TWI777671B - Fastening member and manufacturing method thereof - Google Patents
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本發明係關於由鋁合金所形成的緊固構件。詳細而言，係關於鋁合金基材的表面具有耐蝕性優良之皮膜的緊固構件及其製造方法。 The present invention relates to a fastening member formed of an aluminum alloy. In detail, it relates to the fastening member which has the film|membrane excellent in corrosion resistance on the surface of an aluminum alloy base material, and its manufacturing method.
鋁合金因為輕量，一般以各種零件的輕量化為目的而被廣泛應用於汽車、飛機及其他工業領域，其應用範圍逐漸擴大。特別是在汽車領域的緊固構件中，以藉由車體輕量化來改善燃料費為目的，較輕量的鋁合金製緊固構件係代替以往的鋼鐵製緊固構件而受到矚目。 Aluminum alloys are widely used in automobiles, aircrafts and other industrial fields for the purpose of lightening various parts because of their light weight, and their application scope is gradually expanding. Especially in the fastening members in the automotive field, for the purpose of improving fuel efficiency by reducing the weight of the vehicle body, relatively lightweight aluminum alloy fastening members have been attracting attention instead of conventional steel fastening members.
對於熔點較低的鋁合金而言，上述用途的使用環境可說是高溫環境。因此具有因鋁合金材的表面氧化導致腐蝕的疑慮。鋁若放置於空氣中，則會生成自然氧化膜而鈍化，但因為此自然氧化皮膜的厚度為數奈米左右，在極端的濕氣、酸或鹼環境中容易腐蝕。於是，以往即有人研究用以提升鋁合金材之耐蝕性的表面處理方法。目前因應使用環境，除了鋁陽極(alumite)處理、水鋁石(boehmite)處理及鍍覆處理以外，已知磷酸鉻酸鹽(chromate-phosphate)處理、鉻酸鉻處理、磷酸鋅處理、非鉻酸鹽處理等化學處理(例如專利文獻1及專利文獻2)。在此等各種化學處理中，使作為 被處理材的鋁合金接觸包含H2SO4等酸、鹼、或Cr等重金屬離子的處理液或是浸漬於其中，而在合金表面形成防蝕皮膜。 For aluminum alloys with a low melting point, the use environment for the above-mentioned applications can be said to be a high temperature environment. Therefore, there is a concern that corrosion may be caused by surface oxidation of the aluminum alloy material. If aluminum is placed in the air, a natural oxide film will be formed and passivated, but because the thickness of this natural oxide film is about several nanometers, it is easy to corrode in extreme humidity, acid or alkali environment. Therefore, a surface treatment method for improving the corrosion resistance of aluminum alloy materials has been studied in the past. At present, according to the use environment, in addition to aluminum anode (alumite) treatment, boehmite (boehmite) treatment and plating treatment, chromate-phosphate treatment, chromium chromate treatment, zinc phosphate treatment, non-chromate treatment are known. Chemical treatment such as acid salt treatment (for example, Patent Document 1 and Patent Document 2). In these various chemical treatments, the aluminum alloy as the material to be treated is brought into contact with or immersed in a treatment solution containing an acid such as H 2 SO 4 , an alkali, or a heavy metal ion such as Cr to form a corrosion-resistant film on the surface of the alloy.
[先前技術文獻] [Prior Art Literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本特開2008-232366號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2008-232366
[專利文獻2]日本特開平9-112521號公報 [Patent Document 2] Japanese Patent Application Laid-Open No. 9-112521
如上述之化學處理等表面處理技術中，有著特殊處理液的調度及用於處理廢液的成本增加的問題、以及對於環境之負載的問題。又，將此等表面處理技術應用於形狀複雜之緊固構件的情況，因為係在處理液中(液相中)實施，因此難以形成均勻的防蝕皮膜，處理液中的氣泡會阻礙防蝕皮膜的穩定形成。尤其明顯難以對於緊固構件的螺牙部等形成防蝕皮膜。未穩定形成均勻防蝕皮膜的緊固構件，會因為腐蝕造成強度降低而具有斷裂的疑慮。 In the surface treatment technologies such as the above-mentioned chemical treatment, there are problems such as the scheduling of special treatment liquids, the increase in cost for treating waste liquids, and the problems of load on the environment. In addition, when these surface treatment techniques are applied to fastening members with complicated shapes, since they are carried out in the treatment liquid (in the liquid phase), it is difficult to form a uniform anti-corrosion film, and air bubbles in the treatment liquid hinder the corrosion-resistant film. stable formation. In particular, it is obviously difficult to form an anti-corrosion coating on a screw portion of a fastening member or the like. Fastening members that do not stably form a uniform anti-corrosion film may be broken due to a decrease in strength due to corrosion.
為了提升鋁合金材的耐蝕性，本案發明人等揭示了一種使預定溫度範圍的水蒸氣接觸合金表面的表面處理方法。在這種鋁合金材的水蒸氣處理中，在表面上形成以羥基氧化鋁(AlO(OH))(Aluminium hydroxide oxide)作為主成分的皮膜，藉由此皮膜的防蝕作用而提升耐蝕性。 In order to improve the corrosion resistance of the aluminum alloy material, the inventors of the present application disclosed a surface treatment method in which water vapor in a predetermined temperature range is brought into contact with the surface of the alloy. In the steam treatment of such an aluminum alloy material, a film mainly composed of aluminum hydroxide oxide (AlO(OH)) is formed on the surface, and the corrosion resistance is improved by the anti-corrosion effect of the film.
水蒸氣處理，除了從廢液處理等的觀點來看具有安全性、環 境適性以外，可較簡易地在鋁合金材上形成防蝕皮膜而賦予耐蝕性。但是考慮到上述鋁合金材的應用範圍有擴大的傾向時，期望有一種耐蝕性與以往化學處理等表面處理技術同等優良或在其之上的防蝕皮膜。又，將水蒸氣處理應用於緊固構件的情況，由於在緊固時或緊固後會施加應力，因此亦要求防蝕皮膜高硬度且密合性優良。 Water vapor treatment, in addition to being safe, environmentally friendly, and In addition to environmental suitability, it is possible to relatively easily form a corrosion-resistant film on an aluminum alloy material to impart corrosion resistance. However, considering that the application range of the above-mentioned aluminum alloy material tends to expand, there is a desire for a corrosion-resistant coating that is equivalent to or superior to conventional surface treatment techniques such as chemical treatment. In addition, when the water vapor treatment is applied to the fastening member, since stress is applied during or after the fastening, the anti-corrosion film is required to have high hardness and excellent adhesion.
然而，關於以水蒸氣處理提升鋁合金材之耐蝕性的效果，尚有許多不明之處，預期在防蝕皮膜的構成等仍有改良的空間。特別是關於將螺栓等緊固構件之類具有複雜形狀的構件表面充分被覆並且具有密合性的防蝕皮膜，尚未有具體且詳細的見解。 However, there are still many unclear points about the effect of improving the corrosion resistance of aluminum alloy materials by steam treatment, and it is expected that there is still room for improvement in the composition of the anti-corrosion film. In particular, there is no specific and detailed knowledge about an anti-corrosion film that sufficiently coats the surface of a member having a complex shape such as a bolt or the like and has adhesiveness.
本發明係根據上述背景而完成，目的在於提供一種緊固構件，其係由鋁合金所形成，其具有均勻、穩定且密合性優良的防蝕皮膜。又亦揭示一種耐蝕性與強度同時經過改善的緊固構件。再者亦明確揭示一種緊固構件的製造方法，其能夠藉由進行一個處理步驟來達到前述防蝕皮膜的形成與強度提升的兩種效果。 The present invention was made in view of the above-mentioned background, and an object of the present invention is to provide a fastening member formed of an aluminum alloy and having a uniform, stable, and highly adhesive anti-corrosion film. Also disclosed is a fastening member with improved corrosion resistance and strength. Furthermore, a method for manufacturing a fastening member is also explicitly disclosed, which can achieve the two effects of forming the anti-corrosion film and enhancing the strength by performing one processing step.
本案發明人為了解決上述課題而進行詳細研究，發現在由鋁合金所形成的緊固構件的表面上形成包含針對特定結晶面之配向性高的羥基氧化鋁(AlO(OH))的防蝕皮膜，藉此提升耐蝕性，對於密合性優良的緊固構件有用。 In order to solve the above-mentioned problems, the inventors of the present invention conducted detailed studies and found that a corrosion-resistant film containing aluminum oxyhydroxide (AlO(OH)) having a high orientation to a specific crystal plane is formed on the surface of a fastening member made of an aluminum alloy. Thereby, corrosion resistance is improved, and it is useful for a fastening member excellent in adhesiveness.
亦即，本發明之緊固構件，具有由鋁合金所形成的基材、以及被覆前述基材的防蝕皮膜，其中前述防蝕皮膜包含羥基氧化鋁(AlO(OH))，在針對前述緊固構件進行使用Cu-Kα線的X光繞射分析時的分布圖(profile)中，在將羥基氧化鋁的(020)面之繞射波峰的波峰強度設為 IB(020)、將屬於主波峰的鋁(200)面之繞射波峰的波峰強度設為IAl(200)時，波峰強度比R(IB(020)/IAl(200))為0.003以上0.1以下。以下針對本發明之緊固構件，詳細說明其構成。 That is, the fastening member of the present invention has a base material formed of an aluminum alloy, and an anti-corrosion film covering the base material, wherein the anti-corrosion film includes aluminum oxyhydroxide (AlO(OH)). In the profile at the time of X-ray diffraction analysis using Cu-Kα rays, the peak intensity of the diffraction peak of the (020) plane of aluminum oxyhydroxide is set as I B(020) , and the peak intensity belonging to the main peak is set as IB(020). When the peak intensity of the diffraction peak of the aluminum (200) plane is I Al(200) , the peak intensity ratio R(I B(020) /I Al(200) ) is 0.003 or more and 0.1 or less. Hereinafter, the structure of the fastening member of the present invention will be described in detail.
