JP5614883B2 - Fluxless brazing method of aluminum material, aluminum alloy brazing sheet for fluxless brazing, and aluminum alloy brazing material for fluxless brazing - Google Patents
Fluxless brazing method of aluminum material, aluminum alloy brazing sheet for fluxless brazing, and aluminum alloy brazing material for fluxless brazing Download PDFInfo
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Description
本発明は、非酸化性雰囲気でフラックスを使用せずに、ろう付可能なアルミニウム材のフラックスレスろう付方法、フラックスレスろう付用アルミニウム合金ブレージングシートおよびフラックスレスろう付用アルミニウム合金ろう材に関する。 The present invention relates to a fluxless brazing method for an aluminum material that can be brazed without using a flux in a non-oxidizing atmosphere, an aluminum alloy brazing sheet for fluxless brazing, and an aluminum alloy brazing material for fluxless brazing.
ラジエータやコンデンサをはじめ、インタークーラー等を代表とする自動車用熱交換器や、その他アルミニウム合金にて製造される熱交換器や放熱器等は、現在、非腐食性のフッ化物系フラックスを用いてろう付けされるか、ろう材に０．５〜１．５質量％程度のＭｇを添加して真空下でろう付けされる工法が主流となっている。
上記フラックスを用いる場合、多くがろう付け対象部材をプレス成形等で加工後、所望の組み付け状態とし、フラックス粉末を溶媒に溶いた混濁液を組み付け体に塗着・乾燥させ、高純度窒素ガス雰囲気等の非酸化性雰囲気中で加熱ろう付けしている。この場合、フラックスを使用すること自体、或いは、その塗布工程の設置や管理にコストを要するという問題がある。また、フラックスは、その一部がろう付け加熱過程で蒸発し、炉内壁に付着、堆積することが知られており、堆積物の除去を目的とした定期的な炉のメンテナンスも必要コストとして生じる。そして昨今、自動車の軽量化促進に伴い、自動車用熱交換器でも材料の薄肉高強度化が求められ、アルミニウム材料の高強度化には、アルミニウム合金へのＭｇ添加が有効であることは一般的に知られているが、フラックスを用いたろう付けではＭｇとフラックスが反応して高融点のＭｇＦ２を生成することから、これがろう付け阻害要因となったり、材料中のＭｇを消費してしまうため、折角添加したＭｇが高強度化にあまり役立たないという問題がある。すなわち、フラックスろう付けでは製品中のＭｇ添加部位や量に制限があり、積極的に材料高強度化手法として用いることができていないのが現状である。
Heat exchangers for automobiles, such as radiators and condensers, intercoolers, etc., and other heat exchangers and radiators manufactured from aluminum alloys, now use non-corrosive fluoride fluxes. The mainstream is a method of brazing or brazing under vacuum by adding about 0.5 to 1.5% by mass of Mg to the brazing material.
In the case of using the above-mentioned flux, most of the members to be brazed are processed by press molding or the like, and then put into a desired assembled state, and a turbid liquid in which flux powder is dissolved in a solvent is applied to the assembled body and dried, and a high-purity nitrogen gas atmosphere Heat brazing in a non-oxidizing atmosphere such as In this case, there is a problem that the use of the flux itself, or the cost of installation and management of the coating process is required. In addition, it is known that a part of the flux evaporates during the brazing heating process and adheres to and accumulates on the inner wall of the furnace, and periodic furnace maintenance for removing the deposits also occurs as a necessary cost. . In recent years, with the promotion of weight reduction of automobiles, the heat exchangers for automobiles are also required to increase the thickness and strength of materials, and it is common to add Mg to aluminum alloys to increase the strength of aluminum materials. However, when brazing using a flux, Mg and the flux react to produce high melting point MgF 2 , which may cause brazing inhibition or consume Mg in the material. However, there is a problem that the added Mg is not very useful for increasing the strength. That is, in flux brazing, there are limitations on the sites and amounts of Mg added in the product, and the current situation is that they cannot be actively used as a method for increasing the strength of materials.
