TWI779180B - Surface-treated aluminum alloy material and method for producing the same - Google Patents
Surface-treated aluminum alloy material and method for producing the same Download PDFInfo
- Publication number
- TWI779180B TWI779180B TW108110035A TW108110035A TWI779180B TW I779180 B TWI779180 B TW I779180B TW 108110035 A TW108110035 A TW 108110035A TW 108110035 A TW108110035 A TW 108110035A TW I779180 B TWI779180 B TW I779180B
- Authority
- TW
- Taiwan
- Prior art keywords
- oxide film
- film layer
- aluminum oxide
- aluminum alloy
- alloy material
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
- B21B1/24—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length in a continuous or semi-continuous process
- B21B1/26—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length in a continuous or semi-continuous process by hot-rolling, e.g. Steckel hot mill
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
- B22D27/04—Influencing the temperature of the metal, e.g. by heating or cooling the mould
-
- 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
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
- C22F1/043—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with silicon as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Laminated Bodies (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Chemical Treatment Of Metals (AREA)
- Powder Metallurgy (AREA)
Abstract
本發明係一種表面處理鋁合金材及其製造方法,其課題為提供:作為設置於含有Si之鋁合金所成之基材的表面之氧化皮膜層,具有可確實提升與樹脂層之密著性及接著性構成之表面處理鋁合金材者。 解決手段為具有:含有Si之基材(2),和經由在鹼性液體中之交流電解處理而形成於基材(2)之一部分或全部的表面之氧化皮膜層(3)的表面處理鋁合金材(1)。氧化皮膜層(3)係具有:形成於表面側之厚度20~1000nm多孔性鋁氧化皮膜層(31),和形成於基材(2)側之厚度3~50nm的阻障型鋁氧化皮膜層(32)。對於多孔性鋁氧化皮膜層(31)內係存在多數有直徑3~50nm之小孔(4)的同時,含有Si之金屬間化合物或單體Si所成之晶析物(5)的圓當量直徑為平均15μm以下,而晶析物(5)則在15%以下的面積率存在者。The present invention is a surface-treated aluminum alloy material and its production method. The object of the present invention is to provide an oxide film layer provided on the surface of a base material made of an aluminum alloy containing Si, which can reliably improve the adhesion to the resin layer. And surface-treated aluminum alloy materials with adhesive composition. The solution is to have: a substrate (2) containing Si, and an oxide film layer (3) formed on a part or the entire surface of the substrate (2) by alternating-current electrolytic treatment in an alkaline liquid. alloy material (1). The oxide film layer (3) has: a porous aluminum oxide film layer (31) with a thickness of 20 to 1000 nm formed on the surface side, and a barrier aluminum oxide film layer with a thickness of 3 to 50 nm formed on the substrate (2) side (32). For the porous aluminum oxide film layer (31) there are many small pores (4) with a diameter of 3-50nm, and the circle equivalent of the crystallization (5) formed by the intermetallic compound containing Si or Si alone The average diameter is 15 μm or less, and the area ratio of the crystallized product (5) is 15% or less.
Description
本發明係有關表面處理鋁合金材及其製造方法。The invention relates to a surface-treated aluminum alloy material and a manufacturing method thereof.
鋁材係為輕量,且具備適度之機械性特性,廣泛適用於種種之構造構件。由施以表面處理於此等鋁材之一部分或全體者,賦予耐蝕性,密著性,絕緣性,抗菌性,耐磨耗性等之性質,或者使此等性質提升而加以使用者為多。Al-Si系合金所成之鋁合金材係被多使用作為以往模鑄等之鑄造模具用,但對於經由延壓而成形為板狀而使用之情況,係發揮Al-Si系合金為低融點之特徵,作為熱交換器用材料之焊料材而使用情況為多。另外,在近年中,檢討利用Al-Si系合金所成之鋁合金材所具有之低熱膨脹率或耐熱性,陽極氧化處理時之發色性(合金發色),而適用於板材之構造構件。使用如此之鋁材的構造構件係特別是,多適用於汽車,航空機等之運輸材,或電子基板,IT機器等之電子構件,為了更加輕量化,機能性提升,而亦有與樹脂材料組合而加以使用者。Aluminum is lightweight and has moderate mechanical properties, and is widely used in various structural components. By applying surface treatment to a part or the whole of these aluminum materials, properties such as corrosion resistance, adhesion, insulation, antibacterial properties, wear resistance, etc. are given, or these properties are improved and used for many users. . Aluminum alloy materials made of Al-Si alloys are widely used as casting molds such as die casting in the past. The characteristic of this point is that it is often used as a solder material for heat exchanger materials. In addition, in recent years, the low thermal expansion rate or heat resistance of the aluminum alloy material made of Al-Si alloy has been reviewed, and the color development (alloy color development) during anodic oxidation treatment has been reviewed, and it is suitable for structural members of the plate. . Structural components using such aluminum materials are especially suitable for transportation materials such as automobiles and aircraft, or electronic components such as electronic substrates and IT equipment. In order to reduce weight and improve functionality, they are also combined with resin materials. And be used.
例如,如在專利文獻1所示地,Al-Si系合金板係有使用於印刷配線板之基板者。此印刷配線板係形成陽極氧化皮膜於成為基板之Al-Si系合金板的表面,於其陽極氧化皮膜上,形成作為樹脂層之絕緣接著劑層,更且於其上方成為配置有Cu箔之構成。For example, as disclosed in
在如此之印刷配線板中,基板與樹脂層之接著性或者密著性則為重要,但此特性係根據基板的表面之氧化皮膜的特性而被左右。一般而言,Al-Si系合金係含於合金中的Si則阻礙陽極氧化皮膜之形成之故,氧化皮膜形成則成為不均一,而無法得到期望之性能情況為多。In such a printed wiring board, the adhesiveness or adhesion between the substrate and the resin layer is important, but this characteristic is controlled by the characteristics of the oxide film on the surface of the substrate. In general, since Si contained in the Al-Si alloy system inhibits the formation of anodic oxide film, the formation of the oxide film becomes uneven, and in many cases, desired performance cannot be obtained.
另一方面,對於專利文獻2係提案有:作為形成氧化皮膜於Al-Si系合金表面之方法,並非使用如專利文獻1,以硫酸浴之直流電流的陽極氧化方法,而是在鹼性溶液中進行交流電解處理之方法。
[先前技術文獻]
[專利文獻]On the other hand, the
[專利文獻1]日本特開平6-41667號公報 [專利文獻2]日本特開2015-67844號公報[Patent Document 1] Japanese Patent Application Laid-Open No. 6-41667 [Patent Document 2] Japanese Unexamined Patent Publication No. 2015-67844
[發明欲解決之課題][Problem to be solved by the invention]
專利文獻2之交流電解處理方法係特別是作為對應於Si含有量為1.7質量%以下之Al-Si系合金的構成而加以顯示,而對於Si量超過1.7質量%而增加之情況,係作為阻礙均一之氧化皮膜的形成。另外,Si量為1.7質量%以下之情況,亦認為未完全地形成有均一之氧化皮膜之情況。The AC electrolytic treatment method of
但將對於與樹脂層之密著性及接著性優越者作為目的情況,不能說是必須完全形成均一之氧化皮膜。因此,弄清楚對於與樹脂層之密著性及接著性優越之氧化皮膜層之構成則滿足哪種要件者則為重要。However, it cannot be said that it is absolutely necessary to form a uniform oxide film when the target is superior in adhesion and adhesion to the resin layer. Therefore, it is important to clarify which requirements are satisfied for the composition of an oxide film layer excellent in adhesion and adhesion to the resin layer.
本發明係有鑑於有關的背景所作為之構成,而作為設置於含有Si之鋁合金所成之基材的表面之氧化皮膜層,作為欲提供具有可確實地提升與樹脂層之密著性及接著性提升之構成的表面處理鋁合金材者。 [為了解決課題之手段]The present invention is constituted in view of the relevant background, and as an oxide film layer provided on the surface of a base material made of an aluminum alloy containing Si, it is intended to provide an oxide film layer capable of reliably improving the adhesion with the resin layer and Surface-treated aluminum alloy materials with improved adhesive properties. [Means to solve the problem]
本發明之一形態,一種表面處理鋁合金材係具有:含有Si之鋁合金所成之基材,和經由在鹼性液體中之交流電解處理而形成於前述基材之一部分或全部的表面之氧化皮膜層的表面處理鋁合金材,其特徵為 前述氧化皮膜層係具有:形成於表面側之厚度20~1000nm多孔性鋁氧化皮膜層,和形成於基材側之厚度3~50nm的阻障型鋁氧化皮膜層, 對於前述多孔性鋁氧化皮膜層內係存在多數有直徑3~50nm之小孔的同時,含有Si之金屬間化合物或單體Si所成之晶析物的圓當量直徑為平均15μm以下,而該晶析物則在15%以下的面積率存在者。 [發明效果]In an aspect of the present invention, a surface-treated aluminum alloy material has: a substrate made of an aluminum alloy containing Si, and a part or all of the surface of the substrate formed by alternating current electrolytic treatment in an alkaline liquid A surface-treated aluminum alloy material with an oxide film layer, characterized by The aforementioned oxide film layer system has: a porous aluminum oxide film layer with a thickness of 20 to 1000 nm formed on the surface side, and a barrier aluminum oxide film layer with a thickness of 3 to 50 nm formed on the substrate side, For the above-mentioned porous aluminum oxide film layer, there are many small pores with a diameter of 3~50nm, and the equivalent circle diameter of the intermetallic compound containing Si or the crystallization of Si alone is less than 15 μm on average, and the Crystallization exists in the area ratio of 15% or less. [Invention effect]
對於含有Si的鋁合金而言施以在鹼性液體中之交流電解處理加以形成之氧化皮膜層,係含有包含Si之金屬間化合物或單體Si所成之晶析物,而完全消除此等係目前為困難。但本形態之表面處理鋁合金材係存在於前述多孔性鋁氧化皮膜層內的包含Si之金屬間化合物或單體Si所成之晶析物則在圓當量直徑為平均15μm以下,且具備其晶析物則在15%以下的面積率而存在之條件者。本發明者們係在許多的檢討之結果,只要具有此構成,發現確實可提升與樹脂層之密著性及接著性者。For aluminum alloys containing Si, the oxide film layer formed by AC electrolytic treatment in alkaline liquid contains intermetallic compounds containing Si or crystallization of Si alone, and completely eliminates these The system is currently difficult. However, the surface-treated aluminum alloy material of this form is an intermetallic compound containing Si existing in the aforementioned porous aluminum oxide film layer or a crystallization product formed of Si alone, with an average equivalent circle diameter of 15 μm or less, and having other Crystallization is the condition that the area ratio of 15% or less exists. As a result of many examinations, the present inventors have found that as long as it has this structure, it can indeed improve the adhesion and adhesiveness with the resin layer.