(A)本發明之緊固構件的構成 (A) Configuration of the fastening member of the present invention
(A-1)基材 (A-1) Substrate
如上所述，構成本發明之緊固構件的基材，係由鋁合金所形成。作為該鋁合金，係以鋁作為主成分並且至少添加1種添加元素而成的合金。其係以添加了鋅(Zn)、鎂(Mg)、矽(Si)、銅(Cu)、錳(Mn)、鋰(Li)、鐵(Fe)、鎳(Ni)、銀(Ag)、鋯(Zr)、鉻(Cr)中至少1種以上的元素作為添加元素的鋁合金作為基材。本發明的基材中，較佳為總計包含0.1質量%以上且未達50質量%之該等添加元素的鋁合金。 As described above, the base material constituting the fastening member of the present invention is formed of an aluminum alloy. The aluminum alloy is an alloy containing aluminum as a main component and adding at least one additive element. It is based on the addition of zinc (Zn), magnesium (Mg), silicon (Si), copper (Cu), manganese (Mn), lithium (Li), iron (Fe), nickel (Ni), silver (Ag), An aluminum alloy in which at least one element of zirconium (Zr) and chromium (Cr) is an additive element is used as a base material. In the base material of the present invention, an aluminum alloy containing these additive elements in a total of 0.1 mass % or more and less than 50 mass % is preferable.
此處，鋁合金基材的材料組織較佳為在作為母相的鋁中析出並分散有包含添加元素之化合物而成的組織。此化合物係以鋁合金的添加元素所構成的化合物。化合物的具體構成，係根據成為基材的鋁合金之組成而設。如上所述，作為鋁合金基材的添加元素，大多是添加鋅、鎂、矽、銅、錳、鋰、鐵、鎳、銀、鋯、鉻等。此情況中，分散於鋁合金基材之中的化合物，係由此等金屬元素中的至少1種元素所形成。具體而言，係分散有Mg-Si系化合物(Mg2Si等)、Mg-Zn系化合物(MgZn2等)、Al-Mg-Zn系化合物(Mg3Zn3Al2等)、Cu-Mg系化合物(CuMg2等)、Al-Fe系化合物(AlFe2等)、Al-Fe-Si系化合物(Al12Fe3Si等)、Al-Cu系化合物(CuAl2等)、Al-Cu-Mg系化合物(AlCuMg、Al2CuMg等)、Al-Mn系化合物(Al6Mn等)、Al-Mn-Fe系化合物(Al6MnFe等)、Al-Mn-Si系化合物、Al-Fe-Mn-Si系化合物等化合物。 Here, the material structure of the aluminum alloy base material is preferably a structure in which a compound containing an additive element is precipitated and dispersed in aluminum as a parent phase. This compound is a compound composed of additive elements of aluminum alloys. The specific structure of a compound is set according to the composition of the aluminum alloy used as a base material. As described above, zinc, magnesium, silicon, copper, manganese, lithium, iron, nickel, silver, zirconium, chromium, etc. are often added as elements to be added to the aluminum alloy base material. In this case, the compound dispersed in the aluminum alloy base material is formed by at least one of these metal elements. Specifically, Mg-Si based compounds (Mg 2 Si etc.), Mg-Zn based compounds (MgZn 2 etc.), Al-Mg-Zn based compounds (Mg 3 Zn 3 Al 2 etc.), Cu-Mg based compounds (Mg 3 Zn 3 Al 2 etc.), Al-Fe-based compounds (CuMg 2 , etc.), Al-Fe-based compounds (AlFe 2 , etc.), Al-Fe-Si-based compounds (Al 12 Fe 3 Si, etc.), Al-Cu-based compounds (CuAl 2 , etc.), Al-Cu- Mg-based compounds (AlCuMg, Al 2 CuMg, etc.), Al-Mn-based compounds (Al 6 Mn, etc.), Al-Mn-Fe-based compounds (Al 6 MnFe, etc.), Al-Mn-Si-based compounds, Al-Fe- Compounds such as Mn-Si based compounds.
作為具體的鋁合金，可列舉國際鋁合金命名所規定的各種鋁合金。例如，較佳為2000系合金的Al-Cu系合金、4000系合金的Al-Si系合金、5000系的Al-Mg系合金、6000系合金的Al-Mg-Si系合金、7000系合金的Al-Zn-Mg系合金，特佳為Al-Cu、Al-Mg-Si、Al-Zn-Mg系合金等析出硬化型的各種鋁合金。惟不限於此等經規格化的合金系，可應用廣泛組成的合金系。 As a specific aluminum alloy, various aluminum alloys prescribed|regulated by International Aluminum Alloy Nomenclature can be mentioned. For example, Al-Cu-based alloys of 2000-series alloys, Al-Si-based alloys of 4000-series alloys, Al-Mg-based alloys of 5000-series alloys, Al-Mg-Si-based alloys of 6000-series alloys, and 7000-series alloys are preferred. Al-Zn-Mg-based alloys are particularly preferably various aluminum alloys of precipitation-hardening type such as Al-Cu, Al-Mg-Si, and Al-Zn-Mg-based alloys. However, it is not limited to these standardized alloy systems, and a wide range of alloy compositions can be used.
(A-2)防蝕皮膜 (A-2) Anti-corrosion film
由構成本發明之緊固構件的鋁合金所形成之基材的表面，由包含羥基氧化鋁的防蝕皮膜所被覆。本發明中所使用的羥基氧化鋁，亦稱為水鋁石，其係被表記為γ-AlO(OH)或是僅被表記為AlO(OH)的鋁化物。用於本發明之羥基氧化鋁的鋁源並未特別限定，較佳係以構成基材之鋁合金中所含有的鋁作為原料。又，防蝕皮膜係以羥基氧化鋁作為主成分，此外亦容許基材之鋁合金所含有之鋁以外的各種添加元素、氫氧化鋁(Al(OH)3)、類水鋁石等以作為不可避免的雜質。 The surface of the base material which consists of the aluminum alloy which comprises the fastening member of this invention is covered with the corrosion-resistant film|membrane containing aluminum hydroxide. The alumina oxyhydroxide used in the present invention is also referred to as diaspore, which is an aluminide represented by γ-AlO(OH) or only by AlO(OH). The aluminum source used in the aluminum oxyhydroxide of the present invention is not particularly limited, but it is preferable to use aluminum contained in the aluminum alloy constituting the base material as a raw material. In addition, the anti-corrosion film is mainly composed of aluminum hydroxide, and various additive elements other than aluminum contained in the aluminum alloy of the base material, aluminum hydroxide (Al(OH) 3 ), diaspore-like, etc., are also allowed as impossibility. Avoid impurities.
(A-2-1)X光繞射圖案 (A-2-1) X-ray diffraction pattern
本發明之緊固構件的構成，可根據由X光繞射法(XRD)所得之分布圖(X光繞射圖案)來鑑定構成。關於X光繞射法的X光源，係根據藉由將Cu用於X光源的Cu-Kα射線所得到的分布圖來鑑定構成。X光繞射法可根據該分布圖來鑑定測量對象物的結晶面(米勒指數)等，可從所得之繞射波峰(波峰強度)確認其存在比例。本發明之緊固構件中，亦可針對作為構成基材的鋁合金之母相的鋁與被覆前述基材之防蝕皮膜的羥基氧化鋁，確認結晶面與其存在比例(X光繞射分析)。 The structure of the fastening member of the present invention can be identified from a distribution diagram (X-ray diffraction pattern) obtained by X-ray diffraction (XRD). The X-ray light source of the X-ray diffraction method was identified based on the distribution diagram obtained by using Cu for the Cu-Kα ray of the X-ray light source. The X-ray diffraction method can identify the crystal plane (Miller index) and the like of the object to be measured from the distribution map, and the existence ratio can be confirmed from the obtained diffraction peak (peak intensity). In the fastening member of the present invention, it is also possible to confirm the crystal plane and its existence ratio (X-ray diffraction analysis) with respect to aluminum, which is the parent phase of the aluminum alloy constituting the base material, and aluminum oxyhydroxide, which coats the anti-corrosion film of the base material.
本發明之緊固構件，其特徵係在進行使用Cu-Kα線的X光繞射分析時的分布圖中，在將羥基氧化鋁的(020)面的繞射波峰的波峰強度 設為IB(020)、將屬於主波峰之鋁(200)面的繞射波峰的波峰強度設為IAl(200)時，以IB(020)除以IAl(200)所算出的波峰強度比R(IB(020)/IAl(200))為0.003以上0.1以下。亦即，本發明中的防蝕皮膜的特徵，係羥基氧化鋁的特定結晶面(020)相對於成為基材母相的鋁，其以波峰強度比R表示之在特定範圍的存在比例。 The fastening member of the present invention is characterized in that, in a profile when X-ray diffraction analysis using Cu-Kα rays is performed, the peak intensity of the diffraction peak of the (020) plane of aluminum oxyhydroxide is defined as I B (020) When the peak intensity of the diffraction peak of the aluminum (200) plane belonging to the main peak is set as I Al (200) , the peak intensity ratio R calculated by dividing I B (020) by I Al (200) (I B(020) /I Al(200) ) is 0.003 or more and 0.1 or less. That is, the anti-corrosion coating in the present invention is characterized by the presence ratio of the specific crystal plane (020) of aluminum oxyhydroxide to aluminum serving as the matrix phase of the substrate in a specific range expressed by the peak intensity ratio R.