一方、真空ろう付けでは、ろう材に添加されたＭｇがろう付け昇温過程で材料中から蒸発し、その際に、ろう付け阻害要因であるアルミニウム材料表面の酸化皮膜を破壊、雰囲気中では水分や酸素と結合するゲッター作用により、炉内雰囲気をろう付け可能な状態としている。本手法では、フラックス工程管理は必要ないものの、真空炉が高価な設備であること、炉の気密性管理等に相応のコストが生じる問題がある。また、自動車用熱交換器等では、製品の耐食性確保を目的にＺｎが添加されるが、真空加熱下ではＺｎが蒸発してしまい、製品材料中に十分なＺｎを残すことができないというデメリットもある。更に、炉内壁には蒸発したＭｇやＺｎが堆積することから、定期的な炉内清掃も必要となる。 On the other hand, in vacuum brazing, Mg added to the brazing material evaporates from the material during the brazing temperature rising process, and at that time, the oxide film on the surface of the aluminum material, which is a brazing inhibiting factor, is destroyed, and moisture is contained in the atmosphere. The atmosphere inside the furnace can be brazed by the getter action combined with oxygen and oxygen. Although this method does not require the flux process control, there are problems that the vacuum furnace is an expensive facility and that the corresponding cost is required for the airtightness management of the furnace. In addition, in heat exchangers for automobiles, Zn is added for the purpose of ensuring the corrosion resistance of the product. However, there is a demerit that Zn is evaporated under vacuum heating, and sufficient Zn cannot be left in the product material. is there. Furthermore, since evaporated Mg and Zn accumulate on the inner wall of the furnace, periodic cleaning of the furnace is also required.
これらに対し、最近では上記問題を解消しようとする大気圧下のフラックスレスろう付けが提案されている。例えば特許文献１では、被ろう付け部材、もしくはそれ以外の部位にＭｇ含有物を配置し、且つ、被ろう付け物に覆いをすることによって非酸化性雰囲気大気圧下のフラックスレスろう付けを提案している。しかし、この技術では覆いをすることが必須となっており、覆いを製品サイズ別に用意したり、量産で想定される使用個数を準備する必要があったり、更に、覆いのメンテナンス等が必要となり、量産適用においては手間やコストがかかるという問題がある。また、覆いをすることにより被ろう付け物の昇温速度が低下してしまい、生産性を低下させてしまうという問題もある。 On the other hand, fluxless brazing under atmospheric pressure has recently been proposed to solve the above problems. For example, Patent Document 1 proposes flux-less brazing under a non-oxidizing atmosphere and atmospheric pressure by placing an Mg-containing material on a brazed member or other part and covering the brazed material. doing. However, in this technology, it is essential to cover, and it is necessary to prepare covers for each product size, it is necessary to prepare the number of pieces used in mass production, and further maintenance of the cover is required. There is a problem that it takes time and cost in mass production. Moreover, there is also a problem that the temperature rise rate of the brazed object is lowered by covering, and the productivity is lowered.
上記問題に対し、特許文献２では、予めろう付け炉内で加熱された風除け冶具（覆い）によって炉内で被ろう付け部材を覆うような仕組みを提案し、昇温速度の低下を改善している。しかし、本方法においては、炉内に風除け冶具の動作を制御する機構を設ける必要があり、設備の導入や維持にコストと手間が掛かるという問題がある。
To solve the above problem,
一方、覆いを必要としないフラックスレスろう付けとしては、特許文献３では、クラッド材のろう材にＭｇを添加し、そのクラッド材で成形された熱交換器チューブの内側を不活性雰囲気中大気圧下でフラックスレスろう付けする方法が提案されている。
On the other hand, as a fluxless brazing that does not require a cover, in
また、同じく覆いを必要としないものとして、特許文献４では、ろう材表面に酸化防止層をクラッドし、そのクラッド材を積層構造としたもので大気雰囲気中のろう付けを可能にするという提案もある。 Similarly, as a method that does not require a cover, Patent Document 4 proposes a method in which a brazing material surface is clad with an antioxidant layer and the clad material is laminated to enable brazing in an air atmosphere. is there.
