JP6722981B2 - Aluminum alloy clad material - Google Patents
Aluminum alloy clad material Download PDFInfo
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- JP6722981B2 JP6722981B2 JP2015105401A JP2015105401A JP6722981B2 JP 6722981 B2 JP6722981 B2 JP 6722981B2 JP 2015105401 A JP2015105401 A JP 2015105401A JP 2015105401 A JP2015105401 A JP 2015105401A JP 6722981 B2 JP6722981 B2 JP 6722981B2
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- 239000000463 material Substances 0.000 title claims description 190
- 229910000838 Al alloy Inorganic materials 0.000 title claims description 29
- 238000005219 brazing Methods 0.000 claims description 213
- 239000011162 core material Substances 0.000 claims description 45
- 238000010438 heat treatment Methods 0.000 claims description 38
- 239000013078 crystal Substances 0.000 claims description 19
- 239000011856 silicon-based particle Substances 0.000 claims description 18
- 230000005496 eutectics Effects 0.000 claims description 17
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 description 67
- 238000005260 corrosion Methods 0.000 description 67
- 238000012360 testing method Methods 0.000 description 31
- 230000000694 effects Effects 0.000 description 24
- 239000011701 zinc Substances 0.000 description 19
- 239000000945 filler Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 238000005096 rolling process Methods 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000000265 homogenisation Methods 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 238000005097 cold rolling Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910018131 Al-Mn Inorganic materials 0.000 description 1
- 229910018461 Al—Mn Inorganic materials 0.000 description 1
- 229910018473 Al—Mn—Si Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910000952 Be alloy Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、自動車熱交換器用部品等に用いられるアルミニウム合金クラッド材に関する。 The present invention relates to an aluminum alloy clad material used for automobile heat exchanger parts and the like.
近年、電気自動車や燃料電池車に代表される環境対応車の登場により、自動車用熱交換器には従来よりも高性能化や形状の複雑化の要求が高まっている。この自動車用熱交換器の部品等にブレージングシートと称されるアルミニウム合金クラッド材が用いられている。
このアルミニウム合金クラッド材は、芯材の両面に皮材がクラッドされた構成であり、皮材の一方が犠牲材層、他方がろう材層として機能している。
In recent years, with the advent of environment-friendly vehicles typified by electric vehicles and fuel cell vehicles, there has been an increasing demand for automobile heat exchangers with higher performance and more complicated shapes than ever before. An aluminum alloy clad material called a brazing sheet is used for parts of this automobile heat exchanger.
The aluminum alloy clad material has a structure in which skin materials are clad on both sides of a core material, and one of the skin materials functions as a sacrificial material layer and the other functions as a brazing material layer.
このアルミニウム合金クラッド材において、従来では耐食性確保のため犠牲材が適用されていた熱交換器冷却水側についてもろう付を実施する例が増えており、高い耐食性を有するろう材が求められている。 With this aluminum alloy clad material, there are an increasing number of examples of brazing on the cooling water side of the heat exchanger, where a sacrificial material was conventionally applied to ensure corrosion resistance, and a brazing material with high corrosion resistance is required. ..
特許文献１では、ろう材の耐食性を向上させるため、皮材に亜鉛（Ｚｎ）を添加しており、Ｓｉ：３〜６％、Ｚｎ：２〜８％を含有し、さらにＭｎ：０．３〜１．８％、Ｔｉ：０．０５〜０．３０％の１種または２種を含有し、残部Ａｌおよび不可避的不純物からなるアルミニウム合金により皮材を構成している。この亜鉛添加により、ろう付時に皮材中のＺｎが芯材中へ拡散し、芯材の板厚方向にＺｎの濃度勾配を形成し、これにより皮材が芯材より電位的に卑となり犠牲陽極材として作用するため、板厚方向への腐食の進展を抑制できると記載されている。
特許文献２〜４でも、皮材となるろう材に亜鉛を含有したものが記載されている。
In Patent Document 1, zinc (Zn) is added to the skin material in order to improve the corrosion resistance of the brazing material, and contains Si: 3 to 6%, Zn: 2 to 8%, and further Mn: 0.3. .About.1.8%, Ti: 0.05 to 0.30% of 1 type or 2 types, and the skin material is made of an aluminum alloy containing the balance Al and unavoidable impurities. This addition of zinc causes Zn in the skin material to diffuse into the core material during brazing, forming a Zn concentration gradient in the thickness direction of the core material, which causes the skin material to become base potential lower than the core material and sacrifice. It is described that since it acts as an anode material, the progress of corrosion in the plate thickness direction can be suppressed.
Patent Documents 2 to 4 also describe a brazing filler metal as a skin material containing zinc.
しかし、ろう材に亜鉛を添加した場合、ろう付熱処理の際にろう材が流動することで、材料表面に均一に亜鉛が分布しないことや、ろう材共晶部へ局所的に腐食が進行することが問題となっている。 However, when zinc is added to the brazing filler metal, the brazing filler metal flows during the brazing heat treatment, so that the zinc is not evenly distributed on the material surface, and corrosion locally progresses to the eutectic part of the brazing filler metal. Is a problem.
本発明はこのような背景に鑑みてなされたものであり、溶融ろうの流動を制御して、腐食の進行を抑制し、耐食性に優れるアルミニウム合金クラッド材を提供することを目的とする。 The present invention has been made in view of such a background, and an object thereof is to provide an aluminum alloy clad material that controls the flow of molten brazing material to suppress the progress of corrosion and has excellent corrosion resistance.