波峰強度比R為0.003以上0.1以下的緊固構件之耐蝕性有所提升，有用於作為緊固構件。波峰強度比R若未達0.003，則羥基氧化鋁的成長不充分，作為防蝕皮膜的效果不佳。另一方面，包含超過0.1之羥基氧化鋁的防蝕皮膜，亦具有耐蝕性降低的傾向。又，過度成長的羥基氧化鋁，防蝕皮膜的密合性降低，因而不佳。關於波峰強度比R的範圍，下限值較佳為0.005，更佳為0.01。上限值較佳為0.05，更佳為0.03。 The corrosion resistance of the fastening member whose peak strength ratio R is 0.003 or more and 0.1 or less is improved, and it is useful as a fastening member. If the peak intensity ratio R is less than 0.003, the growth of aluminum oxyhydroxide is insufficient, and the effect as an anti-corrosion film is not good. On the other hand, the anti-corrosion coating containing aluminum oxyhydroxide exceeding 0.1 also has the tendency for corrosion resistance to fall. In addition, the excessively grown aluminum oxyhydroxide is unfavorable because the adhesiveness of the anti-corrosion film is lowered. Regarding the range of the peak intensity ratio R, the lower limit is preferably 0.005, more preferably 0.01. The upper limit is preferably 0.05, more preferably 0.03.
又，由上述X光繞射法所得到的分布圖中，本發明之緊固構件中，羥基氧化鋁的(020)面的繞射波峰的半值寬度較佳為0.20°以下。藉由使繞射波峰的半值寬度為0.20°以下，確認到結晶性高的羥基氧化鋁的成長。此結晶性高的羥基氧化鋁，作為緊固構件的防蝕皮膜可發揮高密合性與耐蝕性。此外，本發明的半值寬度係使用半值全寬。半值全寬，係以繞射波峰高度的1/2之寬度所定義。因此，半值寬度(半值全寬)的最小值不會為0而是超過0。 In addition, in the distribution diagram obtained by the above-mentioned X-ray diffraction method, in the fastening member of the present invention, the half width of the diffraction peak of the (020) plane of aluminum oxyhydroxide is preferably 0.20° or less. By setting the half-value width of the diffraction peak to 0.20° or less, growth of aluminum oxyhydroxide with high crystallinity was confirmed. This highly crystalline aluminum oxyhydroxide can exhibit high adhesion and corrosion resistance as a corrosion-resistant film for a fastening member. In addition, the full width at half maximum is used as the half value width of the present invention. The full width at half maximum is defined by the width of 1/2 of the height of the diffraction peak. Therefore, the minimum value of the half-value width (full width at half-value) is not 0 but exceeds 0.
(A-2-2)防蝕皮膜的厚度 (A-2-2) Thickness of anti-corrosion film
本發明之緊固構件的防蝕皮膜之厚度較佳為1μm至15μm。若未達1μm，則作為緊固構件的耐蝕性不足，因而不佳。若超過15μm，則與基材的密合性降低，因此具有會因為緊固時或緊固後的應力而剝離的疑慮。 The thickness of the anticorrosive film of the fastening member of the present invention is preferably 1 μm to 15 μm. If it is less than 1 μm, the corrosion resistance as a fastening member is insufficient, and thus it is not good. If it exceeds 15 micrometers, since the adhesiveness with a base material will fall, there exists a possibility that it may peel by the stress at the time of fastening or after fastening.
(A-3)本發明之緊固構件的強度 (A-3) Strength of the fastening member of the present invention
本發明之緊固構件，其強度亦優良。具體而言，其維氏硬度較佳為 100Hv至250Hv。此硬度係相對於由同組成的鋁合金所形成的同種緊固構件的2倍至5倍。此經改善之硬度，與其說是防蝕皮膜的效果，不如說是起因於基材本身的硬度上升。如後所述，因為形成防蝕皮膜時的處理溫度，在形成皮膜的同時發生了硬度的提升。 The fastening member of the present invention is also excellent in strength. Specifically, its Vickers hardness is preferably 100Hv to 250Hv. This hardness is 2 to 5 times higher than that of the same type of fastening member formed of an aluminum alloy of the same composition. This improved hardness is not so much the effect of the anti-corrosion film as it is due to the increase in the hardness of the substrate itself. As will be described later, due to the processing temperature at the time of forming the anti-corrosion coating, the hardness is improved at the same time as the coating is formed.
(A-4)本發明之緊固構件的具體態樣 (A-4) Specific aspects of the fastening member of the present invention
本發明之緊固構件，可應用為一般的緊固零件，並未特別限定。例如適用於螺栓、螺絲、螺帽、螺絲攻(tap)、墊圈及鉚釘等一般緊固零件以及使用此等緊固零件的零件等。尤其是針對複雜形狀的緊固零件，可形成穩定的防蝕皮膜，因此有用。具體可列舉螺栓、螺絲、螺帽。 The fastening member of the present invention can be applied as a general fastening component, and is not particularly limited. For example, it is suitable for general fastening parts such as bolts, screws, nuts, taps, washers and rivets, as well as parts using such fastening parts. In particular, it is useful for forming a stable anti-corrosion film for fasteners with complex shapes. Specific examples include bolts, screws, and nuts.
(B)本發明之緊固構件的製造方法 (B) Manufacturing method of the fastening member of the present invention
接著說明本發明之緊固構件的製造方法。本發明之緊固構件的製造中，由作為基材的鋁合金所形成之緊固構件的製造，係以一般的製造步驟進行製造。亦可使用市售之由鋁合金所形成的緊固構件。本發明係藉由對於鋁合金所形成的基材進行水蒸氣處理而形成防蝕皮膜來進行製造。然而，在形成包含在上述特定結晶面配向之羥基氧化鋁的防蝕皮膜之後，對於以往的製造步驟進行改良。具體而言，係在水蒸氣處理之前進行抑制特定雜質元素的清洗。 Next, the manufacturing method of the fastening member of this invention is demonstrated. In the production of the fastening member of the present invention, the production of the fastening member formed of the aluminum alloy as the base material is carried out by a general production procedure. A commercially available fastening member formed of an aluminum alloy can also be used. The present invention is manufactured by subjecting a base material formed of an aluminum alloy to a water vapor treatment to form an anti-corrosion film. However, after the formation of the anti-corrosion film containing the aluminum oxyhydroxide with the above-mentioned specific crystal plane orientation, the conventional manufacturing process is improved. Specifically, cleaning to suppress specific impurity elements is performed before the steam treatment.
亦即，本發明的緊固構件的製造方法，包含：清洗步驟，清洗由鋁合金所形成的基材；固溶步驟，其係進行將前述清洗步驟後之前述基材加熱至460℃以上570℃以下的溫度後再急冷的固溶處理；及防蝕皮膜形成步驟，藉由使固溶處理後的基材接觸水蒸氣而形成皮膜；其中，前述清洗步驟，係將前述基材中含有Fe之異物的附著量清洗至0.6μg/mm2以下為止的步驟，前述防蝕皮膜形成步驟，係使前述基材與230℃至290℃的水蒸氣接觸的步驟。以下說明各步驟。 That is, the manufacturing method of the fastening member of the present invention includes: a cleaning step of cleaning a base material formed of an aluminum alloy; a solid solution step of heating the base material after the cleaning step to a temperature of 460° C. or higher for 570° C. The solution treatment is followed by quenching at a temperature below ℃; and the anti-corrosion film forming step is to form a film by contacting the solution-treated substrate with water vapor; wherein, the cleaning step is to the substrate containing Fe. The step of washing the adhesion amount of foreign matter to 0.6 μg/mm 2 or less, and the step of forming the anti-corrosion film, is a step of bringing the substrate into contact with water vapor at 230°C to 290°C. Each step is explained below.
(B-1)清洗步驟 (B-1) Cleaning step
根據本案發明人的研究，鋁合金表面存在微量Fe時，有時會阻礙作為防蝕皮膜之主成分的羥基氧化鋁的成長。然後，具備這種存在有Fe的基材所形成之防蝕皮膜的緊固構件，其耐蝕性不佳。 According to the research of the present inventors, the presence of a trace amount of Fe on the surface of the aluminum alloy may inhibit the growth of aluminum oxyhydroxide, which is the main component of the anti-corrosion film. Then, the fastening member provided with the anti-corrosion film formed by the base material in which Fe is present has poor corrosion resistance.
作為由鋁合金所形成的緊固構件的表面會存在Fe的主要原因，據認為係在於其製造步驟。在將緊固構件加工時，一般係進行拉製加工、鍛造加工、輥壓加工或切削加工。此等的加工步驟中係使用模或工具進行加工。此處，在實際製造現場中，從產線的效率化等觀點來看，亦大多是共用與以往的鐵鋼製的緊固構件相同的模具及相同的製造設備。因此，即使是鋁合金產品，亦具有許多表面上附著鐵的情況。又，由超硬模等模具本身而來的Fe亦可能附著於鋁合金的表面。使用切削加工製作緊固構件的情況中，切削油所包含的Fe亦可能會附著於鋁合金的表面。 The main reason why Fe exists on the surface of the fastening member formed of the aluminum alloy is considered to lie in the manufacturing process. When processing the fastening member, drawing, forging, rolling, or cutting are generally performed. In these processing steps, a mold or a tool is used for processing. Here, also in an actual manufacturing site, from the viewpoint of the efficiency of the production line, etc., the same molds and the same manufacturing facilities as those of the conventional iron-steel fastening members are often shared. Therefore, even aluminum alloy products have many cases where iron adheres to the surface. In addition, Fe derived from the mold itself, such as a superhard mold, may adhere to the surface of the aluminum alloy. In the case of producing a fastening member by machining, Fe contained in the cutting oil may adhere to the surface of the aluminum alloy.