そして特許文献５では、芯材の表面にＡｌ−Ｓｉ−Ｍｇ系合金からなるろう材をクラッドし、且つ、ろう付け前に材料表面を酸洗浄し酸化皮膜の厚みを２０Å以下とすれば、非酸化性雰囲気中でのフラックスレスろう付けが可能になるという提案がある。
In
しかし、覆いを必要とせずに、大気圧下でのろう付けを可能にする特許文献３〜５においても以下の課題がある。
特許文献３で提案されている方法では、チューブ外面とフィンの接合はフラックスを使用しており、フラックスを使用することによるデメリットは完全に解消されていないという問題がある。
また、特許文献４で提案されている技術では、従来の真空ろう付けやノコロックろう付けに用いる材料に対し、ろう材表面に酸化防止層を設けたクラッド材を準備する必要があり、材料コストが高くなるという問題があり、更に、コアとしては積層構造に限定されるという汎用性の問題がある。
さらに、特許文献５に示される方法では、酸洗浄の工程管理が煩雑となる問題や、酸洗浄工程分のコストが増加するという問題がある。
However,
In the method proposed in
Further, in the technique proposed in Patent Document 4, it is necessary to prepare a clad material in which an anti-oxidation layer is provided on the surface of the brazing material with respect to the material used for the conventional vacuum brazing or nocolok brazing, and the material cost is low. There is a problem that it becomes high, and there is a problem of versatility that the core is limited to a laminated structure.
Furthermore, the method disclosed in
なお、フラックスレスろう付はろう材中に添加したＭｇにより、Ａｌ酸化皮膜（Ａｌ２Ｏ３）の還元分解作用によって接合を可能としている。そのため安定した接合状態を得るためにはろう材や被ろう付け部材へのＭｇ添加が必須であるが、雰囲気中の酸素とＭｇが反応し、Ｍｇの酸化皮膜（ＭｇＯ）が生成すると、著しく接合状態が悪化するため、安定した接合が得られにくいことが課題である。従来は部材成分やろう付条件、さらには接合部の形状、部材の酸化皮膜厚さや皮膜欠陥部の分布密度などを最適化により、接合を可能としているが、接合部の形状や雰囲気によってはまだ十分な接合状態が得られにくく、改善が必要である。
したがって、特に酸素濃度がやや高い雰囲気などでろう付される場合においても、良好なろう付状態を得ることが可能な方法が強く望まれている。
In addition, fluxless brazing enables joining by the reductive decomposition action of the Al oxide film (Al 2 O 3 ) by Mg added to the brazing material. Therefore, in order to obtain a stable joining state, it is essential to add Mg to the brazing material and the brazed member. However, when oxygen in the atmosphere reacts with Mg to form an Mg oxide film (MgO), the joining is remarkably performed. Since the state deteriorates, it is difficult to obtain a stable joint. Conventionally, it is possible to join by optimizing the component components and brazing conditions, as well as the shape of the joint, the oxide film thickness of the member and the distribution density of the film defects, but depending on the shape and atmosphere of the joint It is difficult to obtain a sufficient bonding state, and improvement is necessary.
Therefore, there is a strong demand for a method capable of obtaining a good brazing state even when brazing is performed in an atmosphere having a slightly high oxygen concentration.
このような問題に鑑み、本発明ではフラックス塗布工程や真空設備等の導入運用コストや、ろう付け時に使用する覆い等の副資材コスト、材料酸洗浄等の新たな工程コストを発生させず、且つ、熱交換器等の形状によらない汎用的な大気圧下フラックスレスろう付けが可能なアルミニウム材のフラックスレスろう付方法等を見出すことを目的に開発を進めたものである。 In view of such problems, the present invention does not generate new operation costs such as introduction and operation costs such as flux application process and vacuum equipment, sub-material costs such as a cover used at the time of brazing, and material acid cleaning, and The development has been progressed with the aim of finding a fluxless brazing method of an aluminum material capable of general-purpose fluxless brazing under atmospheric pressure regardless of the shape of a heat exchanger or the like.
そして、本発明者らはＡｌ−Ｓｉ−Ｍｇ系ろう材にＣａを添加することで、従来より酸素濃度が高い雰囲気でも著しくろう付性が向上することを見出し、本発明を完成するに至ったものである。 And the present inventors have found that brazing is significantly improved even in an atmosphere having a higher oxygen concentration than before by adding Ca to the Al—Si—Mg-based brazing material, and the present invention has been completed. Is.