如圖1所示,有關本申請之表面處理鋁合金材1係具有:含有Si之鋁合金所成之基材2,和經由在鹼性液體中之交流電解處理而形成於基材2之一部分或全部的表面之氧化皮膜層3的表面處理鋁合金材。氧化皮膜層3係具有:形成於表面側之厚度20~1000nm多孔性鋁氧化皮膜層31,和形成於基材2側之厚度3~50nm的阻障型鋁氧化皮膜層32。對於多孔性鋁氧化皮膜層31內係存在多數有直徑3~50nm之小孔4的同時,含有Si之金屬間化合物或單體Si所成之晶析物則在圓當量直徑為平均15μm以下,而其晶析物5則在15%以下的面積率存在。
以下,更加詳述之。As shown in Figure 1, the surface-treated
<基材>
作為基材係使用含有Si之鋁合金(Al-Si系合金)。Si含有量之下限值係未特別限制,但在專利文獻2中超過作為並非理想之1.7質量%,特別是2.0質量%以上之情況,取得上述之構成者則為有效。更理想係可作為3.0質量%以上、又更理想係可作為4.0質量%、又再更理想係可作為5.0質量%。另一方面,對於Si含有量之上限值,係如為一般的Al-Si系合金之範圍,未特別限制,但對於Si含有量過多之情況,含有Si之金屬間化合物或單體Si所成之晶析部的控制變為不易之故,理想係作為20質量%以下、更加地作為12質量%以下即可。<Substrate>
An aluminum alloy containing Si (Al—Si alloy) is used as the base material. The lower limit of the Si content is not particularly limited, but in
對於Si以外的元素係可因應適用上述表面處理鋁合金材的用途之要求特性而做適宜添加者。 例如,對於使用於印刷配線板之基板等情況,例如,可採用含有Si:5~20質量%、Fe:0.5~2.0質量%、Cu:0.1~0.5質量%,殘留部為Al及不可避免之不純物所成之化學成分者。Elements other than Si can be appropriately added in accordance with the required characteristics of the application of the above-mentioned surface-treated aluminum alloy material. For example, for substrates used in printed wiring boards, for example, Si: 5-20% by mass, Fe: 0.5-2.0% by mass, Cu: 0.1-0.5% by mass, and the remaining part is Al and unavoidable. The chemical composition of impurities.
<氧化皮膜層> 氧化皮膜層係具有:形成於表面側之厚度20~1000nm多孔性鋁氧化皮膜層,和形成於基材側之厚度3~50nm的阻障型鋁氧化皮膜層所成。另外,氧化皮膜層係如設置於在基材中欲表面改質之部分即可,而僅設置於基材表面之一部分亦可,亦可設置於全面。另外,對於基材為平板狀之情況,僅於一方的表面設置氧化皮膜層亦可,而亦可於雙方的表面設置氧化皮膜層。<Oxide film layer> The oxide film layer is composed of: a porous aluminum oxide film layer with a thickness of 20-1000nm formed on the surface side, and a barrier-type aluminum oxide film layer with a thickness of 3-50nm formed on the substrate side. In addition, the oxide film layer may be provided only on a part of the surface of the substrate, or may be provided on the entire surface of the substrate. In addition, when the base material is flat, the oxide film layer may be provided on only one surface, or the oxide film layer may be provided on both surfaces.
<多孔性鋁氧化皮膜層> 多孔性鋁氧化皮膜層之厚度係20~1000nm,而理想為50~500nm。在多孔性鋁氧化皮膜層之厚度不足20nm中,厚度不充份之故,後述之小孔構造的形成則容易成為不充分,而與樹脂層之接著力或密著性降低。因此,更理想係作為50nm以上即可。另一方面,當多孔性鋁氧化皮膜層之厚度超過1000nm時,多孔性鋁氧化皮膜層本身則容易產生凝集破壞,而與樹脂層之接著力或密著性降低。因此,更理想係作為500nm以下即可。<Porous aluminum oxide film layer> The thickness of the porous aluminum oxide film layer is 20~1000nm, preferably 50~500nm. When the thickness of the porous aluminum oxide film layer is less than 20nm, the thickness is not sufficient, and the formation of the pore structure described later is likely to be insufficient, and the adhesion or adhesion with the resin layer is reduced. Therefore, it is more preferable to set it as 50 nm or more. On the other hand, when the thickness of the porous aluminum oxide film layer exceeds 1000 nm, the porous aluminum oxide film layer itself is prone to coagulation failure, and the adhesion or adhesion with the resin layer is reduced. Therefore, it is more desirable to set it as 500 nm or less.
對於多孔性鋁氧化皮膜層之厚度的測定係作為一例,可使用經由透過型電子顯微鏡(TEM)之剖面觀察者。具體而言,係經由超薄片機等而將多孔性鋁氧化皮膜層部分加工成薄片,經由TEM觀察而加以測定。然而,依據在一個之觀察視野之複數處的測定值之算術平均值,作為多孔性鋁氧化皮膜層之厚度。As an example, the measurement of the thickness of the porous aluminum oxide film layer can use a cross-sectional observer through a transmission electron microscope (TEM). Specifically, the porous aluminum oxide film layer is partially processed into a thin slice by an ultra-thin slicer or the like, and measured by TEM observation. However, the thickness of the porous aluminum oxide film layer is based on the arithmetic mean value of the measured values at multiple places in one observation field of view.
如圖1所示,多孔性鋁氧化皮膜層31係具有具備自其表面朝向深度方向之小孔4的多孔構造。小孔4之直徑係3~50nm,而理想為5~30nm。此小孔4係使樹脂層或接著層等與鋁氧化皮膜層3(31)之接觸面積增大,發揮增大其接著力或密著力之效果者。在小孔4之直徑不足3nm中,接觸面積不足之故而有無法得到充分之接著力或密著力之虞。另一方面,當小孔4之直徑超過50nm時,多孔性鋁氧化皮膜層全體則變脆而產生凝集破壞,而有接著力或密著力降低之虞。As shown in FIG. 1 , the porous aluminum
對於多孔性鋁氧化皮膜層之表面積而言之小孔的全孔面積的比,係未特別加以限制,但作為對於多孔性鋁氧化皮膜層之外觀上的表面積(未考慮表面之微小的凹凸,而以長度與寬度的乘算所表示之面積)而言之小孔的全孔面積的比,25~75%則為理想。在此比不足25%中,有著接觸面積不足而無法得到充分之接著力或密著力之情況。另一方面,當此比超過75%時,多孔性鋁氧化皮膜層全體則變脆而產生凝集破壞,而有接著力或密著力降低之情況。The ratio of the small pores to the total pore area of the surface area of the porous aluminum oxide film layer is not particularly limited, but it is used as the apparent surface area of the porous aluminum oxide film layer (without considering the small unevenness of the surface, In terms of the area expressed by the multiplication of the length and width) to the ratio of the total hole area of the small hole, 25~75% is ideal. When this ratio is less than 25%, the contact area may be insufficient and sufficient adhesion or adhesion may not be obtained. On the other hand, when this ratio exceeds 75%, the entire porous aluminum oxide film layer becomes brittle, coagulation failure occurs, and adhesive force or adhesion force may decrease.
對於在上述多孔構造之小孔的直徑及面積占有率的測定,係作為一例而可使用經由電場釋放形電子顯微鏡(FE-SEM)之表面觀察及經由畫像解析軟體A像君(Asahi Kasei Engineering公司製ver. 2.50)之粒子解析者。具體而言,經由電場釋放形電子顯微鏡(FE-SEM),將在加速電壓2kV、觀察視野1μm×0.7μm進行複數處攝影之二次電子像,導入至畫像解析軟體,實施將在多孔性鋁氧化皮膜層之表面所觀察之小孔部分看作粒子之各處的粒子解析者。For the measurement of the diameter and area occupancy of the small pores in the above-mentioned porous structure, as an example, surface observation through an electric field emission electron microscope (FE-SEM) and image analysis software Axiangjun (Asahi Kasei Engineering Co., Ltd.) can be used. Particle analyzer for ver. 2.50). Specifically, through an electric field emission electron microscope (FE-SEM), the secondary electron image taken at multiple places at an accelerating voltage of 2 kV and an observation field of view of 1 μm×0.7 μm was imported into the image analysis software, and the porous aluminum The small hole portion observed on the surface of the oxide film layer is regarded as the particle analyzer of each particle.
<含有多孔性鋁氧化皮膜層內之Si的金屬間化合物或單體Si> 對於多孔性鋁氧化皮膜層內係含有Si之金屬間化合物或單體Si所成之晶析物的圓當量直徑為平均15μm以下,該晶析物則可在15%以下的面積率而存在者。多孔性鋁氧化皮膜層內之含有Si之金屬間化合物或單體Si的晶析物(以下,適宜,稱為Si系粒子)係存在於基材中的含有Si之金屬間化合物或單體Si所成之晶析物則在交流電解處理後,殘存於多孔性鋁氧化皮膜層內者。<Intermetallic compound or Si alone containing Si in the porous aluminum oxide film layer> For the porous aluminum oxide film layer, the crystallization formed by an intermetallic compound containing Si or Si alone has an equivalent circle diameter of 15 μm or less on average, and the crystallization can exist at an area ratio of 15% or less . The Si-containing intermetallic compound or simple Si crystallization in the porous aluminum oxide film layer (hereinafter, referred to as Si-based particles as appropriate) is the Si-containing intermetallic compound or simple Si present in the base material. The resulting crystallization remains in the porous aluminum oxide film layer after AC electrolytic treatment.