目前為止的緊固構件，在最終加工步驟之後一般具有清洗步驟。然而，此清洗步驟其目的並非係去除Fe這樣的特定元素，而是去除污渣(sludge)或有機物等髒汙。這種一般的清洗步驟，並無法充分去除Fe。然後，殘留的Fe如上所述，會阻礙有效的防蝕皮膜之形成。 The fastening members so far generally have a cleaning step after the final processing step. However, the purpose of this cleaning step is not to remove a specific element such as Fe, but to remove dirt such as sludge and organic matter. This general cleaning step cannot sufficiently remove Fe. Then, as described above, the remaining Fe hinders the formation of an effective anti-corrosion film.
於是，本案發明人等，針對關於本發明之緊固構件的製造方法，必要性地追加將成為基材之緊固構件的含有Fe之異物的附著量清洗至0.6μg/mm2以下為止的清洗步驟。只要由鋁合金所形成之基材的表面上含有Fe之異物的附著量在0.6μg/mm2以下，則不會阻礙而是促進羥基氧化鋁的(020)面的成長，而能夠形成對於(020)面之配向性高的均質防蝕皮膜。 Therefore, the inventors of the present application, with regard to the manufacturing method of the fastening member of the present invention, need to additionally wash the adhesion amount of the Fe-containing foreign matter to be 0.6 μg/mm 2 or less of the fastening member serving as the base material. step. As long as the adhesion amount of the Fe-containing foreign matter on the surface of the base material made of aluminum alloy is 0.6 μg/mm 2 or less, the growth of the (020) plane of aluminum hydroxide is not hindered but promoted, and the (020) plane can be formed for ( 020) homogeneous anti-corrosion film with high orientation.
本發明之清洗步驟中的清洗方法，只要具有降低Fe附著量的效果，則可為任何方法，可應用既有的清洗方法。可列舉例如：電解法、以酸性溶液所進行的清洗法(酸洗)、烴系清洗劑等。 The cleaning method in the cleaning step of the present invention may be any method as long as it has the effect of reducing the Fe adhesion amount, and an existing cleaning method can be applied. For example, an electrolytic method, a cleaning method (acid cleaning) with an acidic solution, a hydrocarbon-based cleaning agent, etc. are mentioned.
作為具體的清洗步驟，較佳係由包含作為第1步驟的超音波清洗步驟、作為第2步驟的蒸氣清洗步驟、及作為第3步驟的乾燥步驟的步驟所形成。作為第1步驟的減壓超音波清洗步驟，係在清洗槽中使用烴系清洗劑進行超音波清洗，藉此去除基材表面的異物。作為第2步驟的蒸氣清洗步驟，係藉由將烴系清洗劑所形成的高溫蒸氣導入清洗槽，在進行基材的最後清洗的同時，亦進行基材的加熱。藉由對於基材進行這種2階段清洗，可大幅降低基材表面的異物附著量。作為第3步驟的乾燥步驟，在排出烴系清洗劑後，使清洗槽中成為高真空的環境，藉此進行基材的真空乾燥。此真空乾燥時，藉由經過第2步驟加熱之基材的餘熱促進基材表面上所附著之烴系清洗劑揮發，將基材在未發生變色的情況下進行乾燥。 As a specific cleaning step, it is preferable to form a step including an ultrasonic cleaning step as the first step, a steam cleaning step as the second step, and a drying step as the third step. The reduced-pressure ultrasonic cleaning step of the first step is to perform ultrasonic cleaning using a hydrocarbon-based cleaning agent in a cleaning tank, thereby removing foreign matter on the surface of the substrate. In the steam cleaning step of the second step, the heating of the substrate is performed simultaneously with the final cleaning of the substrate by introducing the high-temperature steam formed by the hydrocarbon-based cleaning agent into the cleaning tank. By performing such two-stage cleaning on the base material, the amount of foreign matter adhering to the base material surface can be greatly reduced. As the drying step of the third step, after the hydrocarbon-based cleaning agent is discharged, the vacuum drying of the substrate is performed by making the cleaning tank a high-vacuum environment. During this vacuum drying, the residual heat of the substrate heated in the second step promotes volatilization of the hydrocarbon-based cleaning agent attached to the surface of the substrate, and the substrate is dried without discoloration.
可根據以殘渣測量檢查所進行的重量法，算出基材的含有Fe之異物的附著量(μg/mm2)。以殘渣測量檢查所進行的重量法，係以薄膜過濾器將上述清洗步驟中所使用的烴系清洗劑過濾，並且測量過濾前後薄膜過濾器本身重量的變化量，藉此可測量附著於基材表面上的異物之重量。之後，以前述異物的重量除以上述清洗步驟中進行清洗的所有基材之表面積，可算出基材表面的異物附著量(μg/mm2)。此外，可使用掃描式電子顯微鏡針對過濾後的薄膜過濾器上所附著之前述異物進行定性分析來確認異物是否包含Fe。 The adhesion amount (μg/mm 2 ) of the Fe-containing foreign matter on the base material can be calculated by the gravimetric method by the residue measurement inspection. In the gravimetric method of residue measurement and inspection, the hydrocarbon-based cleaning agent used in the above cleaning step is filtered with a membrane filter, and the amount of change in the weight of the membrane filter itself before and after filtration is measured. The weight of the foreign object on the surface. Then, the foreign matter adhesion amount (μg/mm 2 ) on the substrate surface can be calculated by dividing the weight of the foreign matter by the surface area of all the substrates cleaned in the cleaning step. In addition, it is possible to confirm whether or not the foreign matter contains Fe by qualitatively analyzing the foreign matter adhering to the membrane filter after filtration using a scanning electron microscope.
(B-2)固溶處理步驟 (B-2) Solution treatment step
在製造完成/市售品的一般鋁合金材中，預期可能會有所謂的不規則化合物的分散、粗大化合物的分散、或是化合物不足等使皮膜的形成不均勻/不規則的材料組織。為此，會藉由固溶處理使基材的組織狀態均質化，可得到特性穩定的合金材。固溶處理，係將基材加熱至460℃至570℃後進行 冷卻。加熱時間較佳為0.1小時至48小時。冷卻較佳為水冷，再佳係使用5℃以下的水冷。 In general aluminum alloy materials that are manufactured/commercially available, it is expected that so-called irregular compound dispersion, coarse compound dispersion, or compound shortage may cause uneven/irregular material structure in film formation. Therefore, the microstructure of the base material is homogenized by the solution treatment, and an alloy material with stable properties can be obtained. Solution treatment is carried out after heating the substrate to 460°C to 570°C cool down. The heating time is preferably 0.1 hour to 48 hours. The cooling is preferably water cooling, and it is even more preferable to use water cooling below 5°C.
(B-3)防蝕皮膜形成步驟 (B-3) Anti-corrosion film formation step
然後，針對經過如上述之清洗步驟及固溶步驟的基材進行水蒸氣處理以使基材接觸水蒸氣，藉此在基材的表面上形成防蝕皮膜，而成為本發明之緊固構件。藉由水蒸氣處理所得到的防蝕皮膜，係一方面以基材的鋁合金所包含的鋁作為羥基氧化鋁的原料，一方面在基材表面上直接進行皮膜成長所形成，因此可形成對基材形狀有高度追隨性的皮膜。因此，對於在具有複雜形狀的緊固構件上形成防蝕皮膜有用，即使對於緊固構件的螺牙部等，亦可穩定形成均勻的防蝕皮膜。 Then, the substrate subjected to the above-mentioned cleaning step and solution step is subjected to water vapor treatment to contact the substrate with water vapor, thereby forming an anti-corrosion film on the surface of the substrate to form the fastening member of the present invention. The anti-corrosion film obtained by steam treatment is formed by using aluminum contained in the aluminum alloy of the base material as the raw material of aluminum hydroxide, and on the other hand, the film is grown directly on the surface of the base material, so it can form a base material. The shape of the material has a high follow-up film. Therefore, it is useful for forming an anti-corrosion film on a fastening member having a complicated shape, and a uniform anti-corrosion film can be stably formed even on the screw portion of the fastening member and the like.
用以形成此防蝕皮膜的水蒸氣處理步驟中，係使水蒸氣的溫度為230℃至290℃。230℃至290℃的範圍之外的水蒸氣處理無法形成能夠成為較佳防蝕皮膜的羥基氧化鋁，而無法形成耐蝕性與密合性優良的防蝕皮膜。水蒸氣的溫度更佳為250至280℃。又，水蒸氣處理的處理時間較佳為1小時至48小時。 In the water vapor treatment step for forming this anti-corrosion film, the temperature of the water vapor is set to 230°C to 290°C. Water vapor treatment outside the range of 230° C. to 290° C. cannot form aluminum oxyhydroxide that can be a preferable anti-corrosion film, and cannot form an anti-corrosion film excellent in corrosion resistance and adhesion. The temperature of the water vapor is more preferably 250 to 280°C. In addition, the treatment time of the steam treatment is preferably from 1 hour to 48 hours.