すなわち、本発明のアルミニウム材のフラックスレスろう付方法のうち、第１の本発明は、質量％で、Ｍｇを０．１〜５．０％、Ｓｉを３〜１３％、Ｃａ：０．００１〜１．０％を含有するＡｌ−Ｓｉ系ろう材が最表面に位置するアルミニウムクラッド材を用いるろう付け方法であって、前記Ａｌ−Ｓｉ系ろう材に含まれるＳｉ粒子は、ろう材表層面方向の観察において、円相当径で０．８μｍ以上の径をもつものの数の内、円相当径で１．７５μｍ以上の径のものの数が２５％以上であり、減圧を伴わない非酸化性雰囲気で、前記Ａｌ−Ｓｉ系ろう材と被ろう付け部材とを接触密着させ、加熱温度５５９〜６２０℃において、前記Ａｌ−Ｓｉ系ろう材によりフラックスレスで接触密着部の密着面において前記芯材と前記被ろう付け部材とを接合することを特徴とする。 That is, among the fluxless brazing methods for aluminum materials of the present invention, the first invention is mass%, Mg is 0.1 to 5.0%, Si is 3 to 13%, Ca: 0.001. A brazing method using an aluminum clad material in which an Al-Si brazing material containing -1.0% is located on the outermost surface, wherein the Si particles contained in the Al-Si brazing material are In the observation of the direction, among the number of equivalent circle diameters of 0.8 μm or more, the number of equivalent circle diameters of 1.75 μm or more is 25% or more, and non-oxidizing atmosphere without decompression Then, the Al-Si brazing material and the member to be brazed are brought into contact and intimate contact, and at a heating temperature of 559 to 620 ° C., the Al-Si brazing material is flux-free by the Al-Si brazing material on the adhesion surface of the contact adhesion portion. Connect the brazed member It is characterized by combining.
第２の本発明のアルミニウム材のフラックスレスろう付方法は、前記第１の本発明において、前記Ａｌ−Ｓｉ系ろう材は、さらに質量％で、Ｂｅを０．０００１〜０．１％含有することを特徴とする。 The fluxless brazing method for aluminum material of the second aspect of the present invention is the method according to the first aspect of the present invention, wherein the Al—Si based brazing material further contains% by mass and 0.0001 to 0.1% of Be. It is characterized by that.
第３の本発明のアルミニウム材のフラックスレスろう付方法は、前記第１または第２の本発明において、前記Ａｌ−Ｓｉ系ろう材は、さらに質量％でＢｉを０．０１〜１．０％含有することを特徴とする。 The fluxless brazing method for an aluminum material according to a third aspect of the present invention is the method according to the first or second aspect , wherein the Al-Si brazing material further contains Bi in an amount of 0.01 to 1.0% by mass. It is characterized by containing.
第４の本発明のアルミニウム材のフラックスレスろう付方法は、前記第１〜第３の本発明のいずれかにおいて、前記Ａｌ−Ｓｉ系ろう材は、さらに質量％でＺｎを０．１〜５．０％含有することを特徴とする。 Fourth fluxless brazing method of the aluminum material of the present invention, the first to third any crab Oite of the present invention, the Al-Si based brazing material, a Zn further mass% 0.1 It is characterized by containing ˜5.0%.
第５の本発明のフラックスレスろう付用アルミニウム合金ブレージングシートは、前記第１〜第４の本発明のいずれかに記載のＡｌ−Ｓｉ系ろう材が芯材にクラッドされて最表面に位置しており、減圧を伴わない非酸化性雰囲気で、前記Ａｌ−Ｓｉ系ろう材を被ろう付け部材に接触密着させて前記Ａｌ−Ｓｉ系ろう材により接触密着面において前記被ろう付け部材と接合するようにフラックスレスのろう付けに供されることを特徴とする。 Fifth fluxless brazing an aluminum alloy brazing sheet with the present invention is located in the first to fourth cladding has been uppermost surface core material Al-Si based brazing material according to any one of the present invention In a non-oxidizing atmosphere without pressure reduction, the Al—Si brazing material is brought into contact and contact with the brazed member, and the Al—Si brazing material is joined to the brazed member at the contact adhesion surface. As described above, it is characterized by being subjected to fluxless brazing.