本発明のアルミニウム合金クラッド材は、芯材の一方または両方の面にろう材層がクラッドされており、前記ろう材層が質量％でＳｉ：２．５〜６．５％、Ｚｎ：２．０〜６．０％含有し、残部がＡｌおよび不可避不純物からなり、ろう材層には円相当径で１μｍ程度のＳｉ粒子が多数存在する、アルミニウム合金クラッド材であって、上記アルミニウム合金クラッド材を、同室温から４００℃の到達時間が６分、４００℃から５５０℃の到達時間が１分３０秒、５５０℃から目標温度までの到達時間が４分となるような昇温速度で加熱し、６００℃の目標温度で３分間保持し、その後、３００℃まで約１００℃／ｍｉｎで冷却した後、室温まで空冷を行なうろう付相当熱処理を施してろう付けすると、前記ろう付け前のろう材層の厚さをＡ、前記ろう付後の残存ろう材層の厚さをＢとした時、Ｂ／Ａが０．８以上となり、前記ろう付後のろう材層内に円相当径３μｍ〜８μｍのシリコン粒子が８×１０〜８×１０２個／ｍｍ２の範囲で分散し、かつ、前記ろう付後のろう材初晶と前記芯材間の孔食電位差が１００〜２００ｍＶであり、前記ろう付後の前記残存ろう材層の板厚中心から該残存ろう材層と芯材の界面にかけての領域内におけるろう共晶の面積占有率が５〜３０％の範囲になる。 Aluminum alloy clad material of the present invention is a brazing material layer is clad on one or both surfaces of the core material, Si the brazing material layer is in mass%: 2.5~6.5%, Zn: 2 . An aluminum alloy clad material, which contains 0 to 6.0%, the balance being Al and unavoidable impurities, and a large number of Si particles having an equivalent circle diameter of about 1 μm are present in the brazing material layer. Is heated at a temperature rising rate such that the arrival time from the same room temperature to 400° C. is 6 minutes, the arrival time from 400° C. to 550° C. is 1 minute 30 seconds, and the arrival time from 550° C. to the target temperature is 4 minutes. , held for 3 minutes at the target temperature of 600 ° C., then, after cooling at about 100 ° C. / min up to 300 ° C., the brazed subjected to considerable heat treatment brazing performing air-cooled to room temperature, the before brazing the brazing material When the thickness of the layer is A and the thickness of the remaining brazing material layer after brazing is B, B/A is 0.8 or more, and a circle equivalent diameter of 3 μm or more in the brazing material layer after brazing. 8 μm silicon particles are dispersed in the range of 8×10 to 8×10 2 pieces/mm 2 , and the pitting potential difference between the brazing material primary crystal and the core material after brazing is 100 to 200 mV, The area occupancy rate of the braze eutectic in the region from the plate thickness center of the remaining brazing material layer after brazing to the interface between the remaining brazing material layer and the core material is in the range of 5 to 30%.
本発明では、亜鉛含有ろう材へ添加されるシリコン（Ｓｉ）量を制御することで、ろう付熱処理時に流動するろう材量を適正化し、材料表面に残存するろう材層の厚さおよびろう共晶組織の制御を行なっている。 In the present invention, by controlling the amount of silicon (Si) added to the zinc-containing brazing filler metal, the amount of the brazing filler metal that flows during the brazing heat treatment is optimized, and the thickness of the brazing filler metal layer remaining on the surface of the material and the brazing filler metal The crystal structure is controlled.
ろう材層成分のＳｉは、材料の融点を低下させるので、ろう付時に溶融して他部材と接合する機能を付与してろう付性を向上させる効果があり、２．５質量％未満では、その効果が十分に発揮されず、６．５質量％を超えると、ろう付時の溶融ろうの流動性が高くなり過ぎて、ろう付後に残存するろう材層の厚さが低下する。 Since Si of the brazing material layer component lowers the melting point of the material, it has the effect of melting at the time of brazing and imparting a function of joining with other members to improve brazing property. If the effect is not sufficiently exhibited and the content exceeds 6.5 mass %, the fluidity of the molten brazing material during brazing becomes too high, and the thickness of the brazing material layer remaining after brazing decreases.
Ｚｎは、材料の電位を卑にするので、ろう材層の電位を卑にして芯材を防食する効果がある。２．０質量％未満では、その効果が十分発揮されず、６．０質量％を超えると、腐食速度が速くなり過ぎて、ろう材層が早期に腐食、消耗することで耐食性が低下する。 Since Zn makes the electric potential of the material base, it has the effect of making the electric potential of the brazing material layer base to prevent corrosion of the core material. If it is less than 2.0% by mass, the effect is not sufficiently exhibited, and if it exceeds 6.0% by mass, the corrosion rate becomes too fast, and the brazing filler metal layer is corroded and consumed at an early stage, thereby lowering the corrosion resistance.
ろう付前のろう材層の厚さをＡ、ろう付相当熱処理後の残存ろう材層の厚さをＢとした時、ろう付相当熱処理前後のろう材層の厚さの比率Ｂ／Ａは耐食性に影響し、Ｂ／Ａが０．８以上で耐食性が良好である。Ｂ／Ａが０．８未満ではろう付相当熱処理後にろう材表面で防食層として作用するろう材層が減少し、ろう材層が早期に腐食、消耗することで耐食性が低下する。 When the thickness of the brazing material layer before brazing is A and the thickness of the remaining brazing material layer after the heat treatment equivalent to brazing is B, the ratio B/A of the thickness of the brazing material layer before and after the heat treatment equivalent to brazing is Affects the corrosion resistance, and B/A is 0.8 or more, and the corrosion resistance is good. When B/A is less than 0.8, the brazing material layer acting as a corrosion-preventing layer on the surface of the brazing material after heat treatment equivalent to brazing is reduced, and the brazing material layer is corroded and consumed at an early stage, resulting in deterioration of corrosion resistance.
また、シリコン粒子が所定の大きさで所定量分散していることは、耐食性を向上させる効果があり、ろう初晶内に分散するシリコン粒子の大きさを上記のように制御することで、ろう初晶内のシリコン固溶度を低下させることや、これらがＡｌ―Ｍｎ―Ｓｉ系化合物等の金属間化合物の析出サイトとなり、初晶内への分散粒子の析出を促進させることで、ろう初晶内の孔食電位を卑とすることができる。これより、ろう共晶部への局所的な腐食の進行を抑制し、腐食形態を面状に近い形態にすることで冷却水側での耐食性に優れるブレージングシートとすることができる。 Further, the fact that the silicon particles are dispersed in a predetermined amount in a predetermined size has the effect of improving the corrosion resistance, and by controlling the size of the silicon particles dispersed in the brazing primary crystal as described above, By reducing the solid solubility of silicon in the primary crystal and by forming a precipitation site for an intermetallic compound such as an Al-Mn-Si-based compound and promoting the precipitation of dispersed particles in the primary crystal, The pitting potential inside the crystal can be made base. As a result, a brazing sheet having excellent corrosion resistance on the cooling water side can be obtained by suppressing the local progress of corrosion to the braze eutectic part and making the corrosion form close to a planar form.
シリコン粒子の円相当径が３μｍ未満、あるいは個数が８×１０個／ｍｍ2未満では、ろう材層内のＳｉ固溶度低下やろう初晶内への分散粒子の析出促進が不十分で、耐食性向上の効果が十分に発揮されず、円相当径が８μｍを超え、あるいは個数が８×１０２個／ｍｍ2を超えると、ろう付性が低下するおそれがある。 If the equivalent circle diameter of the silicon particles is less than 3 μm, or if the number is less than 8×10/mm 2 , the solid solubility of Si in the brazing material layer is lowered and the precipitation of dispersed particles in the brazing primary crystal is insufficiently promoted. When the equivalent circle diameter exceeds 8 μm or the number exceeds 8×10 2 pieces/mm 2 , the brazing property may be deteriorated because the effect of improving the corrosion resistance is not sufficiently exerted.