與基材接觸的水蒸氣，係由水的加熱/氣化所生成，作為水蒸氣源的水，可使用工業用水或自來水，較佳係使用純水。又，亦可使用含有適當之鹽的水溶液。使用純水的情況，較佳係使用導電率為1mS/m以下的離子交換水、蒸餾水、超純水。又，作為含鹽的水溶液，可利用碳酸鹽、硝酸鹽、硫酸鹽、氟化物鹽之水溶液的蒸氣。此等的鹽，除了鹼金屬(鋰、鈉、鉀等)的鹽(碳酸鈉、硝酸鈉等)、鹼土金屬(鈣、鍶、鋇等)的鹽(碳酸鈣、硝酸鈣等)以外，可應用貴金屬的鹽、一般金屬的鹽等。可使用將此等鹽組合1種或多種而成的水溶液。 The water vapor that comes into contact with the substrate is generated by heating and vaporizing water. As the water vapor source, industrial water or tap water can be used, and pure water is preferably used. In addition, an aqueous solution containing an appropriate salt can also be used. When using pure water, it is preferable to use ion-exchanged water, distilled water, and ultrapure water having a conductivity of 1 mS/m or less. Moreover, as the aqueous solution containing salt, the vapor of the aqueous solution of carbonate, nitrate, sulfate, and fluoride salt can be used. Such salts, in addition to alkali metal (lithium, sodium, potassium, etc.) salts (sodium carbonate, sodium nitrate, etc.), alkaline earth metal (calcium, strontium, barium, etc.) salts (calcium carbonate, calcium nitrate, etc.) Precious metal salts, general metal salts, etc. are used. An aqueous solution in which one or more of these salts are combined can be used.
水蒸氣的壓力較佳為0.1MPa至10MPa的範圍。水蒸氣的壓 力更佳為2MPa至8MPa。若應用加壓水蒸氣，則成為飽和蒸氣與次臨界水(subcritical water)的2相平衡狀態，可促進對於防蝕皮膜之形成的反應性。藉由在處理時保持固定的水蒸氣壓力，可形成均勻的防蝕皮膜。 The pressure of the water vapor is preferably in the range of 0.1 MPa to 10 MPa. pressure of water vapour The force is more preferably 2 MPa to 8 MPa. When pressurized water vapor is applied, it becomes a two-phase equilibrium state of saturated vapor and subcritical water, and the reactivity with respect to the formation of an anticorrosion film can be accelerated|stimulated. By maintaining a constant water vapor pressure during processing, a uniform anti-corrosion film can be formed.
關於使水蒸氣與鋁合金基材接觸的方法，並未特別限定。亦可將作為處理材的鋁合金暴露於預定的反應器/容器等密閉空間內的水蒸氣來進行水蒸氣處理。作為具體的手法，可將基材與水一起配置於容器中，使基材曝露於控制溫度/壓力所產生的水蒸氣環境中以進行處理。又，亦可將水蒸氣直接噴射於處理材以進行處理。 The method of bringing water vapor into contact with the aluminum alloy base material is not particularly limited. The steam treatment may be performed by exposing the aluminum alloy as the treatment material to steam in a closed space such as a predetermined reactor/container. As a specific method, the base material can be disposed in a container together with water, and the base material can be treated by exposing the base material to a water vapor environment generated by controlling temperature and pressure. Moreover, you may inject|spray water vapor|steam directly to a process material, and can process it.
以上的水蒸氣處理，在形成防蝕皮膜的同時，亦具有提升基材硬度(提升強度)的效果。此硬度提升係起因於上述經固溶處理之鋁合金的時效效果。本發明之方法中的水蒸氣處理，如上所述，係在230℃以上的溫度進行。此處理溫度係高於以往水蒸氣處理中的較佳溫度範圍。據認為藉由此高溫的水蒸氣處理會進行時效(Aging)。上述水蒸氣處較佳處理時間，係考量用以產生時效效果的時間以及避免發生過時效。 The above steam treatment has the effect of increasing the hardness (strength) of the substrate while forming the anti-corrosion film. This increase in hardness is due to the aging effect of the solution-treated aluminum alloy described above. The steam treatment in the method of the present invention is carried out at a temperature of 230°C or higher as described above. This treatment temperature is higher than the preferred temperature range in previous steam treatment. It is considered that aging (Aging) is performed by the steam treatment at this high temperature. The above-mentioned preferred treatment time in the water vapor is considered in consideration of the time for producing the aging effect and avoiding over-aging.
如以上所說明，本發明之緊固構件，可低價地對於具有複雜形狀的鋁合金製基材形成均勻且穩定的防蝕皮膜，而防蝕皮膜與基材的密合性優良且為高硬度，並且具有優於以往的耐蝕性，因此可用作為緊固零件。 As described above, the fastening member of the present invention can form a uniform and stable anti-corrosion film on an aluminum alloy base material having a complex shape at a low cost, and the anti-corrosion film has excellent adhesion to the base material and high hardness, And it has better corrosion resistance than the conventional one, so it can be used as a fastener.
圖1係用以大致說明本實施型態中所使用的蒸氣養護(steam curing)裝 置之構成的圖。 FIG. 1 is used to roughly illustrate the steam curing device used in this embodiment. A diagram of the composition.
圖2係第1實施型態之緊固構件表面(防蝕皮膜)的SEM影像。 FIG. 2 is an SEM image of the surface (corrosion-resistant film) of the fastening member of the first embodiment.
圖3係第1實施型態之緊固構件的XRD分布圖。 Fig. 3 is an XRD distribution diagram of the fastening member of the first embodiment.
第1實施型態：以下說明本發明的較佳實施型態。本實施型態中，係使用由屬於6000系鋁合金的Al-Mg-Si系合金(A6061合金)所形成的螺栓作為鋁合金的基材，並對其進行水蒸氣處理，以製作由形成有防蝕皮膜之緊固構件所形成的緊固零件。 1st Embodiment: The preferred embodiment of the present invention will be described below. In this embodiment, a bolt formed of an Al-Mg-Si-based alloy (A6061 alloy) belonging to a 6000-series aluminum alloy is used as a base material of the aluminum alloy and subjected to steam treatment to produce a bolt formed with a Fastening parts formed by fastening members of anti-corrosion films.
[緊固構件的製造] [Manufacture of Fastening Member]
本實施型態中，以市售的A6061合金的螺栓作為基材。首先，作為基材的清洗步驟，進行清洗處理直到基材表面的含有Fe之異物之附著量為0.6μg/mm2以下為止。清洗步驟係使用單槽式烴系清洗機(AQUA CHEMICAL股份有限公司製TETRA)，使用烴系清洗劑(產品名稱：AQUA CHEMICAL股份有限公司製Aqua Solvent)分別進行基材的超音波清洗及蒸氣清洗各10分鐘後，進行基材的真空乾燥。之後，根據以殘渣測量檢查所進行的重量法算出基材的含有Fe之異物的附著量(μg/mm2)。此外，使用掃描式電子顯微鏡對經由烴系清洗劑過濾後的薄膜過濾器上所附著的異物進行定性分析來確認異物所包含之Fe的存在。 In this embodiment, a commercially available A6061 alloy bolt is used as the base material. First, as a cleaning step of the substrate, cleaning treatment is performed until the adhesion amount of the Fe-containing foreign matter on the surface of the substrate is 0.6 μg/mm 2 or less. In the cleaning step, a single-tank hydrocarbon-based cleaning machine (TETRA, manufactured by Aqua Chemical Co., Ltd.) was used, and a hydrocarbon-based cleaning agent (product name: Aqua Solvent, manufactured by Aqua Chemical Co., Ltd.) was used to perform ultrasonic cleaning and steam cleaning of the substrate, respectively. After each 10 minutes, vacuum drying of the substrate was performed. Then, the adhesion amount (μg/mm 2 ) of the Fe-containing foreign matter on the base material was calculated by the gravimetric method by the residue measurement inspection. Furthermore, the presence of Fe contained in the foreign matter was confirmed by qualitative analysis of the foreign matter adhering to the membrane filter after filtration with the hydrocarbon-based cleaning agent using a scanning electron microscope.
接著，針對清洗步驟後的基材進行固溶處理。固溶處理係將基材在560℃的鹽浴中加熱後再進行冷卻。加熱時間為0.5小時。冷卻係使用0℃的冰水進行。 Next, solution treatment is performed on the substrate after the cleaning step. The solution treatment system heats the base material in a salt bath at 560° C. and then cools it. The heating time was 0.5 hours. The cooling system was performed using ice water at 0°C.
針對經固溶處理之基材實施水蒸氣處理以進行防蝕皮膜形成。水蒸氣處理中，使用圖1所示的蒸氣養護裝置。圖1的蒸氣養護裝置 係橫向型的高壓釜，下部注入作為處理液的純水(20ml)，其成為蒸氣源。裝置上部可懸吊複數個試料(基材)。防蝕皮膜形成的條件，係使溫度為200℃(參考例1)、240℃(實施例1)、260℃(實施例2)、290℃(實施例3)，使壓力為1.5MPa(參考例1)、3.3MPa(實施例1)、4.6MPa(實施例2)、7.4MPa(實施例3)，使處理時間為24小時，並且保持溫度及壓力以進行處理。 Water vapor treatment is performed on the solution-treated substrate to form an anti-corrosion film. In the steam treatment, the steam curing apparatus shown in Fig. 1 was used. The steam curing device of Figure 1 It was a horizontal autoclave, and pure water (20 ml) as a treatment liquid was injected into the lower part, and this was used as a steam source. A plurality of samples (substrates) can be suspended from the upper part of the device. The conditions for the formation of the anti-corrosion film were that the temperature was 200°C (Reference Example 1), 240°C (Example 1), 260°C (Example 2), and 290°C (Example 3), and the pressure was 1.5 MPa (Reference Example 1). 1), 3.3 MPa (Example 1), 4.6 MPa (Example 2), 7.4 MPa (Example 3), the treatment time was 24 hours, and the temperature and pressure were maintained for treatment.