第６の本発明のフラックスレスろう付用アルミニウム合金ろう材は、質量％で、Ｍｇを０．１〜５．０％、Ｓｉを３〜１３％、Ｃａ：０．００１〜１．０％を含有し、残部がＡｌおよび不可避不純物からなる組成を有し、ろう材表層面方向の観察において、円相当径で０．８μｍ以上の径をもつものの数の内、円相当径で１．７５μｍ以上の径のものの数が２５％以上であるＳｉ粒子を有し、減圧を伴わない非酸化性雰囲気でフラックスレスろう付けに供されるものであることを特徴とする。 The aluminum alloy brazing material for fluxless brazing according to the sixth aspect of the present invention is, by mass, 0.1 to 5.0% Mg, 3 to 13% Si, and 0.001 to 1.0% Ca. contains has the composition balance ing of Al and inevitable impurities, in the brazing material surface layer direction of observation, among the number of those with diameters of more than 0.8μm in equivalent circle diameter, 1.75 [mu] m in circle equivalent diameter It has Si particles whose number of the above diameters is 25% or more, and is subjected to fluxless brazing in a non-oxidizing atmosphere without decompression.
第７の本発明のフラックスレスろう付用アルミニウム合金ろう材は、前記第６の本発明において、さらに質量％で、Ｂｅを０．０００１〜０．１％を含有することを特徴とする。 The aluminum alloy brazing material for fluxless brazing according to the seventh aspect of the present invention is characterized in that, in the sixth aspect of the present invention, Be is further contained in an amount of 0.0001 to 0.1% by mass.
第８の本発明のフラックスレスろう付用アルミニウム合金ろう材は、前記第６または第７の本発明において、さらに質量％でＢｉを０．０１〜１．０％含有することを特徴とする。 The aluminum alloy brazing material for fluxless brazing according to the eighth aspect of the present invention is characterized in that, in the sixth or seventh aspect of the present invention, Bi is further contained in an amount of 0.01 to 1.0% by mass.
第９の本発明のフラックスレスろう付用アルミニウム合金ろう材は、前記第６〜第８の本発明のいずれかにおいて、さらに質量％でＺｎを０．１〜５．０％含有することを特徴とする。 Ninth fluxless brazing aluminum alloy brazing material of the present invention, the first in any of 6 to 8 of the present invention, characterized in that it contains 0.1 to 5.0% of Zn more in mass% And
以下に、本発明で規定する成分等の限定理由について以下に説明する。なお、各成分量はいずれも質量％で示される。 Below, the reason for limitation of the component etc. which are prescribed | regulated by this invention is demonstrated below. In addition, each component amount is shown by mass%.
１．ろう材
本発明では、ろう材としてＡｌ−Ｓｉ系合金をベースに、Ｍｇ、Ｃａを添加したものを用いる。
1. Brazing material In the present invention, a brazing material based on an Al-Si alloy and added with Mg and Ca is used.
Ｓｉ：３〜１３％
ＳｉはＡｌに含有することにより、その融点を低下させ、ろう付温度にて溶融して所定の継手を形成する基本的な元素である。ろうとして機能する適正な含有量の範囲として、３〜１３％とする。３％未満では生成する液相量が不足するため十分な流動性が得られず、１３％を超えると初晶Ｓｉが急激に増加して加工性が悪化するとともに、ろう付時に接合部のろう侵食が著しく促進される。Ｓｉ含有量の一層好ましい下限は６％、上限は１２％である。
また、ろう材表面に存在するＳｉ粒子上ではアルミニウムの緻密な酸化皮膜の成長が抑制され、酸化皮膜の欠陥部が生成する。すなわち、アルミニウム材料表面の酸化皮膜がろう付熱処理中に厚膜となっても、金属間化合物の周辺からろう材の染み出しが発生し、この部位を起点に酸化皮膜の破壊や分断が進み、溶融ろうの濡れ性が向上するため、より安定した接合状態を得ることが可能となる。
Si: 3 to 13%
Si, when contained in Al, is a basic element that lowers its melting point and melts at a brazing temperature to form a predetermined joint. The appropriate content range that functions as a wax is 3 to 13%. If it is less than 3%, sufficient fluidity cannot be obtained because the amount of liquid phase produced is insufficient, and if it exceeds 13%, the primary crystal Si rapidly increases and the workability deteriorates and the brazing of the joint during brazing Erosion is significantly accelerated. The more preferable lower limit of the Si content is 6%, and the upper limit is 12%.