存在有殘存於多孔性鋁氧化皮膜層內之Si系粒子的部分係為形成有上述之小孔之故,幾乎未貢獻於與樹脂層之密著性及接著性之提升。因此,Si系粒子係縮小此等本身的尺寸者則為重要,必須在圓當量直徑之平均值作為15μm以下,而理想係12μm以下,更理想係作為10μm以下即可。作為Si系粒子之圓當量直徑的下限值係越小越理想,但實際上,容易成為2μm以上,而有成為5μm以上之情況,但如維持上述上限值時,未有問題。The portion where the Si-based particles remained in the porous aluminum oxide film layer is due to the formation of the above-mentioned small pores, and hardly contributes to the improvement of the adhesion and adhesiveness with the resin layer. Therefore, it is important to reduce the size of the Si-based particles, and the average equivalent circle diameter must be 15 μm or less, ideally 12 μm or less, more ideally 10 μm or less. The lower limit of the circle-equivalent diameter of Si-based particles is preferably as small as possible, but in practice, it is easy to be 2 μm or more, and sometimes 5 μm or more, but there is no problem if the above upper limit is maintained.
並且,多孔性鋁氧化皮膜層內之前述Si系粒子係必須控制呈在15%以下的面積率存在。對於存在有Si系粒子之面積率超過15%之情況,係具備參與接著之小孔的部分之面積減少,對於樹脂層而言無法得到充分之接觸面積,而接著力或密著力降低。多孔性鋁氧化皮膜層內之前述Si系粒子的面積率係越小越佳,但作為不足1%之情況係實際上為困難。In addition, the aforementioned Si-based particles in the porous aluminum oxide film layer must be present in an area ratio of 15% or less. When the area ratio of Si-based particles exceeds 15%, the area of the portion having small holes participating in bonding decreases, and a sufficient contact area cannot be obtained for the resin layer, resulting in reduced adhesion or adhesion. The smaller the area ratio of the aforementioned Si-based particles in the porous aluminum oxide film layer, the better, but it is practically difficult to make it less than 1%.
含有前述Si之金屬間化合物或單體Si的晶析物(Si系粒子)之面積率的測定係作為一例,使用經由電場釋放形掃描電子顯微鏡(FE-SEM)之表面觀察。具體而言,由FE-SEM(Hitachi High-Technologies公司製 SU8200),以加速電壓1kV、觀察視野126μm×85μm(約1000倍)進行5視野攝影,求取圓當量直徑0.01μm以上之含有Si之金屬間化合物或單體Si粒子之表面積及個數,計算存在於觀察視野之含有Si之金屬間化合物或單體Si粒子之全表面積。以視野全面積除以所算出之含有Si之金屬間化合物或單體Si粒子之全表面積,再算出對於含有Si之金屬間化合物或單體Si粒子之鋁合金而言之面積率。The measurement of the area ratio of the intermetallic compound containing Si or the crystallization product (Si-based particles) of simple Si is, as an example, using surface observation with a field-emission scanning electron microscope (FE-SEM). Specifically, by FE-SEM (SU8200 manufactured by Hitachi High-Technologies Co., Ltd.), 5-field photography was performed at an accelerating voltage of 1 kV and an observation field of view of 126 μm×85 μm (about 1000 times), and Si-containing particles with an equivalent circle diameter of 0.01 μm or more were obtained. The surface area and number of intermetallic compounds or single Si particles are calculated from the total surface area of Si-containing intermetallic compounds or single Si particles present in the observation field. Divide the total area of the field of view by the calculated total surface area of intermetallic compounds containing Si or Si particles alone, and then calculate the area ratio for aluminum alloys containing intermetallic compounds or Si particles alone.
<阻障型鋁氧化皮膜層> 阻障型鋁氧化皮膜層之厚度係3~50nm,而理想為5~30nm。在此厚度不足5nm中,作為多孔性鋁氧化皮膜層與鋁質地之間的介在層,無法賦予充分的結合力於兩者之結合,而特別是在高溫・多濕等之嚴酷環境之結合力則成為不充分。另一方面,當其厚度超過50nm時,其緻密性之故而阻障型鋁氧化皮膜層則容易產生凝集破壞,而反而接著力或密著力降低。對於阻障型鋁氧化皮膜層之厚度的測定,與多孔性鋁氧化皮膜層相同,可使用經由透過型電子顯微鏡(TEM)之剖面觀察者。具體而言,係經由超薄片機等而將阻障型鋁氧化皮膜層部分加工成薄片,經由TEM觀察而加以測定。然而,依據在一個之觀察視野之複數處的測定值之算術平均值,作為阻障型鋁氧化皮膜層之厚度。<Barrier aluminum oxide film layer> The thickness of the barrier aluminum oxide film layer is 3~50nm, and ideally 5~30nm. When the thickness is less than 5nm, as an intervening layer between the porous aluminum oxide film layer and the aluminum texture, it is impossible to impart sufficient bonding force to the combination of the two, especially in severe environments such as high temperature and humidity. becomes insufficient. On the other hand, when the thickness exceeds 50nm, the barrier-type aluminum oxide film layer is prone to coagulation failure due to its compactness, and on the contrary, the adhesive force or adhesion force is reduced. As for the measurement of the thickness of the barrier aluminum oxide film layer, a cross-sectional observer through a transmission electron microscope (TEM) can be used as in the case of the porous aluminum oxide film layer. Specifically, the barrier-type aluminum oxide film layer is partially processed into thin slices with an ultra-thin slicer, and measured through TEM observation. However, the thickness of the barrier-type aluminum oxide film layer is based on the arithmetic mean of the measured values at multiple places in one observation field of view.
<基材之製造方法> 基材係經由鑄造而製作具有期望之化學成分之板材,經由至少施以熱間壓延於此板材而可製造。因應必要而可加上冷間壓延等。<Manufacturing method of base material> The base material can be manufactured by casting to produce a plate with the desired chemical composition, and at least applying hot rolling to the plate. Cold rolling can be added if necessary.
在此,在上述之鑄造中,自板材的表面,將100mm之部位的冷卻速度,以0.5℃/sec以上而進行鑄造,且將由熱間壓延而延壓板材時之最終通過的壓下率,在20%~70%之範圍內進行者為有效。經由具備此等之2要件,首先,係成為可將包含含於基材中之Si的金屬間化合物或單體Si所成之晶析物(Si系粒子)之存在狀態,控制為最佳的範圍者。Here, in the above-mentioned casting, casting is performed with a cooling rate of 0.5°C/sec or more at a portion of 100 mm from the surface of the sheet, and the final pass reduction rate when rolling the sheet by hot rolling is, It is effective if it is carried out within the range of 20%~70%. By satisfying these two requirements, first, it becomes possible to control the state of existence of the intermetallic compound containing Si contained in the base material or the crystallized product (Si-based particles) formed by Si alone. rangers.
經由將包含含於基材中之Si的金屬間化合物或單體Si所成之晶析物的尺寸及數量等之存在狀態作為最佳的範圍之時,可將經由之後的交流電解處理所得到之存在於多孔性鋁氧化皮膜層內,含有Si的金屬間化合物或單體Si所成之晶析物的狀態,控制成前述特定的範圍者。When the size and quantity of the crystallization of the intermetallic compound containing Si contained in the base material or the crystallization of the single Si are set as the optimal range, the resulting AC electrolytic treatment can be obtained The state of the intermetallic compound containing Si or the crystallized product of simple Si existing in the porous aluminum oxide film layer is controlled within the above-mentioned specific range.
包含含於基材中之Si的金屬間化合物或單體Si所成之晶析物之最佳的存在狀態係在交流電解處理前的表面觀察中,在圓當量直徑平均15μm以下之晶析物則呈在15%以下的面積率存在之狀態。The best state of existence of intermetallic compounds containing Si contained in the base material or crystallization of Si alone is in the surface observation before AC electrolytic treatment, the average circle equivalent diameter of the crystallization is less than 15 μm Then, it is in a state where the area ratio is 15% or less.
自鑄造時之板材的表面100mm之部位的冷卻速度係如上述,作為0.5℃/sec以上。理想係1℃/sec以上即可。然而,冷卻速度的上限係未特別限制,但實質上作為成20℃/sec以上之情況係製造裝置之限制上通常係為困難。在冷卻速度不足0.5℃/sec中,含有Si的金屬間化合物或單體Si粒子之粒子徑則有變為過大之虞。The cooling rate at a portion 100 mm from the surface of the sheet material at the time of casting is 0.5° C./sec or more as described above. The ideal system should be above 1°C/sec. However, the upper limit of the cooling rate is not particularly limited, but it is usually difficult due to the limitation of the manufacturing equipment in the case of substantially 20° C./sec or more. When the cooling rate is less than 0.5° C./sec, the particle size of Si-containing intermetallic compounds or simple Si particles may become too large.
自板材表面100mm之鑄造時之冷卻速度係測定枝晶2次間距(Dendrite Arm Spacing:以下、單記述為DAS)而算出。對於鋁合金的冷卻速度Cα(℃/秒),和以公線法而測定之DAS、dr(μm)係有下述的關係。 冷卻速度與DAS之關係:dr=41Cα-0.32 The cooling rate at the time of casting at 100 mm from the surface of the plate was calculated by measuring the dendrite arm spacing (Dendrite Arm Spacing: hereinafter, simply described as DAS). There is the following relationship between the cooling rate Cα (°C/sec) of the aluminum alloy and DAS and dr (μm) measured by the common line method. The relationship between cooling rate and DAS: dr=41Cα -0.32
DAS係可經由鑄造後之板材的剖面觀察而求得者。即,將以同一條件鑄造之板材,沿著鑄造方向而自表面切斷100mm之部分,沿著厚度方向而切斷板材中央部分之後,在切斷之總剖面及橫剖面中,在進行剖面研磨之後,經由光學顯微鏡而以倍率500倍,觀察板厚中央剖面之金屬組織,經由交線法而求的DAS。然而,對於DAS之關係式及測定法本身係依照「鋁的枝晶間距與冷卻速度之測定法」、輕金屬學會研究會報告書No20(1988年)、46~52頁之記載。DAS can be obtained by observing the section of the plate after casting. That is, after cutting a 100mm part of the plate casted under the same conditions from the surface along the casting direction, and cutting the central part of the plate along the thickness direction, the section grinding is performed on the total section and the cross section of the cut. After that, observe the metal structure of the central section of the plate through an optical microscope at a magnification of 500 times, and obtain the DAS by the intersection method. However, the relational expression and measurement method of DAS are based on the "Measurement Method of Dendrite Spacing and Cooling Rate of Aluminum", Report No. 20 (1988) of the Society for Light Metal Research, pp. 46-52.