比較例1、2：針對與上述實施例1等相同的螺栓進行清洗，但使基材所包含的Fe等的異物附著量超過0.6μg/mm2。此清洗步驟中，僅將緊固構件浸漬於烴系清洗劑中5分鐘。然後，以與上述實施例2相同的條件進行水蒸氣處理，形成防蝕皮膜(比較例1)。又，準備由未形成有防蝕皮膜的A6061合金所形成的螺栓(未處理品)作為比較例2。 Comparative Examples 1 and 2: The same bolts as in Example 1 and the like were cleaned, but the amount of foreign matter adhesion, such as Fe, contained in the base material was made to exceed 0.6 μg/mm 2 . In this cleaning step, only the fastening member was immersed in the hydrocarbon-based cleaning agent for 5 minutes. Then, the water vapor treatment was performed under the same conditions as those of the above-mentioned Example 2 to form an anti-corrosion film (Comparative Example 1). In addition, as Comparative Example 2, a bolt (untreated product) formed of an A6061 alloy on which the anti-corrosion film was not formed was prepared.
針對以上述步驟所製造之實施例1至3、參考例1、比較例1、2的緊固構件進行各種評價。 Various evaluations were performed with respect to the fastening members of Examples 1 to 3, Reference Example 1, Comparative Examples 1 and 2 manufactured by the above-mentioned steps.
[以SEM觀察防蝕皮膜的表面型態] [Observation of the surface morphology of the anti-corrosion film by SEM]
以掃描式電子顯微鏡(SEM)觀察防蝕皮膜的表面型態。圖2係顯示以各水蒸氣處理溫度在實施例1至3的A5056合金之螺栓表面形成的防蝕皮膜之表面型態的SEM影像。由圖2確認，在任一溫度中皆在實施例1至3的螺栓表面上緻密地形成了追隨基材形狀，推定其為AlO(OH)的結晶。 The surface morphology of the anti-corrosion film was observed with a scanning electron microscope (SEM). FIG. 2 is a SEM image showing the surface morphology of the anti-corrosion films formed on the surfaces of the A5056 alloy bolts of Examples 1 to 3 at various steam treatment temperatures. From FIG. 2 , it was confirmed that the bolt surfaces of Examples 1 to 3 were densely formed to follow the shape of the base material at any temperature, and were presumed to be AlO(OH) crystals.
[以X光繞射法(XRD)所進行的分析] [Analysis by X-ray Diffraction (XRD)]
接著以X光繞射法(XRD)對本實施型態及比較例的緊固構件進行分析。XRD係以Cu-Kα作為X光源，於電壓40kV、電流30mA進行測量。針對形成有防蝕皮膜的本實施型態及比較例之緊固構件、以及未形成有防蝕皮膜的緊固構件(未處理品：比較例2)進行XRD。 Next, the fastening members of the present embodiment and the comparative example were analyzed by X-ray diffraction (XRD). The XRD system was measured at a voltage of 40 kV and a current of 30 mA using Cu-Kα as an X light source. XRD was performed on the fastening members of the present embodiment and the comparative example on which the anti-corrosion film was formed, and the fastening member without the anti-corrosion film (untreated product: Comparative Example 2).
圖3係對於以各種水蒸氣溫度形成有防蝕皮膜的緊固構件與未處理品之緊固構件進行XRD所得到的分布圖。由圖3可確認，本實施型態中，羥基氧化鋁的(020)面中的繞射波峰強。圖3中，從羥基氧化鋁的(020)面的波峰強度與由鋁合金所形成之基材的鋁的(200)面的波峰強度算出波峰強度比R。又，根據所測量之XRD的分布圖，測量半值寬度。半值寬度的測量，係測量繞射波峰高度之1/2的寬度。表1中顯示各種水蒸氣處理溫度的實施例、參考例、比較例的波峰強度比R的值與半值寬度的值。 FIG. 3 is a distribution diagram obtained by performing XRD with respect to the fastening member having the anti-corrosion film formed at various water vapor temperatures and the fastening member of the untreated product. From FIG. 3 , it can be confirmed that in this embodiment, the diffraction peak in the (020) plane of aluminum oxyhydroxide is strong. In FIG. 3 , the peak intensity ratio R is calculated from the peak intensity of the (020) plane of aluminum oxyhydroxide and the peak intensity of the (200) plane of aluminum of the base material formed of the aluminum alloy. Furthermore, from the measured XRD profile, the half-value width was measured. The half-value width is measured by measuring the width of 1/2 of the height of the diffraction peak. Table 1 shows the value of the peak intensity ratio R and the value of the half-value width of Examples, Reference Examples, and Comparative Examples at various steam treatment temperatures.
[表1]
[CASS試驗] [CASS test]
針對本實施型態及比較例的緊固構件，使用依照JIS H 8502的CASS試驗(銅加速鹽霧試驗，Copper Accelerated Salt Spray Test)進行耐蝕性的評價。CASS試驗，係使用CASS試驗裝置等，於將溶液噴霧的環境中，調查鍍覆之耐蝕性的試驗方法，其中，該溶液係在乙酸酸性的氯化鈉溶液 中添加氯化銅(II)二水合物而成者。使試驗時間設為1至24小時，使用CASS試驗裝置(JIS Z 2371)，以表2的條件進行CASS試驗。 Corrosion resistance was evaluated using the CASS test (Copper Accelerated Salt Spray Test) according to JIS H 8502 for the fastening members of the present embodiment and the comparative example. CASS test is a test method for investigating the corrosion resistance of plating in an environment in which a solution is sprayed using a CASS test apparatus, etc., wherein the solution is an acetic acid acid sodium chloride solution It is made by adding copper(II) chloride dihydrate. The test time was set to 1 to 24 hours, and the CASS test was performed under the conditions of Table 2 using a CASS test apparatus (JIS Z 2371).
[表2]
針對CASS試驗後的緊固構件，以目視觀察外觀，未產生腐蝕者評價為「A」，確認到部分腐蝕者評價為「B」，確認到整體皆有腐蝕者則評價為「C」。CASS試驗，原則上是進行至整體發生腐蝕的階段(評價為C的階段)為止。CASS試驗的結果顯示於表3。 The appearance of the fastening members after the CASS test was visually observed, and those with no corrosion were rated as "A", those with partial corrosion were rated as "B", and those with corrosion in the entirety were rated as "C". In principle, the CASS test is performed until the stage where the entire corrosion occurs (stage evaluated as C). The results of the CASS test are shown in Table 3.
[表3]
從表3可確認在未進行水蒸氣處理的鋁合金(比較例2)中，僅1小時即發生全面性腐蝕，因此可確認各實施例及比較例1等所形成之防蝕皮膜的有效性。然後可知各實施例的緊固構件，對於CASS試驗的鹽 水維持6小時以上的整體未腐蝕的狀態。尤其是，以260℃進行水蒸氣處理的實施例2中，直到24小時為止皆維持良好的狀態。 From Table 3, it was confirmed that in the aluminum alloy (Comparative Example 2) not subjected to the steam treatment, general corrosion occurred in only 1 hour. Therefore, the effectiveness of the anticorrosion films formed in the Examples and Comparative Example 1 was confirmed. Then, it can be seen that the fastening member of each example, for the salt of the CASS test The water is maintained in an uncorroded state as a whole for more than 6 hours. In particular, in Example 2 in which the steam treatment was performed at 260° C., a favorable state was maintained until 24 hours.
然而，關於對於緊固構件的水蒸氣處理，必須以適當的處理溫度進行。如參考例1般，處理溫度為200℃時，6小時即發生全面性腐蝕，可說是並未生成可發揮充分耐蝕性的防蝕皮膜。然後，為了在由鋁合金所形成之緊固構件上形成防蝕效果高的皮膜，必須以清洗來限制鐵附著量。如比較例1，在經過未限制鐵附著量的一般清洗的緊固構件中，形成了不充分的皮膜，其防蝕效果與參考例1相同。 However, with regard to the steam treatment of the fastening member, it must be performed at an appropriate treatment temperature. As in Reference Example 1, when the treatment temperature was 200° C., general corrosion occurred in 6 hours, and it can be said that a corrosion-inhibiting film capable of exhibiting sufficient corrosion resistance was not formed. Then, in order to form a film with a high anti-corrosion effect on a fastening member formed of an aluminum alloy, it is necessary to limit the amount of iron adhesion by cleaning. As in Comparative Example 1, an insufficient film was formed in the fastening member subjected to general cleaning without limiting the amount of iron adhesion, and the anti-corrosion effect was the same as that of Reference Example 1.