In addition, on the Si particles existing on the surface of the brazing material, the growth of a dense oxide film of aluminum is suppressed, and a defective portion of the oxide film is generated. That is, even if the oxide film on the surface of the aluminum material becomes a thick film during the brazing heat treatment, the brazing material oozes out from the periphery of the intermetallic compound, and the destruction and fragmentation of the oxide film proceeds from this site, Since the wettability of the molten solder is improved, a more stable joined state can be obtained.
Ｍｇ：０．１〜５．０％
Ｍｇは材料表面のアルミニウムの緻密な酸化皮膜（Ａ１２０３）をろう付加熱時に還元、分解して、接合性とろうの濡れ性を向上する効果を有する。本発明において十分な接合を得るためのＭｇ含有量は０．１〜５．０％である。０．１％未満では本発明の効果であるろう付時接合面の酸化皮膜破壊効果が得られず、５．０％を越えるとその効果が飽和し、かつ、アルミニウム材料の加工性に難を生じる。
本発明では、上記Ｍｇ成分範囲における酸化皮膜破壊活動のみでもろう付性を確保できるが、さらに、Ｍｇ含有量を最適化してＡｌ−Ｓｉ−Ｍｇ系ろう材の固相線温度の低下効果を利用すれば、優れたろう付性を発揮できる。この場合のＭｇの最適含有量は、Ｓｉ含有量により変動するが、例えばＳｉ含有量が６〜１２％の場合は、Ｍｇ含有量は０．７５〜１．５％が好ましい。この範囲であれば、ろうの融点低下が十分に得られ、Ｍｇによる酸化皮膜破壊効果との相乗効果により、より良好なろう付性を得ることが可能となる。具体的には、Ａｌ−Ｓｉ−Ｍｇ合金で最も低い固相線温度の５５９℃以上でろう付が可能となる。
Mg: 0.1-5.0%
Mg reduces and decomposes a dense oxide film (A1 2 0 3 ) of aluminum on the surface of the material when brazing is applied, and has the effect of improving the bondability and the wettability of the wax. In the present invention, the Mg content for obtaining sufficient bonding is 0.1 to 5.0%. If the content is less than 0.1%, the effect of the present invention is not obtained by the effect of destroying the oxide film on the joint surface during brazing. If the content exceeds 5.0%, the effect is saturated and the workability of the aluminum material is difficult. Arise.
In the present invention, brazing properties can be ensured only by the oxide film breaking activity in the above Mg component range, but further, the Mg content is optimized and the effect of lowering the solidus temperature of the Al—Si—Mg brazing material is utilized. If this is the case, excellent brazing properties can be exhibited. The optimum Mg content in this case varies depending on the Si content. For example, when the Si content is 6 to 12%, the Mg content is preferably 0.75 to 1.5%. If it is this range, the melting | fusing point fall of solder | brazing | wax will fully be obtained and it will become possible to obtain a more favorable brazing property by the synergistic effect with the oxide film destruction effect by Mg. Specifically, brazing can be performed at the lowest solidus temperature of 559 ° C. or higher with an Al—Si—Mg alloy.
Ｃａ：０．００１〜１．０％
Ｃａは、ろう材表面に生成したＡｌおよびＭｇの酸化皮膜を還元分解し、良好なろう付接合を可能とする。Ｃａ含有量が下限未満であると効果が不十分であり、上限を超えるとろう材表面の酸化が促進され、接合率が低下するので、上記範囲に定める。なお、同様の理由で下限を０．００５％、上限を０．７５％とするのが望ましい。
Ca: 0.001 to 1.0%
Ca reductively decomposes the Al and Mg oxide films formed on the surface of the brazing material to enable good brazing joining. If the Ca content is less than the lower limit, the effect is insufficient, and if the Ca content exceeds the upper limit, oxidation of the brazing filler metal surface is promoted and the bonding rate is lowered. For the same reason, it is desirable that the lower limit is 0.005% and the upper limit is 0.75%.