另外,如上述,熱間壓延之最終通過的壓下率係作為20~70%,而理想為作為30~60%。在熱間壓延之最終通過的壓下率為不足20%中,作為包含含於基材中之Si的金屬間化合物或單體Si所成之晶析物,有著殘存有尺寸大的粒子之虞。另一方面,當在熱間壓延之最終通過的壓下率為超過70%時,在延壓時容易產生斷裂,而基材的製造則成為困難。In addition, as mentioned above, the rolling reduction in the final pass of hot rolling is 20 to 70%, preferably 30 to 60%. When the rolling reduction in the final pass of hot rolling is less than 20%, there is a possibility that large-sized particles may remain as an intermetallic compound containing Si contained in the base material or a crystallized product of Si alone. . On the other hand, when the rolling reduction in the final pass of hot rolling exceeds 70%, cracks are likely to occur during rolling, making it difficult to manufacture the base material.
<交流電解處理> 基材表面之氧化皮膜層係經由在鹼性液體中,施以交流電解處理於基材而形成。作為具體的方法係準備將基材作為一方的電極之同時,對向於此之對電極,以pH9~13將35~80℃之鹼性水溶液作為電解溶液,由頻率數20~100Hz、電流密度4~50A/dm2 及電解時間5~600秒間之條件,經由將交流電流通電至兩電極間而進行。<Alternating Current Electrolytic Treatment> The oxide film layer on the surface of the base material is formed by applying alternating current electrolytic treatment to the base material in alkaline liquid. As a specific method, while preparing the substrate as one electrode, and facing the counter electrode, use an alkaline aqueous solution at 35-80°C as the electrolytic solution with a pH of 9-13, and use a frequency of 20-100 Hz and a current density The conditions of 4~50A/dm 2 and electrolysis time of 5~600 seconds are carried out by passing AC current between the two electrodes.
基材所成之電極與對電極之形狀係未特別加以限定者,但將兩電極間的距離作為均一而為了進行安定的處理,使用板形狀之構成者為佳。具體而言,圖2所示,準備基材2所成之電極61與2片的對電極62,63,如同圖所示,將此等連接於交流電源71。對於交流電源71與一方的對電極63之間,係設置有開啟關閉通電狀態之連接開關72。The shapes of the electrode and the counter electrode made of the base material are not particularly limited, but it is preferable to use a plate-shaped configuration for stable processing by making the distance between the two electrodes uniform. Specifically, as shown in FIG. 2 , an
各電極係於加入有鹼性水溶液之電解溶液8的電解槽內,呈夾持基材2所成之電極61於對向配置之一對的對電極62,63之間地配置,此等3片的電極61~63則以等間隔,呈成為略平行地配置。對電極62,63係使用與基材2所成之電極61同等以上的尺寸者為佳,將所有的電極作為靜止狀態而進行電解操作者為佳。然而,對於僅處理基材2之一方的表面情況,經由將連接開關72作為關閉之時,可僅處理對面於基材2所成之電極61之對電極62側的表面。Each electrode is placed in an electrolytic cell filled with an
使用於交流電解處理之對電極62,63係例如,可使用石墨,鋁,鈦電極等之公知的電極,但必須使用對於電解溶液的鹼成分或溫度而言未使其劣化,而對於導電性優越,更且,其本身未引起電性化學性反應的材質者。從如此的點,作為對電極係最佳使用石墨電極。此係因石墨電極化學性安定,且加上於容易以廉價入手之情況,經由存在於石墨電極之許多的氣孔之作用,而在交流電解工程中,電力線適度地擴散,而多孔性鋁氧化皮膜層及阻障型鋁氧化皮膜層則經由同時容易成為均一之故。The
作為電解溶液8而使用之鹼性水溶液係可使用氫氧化鈉及氫氧化鉀等之鹼金屬氫氧化物:磷酸鈉,磷酸氫鈉,焦磷酸鈉,焦磷酸鉀及次磷酸鈉等之磷酸鹽:碳酸鈉,碳酸氫鈉,碳酸鉀等之碳酸鹽:氫氧化銨:或者,含有此等混合物之水溶液者。如後述,從必須將電解溶液的ph保持為特定的範圍情況,使用含有可期待緩衝效果之磷酸鹽物質之鹼水溶液者為佳。含於如此之鹼水溶液之鹼成分的濃度係呈成為所期望的值地適宜調整電解溶液的ph,但通常,1×10-4
~1莫耳/公升,理想為1×10-3
~0.8莫耳/公升。然而,對於此等鹼性水溶液,係為了提升鋁合金材表面的清淨度而添加界面活性劑等亦可。The alkaline aqueous solution used as the
作為電解溶液8之鹼水溶液的ph係9~13,而理想為9.5~12.5。在ph不足9中,電解溶液之鹼蝕刻力不足之故,多孔性鋁氧化皮膜層之多孔構造的成長速度變慢的結果,多孔性鋁氧化皮膜層厚度則變薄,而密著耐久性則降低。另一方面,當ph超過13時,鹼蝕刻力成為過剩之故,而多孔性鋁氧化皮膜層之多孔構造則產生溶解,而無法得到期望之密著性。The pH of the alkaline aqueous solution as the
電解溶液8之電解溶液的溫度係作為35~80℃,而理想係作為40~75℃。對於電解溶液的溫度不足35℃之情況,係鹼蝕刻力不足之故,而多孔性鋁氧化皮膜層之形成則成為不定形,密著耐久性則降低。另一方面,對於電解溶液的溫度超過80℃之情況,係鹼蝕刻力成為過剩之故,多孔性鋁氧化皮膜層之小孔的密度變小,而成為不易得到對於與樹脂等之密著性必要之定準效果,密著耐久性則降低。The temperature of the electrolytic solution of the
電解時間係作為2~600秒,而理想係作為5~300秒,更理想係作為10~60秒。對於電解時間不足2秒之情況係多孔性鋁氧化皮膜層之多孔構造則不足,而與樹脂等之密著性則降低。另一方面,當電解時間超過600秒時,多孔性鋁氧化皮膜層之多孔構造則產生再溶解,另外,生產性亦降低。The electrolysis time is 2 to 600 seconds, ideally 5 to 300 seconds, and more ideally 10 to 60 seconds. When the electrolysis time is less than 2 seconds, the porous structure of the porous aluminum oxide film layer is insufficient, and the adhesion with resin etc. is reduced. On the other hand, when the electrolysis time exceeds 600 seconds, the porous structure of the porous aluminum oxide film layer is redissolved, and productivity is also reduced.
交流頻率數係10~100Hz,而理想為20~80Hz。在交流頻率數不足20Hz中,作為電性分解係直流的要素提高之結果,多孔性鋁氧化皮膜層之多孔構造的形成則未進行,而與樹脂等之密著性則降低。另一方面,對於交流頻率數超過100Hz之情況,陽極與陰極之反轉則過快之故,鋁氧化皮膜全體之形成則極端地變慢,對於得到多孔性鋁氧化皮膜層之多孔構造的特定厚度係成為需要極長時間。然而,在交流電解之電解波形係未特別加以限定,而可使用正弦波,矩形波,梯形波,三角波等之波形者。The AC frequency number is 10~100Hz, and the ideal is 20~80Hz. When the frequency of alternating current is less than 20 Hz, the formation of the porous structure of the porous aluminum oxide film layer does not proceed as a result of the increase in the factor of direct current in electrical decomposition, and the adhesion to resin or the like decreases. On the other hand, when the AC frequency exceeds 100Hz, the reversal of the anode and the cathode is too fast, and the formation of the entire aluminum oxide film is extremely slow. For the specific porous structure of the porous aluminum oxide film layer It takes an extremely long time for the thickness system to become. However, the electrolysis waveform in alternating current electrolysis is not particularly limited, and waveforms such as sine wave, rectangular wave, trapezoidal wave, and triangular wave can be used.
電流密度係作為4~50A/dm2 ,而理想作為5~40A/dm2 。在電流密度不足4A/dm2 ,係鋁氧化皮膜之中,多孔性鋁氧化皮膜層之成長速度為慢之故,只能得到阻障型鋁氧化皮膜層。另一方面,當電流密度超過50A/dm2 時,電流變為過大之故,多孔性鋁氧化皮膜層及阻障型鋁氧化皮膜層之厚度控制則變為困難而容易引起處理不勻。其結果,多孔性鋁氧化皮膜層則在極端為厚之部分中,有著自鋁質地脫落之情況。The current density is 4~50A/dm 2 , and ideally 5~40A/dm 2 . When the current density is less than 4A/dm 2 , among the aluminum oxide films, the growth rate of the porous aluminum oxide film layer is slow, and only a barrier type aluminum oxide film layer can be obtained. On the other hand, when the current density exceeds 50A/dm 2 , the current becomes too large, and it becomes difficult to control the thickness of the porous aluminum oxide film layer and the barrier aluminum oxide film layer, which tends to cause uneven treatment. As a result, the porous aluminum oxide film layer may fall off from the aluminum base in an extremely thick portion.
含有於電解溶液的溶存鋁濃度係作為5~1000ppm者為佳。溶存鋁濃度不足5ppm之情況係急遽地引起在電解反應初期之鋁氧化皮膜的形成反應之故,有受到處理工程之不均(Al-Si系合金基材表面之污染狀態或Al-Si系合金基材安裝狀態等)之影響。其結果,成為形成有局部為厚之鋁氧化皮膜之情況。另一方面,當溶存鋁濃度超過1000ppm之情況係電解溶液的黏度則增大而在電解工程中,妨礙Al-Si系合金基材之電極表面附近的均一之對流之同時,溶存鋁則作用於抑制鋁氧化皮膜形成之方向。其結果,成為形成有局部為薄之鋁氧化皮膜之情況。如此,溶存鋁濃度自上述範圍脫離時,鋁氧化皮膜之厚度則局部變厚,以及抑制鋁氧化皮膜之形成之故,而有引起所得到之鋁氧化皮膜之接著力及密著力的降低情況。The concentration of dissolved aluminum contained in the electrolytic solution is preferably 5 to 1000 ppm. The case where the dissolved aluminum concentration is less than 5ppm is due to the rapid formation reaction of the aluminum oxide film in the early stage of the electrolytic reaction, and the unevenness of the treatment process (contamination of the surface of the Al-Si alloy base material or the contamination state of the Al-Si alloy substrate) substrate installation status, etc.). As a result, a locally thick aluminum oxide film may be formed. On the other hand, when the dissolved aluminum concentration exceeds 1000ppm, the viscosity of the electrolytic solution increases and in the electrolysis process, while hindering the uniform convection near the electrode surface of the Al-Si alloy substrate, the dissolved aluminum acts on Suppresses the direction of aluminum oxide film formation. As a result, a locally thin aluminum oxide film may be formed. Thus, when the dissolved aluminum concentration deviates from the above-mentioned range, the thickness of the aluminum oxide film becomes thicker locally, and the formation of the aluminum oxide film is suppressed, which may cause a decrease in the adhesion and adhesion of the obtained aluminum oxide film.
