up with deionized water, then at normal temperatures, under the infrared lamp, carry out drying in baking oven or the vacuum drying oven, obtain having the solid surface of micron and nanostructure after the drying.
2. method according to claim 1 is characterized in that: described strong base solution comprises: sodium hydroxide, potassium hydroxide or their mixing solutions.
3. method according to claim 1 is characterized in that: the aperture of described anode multiaperture pellumina is 50～500nm.
4. method according to claim 3 is characterized in that: the aperture of described anode multiaperture pellumina is 100～200nm.
5. method according to claim 1, it is characterized in that: described aperture with the micron order hole in the micron and the solid surface of nanostructure is 0.5～60 μ m, micron order hole wall thickness is 0.5～2 μ m, and the micron order hole wall is that the nano aperture structure of 50～500nm and nano thread structure that width is 20～500nm are formed by the aperture.
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| CNB2004100463442A CN100343422C (en) | 2004-06-04 | 2004-06-04 | Prepn process of solid surface in micron and nanometer structure |
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| CNB2004100463442A CN100343422C (en) | 2004-06-04 | 2004-06-04 | Prepn process of solid surface in micron and nanometer structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101423945B (en) * | 2007-11-02 | 2010-10-27 | 中国科学院宁波材料技术与工程研究所 | Method for preparing light metal super-hydrophobic surface |
| CN102480879A (en) * | 2010-11-26 | 2012-05-30 | 鸿富锦精密工业（深圳）有限公司 | Aluminum product and preparation method thereof |
| WO2013123773A1 (en) * | 2012-02-24 | 2013-08-29 | Shenzhen Byd Auto R & D Company Limited | Aluminum alloy, aluminum alloy resin composite and method of preparing the same |
| CN104711651A (en) * | 2012-02-24 | 2015-06-17 | 比亚迪股份有限公司 | Aluminum alloy resin complex |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09316692A (en) * | 1996-05-30 | 1997-12-09 | Fine Ceramics Center | Alumina film having fine pore and its production |
| CN1271248C (en) * | 2003-05-19 | 2006-08-23 | 中国科学院物理研究所 | Production process of alumina template with nano holes |
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- 2004-06-04 CN CNB2004100463442A patent/CN100343422C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101423945B (en) * | 2007-11-02 | 2010-10-27 | 中国科学院宁波材料技术与工程研究所 | Method for preparing light metal super-hydrophobic surface |
| CN102480879A (en) * | 2010-11-26 | 2012-05-30 | 鸿富锦精密工业（深圳）有限公司 | Aluminum product and preparation method thereof |
| US9808974B2 (en) | 2012-02-24 | 2017-11-07 | Shenzhen Byd Auto R&D Company Limited | Method of preparing aluminum alloy resin composite and aluminum alloy-resin composite obtainable by the same |
| CN104711651A (en) * | 2012-02-24 | 2015-06-17 | 比亚迪股份有限公司 | Aluminum alloy resin complex |
| CN104711651B (en) * | 2012-02-24 | 2017-05-31 | 比亚迪股份有限公司 | A kind of aluminum alloy resin complex |
| US9770884B2 (en) | 2012-02-24 | 2017-09-26 | Shenzhen Byd Auto R&D Company Limited | Metal-resin composite and method for producing the same |
| US9802388B2 (en) | 2012-02-24 | 2017-10-31 | Shenzhen Byd Auto R&D Company Limited | Aluminum alloy resin composite and method of preparing the same |
| US9809895B2 (en) | 2012-02-24 | 2017-11-07 | Shenzhen Byd Auto R&D Company Limited | Method of preparing aluminum alloy resin composite and aluminum alloy-resin composite obtainable by the same |
| WO2013123773A1 (en) * | 2012-02-24 | 2013-08-29 | Shenzhen Byd Auto R & D Company Limited | Aluminum alloy, aluminum alloy resin composite and method of preparing the same |
| US9862131B2 (en) | 2012-02-24 | 2018-01-09 | Byd Company Limited | Method for integrally molding metal and resin and metal-resin composite structure obtainable by the same |
| US9889588B2 (en) | 2012-02-24 | 2018-02-13 | Shenzhen Byd Auto R&D Company Limited | Method for integrally molding metal and resin and metal-resin composite structure obtainable by the same |
| US9956744B2 (en) | 2012-02-24 | 2018-05-01 | Shenzhen Byd Auto R&D Company Limited | Shell, method of preparing the shell and electronic product comprising the shell |
| US9783894B2 (en) | 2012-05-28 | 2017-10-10 | Byd Company Limited | Metal composite and method of preparing the same, metal-resin composite and method of preparing the same |
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|---|---|
| CN100343422C (en) | 2007-10-17 |
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