本発明のろう材は、上記Ｓｉ、Ｍｇ、Ｃａを含有し、その他をＡｌと不可避不純物とするものでもよく、また、上記Ｓｉ、Ｍｇ、Ｃａの作用を損なわないように、その他の成分を含有するものであってもよい。以下に、所望によって含有するその他の成分を説明する。 The brazing material of the present invention may contain the above Si, Mg, Ca, and the other may be Al and inevitable impurities, and contains other components so as not to impair the action of the above Si, Mg, Ca. You may do. Below, the other component contained depending on necessity is demonstrated.
Ｂｅ：０．０００１〜０．１％
Ｂｅは、ろう付に際し溶融ろうの表面に形成する酸化皮膜の成長を抑制し、雰囲気の酸素濃度が高い状態でも良好な接合状態が得られるので所望により含有させる。このため、０．０００１％以上の含有が必要であり、下限未満では上記作用が十分に得られない。一方、上限を超えると、効果が飽和し、さらに、材料コストが増大するためＢｅの含有量を上記範囲に定める。なお、同様の理由で下限を０．０００２％、上限を０．０１％とするのが望ましい。
Be: 0.0001 to 0.1%
Be suppresses the growth of an oxide film formed on the surface of the molten brazing during brazing, and a good bonding state can be obtained even when the oxygen concentration in the atmosphere is high. For this reason, the content of 0.0001% or more is necessary, and if the content is less than the lower limit, the above-described effect cannot be obtained sufficiently. On the other hand, if the upper limit is exceeded, the effect is saturated and the material cost increases, so the content of Be is set in the above range. For the same reason, it is desirable that the lower limit is 0.0002% and the upper limit is 0.01%.
Ｂｉ：０．０１〜１．０％
Ｂｉは、材料表面の再酸化を抑制し、ろう材の濡れ拡がり性を向上させる。下限未満では効果が不十分であり、上限を超えても一層の効果は得られない。このため、Ｂｉの含有量は、上記範囲が望ましい。
Bi: 0.01 to 1.0%
Bi suppresses re-oxidation of the material surface and improves the wetting and spreading property of the brazing material. If it is less than the lower limit, the effect is insufficient, and even if the upper limit is exceeded, no further effect can be obtained. For this reason, the above range is desirable for the Bi content.
Ｚｎ：０．１〜５．０％
Ｚｎはろう材の電位を低下させ、犠牲陽極効果によりブレージングシートの耐食性を向上させる効果を有するので所望によりろう材に含有させる。Ｚｎの含有量は０．１〜５．０％が望ましい。０．１％未満では電位がほとんど変化しないため十分な耐食性向上効果が得られず、５．０％を超えると腐食速度が著しく増大する。なお、Ｚｎ含有量の一層好ましい下限は０．５％、上限は３．０％である。また、Ｚｎを積極的に添加しない場合でも、該Ｚｎを不可避不純物として０．１％未満で含むものであってもよい。
Zn: 0.1 to 5.0%
Zn lowers the potential of the brazing material and has the effect of improving the corrosion resistance of the brazing sheet by the sacrificial anode effect, so it is optionally contained in the brazing material. The Zn content is preferably 0.1 to 5.0%. If it is less than 0.1%, the potential hardly changes, so that a sufficient corrosion resistance improving effect cannot be obtained. If it exceeds 5.0%, the corrosion rate increases remarkably. In addition, the more preferable minimum of Zn content is 0.5%, and an upper limit is 3.0%. Even when Zn is not actively added, the Zn may be contained as an inevitable impurity in an amount of less than 0.1%.