<樹脂層> 經由更加被覆樹脂層於前述表面處理鋁合金材的處理面而作為樹脂被覆表面處理鋁合金材之時,可使用於更多之用途。在此,作為樹脂層係亦可使用熱硬化性樹脂與熱可塑性樹脂之任一,與上述之特定構造之鋁氧化皮膜相互結合,可賦予各種之效果。<Resin layer> When the treated surface of the aforementioned surface-treated aluminum alloy material is coated with a resin layer to form a resin-coated surface-treated aluminum alloy material, it can be used in more applications. Here, either thermosetting resin or thermoplastic resin can be used as the resin layer system, and various effects can be imparted by combining with the aluminum oxide film of the above-mentioned specific structure.
通常,鋁材與樹脂層之接合體係從比較於鋁材,樹脂之熱膨脹率為大之情況,在鋁材與樹脂層之界面中,容易產生剝離,斷裂,切割等之損傷。但在前述表面處理鋁合金材中,係使用Al-Si系合金所成之基材。此Al-Si系合金係具備:比較於其他的鋁合金材,熱膨脹率為低之故,不易隨著所被覆之樹脂層的膨脹,而在表面處理鋁合金材與樹脂層之界面中不易產生有前述損傷之特徵。因此,作為層積於前述表面處理鋁合金材之樹脂層係其線膨脹係數則80×10-5 K-1 以下為佳,而50×10-5 K-1 以下為更佳。Usually, the bonding system of aluminum material and resin layer is compared with aluminum material, and the thermal expansion rate of resin is large, and the interface between aluminum material and resin layer is prone to damage such as peeling, fracture, cutting, etc. However, in the above-mentioned surface-treated aluminum alloy materials, the base material made of Al-Si alloy is used. This Al-Si alloy system has: Compared with other aluminum alloy materials, the thermal expansion rate is low, it is not easy to expand with the coated resin layer, and it is not easy to produce in the interface between the surface treated aluminum alloy material and the resin layer. Has the characteristics of the aforementioned damage. Therefore, the linear expansion coefficient of the resin layer laminated on the aforementioned surface-treated aluminum alloy material is preferably 80×10 -5 K -1 or less, and more preferably 50×10 -5 K -1 or less.
特別是,對於樹脂層使用熱可塑性樹脂之樹脂被覆表面處理鋁合金材係作為具有輕量,高剛性之運輸機器用的複合材料,具體而言係最佳使用於航空・太空領域,汽車,船舶,鐵道車輛等之構造構件,更且亦最佳使用於必須為高設計性或高絕緣性之電子機器。作為樹脂層之被覆方法係一般使用熱壓著熱可塑性樹脂構件的方法,在由射出成形而製造熱可塑性樹脂構件時,插入表面處理鋁合金材於射出成形之金屬模具內而使其接合之方法等。另外,對於表面處理鋁合金材為板狀之情況,係層積熱可塑性樹脂薄膜亦可。In particular, the resin-coated surface-treated aluminum alloy material that uses thermoplastic resin for the resin layer is used as a composite material for lightweight, high-rigidity transportation equipment, and specifically, it is optimally used in the fields of aviation and space, automobiles, and ships. , Structural components of railway vehicles, etc., and it is also best used in electronic equipment that must be highly designed or highly insulated. The coating method of the resin layer is generally a method of hot-pressing a thermoplastic resin member. When manufacturing a thermoplastic resin member by injection molding, inserting a surface-treated aluminum alloy material into a metal mold for injection molding and bonding it Wait. In addition, when the surface-treated aluminum alloy material is in the form of a plate, a thermoplastic resin film may be laminated.
作為熱可塑性樹脂係可使用:聚乙烯,聚丙烯等之聚烯烴;聚氯乙烯;聚乙烯對苯二甲酸酯,聚對苯二甲酸丁二酯等之聚酯;聚醯胺;聚苯硫醚;聚醚醚酮,聚醚酮等之芳香族聚醚酮;聚苯乙烯;聚四氟乙烯,聚氯三氟乙烯等之氟樹脂;聚甲基丙烯酸甲酯等之丙烯酸樹脂;ABS樹脂;聚碳酸酯;熱可塑性聚醯亞胺等者。As thermoplastic resins, polyolefins such as polyethylene and polypropylene can be used; polyvinyl chloride; polyethylene terephthalate, polyester such as polybutylene terephthalate; polyamide; polyphenylene Sulfide; aromatic polyetherketone such as polyetheretherketone and polyetherketone; polystyrene; fluorine resin such as polytetrafluoroethylene and polychlorotrifluoroethylene; acrylic resin such as polymethyl methacrylate; ABS Resin; polycarbonate; thermoplastic polyimide, etc.
對於樹脂層使用熱硬化性樹脂之樹脂被覆表面處理鋁合金材係最佳使用於設計性塗裝板,電子材料的絕緣被覆用途等。作為樹脂層之被覆方法係使用將熱硬化性樹脂作為流動狀態,使其接觸・浸透於多孔性鋁氧化皮膜層,之後使熱硬化性樹脂加熱硬化之方法。作為熱硬化性樹脂係可使用:苯酚樹脂;雙酚A型及酚醛型等之環氧樹脂;三聚氰胺樹脂;尿素樹脂;不飽和聚酯樹脂;醇酸樹脂;聚胺酯樹脂;熱硬化性聚醯亞胺等;。The resin-coated surface-treated aluminum alloy material that uses a thermosetting resin for the resin layer is best used for design-coated panels, insulation coating applications for electronic materials, and the like. As a coating method of the resin layer, a method of using a thermosetting resin in a fluid state, making it contact and permeate the porous aluminum oxide film layer, and then heating and curing the thermosetting resin is used. As thermosetting resins, phenol resins; epoxy resins such as bisphenol A and novolak; melamine resins; urea resins; unsaturated polyester resins; alkyd resins; polyurethane resins; thermosetting polyamides Amines, etc.;
然而,前述熱可塑性樹脂與熱硬化性樹脂係各自亦可以單一使用,而作為混合複數種之熱可塑性樹脂或複數種之熱硬化性樹脂的聚合混合體而使用亦可。另外,經由各添加各種填充物於前述熱可塑性樹脂與熱硬化性樹脂之時,可改善樹脂之強度或熱膨脹率等之物性。作為如此之填充物係可使用:玻璃纖維,碳纖維,醯胺纖維等之各種纖維;碳酸鈣,碳酸鎂,二氧化矽,滑石,玻璃等之無機物質;黏土;等之公知物質者。 [實施例]However, each of the aforementioned thermoplastic resins and thermosetting resins may be used singly, or may be used as a polymer mixture in which plural types of thermoplastic resins or plural types of thermosetting resins are mixed. In addition, when various fillers are added to the above-mentioned thermoplastic resin and thermosetting resin, physical properties such as strength and thermal expansion rate of the resin can be improved. As such a filler, various fibers such as glass fiber, carbon fiber, and amide fiber; inorganic substances such as calcium carbonate, magnesium carbonate, silicon dioxide, talc, and glass; clay; and other known substances can be used. [Example]
以下,依據實施例及比較例,詳細說明在本發明之最佳的實施形態。Hereinafter, the best embodiment of the present invention will be described in detail based on examples and comparative examples.
作為使用於基材2之Al-Si系鋁合金,溶解・鑄造表1及表2所示之具有Si含有量之構成,在熱間壓延後,施以冷間壓延,作成最終板厚1.0mm之延壓板。此時,作為製造條件係鑄造時之冷卻速度與熱間壓延時之最終通過的壓下率係採用表1及表2所示之條件,除此以外係作成公知的通常之條件。並且,製作切斷加工成縱600mm×橫50mm×板厚1.0mm之基板。As the Al-Si-based aluminum alloy used for the
如圖2所示,將所得到之基板使用於一方的電極61,作為對電極62,63而使用2片縱150mm×橫100mm×厚度2.0mm之平板的石墨電極,接線成如同圖所示。作為電解溶液8係使用具有表1及表2所示之ph及溫度,將焦磷酸鈉作為主成分之鹼性水溶液。pH係以1莫耳/公升之NaOH水溶液做適宜調整。電解質濃度係做成0.1莫耳/公升。並且,以表1~3所示之頻率數,電流密度,電解時間之條件而施以交流電解處理。在此,在比較例5及6中,以1莫耳/公升之硫酸水溶液而將ph各調整成8.5與3。然而,使鋁合金板之電極61及石墨對電極62,63之縱方向一致於電解槽之深度方向。另外,對於比較例15係為了比較,將基材所成之電極作為陽極而流動直流電流。As shown in FIG. 2, the obtained substrate was used for one
對於如以上作為所製作之表面處理鋁合金材的試料,進行以下的測定與評估。The following measurements and evaluations were performed on the samples of the surface-treated aluminum alloy materials produced as above.
首先,作為氧化皮膜層之評估,氧化皮膜層之[構造]則將「多孔性鋁氧化皮膜層與阻障型鋁氧化皮膜層」之情況作為「二層」、而任一方的情況作為「一層」。First of all, as an evaluation of the oxide film layer, the [structure] of the oxide film layer regards the case of "porous aluminum oxide film layer and barrier aluminum oxide film layer" as "two layers", and the case of either one as "one layer". ".
另外,對於在氧化皮膜層中,多孔性鋁氧化皮膜層係測定「多孔性鋁氧化皮膜層之厚度(nm)」、「內在於多孔性鋁氧化皮膜層內之Si系粒子(含有Si之金屬間化合物或單體Si所成晶析物)之平均圓當量直徑(μm)及面積率(%)」、「存在於多孔性鋁氧化皮膜層內之小孔的直徑(nm)」。In addition, for the porous aluminum oxide film layer in the oxide film layer, the "thickness (nm) of the porous aluminum oxide film layer" and "Si-based particles (metal containing Si) contained in the porous aluminum oxide film layer were measured. The average circle-equivalent diameter (μm) and area ratio (%) of an inter-compound or a crystallized product of Si alone), "the diameter of pores existing in the porous aluminum oxide film layer (nm)".