ろう付相当熱処理後のろう材初晶と芯材間の孔食電位差は、この電位差による犠牲陽極効果が発揮されるため、ろう材側からの腐食による貫通孔の発生を防ぐことができる。孔食電位差が１００ｍＶ未満ではその効果が十分発揮されず、２００ｍＶを超えると腐食速度の増加を招く。 The pitting corrosion potential difference between the brazing material primary crystal and the core material after the brazing-corresponding heat treatment exhibits the sacrificial anode effect due to this potential difference, so that the formation of through holes due to corrosion from the brazing material side can be prevented. If the pitting potential difference is less than 100 mV, the effect is not sufficiently exhibited, and if it exceeds 200 mV, the corrosion rate increases.
なお、ろう付相当熱処理は、基準となる例を挙げれば、室温から４００℃の到達時間が６分、４００℃から５５０℃の到達時間が１分３０秒、５５０℃から目標温度までの到達時間が４分となる昇温速度で加熱し、６００℃の目標温度で３分間保持し、その後、３００℃まで１００℃／ｍｉｎで冷却した後、室温まで空冷を行なう熱処理である。
ただし、通常のろう付に要する熱処理であれば、必ずしも、この条件に厳密に一致したものでなくてもよい。
In addition, for the brazing equivalent heat treatment, for example, the arrival time from room temperature to 400° C. is 6 minutes, the arrival time from 400° C. to 550° C. is 1 minute 30 seconds, and the arrival time from 550° C. to the target temperature Is heated at a temperature rising rate of 4 minutes, held at a target temperature of 600° C. for 3 minutes, cooled to 300° C. at 100° C./min, and then air-cooled to room temperature.
However, the heat treatment required for ordinary brazing does not necessarily have to be exactly the same as this condition.
腐食はろう材組織の共晶部分から優先的に進行するため、残存ろう材層の板厚中心からろう材層と芯材の界面にかけての領域内におけるろう共晶が多いと、腐食が早期に芯材にまで到達する。したがって、その領域内におけるろう共晶の面積占有率は、小さいほど耐食性が向上するが、その面積占有率が５％未満ではろう付性が低下する。面積占有率が３０％を超えると耐食性が低下する。 Corrosion proceeds preferentially from the eutectic part of the brazing filler metal structure, so if there is a large amount of braze eutectic in the region from the thickness center of the residual brazing filler metal layer to the interface between the brazing filler metal layer and the core material, corrosion will occur earlier. Reach the core material. Therefore, the smaller the area occupancy rate of the braze eutectic in the region, the higher the corrosion resistance, but the area occupancy rate of less than 5% lowers the brazing property. If the area occupancy exceeds 30%, the corrosion resistance decreases.
本発明のアルミニウム合金クラッド材において、前記ろう材層は、質量％でＭｎ：０．０５〜１．０％、Ｃｒ：０．０５〜０．５％、Ｔｉ：０．０５〜０．３％、Ｚｒ：０．０５〜０．３％、Ｓｒ：０．００５〜０．１％から選択される１種または２種以上をさらに含有するとよい。 In the aluminum alloy clad material of the present invention, the brazing material layer has a mass% of Mn: 0.05 to 1.0%, Cr: 0.05 to 0.5%, and Ti: 0.05 to 0.3%. , Zr: 0.05 to 0.3% and Sr: 0.005 to 0.1% may be further contained.
Ｍｎ、Ｃｒ、Ｔｉ、Ｚｒは、アルミニウムと化合物を形成して、孔食を分散させることにより、耐食性を向上させる効果がある。Ｓｒは、Ｓｉ粒子の分散を均一にする効果があり、耐食性を向上させる。いずれも、その含有量が下限値未満では、効果が十分に発揮されず、上限値を超えて含有しても効果は飽和する。 Mn, Cr, Ti, and Zr form a compound with aluminum to disperse pitting corrosion, and thus have the effect of improving corrosion resistance. Sr has the effect of making the dispersion of Si particles uniform and improves the corrosion resistance. In any case, if the content is less than the lower limit, the effect is not sufficiently exhibited, and if the content exceeds the upper limit, the effect is saturated.
本発明のアルミニウム合金クラッド材において、全体板厚が０．１〜０．５ｍｍの範囲であるのが好ましい。 In the aluminum alloy clad material of the present invention, the total plate thickness is preferably in the range of 0.1 to 0.5 mm.
本発明によれば、腐食の進行を抑制し、耐食性に優れるアルミニウム合金クラッド材を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, progress of corrosion can be suppressed and the aluminum alloy clad material excellent in corrosion resistance can be provided.
以下、本発明に係るアルミニウム合金クラッド材の実施形態を説明する。
このアルミニウム合金クラッド材は、自動車熱交換器用部品として用いられるもので、芯材の両面にろう材層がクラッドされており、ろう材層は、質量％でＳｉ：２．５〜６．５％、Ｚｎ：２．０〜６．０％含有し、残部がＡｌおよび不可避不純物からなる。芯材は、例えばＡｌ−Ｍｎ系合金が用いられる。
Hereinafter, embodiments of the aluminum alloy clad material according to the present invention will be described.
This aluminum alloy clad material is used as a component for an automobile heat exchanger, and a brazing material layer is clad on both surfaces of a core material, and the brazing material layer has a mass% of Si: 2.5 to 6.5%. , Zn: 2.0 to 6.0%, with the balance being Al and unavoidable impurities. For the core material, for example, an Al-Mn-based alloy is used.
また、ろう付前のろう材層の厚さをＡ、ろう付相当熱処理後の残存ろう材層の厚さをＢとした時、Ｂ／Ａが０．８以上であり、ろう材層内に円相当径３μｍ〜８μｍのシリコン粒子が８×１０〜８×１０２個／ｍｍ2の範囲で分散し、かつ、ろう付相当熱処理後のろう材初晶と芯材間の孔食電位差が１００〜２００ｍＶである。
クラッド材全体の厚さは、０．１〜０．５ｍｍの範囲である。
When the thickness of the brazing material layer before brazing is A and the thickness of the remaining brazing material layer after the brazing-corresponding heat treatment is B, B/A is 0.8 or more, and Silicon particles having an equivalent circle diameter of 3 μm to 8 μm are dispersed in the range of 8×10 to 8×10 2 particles/mm 2 , and the pitting potential difference between the brazing material primary crystal and the core material after the brazing equivalent heat treatment is 100. ~200 mV.
The total thickness of the clad material is in the range of 0.1 to 0.5 mm.