此外，由防蝕皮膜而來的防蝕效果，係與羥基氧化鋁的(020)面的繞射波峰之波峰強度與鋁的(200)面的繞射波峰之波峰強度的波峰強度比R(IB(020)/IAl(200))相符合。若參照參考例1與實施例1至3，此波峰強度比從200℃附近至240℃緩慢增加，但之後增加速度上升，超過260℃附近的波峰強度比急遽增加。 In addition, the anti-corrosion effect from the anti-corrosion film is the peak intensity ratio R(I B to the peak intensity of the diffraction peak of the (020) plane of aluminum hydroxide and the peak intensity of the diffraction peak of the aluminum (200) plane (020) /I Al(200) ). Referring to Reference Example 1 and Examples 1 to 3, the peak intensity ratio gradually increased from around 200°C to 240°C, but then the increase rate increased, and the peak intensity ratio above around 260°C increased sharply.
[硬度及防蝕皮膜的厚度] [Hardness and thickness of anti-corrosion film]
針對各實施例及比較例的緊固構件上所形成的防蝕皮膜，進行防蝕皮膜的厚度與基材的硬度相關的評價試驗。使用日本電子股份有限公司製CROSS SECTION POLISHER(註冊商標)對於包含防蝕皮膜與基材的垂直剖面進行剖面加工，再針對該剖面得到場發射掃描電子顯微鏡影像，藉此測量防蝕皮膜的厚度。又，硬度的測量，係針對在測量之前已對於各樣本進行機械研磨而去除皮膜的試料表面進行測量。硬度測量條件，係使用微維氏硬度試驗機(HM-103，Mitutoyo股份有限公司製)，並以試驗載重2.94N、載重時間15s作為測量條件。此評價結果顯示於表4。 With respect to the anti-corrosion films formed on the fastening members of the respective Examples and Comparative Examples, an evaluation test of the thickness of the anti-corrosion films and the hardness of the base material was performed. The thickness of the anti-corrosion film was measured by performing cross-section processing on a vertical cross section including the anti-corrosion film and the substrate using CROSS SECTION POLISHER (registered trademark) manufactured by JEOL Ltd., and obtaining a field emission scanning electron microscope image of the cross-section. In addition, the measurement of the hardness was performed with respect to the surface of the sample from which the film was removed by mechanical polishing of each sample before the measurement. As for the hardness measurement conditions, a micro-Vickers hardness tester (HM-103, manufactured by Mitutoyo Co., Ltd.) was used, and a test load of 2.94 N and a load time of 15 s were used as the measurement conditions. The results of this evaluation are shown in Table 4.
[表4]
由表4的結果可知，藉由水蒸氣處理形成了厚度充分的防蝕皮膜。然後可知藉由水蒸氣處理，基材硬度最多增加2倍以上。因此可確認形成了其強度可充分承受緊固時或緊固後之應力的緊固構件。 As can be seen from the results in Table 4, a sufficient thickness of the anti-corrosion film was formed by the steam treatment. Then, it can be seen that the hardness of the substrate can be increased by more than 2 times at most by the water vapor treatment. Therefore, it was confirmed that a fastening member having sufficient strength to withstand the stress at the time of fastening or after fastening was formed.
第2實施型態：本實施型態中，使用由屬於7000系鋁合金的Al-Cu-Mg系合金(A7075合金)所形成的螺栓作為鋁合金的基材，對其進行水蒸氣處理，製作由形成有防蝕皮膜的緊固構件所形成的緊固零件，並進行各種討論。 Second Embodiment: In this embodiment, a bolt formed of an Al-Cu-Mg-based alloy (A7075 alloy) belonging to a 7000-series aluminum alloy is used as the base material of the aluminum alloy, and the bolt is subjected to steam treatment to produce Various discussions have been made on the fastening parts formed by the fastening members formed with the anti-corrosion films.
首先，將市售的A7075合金的螺栓進行清洗以作為基材。基材的清洗步驟，係使用與第1實施型態相同的裝置及清洗劑並以相同條件進行清洗，進行清洗處理至基材表面的含有Fe之異物的附著量為0.6μg/mm2以下。然後對於清洗步驟後的基材進行固溶處理。固溶處理係在470℃的鹽浴中將基材加熱後再進行冷卻。加熱時間為2小時。冷卻係使用0℃的冰水進行。 First, a commercially available A7075 alloy bolt was washed to serve as a base material. The cleaning process of the substrate is performed under the same conditions using the same apparatus and cleaning agent as in the first embodiment, and the cleaning process is performed until the adhesion amount of Fe-containing foreign matter on the surface of the substrate is 0.6 μg/mm 2 or less. The substrate after the cleaning step is then subjected to solution treatment. In the solution treatment, the base material is heated in a salt bath at 470° C. and then cooled. The heating time was 2 hours. The cooling system was performed using ice water at 0°C.
然後，針對已進行固溶處理的基材實施水蒸氣處理，以形成防蝕皮膜。水蒸氣處理，係使用與第1實施型態相同的蒸氣養護裝置。防 蝕皮膜形成的條件，係使溫度為180℃(參考例2)、240℃(實施例4)，使壓力為1.0MPa(參考例2)、3.3MPa(實施例4)，使處理時間為24小時，保持溫度及壓力以進行處理。 Then, the solution-treated base material is subjected to water vapor treatment to form an anti-corrosion film. For the steam treatment, the same steam curing device as in the first embodiment was used. Defend The conditions for the formation of the etched film were that the temperature was set to 180°C (Reference Example 2), 240°C (Example 4), the pressure was set to 1.0 MPa (Reference Example 2), 3.3 MPa (Example 4), and the treatment time was set to 24 hours, maintaining temperature and pressure for processing.
比較例3、4：針對與上述實施例4等相同的螺栓進行清洗，但是使基材所包含的Fe等的異物附著量超過0.6μg/mm2。此清洗步驟中，僅將緊固構件浸漬於烴系清洗劑5分鐘。對於清洗後的螺栓進行使用硫酸電解液的鋁陽極處理而形成防蝕皮膜(皮膜厚度5μm至10μm)(比較例3)。又，準備由未形成有防蝕皮膜的A7075合金所形成的螺栓(未處理品)作為比較例4。 Comparative Examples 3 and 4: The same bolts as in Example 4 and the like described above were cleaned, but the adhesion amount of foreign matter such as Fe contained in the base material was made to exceed 0.6 μg/mm 2 . In this cleaning step, only the fastening member was immersed in the hydrocarbon-based cleaning agent for 5 minutes. The washed bolt was subjected to aluminum anodization treatment using a sulfuric acid electrolyte to form an anti-corrosion film (film thickness of 5 μm to 10 μm) (Comparative Example 3). In addition, as Comparative Example 4, a bolt (untreated product) formed of an A7075 alloy on which the anti-corrosion film was not formed was prepared.
針對以上述步驟所製造的實施例4及比較例的緊固構件，以CASS試驗進行耐蝕性評價。CASS試驗的試驗條件與第1實施型態相同。然後，以目視觀察外觀，以與第1實施型態相同的判定基準進行評價。此CASS試驗的結果顯示於表5。 Corrosion resistance was evaluated by the CASS test about the fastening member of Example 4 and the comparative example manufactured by the above-mentioned procedure. The test conditions of the CASS test are the same as those of the first embodiment. Then, the external appearance was visually observed, and the evaluation was performed according to the same criteria as in the first embodiment. The results of this CASS test are shown in Table 5.
[表5]
由表5可確認未進行水蒸氣處理的鋁合金(比較例4)中，僅1小時即發生全面性腐蝕，因而可確認實施例4及參考例2等中所形成之防蝕皮膜的有效性。然後可知，實施例4的緊固構件，對於CASS試驗的鹽水即使24小時以上仍維持整體未腐蝕的良好狀態。然後可知，相較於比較例3中所形成的由鋁陽極處理形成之皮膜，實施例4中形成的防蝕皮膜 大幅度展現了良好的耐蝕性。然而，如參考例2，處理溫度為180℃，6小時即發生全面性腐蝕，並未生成可發揮充分耐蝕性的防蝕皮膜。與第1實施型態相同，確認必須以適當處理溫度進行水蒸氣處理。 From Table 5, it was confirmed that in the aluminum alloy (Comparative Example 4) not subjected to the steam treatment, general corrosion occurred in only 1 hour, and thus the effectiveness of the anticorrosive films formed in Example 4, Reference Example 2, and the like was confirmed. Then, it was found that the fastening member of Example 4 maintained a good state of no corrosion as a whole even in the salt water of the CASS test for 24 hours or more. Then, it can be seen that the anti-corrosion film formed in Example 4 is better than the film formed by aluminum anodization formed in Comparative Example 3. Greatly exhibits good corrosion resistance. However, as in Reference Example 2, when the treatment temperature was 180° C., general corrosion occurred in 6 hours, and a corrosion-resistant film that exhibited sufficient corrosion resistance was not formed. As in the first embodiment, it was confirmed that the steam treatment must be performed at an appropriate treatment temperature.
此外，本實施型態中，亦針對實施例4以SEM觀察防蝕皮膜的表面型態，結果確認緻密地形成了追隨基材形狀，推定其為AlO(OH)的結晶。 In addition, in the present embodiment, also in Example 4, the surface morphology of the anti-corrosion film was observed by SEM. As a result, it was confirmed that the crystals following the shape of the substrate were densely formed, and it was presumed to be a crystal of AlO(OH).
第3實施型態：本實施型態中，使用由屬於4000系鋁合金的Al-Si系合金(ADC12合金)所形成的螺栓作為鋁合金的基材，對其進行水蒸氣處理，以製作由形成有防蝕皮膜的緊固構件所形成的緊固零件，並進行各種討論。 Third Embodiment: In this embodiment, a bolt formed of an Al-Si-based alloy (ADC12 alloy) belonging to a 4000-series aluminum alloy is used as a base material of the aluminum alloy, and is subjected to steam treatment to produce a Various discussions have been made on the fastening parts formed by the fastening members formed with the anti-corrosion coating.