另外,對於在氧化皮膜層中,阻障型鋁氧化皮膜層係測定「阻障型鋁氧化皮膜層之厚度(nm)」。In addition, among the oxide film layers, the "thickness (nm) of the barrier type aluminum oxide film layer" was measured for the barrier type aluminum oxide film layer.
另外,對於基材係測定「內在於基材中之Si系粒子(含有Si之金屬間化合物或單體Si所成晶析物)之平均圓當量直徑(μm)及面積率(%)」。In addition, the "average circle-equivalent diameter (μm) and area ratio (%) of Si-based particles (intermetallic compound containing Si or crystallized product of Si alone) contained in the substrate" was measured for the substrate.
具體之測定方法係如以下。The specific measuring method is as follows.
[多孔性鋁氧化皮膜層及阻障型鋁氧化皮膜層之厚度] 對於表面處理鋁合金材的試料而言,經由TEM而實施沿著鋁氧化皮膜之縱方向的剖面觀察。具體而言係測定多孔性鋁氧化皮膜層及阻障型鋁氧化皮膜層之各厚度。為了測定此等之氧化皮膜層的厚度,使用超薄切片機而自試料製作剖面觀察用薄片試料。接著,在此薄片試料中選擇觀察視野(1μm×1μm)中之任意的100處,經由TEM剖面觀察而測定各氧化皮膜層之厚度。將結果示於表4~6。然而,對於此等氧化皮膜層之厚度,作成100處之測定結果的算術平均值。依據測定的結果,亦判斷氧化皮膜層之構造。[Thickness of porous aluminum oxide film layer and barrier aluminum oxide film layer] For the sample of the surface-treated aluminum alloy material, cross-sectional observation along the longitudinal direction of the aluminum oxide film was performed through TEM. Specifically, the respective thicknesses of the porous aluminum oxide film layer and the barrier aluminum oxide film layer were measured. In order to measure the thickness of these oxide film layers, the thin-section sample for cross-sectional observation was produced from a sample using an ultramicrotome. Next, arbitrary 100 places in the observation field of view (1 μm×1 μm) were selected in this sheet sample, and the thickness of each oxide film layer was measured through TEM cross-sectional observation. The results are shown in Tables 4-6. However, the arithmetic mean value of the measurement results at 100 places was made about the thickness of these oxide film layers. According to the results of the measurement, the structure of the oxide film layer is also judged.
[內在於多孔性鋁氧化皮膜層之Si系粒子的粒子徑測定] 對於表面處理鋁合金材的試料而言,經由根據FE-SEM之表面觀察(觀察視野:126μm×85μm之10處),測定Si系粒子的粒子徑。對於粒子徑,係作成在觀察視野之10處的測定值之算術平均值。[Measurement of Particle Size of Si-based Particles Built in Porous Aluminum Oxide Film Layer] For the sample of the surface-treated aluminum alloy material, the particle size of the Si-based particles was measured through surface observation by FE-SEM (observation field of view: 10 locations of 126 μm×85 μm). As for the particle diameter, the arithmetic mean value of the measured values at 10 positions in the observation field of view was made.
[內在於多孔性鋁氧化皮膜層之Si系粒子的面積率] 對於表面處理鋁合金材的試料而言,經由根據FE-SEM之表面觀察(觀察視野:126μm×85μm之10處),計算Si系粒子的面積。以觀察視野的面積除以所計算的值,算出Si系粒子(Si/Al)之面積率。對於Si系粒子的面積率,係作成在觀察視野之10處的測定值之算術平均值。[Area ratio of Si-based particles embedded in the porous aluminum oxide film layer] For the sample of the surface-treated aluminum alloy material, the area of the Si-based particles was calculated through surface observation by FE-SEM (observation field of view: 10 places of 126 μm×85 μm). The area ratio of Si-based particles (Si/Al) was calculated by dividing the area of the observed field of view by the calculated value. The area ratio of the Si-based particles was calculated as the arithmetic mean value of the measured values at 10 positions in the observation field of view.
[多孔性鋁氧化皮膜層之小孔直徑的測定] 對於表面處理鋁合金材的試料而言,經由根據FE-SEM之表面觀察(觀察視野:0.7μm×1μm之10處),測定多孔性鋁氧化皮膜層之小孔的直徑。對於小孔直徑,係作成在觀察視野之10處的測定值之算術平均值。[Measurement of Pore Diameter of Porous Aluminum Oxide Film Layer] For the sample of the surface-treated aluminum alloy material, the diameter of the pores of the porous aluminum oxide film layer was measured through surface observation by FE-SEM (observation field of view: 10 locations of 0.7 μm×1 μm). The diameter of the small hole is calculated as the arithmetic mean value of the measured values at 10 positions in the observation field of view.
另外,在各實施例及比較例中,以同一條件,對於3個基材而言進行電解處理,將此等3個之算術平均值作成評估用的值。上述之氧化皮膜層及基材的各評估結果係示於表3~5。In addition, in each Example and a comparative example, electrolytic treatment was performed with respect to 3 base materials under the same conditions, and the arithmetic mean value of these 3 was made into the value for evaluation. The evaluation results of the above-mentioned oxide film layer and base material are shown in Tables 3-5.
另外,作為表面處理鋁合金材的氧化皮膜層之代表,將自表面觀察實施例1之照片,示於圖4。對於同圖的照片係觀察多數之粒狀物A,此等者為存在於多孔性鋁氧化皮膜層31內之Si系粒子(含有Si之金屬間化合物或單體Si所成之晶析物)。In addition, as a representative of the oxide film layer of the surface-treated aluminum alloy material, a photograph of Example 1 observed from the surface is shown in FIG. 4 . In the photo of the same figure, many particles A are observed, and these are Si-based particles (intermetallic compounds containing Si or crystallized products of Si alone) existing in the porous aluminum
接著,於上述之各實施例及比較例之表面處理鋁合金材的氧化皮膜層上,配置樹脂層,製作樹脂被覆表面處理鋁合金材。首先,準備20片自如上述所製作之表面處理鋁合金板的試料,切斷成縱45mm×橫18mm之供試材12。作為樹脂層6係使用玻璃纖維含有PPS樹脂(DIC公司製),經由插入成形,製作20組與表面處理鋁合金板的供試材12之接合試驗片。具體而言,由插入表面處理鋁板的供試材12於未圖示之射出成形金屬模具內,閉合金屬模具而加熱至160℃後,與以射出溫度320℃而射出PPS樹脂進行成形之樹脂層6接合者,得到圖3所示之接合試驗片S。接合試驗片係依照ISO19095-2之形式B的形狀。如同圖所示,接合試驗片S係作為具有重疊加以接合之接合部16的構成。接合部16係表面處理鋁板之試料端部的縱10mm×橫5mm之部分。Next, a resin layer was placed on the oxide film layer of the surface-treated aluminum alloy materials of the above-mentioned examples and comparative examples to produce a resin-coated surface-treated aluminum alloy material. First, 20 samples of the surface-treated aluminum alloy plate prepared above were prepared, and cut into
如以上作為,在實施例1~37及比較例1、2、4~14中,得到表面處理鋁合金板與樹脂層之接合體所成之上述的接合試驗片S。然而,在比較例15中,無法接合樹脂層,而無法得到接合體。As above, in Examples 1 to 37 and Comparative Examples 1, 2, 4 to 14, the above-mentioned joint test piece S which was a joint body of a surface-treated aluminum alloy plate and a resin layer was obtained. However, in Comparative Example 15, the resin layer could not be bonded, and a bonded body could not be obtained.
[熱可塑性樹脂之接合評估] 接合評估係依照ISO19095-3之5.2.1.2 Specimen retainer,由拉伸試驗機而以5mm/min.之速度,將如上述所製作之接合試驗片S的10組,拉伸於剪斷方向,測定在接合部之熱可塑性樹脂的凝集破壞率,以下述之基準進行評估。 ◎:凝集破壊率為95%以上之構成 ○:凝集破壊率為85%以上,不足95%之構成 △:凝集破壊率為75%以上,不足85%之構成 ×:凝集破壊率為不足75%之構成 將結果示於表3~5。對於同表係各顯示10組之接合體試料之中的前述◎、○、△、×之個數,但所有為◎或○所成之情況,判定為合格,除此等以外,判定為不合格。[Joint Evaluation of Thermoplastic Resin] Bonding evaluation is based on 5.2.1.2 Specimen retainer of ISO19095-3, with a tensile testing machine at a speed of 5mm/min., 10 groups of bonded test pieces S made as above are stretched in the shearing direction and measured The coagulation failure rate of the thermoplastic resin at the junction was evaluated according to the following criteria. ◎: The coagulation breaking rate is more than 95% ○: The coagulation failure rate is more than 85% and less than 95% △: The coagulation failure rate is more than 75% and less than 85% ×: Composition with a coagulation failure rate of less than 75% The results are shown in Tables 3-5. For the number of the above-mentioned ◎, ○, △, and X among the 10 groups of joint samples shown in the same table, if all the cases are ◎ or ○, it is judged as acceptable, otherwise, it is judged as unfavorable qualified.
[密著耐久性評估] 將如上述作為所製作之接合體試料之10組,加上記載於鹽水噴霧試驗方法(JIS Z 2371)之中性鹽水噴霧試驗,在1000小時後取出,由拉伸試驗機,以5mm/min.之速度而拉伸於剪斷方向,測定在接合部之熱可塑性樹脂的凝集破壞率,以下述之基準進行評估。 ◎:凝集破壊率為80%以上之構成 ○:凝集破壊率為65%以上,不足80%之構成 △:凝集破壊率為50%以上,不足65%之構成 ×:凝集破壊率為不足50%之構成 將結果示於表3~5。對於同表係各顯示10組之接合體試料之中的前述◎、○、△、×之個數,但所有為◎或○所成之情況,判定為合格,除此等以外,判定為不合格。[Adhesion durability evaluation] Take 10 groups of jointed body samples prepared as above, plus the neutral salt spray test described in the salt spray test method (JIS Z 2371), take them out after 1000 hours, and use the tensile testing machine at 5mm/min . The velocity is stretched in the shearing direction, and the coagulation failure rate of the thermoplastic resin at the junction is measured, and evaluated according to the following criteria. ◎: The coagulation breaking rate is more than 80% ○: The coagulation failure rate is more than 65% and less than 80% △: The coagulation failure rate is more than 50% and less than 65% ×: Composition with a coagulation failure rate of less than 50% The results are shown in Tables 3-5. For the number of the above-mentioned ◎, ○, △, and X among the 10 groups of joint samples shown in the same table, if all the cases are ◎ or ○, it is judged as acceptable, otherwise, it is judged as unfavorable qualified.