ろう材層成分のＳｉは、ろう付性を向上させる効果があり、２．５質量％未満では、その効果が十分に発揮されず、６．５質量％を超えると、ろう付時の溶融ろうの流動性が高くなり過ぎて、ろう付後に残存するろう材層の厚さが低下する。 Si as a brazing filler metal layer component has an effect of improving brazing property. If it is less than 2.5% by mass, the effect is not sufficiently exhibited, and if it exceeds 6.5% by mass, molten brazing at the time of brazing is performed. Becomes too high and the thickness of the brazing material layer remaining after brazing decreases.
Ｚｎは、ろう材層の電位を卑にして芯材を防食する効果がある。２．０質量％未満では、その効果が十分発揮されず、６．０質量％を超えると、腐食速度が速くなり過ぎて、ろう材層が早期に腐食、消耗することで耐食性が低下する。 Zn has the effect of making the electric potential of the brazing material layer base and protecting the core material from corrosion. If it is less than 2.0% by mass, the effect is not sufficiently exhibited, and if it exceeds 6.0% by mass, the corrosion rate becomes too fast, and the brazing filler metal layer is corroded and consumed at an early stage, thereby lowering the corrosion resistance.
ろう付相当熱処理前後のろう材層の厚さの比率Ｂ／Ａは耐食性に影響し、Ｂ／Ａが０．８以上で耐食性が良好である。Ｂ／Ａが０．８未満では耐食性が低下する。 The ratio B/A of the thickness of the brazing material layer before and after the heat treatment equivalent to brazing affects the corrosion resistance, and when B/A is 0.8 or more, the corrosion resistance is good. If B/A is less than 0.8, the corrosion resistance decreases.
また、シリコン粒子が所定の径、量の範囲で分散していることは、耐食性を向上させる効果があり、シリコン粒子の円相当径が３μｍ未満、あるいは個数が８×１０個／ｍｍ2未満では、その効果が十分に発揮されず、円相当径が８μｍを超え、あるいは個数が８×１０２個／ｍｍ2を超えると、ろう付性が低下するおそれがある。 Further, the fact that the silicon particles are dispersed within a predetermined diameter and amount range has the effect of improving the corrosion resistance, and when the equivalent circle diameter of the silicon particles is less than 3 μm or the number is less than 8×10/mm 2. However, if the effect is not sufficiently exhibited and the equivalent circle diameter exceeds 8 μm or the number exceeds 8×10 2 pieces/mm 2 , the brazing property may deteriorate.
ろう付相当熱処理後のろう材初晶と芯材間の孔食電位差は、この電位差による犠牲陽極効果が発揮されるため、ろう材側からの腐食による貫通孔の発生を防ぐことができる。孔食電位差が１００ｍＶ未満ではその効果が十分発揮されず、２００ｍＶを超えると腐食速度の増加を招く。 The pitting corrosion potential difference between the brazing material primary crystal and the core material after the brazing-corresponding heat treatment exhibits the sacrificial anode effect due to this potential difference, so that the formation of through holes due to corrosion from the brazing material side can be prevented. If the pitting potential difference is less than 100 mV, the effect is not sufficiently exhibited, and if it exceeds 200 mV, the corrosion rate increases.
このアルミニウム合金クラッド材において、ろう付相当熱処理後の残存ろう材層の板厚中心から残存ろう材層と芯材の界面にかけての領域内において、ろう共晶の面積占有率が５〜３０％の範囲となるとよい。 In this aluminum alloy clad material, the area occupancy of the braze eutectic is 5 to 30% in the region from the plate thickness center of the residual brazing material layer after the brazing equivalent heat treatment to the interface between the residual brazing material layer and the core material. It should be a range.
残存ろう材層の板厚中心からろう材層と芯材の界面にかけての領域内におけるろう共晶の面積占有率は、小さいほど耐食性が向上するが、その面積占有率が５％未満ではろう付性が低下する。面積占有率が３０％を超えると耐食性が低下する。 The smaller the area occupancy rate of the braze eutectic in the region from the plate thickness center of the residual brazing material layer to the interface between the brazing material layer and the core material, the better the corrosion resistance, but if the area occupying rate is less than 5%, brazing Sex decreases. If the area occupancy exceeds 30%, the corrosion resistance decreases.
さらに、ろう材層は、質量％でＭｎ：０．０５〜１．０％、Ｃｒ：０．０５〜０．５％、Ｔｉ：０．０５〜０．３％、Ｚｒ：０．０５〜０．３％、Ｓｒ：０．００５〜０．１％から選択される１種または２種以上を含有していてもよい。 Furthermore, the brazing filler metal layer is mass% Mn:0.05-1.0%, Cr:0.05-0.5%, Ti:0.05-0.3%, Zr:0.05-0. 3%, Sr: 0.005 to 0.1%, and may contain one kind or two or more kinds.
Ｍｎ、Ｃｒ、Ｔｉ、Ｚｒは、アルミニウムと化合物を生成して、孔食を分散させることにより、耐食性を向上させる効果がある。Ｓｒは、Ｓｉ粒子の分散を均一にする効果があり、耐食性を向上させる。いずれも、その含有量が下限値未満では、効果が十分に発揮されず、上限値を超えて含有しても効果は飽和する。 Mn, Cr, Ti, and Zr have the effect of improving corrosion resistance by forming a compound with aluminum and dispersing pitting corrosion. Sr has the effect of making the dispersion of Si particles uniform and improves the corrosion resistance. In any case, if the content is less than the lower limit, the effect is not sufficiently exhibited, and if the content exceeds the upper limit, the effect is saturated.
次に、このアルミニウム合金クラッド材を製造する方法について説明する。
まず、溶解鋳造により芯材用アルミニウム合金、ろう材層用アルミニウム合金を鋳造し、得られた鋳塊について所定温度で均質化処理を行う。
芯材の均質化処理は、５３０℃〜６００℃で８時間〜１６時間の範囲から選択することができる。
Next, a method of manufacturing this aluminum alloy clad material will be described.
First, an aluminum alloy for a core material and an aluminum alloy for a brazing material layer are cast by melt casting, and the obtained ingot is homogenized at a predetermined temperature.
The homogenization treatment of the core material can be selected from the range of 8 hours to 16 hours at 530°C to 600°C.