首先對於市售的ADC12合金的螺栓進行清洗以作為基材。基材的清洗步驟，係使用與第1實施型態相同的裝置及清洗劑，以相同條件進行清洗，進行清洗處理至基材表面的含有Fe之異物的附著量為0.6μg/mm2以下為止。本實施型態中，由於係使用由屬於4000系鋁合金之Al-Si系合金(ADC12合金)所形成的螺栓作為鋁合金的基材，因此並未針對清洗步驟後的基材進行固溶處理。 First, a commercially available ADC12 alloy bolt was cleaned to serve as a base material. In the cleaning step of the substrate, the same equipment and cleaning agent as in the first embodiment are used, and the cleaning is performed under the same conditions, and the cleaning treatment is performed until the adhesion amount of the Fe-containing foreign matter on the surface of the substrate is 0.6 μg/mm 2 or less. . In this embodiment, since a bolt formed of an Al-Si-based alloy (ADC12 alloy) belonging to a 4000-series aluminum alloy is used as the base material of the aluminum alloy, solution treatment is not performed on the base material after the cleaning step. .
對於已進行清洗步驟的基材實施水蒸氣處理，以形成防蝕皮膜。水蒸氣處理，係使用與第1實施型態相同的蒸氣養護裝置。防蝕皮膜形成的條件，係使溫度為240℃(實施例5)，使壓力為3.3MPa(實施例5)，使處理時間為24小時，保持溫度及壓力以進行處理。 The substrate which has been subjected to the cleaning step is subjected to water vapor treatment to form an anti-corrosion film. For the steam treatment, the same steam curing device as in the first embodiment was used. The conditions for the formation of the anti-corrosion film were that the temperature was 240° C. (Example 5), the pressure was 3.3 MPa (Example 5), the treatment time was 24 hours, and the temperature and pressure were maintained for treatment.
比較例5、6：針對與上述實施例5相同的螺栓進行清洗，但使基材所包含的Fe等的異物附著量超過0.6μg/mm2。此清洗步驟中，僅將緊固構件於烴系清洗劑浸漬5分鐘。對於清洗後的螺栓進行使用硫酸電解液的鋁陽極處理，以形成防蝕皮膜(皮膜厚度5μm至10μm)(比較例5)。又， 準備由未形成防蝕皮膜的ADC12合金所形成的螺栓(未處理品)作為比較例6。 Comparative Examples 5 and 6: The same bolts as in Example 5 were cleaned, but the adhesion amount of foreign matter such as Fe contained in the base material was made to exceed 0.6 μg/mm 2 . In this cleaning step, only the fastening member was immersed in the hydrocarbon-based cleaning agent for 5 minutes. The washed bolt was subjected to aluminum anodization using a sulfuric acid electrolyte to form a corrosion-resistant film (film thickness of 5 μm to 10 μm) (Comparative Example 5). In addition, as Comparative Example 6, a bolt (untreated product) formed of ADC12 alloy on which the anti-corrosion film was not formed was prepared.
針對以上述步驟所製造之實施例5及比較例的緊固構件，藉由CASS試驗進行耐蝕性評價。CASS試驗的試驗條件與第1實施型態相同。然後，以目視觀察外觀，以與第1實施型態相同的判定基準進行評價。此CASS試驗的結果顯示於表6。 About the fastening member of Example 5 and the comparative example manufactured by the above-mentioned procedure, the corrosion resistance evaluation was performed by the CASS test. The test conditions of the CASS test are the same as those of the first embodiment. Then, the external appearance was visually observed, and the evaluation was performed according to the same criteria as in the first embodiment. The results of this CASS test are shown in Table 6.
[表6]
本實施型態中，未進行水蒸氣處理的鋁合金(比較例6)，在 尚未經過1小時的時間點即發生全面性的腐蝕。實施例5的鋁合金，可得知係對於CASS試驗的鹽水維持整體未腐蝕的狀態6小時以上。若考量無防蝕皮膜的比較例6的結果，相對於第1實施型態之基材的6000系列鋁合金(Al-Mg-Si系合金)等，本實施型態之基材的4000系列鋁合金(Al-Si系合金)係耐蝕性較低的鋁合金。確認即使對於這種耐蝕性低的鋁合金進行適當處理溫度的水蒸氣處理而形成防蝕皮膜，亦可大幅改善耐蝕性。 In this embodiment, the aluminum alloy (Comparative Example 6) not subjected to the steam treatment is Generalized corrosion occurred before 1 hour had elapsed. In the aluminum alloy of Example 5, it was found that the entire non-corroded state was maintained for 6 hours or more with respect to the salt water of the CASS test. Considering the results of Comparative Example 6 without the anti-corrosion coating, the 4000-series aluminum alloys of the base material of the present embodiment can be compared with the 6000-series aluminum alloys (Al-Mg-Si-based alloys) of the base material of the first embodiment. (Al—Si-based alloy) is an aluminum alloy with low corrosion resistance. It was confirmed that the corrosion resistance can be greatly improved even if a corrosion-resistant film is formed by performing steam treatment at an appropriate treatment temperature with respect to such an aluminum alloy with low corrosion resistance.
又，若與比較例5中所形成的由鋁陽極處理形成之皮膜進行比較，可知實施例5中所形成的防蝕皮膜展現了與其同等的耐蝕性。本案發明的防蝕皮膜，雖需要嚴謹地設定溫度條件，但可藉由較簡易的製程(水蒸氣處理)形成。根據本發明，可說是能夠以比鋁陽極處理等更為簡易的製程賦予其等同等以上的耐蝕性。此外，針對實施例5以SEM觀察防蝕皮膜，結果與第1、第2實施型態相同，確認致密地形成了追隨基材形狀，推定其為AlO(OH)的結晶。 Moreover, when compared with the film formed by the aluminum anodization process formed in the comparative example 5, it turns out that the anticorrosion film formed in the example 5 shows the corrosion resistance equivalent to that. The anti-corrosion film of the present invention can be formed by a relatively simple process (steam treatment), although the temperature conditions need to be set strictly. According to the present invention, it can be said that the corrosion resistance equal to or greater than that can be imparted to it by a simpler process than aluminum anodization or the like. In addition, the anti-corrosion film was observed by SEM in Example 5, and it was confirmed that it was formed to follow the shape of the base material densely, as in the first and second embodiments, and was presumed to be a crystal of AlO(OH).
[產業上的可利用性] [Industrial Availability]
如以上所說明，本發明可提供一種能夠低價地對於具有複雜形狀的鋁合金製基材形成均勻且穩定的防蝕皮膜、防蝕皮膜與基材的密合性優良且為高硬度並且具有優於以往之耐蝕性的緊固構件及其製造方法。因此，可望廣泛地將其使用於應用範圍傾向於逐漸擴大的鋁合金製緊固零件。 As described above, the present invention can provide a uniform and stable anti-corrosion film that can be formed on an aluminum alloy base material having a complex shape at low cost, the anti-corrosion film has excellent adhesion to the base material, has high hardness, and is superior to A conventional corrosion-resistant fastening member and a manufacturing method thereof. Therefore, it is expected to be widely used for aluminum alloy fasteners whose application range tends to gradually expand.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03158476A (en) * | 1989-11-17 | 1991-07-08 | Mitsubishi Materials Corp | Formation of boehmite to aluminum can and aluminum can having boehmite film layer |
| WO2017135363A1 (en) * | 2016-02-05 | 2017-08-10 | 学校法人 芝浦工業大学 | Aluminum alloy material having high strength and high corrosion resistance, method for manufacturing same, and method for surface treatment of aluminum alloy material |
| WO2019163155A1 (en) * | 2018-02-21 | 2019-08-29 | 学校法人 芝浦工業大学 | Aluminum alloy material having excellent corrosion resistance and strength, and method for producing same |
| CN111511941A (en) * | 2017-12-22 | 2020-08-07 | 日本发条株式会社 | Aluminum alloy, aluminum alloy spring, and aluminum alloy fastening member |
-
2021
- 2021-07-14 TW TW110125884A patent/TWI777671B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03158476A (en) * | 1989-11-17 | 1991-07-08 | Mitsubishi Materials Corp | Formation of boehmite to aluminum can and aluminum can having boehmite film layer |
| WO2017135363A1 (en) * | 2016-02-05 | 2017-08-10 | 学校法人 芝浦工業大学 | Aluminum alloy material having high strength and high corrosion resistance, method for manufacturing same, and method for surface treatment of aluminum alloy material |
| CN111511941A (en) * | 2017-12-22 | 2020-08-07 | 日本发条株式会社 | Aluminum alloy, aluminum alloy spring, and aluminum alloy fastening member |
| WO2019163155A1 (en) * | 2018-02-21 | 2019-08-29 | 学校法人 芝浦工業大学 | Aluminum alloy material having excellent corrosion resistance and strength, and method for producing same |
Non-Patent Citations (1)
| Title |
|---|
| 期刊 Hongmei Li等人,Microstructure and cracking behavior of hydroxide films formed on aluminum-alloy sheets prepared by steam coating, Microstructure and cracking behavior of hydroxide films formed on aluminum-alloy sheets prepared by steam coating, Vol. 764, Materials Science & Engineering A, 2019年8月2日出版, 138247 * |
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