[總合評估] 將在前述鋁氧化皮膜之熱可塑性樹脂的接合性評估及密著耐久性評估之雙方為合格者,總合評估為合格,此等各評估之至少一項為不合格者,總合評估作為不合格。[Total evaluation] If both of the evaluation of the adhesion of the thermoplastic resin of the aluminum oxide film and the evaluation of the adhesion durability are passed, the total evaluation is passed, and if at least one of these evaluations is unsatisfactory, the total evaluation is regarded as unsatisfactory. qualified.
如表3~5所示,在實施例1~37中,氧化皮膜層則具備所有「多孔性鋁氧化皮膜層,和阻障型鋁氧化皮膜層之二重構造,多孔性鋁氧化皮膜層之厚度則位於20~1000nm之範圍,阻障型鋁氧化皮膜層之厚度則位於3~50nm之範圍,且,對於多孔性鋁氧化皮膜層內係多數存在有直徑3~50nm之小孔的同時,含有Si之金屬間化合物或單體Si所成之晶析物的圓當量直徑為平均15μm以下,而該晶析物則在15%以下的面積率而存在」之要件之故,對於與樹脂層之接著性優越,且密著耐久性亦為良好,總合評估為合格。As shown in Tables 3 to 5, in Examples 1 to 37, the oxide film layer has a dual structure of "porous aluminum oxide film layer and barrier aluminum oxide film layer, and the porous aluminum oxide film layer The thickness is in the range of 20~1000nm, the thickness of the barrier aluminum oxide film layer is in the range of 3~50nm, and, for the porous aluminum oxide film layer, there are mostly small holes with a diameter of 3~50nm, The circle-equivalent diameter of the crystallized product formed by the intermetallic compound containing Si or Si alone is less than 15 μm on average, and the crystallized product exists in an area ratio of 15% or less. The adhesion is excellent, and the adhesion durability is also good, and the overall evaluation is qualified.
對此,在比較例1~15中,至少製造方法未具備期望的條件之故,無法得到上述期望形態之氧化皮膜層,而因此,在與樹脂層之接合中,接合強度與密著耐久性之至少一方則不合格,總合評估為不合格。In contrast, in Comparative Examples 1 to 15, at least the production method did not meet the desired conditions, and the oxide film layer of the above-mentioned desired form could not be obtained. Therefore, in the bonding with the resin layer, the bonding strength and adhesion durability At least one of them is unqualified, and the overall assessment is unqualified.
具體而言,在比較例1中,鑄造時之冷卻速度過慢之故,含有晶析於基材中之Si的金屬間化合物及單體Si粒子之粒子徑則變大。因此,經由交流電解處理,多孔性鋁氧化皮膜層之厚度係雖收在期望範圍內,但含於多孔性鋁氧化皮膜層內之Si系粒子的圓當量直徑變為過大,與樹脂層之接合性及密著耐久性評估則同時成為不合格,而總合評估成為不合格。Specifically, in Comparative Example 1, since the cooling rate during casting was too slow, the particle diameters of intermetallic compounds containing Si crystallized in the base material and Si particles became large. Therefore, although the thickness of the porous aluminum oxide film layer is within the desired range through the AC electrolytic treatment, the circle-equivalent diameter of the Si-based particles contained in the porous aluminum oxide film layer becomes too large, and the bond with the resin layer The performance and adhesion durability evaluations are simultaneously unsatisfactory, and the overall evaluation is unsatisfactory.
在比較例2中,熱間壓延時之壓下率過低之故,基材中之Si系粒子未變小,而殘存有大的粒子。因此,經由交流電解處理,多孔性鋁氧化皮膜層之厚度係雖收在期望範圍內,但含於多孔性鋁氧化皮膜層內之Si系粒子的圓當量直徑變為過大,與樹脂層之接合性及密著耐久性評估則同時成為不合格,而總合評估成為不合格。In Comparative Example 2, since the rolling reduction during hot rolling was too low, the Si-based particles in the substrate did not become smaller, but large particles remained. Therefore, although the thickness of the porous aluminum oxide film layer is within the desired range through the AC electrolytic treatment, the circle-equivalent diameter of the Si-based particles contained in the porous aluminum oxide film layer becomes too large, and the bond with the resin layer The performance and adhesion durability evaluations are simultaneously unsatisfactory, and the overall evaluation is unsatisfactory.
在比較例3中,熱間壓延時之壓下率過高之故,對於板容易產生斷裂,而本身無法製造。因此,接合性及密著耐久性係作為無法評估,總合評估為不合格。In Comparative Example 3, since the rolling reduction during the hot rolling was too high, the sheet was likely to be broken and could not be produced by itself. Therefore, joint performance and adhesion durability were regarded as unassessable, and the overall evaluation was unacceptable.
在比較例4中,電解溶液之pH過高之故,在多孔性鋁氧化皮膜層之小孔的直徑變為過大,熱可塑性樹脂層與鋁氧化皮膜層之接合面的接觸面積減少。其結果,密著耐久性則成為不合格,總合評估成為不合格。In Comparative Example 4, since the pH of the electrolytic solution was too high, the diameter of the pores in the porous aluminum oxide film layer became too large, and the contact area between the thermoplastic resin layer and the aluminum oxide film layer decreased. As a result, the adhesion durability was unacceptable, and the overall evaluation was unacceptable.
在比較例5中,電解溶液之pH為中性附近之故,多孔性鋁氧化皮膜之皮膜成長為慢,形成薄的多孔質氧化皮膜,熱可塑性樹脂層與鋁氧化皮膜之接合面則減少。其結果,接合性及密著耐久性則成為不合格,總合評估成為不合格。In Comparative Example 5, since the pH of the electrolytic solution was around neutral, the film growth of the porous aluminum oxide film was slow, forming a thin porous oxide film, and the joint surface between the thermoplastic resin layer and the aluminum oxide film was reduced. As a result, adhesion and adhesion durability were unacceptable, and the overall evaluation was unacceptable.
在比較例6中,電解溶液之pH過小之故,形成薄的多孔性鋁氧化皮膜,小孔的直徑則極端變大,熱可塑性樹脂則幾乎無法流入至鋁氧化皮膜中。其結果,接合性及密著耐久性則成為不合格,總合評估成為不合格。In Comparative Example 6, because the pH of the electrolytic solution was too low, a thin porous aluminum oxide film was formed, the diameter of the pores was extremely large, and the thermoplastic resin could hardly flow into the aluminum oxide film. As a result, adhesion and adhesion durability were unacceptable, and the overall evaluation was unacceptable.
在比較例7中,電解溶液之溫度過低之故,多孔性鋁氧化皮膜層之小孔的直徑極端變小,Al/Si之面積率則成為0%,熱可塑性樹脂則幾乎無法流入至皮膜中。其結果,接合性及密著耐久性則成為不合格,總合評估成為不合格。In Comparative Example 7, because the temperature of the electrolytic solution was too low, the diameter of the pores in the porous aluminum oxide film layer became extremely small, the area ratio of Al/Si became 0%, and the thermoplastic resin hardly flowed into the film. middle. As a result, adhesion and adhesion durability were unacceptable, and the overall evaluation was unacceptable.
在比較例8中,電解溶液之溫度過高之故,多孔性鋁氧化皮膜變薄,小孔之直徑則變大,Al/Si之面積率則變為較規定的值為小,熱可塑性樹脂層與鋁氧化皮膜之接合面則減少。其結果,接合性及密著耐久性則成為不合格,總合評估成為不合格。In Comparative Example 8, because the temperature of the electrolytic solution was too high, the porous aluminum oxide film became thinner, the diameter of the pores became larger, and the area ratio of Al/Si became smaller than the specified value. The thermoplastic resin The bonding surface between the layer and the aluminum oxide film is reduced. As a result, adhesion and adhesion durability were unacceptable, and the overall evaluation was unacceptable.
比較例9,在鹼性交流電解之頻率數過低之故,在多孔性鋁氧化皮膜層之小孔的直徑則極端變大。其結果,與熱可塑性樹脂層之接觸面積變小,接合性及密著耐久性則成為不合格,總合評估成為不合格。In Comparative Example 9, the diameter of the pores in the porous aluminum oxide film layer was extremely large because the frequency of alkaline alternating current electrolysis was too low. As a result, the contact area with the thermoplastic resin layer became small, the adhesiveness and adhesion durability were unacceptable, and the overall evaluation was unacceptable.
在比較例10中,在鹼性交流電解之頻率數過高之故,在多孔性鋁氧化皮膜層之小孔的直徑則極端變小,熱可塑性樹脂層與鋁氧化皮膜之接合面則減少。其結果,接合性及密著耐久性則成為不合格,總合評估成為不合格。In Comparative Example 10, because the frequency of alkaline alternating current electrolysis was too high, the diameter of the pores in the porous aluminum oxide film layer became extremely small, and the bonding surface between the thermoplastic resin layer and the aluminum oxide film decreased. As a result, adhesion and adhesion durability were unacceptable, and the overall evaluation was unacceptable.
在比較例11中,在鹼性交流電解之電流密度過小之故,在多孔性鋁氧化皮膜層之小孔的尺寸則極端變小。因此,熱可塑性樹脂則幾乎無法流入至小孔內。其結果,接合性及密著耐久性則成為不合格,總合評估成為不合格。In Comparative Example 11, the size of the pores in the porous aluminum oxide film layer was extremely small because the current density of the alkaline alternating current electrolysis was too small. Therefore, the thermoplastic resin hardly flows into the pores. As a result, adhesion and adhesion durability were unacceptable, and the overall evaluation was unacceptable.