ろう材の均質化処理は、４００〜５５０℃で１〜５時間とする。通常、ブレージングシートの作製工程において、ろう材層へ均質化処理を実施しないことが一般的であり、この工程にて作製されたブレージングシートのろう材層内には円相当径で１μｍ程度のＳｉ粒子が多数存在する。このろう材層内のＳｉ粒子サイズを制御するために、均質化処理が効果的であり、４００〜５５０℃で１〜５時間の範囲から選択することができ、４８０〜５５０℃で１〜３時間の範囲で実施するのがより好ましい。 The homogenization treatment of the brazing material is performed at 400 to 550° C. for 1 to 5 hours. Usually, in the brazing sheet manufacturing process, it is general that the brazing material layer is not subjected to homogenization treatment, and in the brazing material layer of the brazing sheet manufactured in this process, Si having a circle equivalent diameter of about 1 μm is used. There are many particles. In order to control the Si particle size in this brazing material layer, homogenization treatment is effective and can be selected from the range of 400 to 550°C for 1 to 5 hours, and 1 to 480 to 550°C for 1 to 3 hours. More preferably, it is carried out within the range of time.
均質化処理を実施した芯材用アルミニウム合金及び皮材用アルミニウム合金の鋳塊は、熱間圧延を得て合金板とされる。また、鋳造工程と圧延工程とを分けずに、連続鋳造圧延を経て合金板としてもよい。 The ingots of the aluminum alloy for the core material and the aluminum alloy for the skin material, which have been subjected to the homogenization treatment, are hot-rolled to be alloy plates. Alternatively, the alloy sheet may be formed by continuous casting and rolling without dividing the casting step and the rolling step.
そして、これら合金板を適宜のクラッド率でクラッドされる。そのクラッドは一般には圧延により行われる。その後、さらに冷間圧延を施すことにより、所望の厚さのアルミニウム合金クラッド材が得られる。そして、最終焼鈍を例えば３６０℃で３時間行うことにより、Ｏ調質のクラッド材とする。
クラッド材の構成は、例えば、ろう材層：芯材：ろう材層＝１０％：８０％：１０％とすることができるが、これに限定されるものではなく、ろう材層のクラッド率を５％や１５％としてもよい。
Then, these alloy plates are clad at an appropriate clad ratio. The clad is generally made by rolling. Then, by further cold rolling, an aluminum alloy clad material having a desired thickness can be obtained. Then, the final annealing is performed, for example, at 360° C. for 3 hours to obtain an O-tempered clad material.
The structure of the clad material can be, for example, brazing material layer:core material:brazing material layer=10%:80%:10%, but is not limited to this, and the clad ratio of the brazing material layer is It may be 5% or 15%.
熱間圧延、冷間圧延、最終焼鈍は常法によって行えばよいが、冷間圧延工程時に、中間焼鈍を介在させることも可能である。その場合、中間焼鈍としては、例えば２００〜４００℃で１〜６時間の加熱によって行なうことができる。中間焼鈍後の最終圧延では、１０〜５０％の冷間圧延率で圧延を行なう。 Hot rolling, cold rolling, and final annealing may be performed by a conventional method, but it is also possible to intervene intermediate annealing during the cold rolling process. In that case, the intermediate annealing can be performed, for example, by heating at 200 to 400° C. for 1 to 6 hours. In the final rolling after the intermediate annealing, rolling is performed at a cold rolling rate of 10 to 50%.
このようにして製造されたアルミニウム合金クラッド材は、自動車の熱交換器用部材として用いられ、その片面あるいは両面の少なくとも一部が他部品とろう付されて熱交換器に組み付けられる。この場合のろう付条件は、室温から４００℃の到達時間が４分〜９分、４００℃〜５５０℃の到達時間が１分〜２分、５５０℃〜目標温度までの到達時間が３分〜５分となるような昇温速度で加熱し、６００℃の目標温度で３分間保持し、その後、３００℃まで約１００℃/ｍｉｎで冷却した後、室温まで空冷を行なう処理である。 The aluminum alloy clad material manufactured in this manner is used as a member for a heat exchanger of an automobile, and at least a part of one surface or both surfaces of the clad material is brazed to other parts and assembled to the heat exchanger. In this case, the brazing condition is that the arrival time from room temperature to 400°C is 4 minutes to 9 minutes, the arrival time from 400°C to 550°C is 1 minute to 2 minutes, and the arrival time from 550°C to the target temperature is 3 minutes. This is a process of heating at a temperature rising rate of 5 minutes, holding at a target temperature of 600° C. for 3 minutes, then cooling to 300° C. at about 100° C./min, and then performing air cooling to room temperature.
この時、ろう付時間をｔ、Ｚｎの拡散係数をＤとした場合に√（ΣＤｔ）により与えられる入熱量は１８〜２８となる。この熱処理によりろう材は、ろう付時相当の熱を受けて溶融する。この熱処理条件を変更することでろう付熱処理後の共晶組織の存在状態を変化させることができる。 At this time, when the brazing time is t and the diffusion coefficient of Zn is D, the heat input amount given by √(ΣDt) is 18 to 28. By this heat treatment, the brazing material is melted by receiving a considerable amount of heat during brazing. By changing the heat treatment conditions, it is possible to change the existing state of the eutectic structure after the brazing heat treatment.
本発明でいうろう付相当熱処理は、このろう付工程における熱処理に相当するものであるが、必ずしも、上記の条件に厳密に一致したものでなくてもよく、通常のろう付に要する熱処理でよい。 The heat treatment equivalent to brazing in the present invention corresponds to the heat treatment in this brazing step, but it does not necessarily have to be exactly the same as the above conditions, and may be the heat treatment required for ordinary brazing. ..
そして、ろう付後には、ろう材層が薄くなるが、前述したように、ろう付後（ろう付相当熱処理後）の残存ろう材層の厚さをＢとし、ろう付前のろう材層の厚さをＡとしたときに、Ｂ／Ａが０．８以上となる。また、ろう材初晶と芯材間の孔食電位差が１００〜２００ｍＶ、残存ろう材層の板厚中心から残存ろう材層と芯材の界面にかけての領域内におけるろう共晶の面積占有率が５〜３０％の範囲となる。 Then, after brazing, the brazing material layer becomes thin, but as described above, the thickness of the remaining brazing material layer after brazing (after heat treatment equivalent to brazing) is B, and the brazing material layer before brazing is When the thickness is A, B/A is 0.8 or more. Further, the pitting potential difference between the primary crystal of the brazing material and the core material is 100 to 200 mV, and the area occupancy of the brazing eutectic in the region from the plate thickness center of the residual brazing material layer to the interface between the residual brazing material layer and the core material is It is in the range of 5 to 30%.
半連続鋳造により、表１に示す組成のろう材用アルミニウム合金を鋳造した。芯材用アルミニウム合金はＪＩＳ Ａ３００３合金を用いた。得られた芯材は５８０℃で８時間の均質化処理を行なった。また、ろう材は４８０℃で1時間の均質化処理を行なった（ただし、後述の供試材Ｎｏ．１６を除く）。 The aluminum alloy for brazing material having the composition shown in Table 1 was cast by semi-continuous casting. As the aluminum alloy for the core material, JIS A3003 alloy was used. The obtained core material was homogenized at 580° C. for 8 hours. The brazing material was homogenized at 480° C. for 1 hour (however, except for the test material No. 16 described later).
次に、芯材の一方の面にろう材を組み合わせて熱間圧延してクラッド材とし、さらに冷間圧延を行った。その後、所定の圧延率とした冷間圧延により厚さ０．２０ｍｍとした後、最終焼鈍を３６０℃で３時間行い、Ｏ調質のクラッド材（供試材）を作製した。クラッド材の構成は、芯材：ろう材層の厚さ比率で９０％：１０％とした。このクラッド材においてろう付相当熱処理前の芯材の材料板厚は１８０μｍ、ろう材層の厚さ（Ａ）は２０μｍである。また、ろう材層内のシリコン粒子の円相当径及び分布密度を測定した。 Next, a brazing material was combined with one surface of the core material, hot-rolled to form a clad material, and further cold-rolled. After that, the thickness was 0.20 mm by cold rolling with a predetermined rolling ratio, and then final annealing was performed at 360° C. for 3 hours to prepare an O-tempered clad material (test material). The clad material had a thickness ratio of core material: brazing material layer of 90%:10%. In this clad material, the material plate thickness of the core material before brazing equivalent heat treatment is 180 μm, and the thickness (A) of the brazing material layer is 20 μm. Further, the equivalent circle diameter and distribution density of the silicon particles in the brazing material layer were measured.
この供試材について、室温から４００℃の到達時間が６分、４００℃から５５０℃の到達時間が１分３０秒、５５０℃から目標温度までの到達時間が４分となるような昇温速度で加熱し、６００℃の目標温度で３分間保持し、その後、３００℃まで約１００℃／ｍｉｎで冷却した後、室温まで空冷を行なうろう付相当熱処理を施した。後述するように、一部の供試材について、このろう付相当熱処理の条件を変更した。 For this test material, the temperature rising rate is such that the arrival time from room temperature to 400°C is 6 minutes, the arrival time from 400°C to 550°C is 1 minute 30 seconds, and the arrival time from 550°C to the target temperature is 4 minutes. Then, it was held at a target temperature of 600° C. for 3 minutes, then cooled to 300° C. at about 100° C./min, and then subjected to brazing-corresponding heat treatment of air cooling to room temperature. As described later, the conditions of the heat treatment corresponding to brazing were changed for some of the test materials.
ろう付相当熱処理を施した供試材について、残存ろう材層の厚さ（Ｂ）を測定して、ろう付相当熱処理前後のろう材層の厚さの比率Ｂ／Ａを算出し、ろう材初晶と芯材間の孔食電位差、残存ろう材層の板厚中心から残存ろう材層と芯材の界面にかけての領域内におけるろう共晶の面積占有率をそれぞれ測定した。また、耐食性として内部腐食性を評価した。
また、このろう付相当熱処理とは別に、供試材をフィン材にろう付して、ろう付性を評価した。
以上の測定、評価の際の条件は以下の通りである。
The thickness (B) of the remaining brazing material layer is measured for the test material subjected to the brazing equivalent heat treatment, and the ratio B/A of the brazing material layer thickness before and after the brazing equivalent heat treatment is calculated. The pitting potential difference between the primary crystal and the core material, and the area occupancy of the braze eutectic in the region from the plate thickness center of the residual brazing material layer to the interface between the residual brazing material layer and the core material were measured. Moreover, internal corrosion was evaluated as corrosion resistance.
Separately from this heat treatment equivalent to brazing, the test material was brazed to a fin material to evaluate the brazing property.
The conditions for the above measurement and evaluation are as follows.
＜ろう材層又は残存ろう材層の厚さ＞
供試材は、圧延方向平行断面を樹脂埋めし、該断面を鏡面に研磨した後、光学顕微鏡を用いて、２００倍の倍率で写真を撮影した。撮影した像から各ろう材層の厚さを測定した。
<Thickness of brazing material layer or residual brazing material layer>
For the test material, a cross section parallel to the rolling direction was filled with resin, the cross section was polished to a mirror surface, and then a photograph was taken at a magnification of 200 times using an optical microscope. The thickness of each brazing material layer was measured from the photographed image.
＜Ｓｉ粒子の円相当径及び分布密度＞
供試材の断面を研磨、エッチング後、電子顕微鏡により撮影し、その撮影像を画像解析にて解析して円相当直径及び分布密度を求めた。
＜ろう材初晶と芯材間の孔食電位差＞
供試材のろう材初晶および芯材に対し、アノード分極測定を実施し、孔食電位を測定した。アノード分極は飽和カロメル電極を用い、窒素ガスの吹き込みにより脱気した４０℃の２．６７％ＡｌＣｌ3水溶液中で電位掃引速度０．５ｍＶ／ｓで測定した。
＜ろう共晶の面積占有率＞
供試材は、圧延方向平行断面を樹脂埋めし、該断面を鏡面に研磨した後、光学顕微鏡を用いて、任意の３０箇所にて、ろう材層を５００倍の倍率で写真を撮影した。撮影した像を画像解析にて解析して、ろう共晶の面積占有率を求めた。
<Equivalent circle diameter and distribution density of Si particles>
After polishing and etching the cross section of the test material, the cross section was photographed by an electron microscope, and the photographed image was analyzed by image analysis to determine the equivalent circle diameter and the distribution density.
<Potential corrosion potential difference between primary crystal of brazing material and core material>
Anodic polarization measurements were performed on the brazing material primary crystal and the core material of the test material to measure the pitting potential. Anode polarization was measured using a saturated calomel electrode in a 2.67% AlCl 3 aqueous solution degassed by blowing nitrogen gas at a potential sweep rate of 0.5 mV/s.
<Area occupancy rate of braze eutectic>
For the test material, a cross section parallel to the rolling direction was filled with resin, the cross section was polished to a mirror surface, and then a photograph was taken of the brazing material layer at an arbitrary 30 spots at a magnification of 500 times using an optical microscope. The captured image was analyzed by image analysis to determine the area occupancy of the braze eutectic.