在比較例12中,在鹼性交流電解之電流密度過大之故,小孔的尺寸則極端變大。因此,熱可塑性樹脂層與鋁氧化皮膜之接合面積則減少。其結果,密著耐久性則成為不合格,總合評估成為不合格。In Comparative Example 12, because the current density of the alkaline alternating current electrolysis was too high, the size of the small pores became extremely large. Therefore, the bonding area between the thermoplastic resin layer and the aluminum oxide film decreases. As a result, the adhesion durability was unacceptable, and the overall evaluation was unacceptable.
在比較例13中,在鹼性交流電解之電解時間過短之故,阻障型鋁氧化皮膜層則變薄,熱可塑性樹脂層與鋁氧化皮膜之接合面則減少。其結果,接合性及密著耐久性則成為不合格,總合評估成為不合格。In Comparative Example 13, because the electrolysis time of the alkaline AC electrolysis was too short, the barrier aluminum oxide film layer became thinner, and the bonding surface between the thermoplastic resin layer and the aluminum oxide film decreased. As a result, adhesion and adhesion durability were unacceptable, and the overall evaluation was unacceptable.
在比較例14中,在鹼性交流電解之電解時間過長之故,多孔性鋁氧化皮膜層及阻障型鋁氧化皮膜層則變厚,對於熱可塑性樹脂之皮膜中的流入為少。其結果,接合性及密著耐久性則成為不合格,總合評估成為不合格。In Comparative Example 14, the porous aluminum oxide film layer and the barrier aluminum oxide film layer became thicker because the electrolysis time of the alkaline alternating current electrolysis was too long, and the inflow into the film of the thermoplastic resin was small. As a result, adhesion and adhesion durability were unacceptable, and the overall evaluation was unacceptable.
在比較例15中,取代於鹼性交流電解而使用直流電解。在直流電解中,僅形成有阻障型鋁氧化皮膜層,未形成有多孔性鋁氧化皮膜層及其小孔。無法接合熱可塑性樹脂層。其結果,無法評估接合性及密著耐久性。In Comparative Example 15, direct current electrolysis was used instead of alkaline alternating current electrolysis. In direct current electrolysis, only the barrier type aluminum oxide film layer is formed, and the porous aluminum oxide film layer and its pores are not formed. The thermoplastic resin layer cannot be joined. As a result, adhesiveness and adhesion durability could not be evaluated.
在比較例16中,Si含有量為多之故,存在有許多基材中之Si系粒子,伴隨於此,晶析物的面積率則成為較規定值為大。經由Si系粒子之存在而與熱可塑性樹脂層的接合面則減少。其結果,接合性及密著耐久性則成為不合格,總合評估成為不合格。In Comparative Example 16, since the Si content was large, many Si-based particles in the base material existed, and accordingly, the area ratio of the crystallized product became larger than the predetermined value. The bonding surface with the thermoplastic resin layer is reduced by the presence of Si-based particles. As a result, adhesion and adhesion durability were unacceptable, and the overall evaluation was unacceptable.
1‧‧‧表面處理鋁合金材
2‧‧‧基材
3‧‧‧氧化皮膜層
31‧‧‧多孔性鋁氧化皮膜層
32‧‧‧阻障型鋁氧化皮膜層
4‧‧‧小孔
5‧‧‧Si系粒子(含有Si金屬間化合物或單體Si所成之晶析物)
61‧‧‧電極
62‧‧‧對電極
71‧‧‧交流電源
72‧‧‧電源開關
8‧‧‧電解溶液
9‧‧‧樹脂層(熱可塑性樹脂片)1‧‧‧Surface
圖1係顯示在實施例中,形成有鋁氧化皮膜之表面處理鋁合金材的剖面構成之說明圖。 圖2係在實施例中,說明交流電解裝置之構成圖。 圖3係在實施例中,接合表面處理鋁合金材與熱可塑性樹脂片的試驗片之剖面圖。 圖4係在實施例中,以掃描型電子顯微鏡(SEM)而觀察表面處理鋁合金材的表面之圖面代用照片。Fig. 1 is an explanatory diagram showing a cross-sectional structure of a surface-treated aluminum alloy material formed with an aluminum oxide film in an example. Fig. 2 is a diagram illustrating the configuration of an AC electrolysis device in an embodiment. Fig. 3 is a cross-sectional view of a test piece in which a surface-treated aluminum alloy material and a thermoplastic resin piece are joined in an example. FIG. 4 is a drawing-substitution photograph of the surface of a surface-treated aluminum alloy material observed with a scanning electron microscope (SEM) in Examples.
1‧‧‧表面處理鋁合金材 1‧‧‧Surface treatment aluminum alloy
2‧‧‧基材 2‧‧‧Substrate
3‧‧‧氧化皮膜層 3‧‧‧Oxide film layer
4‧‧‧小孔 4‧‧‧small hole
5‧‧‧Si系粒子(含有Si金屬間化合物或單體Si所成之晶析物) 5‧‧‧Si-based particles (containing Si intermetallic compounds or crystallized products of Si alone)
31‧‧‧多孔性鋁氧化皮膜層 31‧‧‧Porous aluminum oxide film layer
32‧‧‧阻障型鋁氧化皮膜層 32‧‧‧Barrier aluminum oxide film layer
Claims (2)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018055155A JP7026547B2 (en) | 2018-03-22 | 2018-03-22 | Surface-treated aluminum alloy material and its manufacturing method |
JP2018-055155 | 2018-03-22 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201940750A TW201940750A (en) | 2019-10-16 |
TWI779180B true TWI779180B (en) | 2022-10-01 |
Family
ID=67987345
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW108110035A TWI779180B (en) | 2018-03-22 | 2019-03-22 | Surface-treated aluminum alloy material and method for producing the same |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP7026547B2 (en) |
KR (1) | KR20200135360A (en) |
CN (1) | CN111742083A (en) |
TW (1) | TWI779180B (en) |
WO (1) | WO2019182021A1 (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015067844A (en) * | 2013-09-27 | 2015-04-13 | 株式会社Uacj | Aluminum alloy material for electrolytic treatment, electrolytically treated aluminum alloy material and method for producing the same |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0641667A (en) | 1992-07-22 | 1994-02-15 | Sky Alum Co Ltd | Al base printed wiring board |
JP2010018875A (en) * | 2008-07-14 | 2010-01-28 | Toyota Central R&D Labs Inc | High strength aluminum alloy, method for producing high strength aluminum alloy casting, and method for producing high strength aluminum alloy member |
JP6168723B2 (en) * | 2012-02-12 | 2017-07-26 | 株式会社Uacj | Surface-treated aluminum material and method for producing the same |
TWI656223B (en) * | 2013-08-01 | 2019-04-11 | 日商Uacj股份有限公司 | Surface-treated aluminum material and manufacturing method thereof |
JP6282518B2 (en) * | 2014-04-12 | 2018-02-21 | 株式会社Uacj | Brazing structure manufacturing method, brazing structure manufactured thereby, aluminum-resin composite structure, and aluminum material used in the manufacturing method |
JP2019026924A (en) * | 2017-08-04 | 2019-02-21 | 株式会社Uacj | Surface treated aluminum alloy material and manufacturing method thereof |
-
2018
- 2018-03-22 JP JP2018055155A patent/JP7026547B2/en active Active
-
2019
- 2019-03-20 CN CN201980014418.9A patent/CN111742083A/en active Pending
- 2019-03-20 KR KR1020207027208A patent/KR20200135360A/en not_active Application Discontinuation
- 2019-03-20 WO PCT/JP2019/011741 patent/WO2019182021A1/en active Application Filing
- 2019-03-22 TW TW108110035A patent/TWI779180B/en active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015067844A (en) * | 2013-09-27 | 2015-04-13 | 株式会社Uacj | Aluminum alloy material for electrolytic treatment, electrolytically treated aluminum alloy material and method for producing the same |
Also Published As
Publication number | Publication date |
---|---|
JP7026547B2 (en) | 2022-02-28 |
JP2019167571A (en) | 2019-10-03 |
WO2019182021A1 (en) | 2019-09-26 |
CN111742083A (en) | 2020-10-02 |
KR20200135360A (en) | 2020-12-02 |
TW201940750A (en) | 2019-10-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1657279B (en) | Treated copper foil and circuit board | |
TWI525037B (en) | Graphite composite film | |
KR102098576B1 (en) | Surface treated aluminum material, method for producing same, and resin-coated surface treated aluminum material | |
JP2003201592A (en) | High fatigue ductility electro-deposited copper foil | |
JP2005248323A (en) | Surface-treated copper foil | |
KR20070033005A (en) | Composite Copper Foil and its Manufacturing Method | |
JP2012140552A (en) | Copper-clad laminate and method for producing the same | |
TWI779180B (en) | Surface-treated aluminum alloy material and method for producing the same | |
JPS63310989A (en) | Electrolytic copper foil and production thereof | |
JP2019026924A (en) | Surface treated aluminum alloy material and manufacturing method thereof | |
KR20220159329A (en) | Composite steel sheet having excellent adhesion and method for manufacturing the same | |
JP6575968B2 (en) | Surface-treated aluminum material, method for producing the same, and surface-treated aluminum material / resin layer assembly | |
TWI762587B (en) | Surface-treated aluminum material and method for manufacuring same, and joined member of surface-treated aluminum material/member to be joined having surface-treated aluminum material and member to be joined such as resin and method for manufacuring same | |
JP2008221739A (en) | Plastic metal laminate | |
CN110312824B (en) | Preparation method of surface-treated aluminum material | |
WO2017026461A1 (en) | Surface-treated aluminum material having excellent resin adhesion, method for manufacturing same, and surface-treated aluminum material/resin joined body | |
WO2019208368A1 (en) | Surface-treated copper foil, copper-cladded laminate plate, and printed wiring board | |
TWI696728B (en) | Surface-treatment aluminum profile with an excellent property in resin adhesion, a method for producing the same, and a surface-treatment aluminum profile/resin combination | |
JP2006272671A (en) | Composite laminated sheet | |
JP2018069540A (en) | Aluminum alloy/resin joined body and method for producing the same | |
TW202246581A (en) | Surface-treated copper foil with low surface roughness and low warpage, copper clad laminate including same, and printed wiring board including same | |
JP2018070940A (en) | Aluminum alloy/resin joined body and method for producing the same | |
JP2014097653A (en) | Composite laminate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
GD4A | Issue of patent certificate for granted invention patent |