＜耐食性（内部耐食性）＞
ろう付相当熱処理後の供試材から３０×５０ｍｍのサンプルを切り出し、ろう材層側について、Ｃｌ−：１９５ｐｐｍ、ＳＯ４ ２−：６０ｐｐｍ、Ｃｕ２＋：１ｐｐｍ、Ｆｅ３+：３０ｐｐｍを含む水溶液中で８０℃×８時間と室温×１６時間との間のサイクルで浸漬試験を４週間実施した。腐食試験後のサンプルを沸騰させたリン酸クロム酸混合溶液に浸漬して腐食生成物を除去した後、最大腐食部の断面観察を実施して腐食深さを測定した結果を内部耐食性とする。腐食深さが３０μｍ以下であったものを◎と評価し、３０μｍ超、５０μｍ以下のものを○と評価し、５０μｍ超、７５μｍ以下のものを△と評価し、７５μｍ超のものを×と評価した。
＜ろう付性＞
ろう付相当熱処理前の供試材から２０×３５ｍｍのサンプルを２枚切り出した後、別途用意したコルゲート加工したフィン材（ＪＩＳ Ａ３００３合金）を供試材で挟むように組み合わせ、ミニコアを作製した。このとき、フィン材に接する面は供試材のろう材側とし、フィン材との接点が５０箇所存在するようにした。
このミニコアをフッ化物フラックス水溶液に浸漬し、フッ化物フラックスを５ｇ／ｍ２で塗布した後、所定のろう付熱処理条件にてろう付を行なった。ろう付後のミニコアからフィンを剥がし、供試材とフィンの接点の中でフィレットが形成されていたものの数をＮとし、ろう付の接合率をＮ／５０として求めた。この接合率が９５％以上であったものを◎、９５％未満、９０％以上のものを○、９０％未満、８５％以上のものを△、８５％未満のものを×と評価した。
これらの結果を表２に示す。
<Corrosion resistance (internal corrosion resistance)>
A sample of 30×50 mm was cut out from the test material after heat treatment equivalent to brazing, and in the brazing material layer side, in an aqueous solution containing Cl − : 195 ppm, SO 4 2 − : 60 ppm, Cu 2+ : 1 ppm, Fe 3+ : 30 ppm. The immersion test was carried out for 4 weeks at a cycle of 80° C.×8 hours and room temperature×16 hours. The sample after the corrosion test is dipped in a boiling chromic acid phosphoric acid mixed solution to remove the corrosion product, and then the cross-section of the maximum corrosion portion is observed to measure the corrosion depth, which is taken as the internal corrosion resistance. Those with a corrosion depth of 30 μm or less are evaluated as ⊚, those of more than 30 μm and 50 μm are evaluated as ◯, those of more than 50 μm and 75 μm are evaluated as Δ, and those of more than 75 μm are evaluated as x. did.
<Brazability>
Two 20×35 mm samples were cut out from the test material before the heat treatment equivalent to brazing, and then separately prepared corrugated fin materials (JIS A3003 alloy) were sandwiched between the test materials and combined to form a minicore. At this time, the surface in contact with the fin material was on the brazing material side of the test material, and there were 50 points of contact with the fin material.
This mini-core was immersed in an aqueous solution of fluoride flux, and after applying the fluoride flux at 5 g/m 2 , brazing was performed under a predetermined brazing heat treatment condition. The fins were peeled off from the mini-core after brazing, the number of fillets formed in the contact points between the test material and the fins was N, and the joining rate of brazing was N/50. Those having a bonding rate of 95% or more were evaluated as ⊚, less than 95%, 90% or more as ◯, less than 90%, 85% or more as Δ, and less than 85% as x.
The results are shown in Table 2.
この表２からわかるように、供試材Ｎｏ．１〜９は合金成分を所定の範囲内とした供試材であり、即ち、ろう付後（ろう付相当熱処理後）の残存ろう材層の厚さをＢとし、ろう付前のろう材層の厚さをＡとしたときに、Ｂ／Ａが０．８以上となる。また、ろう材初晶と芯材間の孔食電位差が１００〜２００ｍＶ、残存ろう材層の板厚中心から残存ろう材層と芯材の界面にかけての領域内におけるろう共晶の面積占有率が５〜３０％の範囲となっている。このため、耐食性およびろう付性に優れる。Ｎｏ．１０の供試材は、ろう付熱処理の加熱時に５５０℃〜６００℃までの到達時間が５分を超えることにより、残存ろう材層の板厚中心から残存ろう材層と芯材の界面にかけての領域内におけるろう共晶の面積占有率が５〜３０％の範囲より若干大きくなる例であり、ろう付性がやや低下するものの耐食性は良好となっていた。 As can be seen from Table 2, the test material No. 1 to 9 are test materials having alloy components within a predetermined range, that is, the thickness of the remaining brazing material layer after brazing (after heat treatment equivalent to brazing) is B, and the brazing material layer before brazing When the thickness of A is A, B/A is 0.8 or more. Further, the pitting potential difference between the primary crystal of the brazing material and the core material is 100 to 200 mV, and the area occupancy of the brazing eutectic in the region from the plate thickness center of the residual brazing material layer to the interface between the residual brazing material layer and the core material is It is in the range of 5 to 30%. Therefore, it has excellent corrosion resistance and brazing property. No. The test material of No. 10 had a time required to reach 550° C. to 600° C. of more than 5 minutes at the time of heating in the brazing heat treatment, so that the thickness of the residual brazing material layer from the center of the thickness to the interface between the residual brazing material layer and the core material was increased. This is an example in which the area occupancy rate of the braze eutectic in the region is slightly larger than the range of 5 to 30%, and although the brazing property is slightly lowered, the corrosion resistance is good.
これらの供試材に対し、Ｎｏ.１１の供試材は、ろう材のＳｉ含有量が望ましい範囲より低くなり過ぎたため、ろう付性に劣る結果となった。Ｎｏ.１２の供試材は、ろう材のＳｉ含有量が望ましい範囲より高くなり過ぎたため、ろう付性に劣る結果となった。Ｎｏ.１３の供試材は、ろう材のＺｎ含有量が望ましい範囲より低くなり過ぎたため、耐食性に劣る結果となった。Ｎｏ.１４の供試材は、ろう材のＺｎ含有量が望ましい範囲より高くなり過ぎたため、耐食性に劣る結果となった。
Ｎｏ.１５の供試材は、ろう付熱処理時の６００℃での保持時間が８分を超えることで、ろう付後の残存ろう材層の厚さをＢとし、ろう付前のろう材層の厚さをＡとしたときに、Ｂ／Ａが０．８未満となり、耐食性に劣る結果となった。Ｎｏ.１６の供試材は、材料作製時にろう材へ均質化処理を実施していないことで、シリコン粒子が所定の径、量の範囲より低くなり、ろう付性に劣る結果となった。Ｎｏ.１７の供試材は、ろう付熱処理時の入熱量√（ΣＤｔ）が２８を超えることで、ろう材初晶と芯材間の孔食電位差が１００〜２００ｍＶの範囲より低くなり、耐食性に劣る結果となった。Ｎｏ.１８の供試材は、ろう材のＺｎ含有量が望ましい範囲より低く、ろう付後の残存ろう材層の厚さをＢとし、ろう付前のろう材層の厚さをＡとしたときに、Ｂ／Ａが０．８未満となり、耐食性に劣る結果となった。Ｎｏ.１９の供試材は、ろう材のＺｎ含有量が望ましい範囲より低く、シリコン粒子が所定の径、量の範囲より低くなり、耐食性に劣る結果となった。Ｎｏ.２０の供試材は、ろう材のＺｎ含有量が望ましい範囲より低く、ろう材初晶と芯材間の孔食電位差が１００〜２００ｍＶの範囲より低くなり、耐食性に劣る結果となった。Ｎｏ.２１の供試材は、ろう材のＺｎ含有量が望ましい範囲より低く、残存ろう材層の板厚中心から残存ろう材層と芯材の界面にかけての領域内におけるろう共晶の面積占有率が５〜３０％の範囲より大きくなり、耐食性に劣る結果となった。Ｎｏ.２２の供試材は、ろう付後の残存ろう材層の厚さをＢとし、ろう付前のろう材層の厚さをＡとしたときに、Ｂ／Ａが０．８未満かつシリコン粒子が所定の径、量の範囲未満かつろう材初晶と芯材間の孔食電位差が１００〜２００ｍＶ未満となり、ろう付性および耐食性に劣る結果となった。
In contrast to these test materials, the test material of No. 11 was inferior in brazing property because the Si content of the brazing material was too lower than the desirable range. The test material of No. 12 was inferior in brazing property because the Si content of the brazing material was higher than the desirable range. The test material of No. 13 was inferior in corrosion resistance because the Zn content of the brazing material was too lower than the desirable range. The test material of No. 14 was inferior in corrosion resistance because the Zn content of the brazing material was higher than the desirable range.
The sample No. 15 had a holding time of 600°C during brazing heat treatment of more than 8 minutes, so that the thickness of the remaining brazing material layer after brazing was B, and the brazing material layer before brazing was When the thickness of A was B, B/A was less than 0.8, resulting in poor corrosion resistance. The test material of No. 16 had the result that the brazing property was inferior because the silicon particles became lower than the predetermined diameter and amount range because the brazing material was not subjected to the homogenization treatment at the time of material preparation. The heat input amount √ (ΣDt) during brazing heat treatment of No. 17 test material exceeds 28, the pitting potential difference between the primary crystal of the brazing material and the core material becomes lower than the range of 100 to 200 mV, and the corrosion resistance The result was inferior to. In the test material of No. 18, the Zn content of the brazing material was lower than the desired range, the thickness of the residual brazing material layer after brazing was B, and the thickness of the brazing material layer before brazing was A. At times, B/A was less than 0.8, resulting in poor corrosion resistance. The test material of No. 19 had a Zn content of the brazing material lower than the desired range and silicon particles lower than the predetermined diameter and quantity range, resulting in poor corrosion resistance. The No. 20 test material had a Zn content of the brazing material lower than the desired range, and the pitting potential difference between the brazing material primary crystal and the core material was lower than the range of 100 to 200 mV, resulting in poor corrosion resistance. .. The sample No. 21 had a Zn content of the brazing material lower than the desired range, and occupied area of the brazing eutectic in the region from the thickness center of the residual brazing material layer to the interface between the residual brazing material layer and the core material. The rate was larger than the range of 5 to 30%, resulting in poor corrosion resistance. When the thickness of the remaining brazing material layer after brazing is B and the thickness of the brazing material layer before brazing is A, the test material of No. 22 has a B/A of less than 0.8 and The silicon particles were less than the predetermined diameter and amount range, and the pitting potential difference between the primary crystal of the brazing material and the core material was less than 100 to 200 mV, resulting in poor brazing and corrosion resistance.
なお、本発明は上記実施形態に限定されるものではなく、本発明の趣旨を逸脱しない範囲において種々の変更を加えることが可能である。 The present invention is not limited to the above-mentioned embodiment, and various modifications can be made without departing from the spirit of the present invention.
Claims (3)
上記アルミニウム合金クラッド材を、同室温から４００℃の到達時間が６分、４００℃から５５０℃の到達時間が１分３０秒、５５０℃から目標温度までの到達時間が４分となるような昇温速度で加熱し、６００℃の目標温度で３分間保持し、その後、３００℃まで約１００℃／ｍｉｎで冷却した後、室温まで空冷を行なうろう付相当熱処理を施してろう付けすると、
前記ろう付け前のろう材層の厚さをＡ、前記ろう付後の残存ろう材層の厚さをＢとした時、Ｂ／Ａが０．８以上となり、前記ろう付後のろう材層内に円相当径３μｍ〜８μｍのシリコン粒子が８×１０〜８×１０２個／ｍｍ２の範囲で分散し、かつ、前記ろう付後のろう材初晶と前記芯材間の孔食電位差が１００〜２００ｍＶであり、
前記ろう付後の前記残存ろう材層の板厚中心から該残存ろう材層と芯材の界面にかけての領域内におけるろう共晶の面積占有率が５〜３０％の範囲になること、を特徴とするアルミニウム合金クラッド材。 A brazing material layer is clad on one or both surfaces of the core material, and the brazing material layer contains Si: 2.5 to 6.5% and Zn: 2.0 to 6.0% in mass%. An aluminum alloy clad material, the balance of which is Al and unavoidable impurities, and a large number of Si particles having an equivalent circle diameter of about 1 μm are present in the brazing material layer.
The aluminum alloy clad material is heated such that the arrival time from the same room temperature to 400°C is 6 minutes, the arrival time from 400°C to 550°C is 1 minute 30 seconds, and the arrival time from 550°C to the target temperature is 4 minutes. When heated at a temperature rate, held at a target temperature of 600° C. for 3 minutes, then cooled to 300° C. at about 100° C./min, and then brazed by performing a brazing-corresponding heat treatment for air cooling to room temperature,
When the thickness of the brazing material layer before brazing is A and the thickness of the remaining brazing material layer after brazing is B, B/A is 0.8 or more, and the brazing material layer after brazing is Silicon particles having an equivalent circle diameter of 3 μm to 8 μm are dispersed within the range of 8×10 to 8×10 2 pieces/mm 2 , and the pitting potential difference between the brazing material primary crystal after brazing and the core material. Is 100 to 200 mV,
The area occupancy rate of the braze eutectic in the region from the plate thickness center of the remaining brazing material layer after brazing to the interface between the remaining brazing material layer and the core material is in the range of 5 to 30%. And aluminum alloy clad material.
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