Ｓｉ粒子の分布：円相当径で０．８μｍ以上の内、１．７５μｍ以上のものが個数比で２５％以上
通常、アルミニウム材料表面には緻密なＡｌ２Ｏ３等の酸化皮膜が存在し、ろう付け熱処理過程ではこれがさらに成長し厚膜となる。酸化皮膜の厚みが増すほど、酸化皮膜の破壊作用を阻害する傾向が強くなるのが一般的な見解である。ろう材表面に粗大なＳｉ粒子が存在することで、粗大Ｓｉ粒子表面にはアルミニウムの緻密な酸化皮膜が成長せず、この部位がアルミニウム材料表面の酸化皮膜欠陥として働く。すなわち、アルミニウム材料表面の酸化皮膜がろう付け熱処理中に厚膜となっても、Ｓｉ粒子部分からろう材の染み出し等が発生し、この部位を起点に酸化皮膜破壊作用や分断作用が進み、溶融ろうの濡れ性を向上させ、より安定した接合状態を得ることを可能にする。
ここで言うＳｉ粒子とは、組成上Ｓｉ単体成分によるＳｉ粒子、及び、例えば、Ｆｅ-Ｓｉ系化合物や、Ｆｅ-Ｓｉを主成分とするＡｌ-Ｆｅ-Ｓｉ系の金属間化合物等をも含むものとする。本発明の説明においては、これらを便宜的にＳｉ粒子と表記する。
具体的には、ろう材表面のＳｉ粒子を円相当径でみなし、０．８μｍ以上のＳｉ粒子数をカウントした場合に１．７５μｍ以上のものが２５％以上存在すると、この効果が十分に得られる。
ろう材表面のＳｉ粒子はそのサイズが小さ過ぎると、酸化皮膜の欠陥部として作用する効果が不十分となる。したがって、１．７５μｍ以上のＳｉ粒子の数が、０．８μｍ以上のＳｉ粒子の数の２５％以上であるのを望ましいものとした。２５％未満では、酸化皮膜の欠陥部として作用する効果が不十分となる。
また、粗大なＳｉ粒子が過剰に存在すると、酸化皮膜の欠陥部は増大するが、鋳造性や圧延性が低下し、切断およびプレス時の金型磨耗が促進されるので、上限は５０％以下が望ましい。
Distribution of Si particles: Equivalent circle diameter of 0.8 μm or more, 1.75 μm or more of number ratio is 25% or more Usually, a dense oxide film such as Al 2 O 3 is present on the aluminum material surface, In the brazing heat treatment process, this further grows and becomes a thick film. The general view is that the greater the thickness of the oxide film, the stronger the tendency to inhibit the destructive action of the oxide film. Due to the presence of coarse Si particles on the surface of the brazing material, a dense oxide film of aluminum does not grow on the surface of the coarse Si particles, and this site works as an oxide film defect on the surface of the aluminum material. That is, even if the oxide film on the surface of the aluminum material becomes a thick film during the brazing heat treatment, exudation of the brazing material from the Si particle portion occurs, and the oxide film destruction action and the breaking action proceed from this site, It improves the wettability of the molten solder and makes it possible to obtain a more stable joined state.
The term “Si particles” as used herein includes Si particles due to the composition of Si as a single component, and also includes, for example, Fe—Si compounds and Al—Fe—Si intermetallic compounds mainly composed of Fe—Si. Shall be. In the description of the present invention, these are referred to as Si particles for convenience.
Specifically, when the Si particles on the surface of the brazing material are regarded as equivalent circle diameters and the number of Si particles of 0.8 μm or more is counted and 25% or more of those having 1.75 μm or more are present, this effect is sufficiently obtained. It is done.
If the size of the Si particles on the surface of the brazing material is too small, the effect of acting as a defective portion of the oxide film becomes insufficient. Therefore, it is desirable that the number of Si particles of 1.75 μm or more is 25% or more of the number of Si particles of 0.8 μm or more. If it is less than 25%, the effect of acting as a defective portion of the oxide film becomes insufficient.
In addition, if there are excessively large Si particles, defects in the oxide film increase, but castability and rollability deteriorate, and die wear during cutting and pressing is promoted, so the upper limit is 50% or less. Is desirable.
上記Ｓｉ粒子の分布は、アルミニウム合金ろう材を製造する際の熱管理によって制御することができる。
例えば、鋳造時の凝固速度や均質化処理の温度と時間、熱間圧延時の最大圧延率等によってＳｉ粒子の大きさを制御でき、添加元素量の最適化、鋳造時の凝固速度によって個数を制御することができる。
すなわち、鋳造時の凝固速度が遅いほど粗大なＳｉ粒子が生成され、凝固速度が速いほど微細なＳｉ粒子が生成される。また、凝固速度が速いほど、Ｓｉ粒子の個数が多くなり、凝固速度が遅いほどＳｉ粒子の個数が少なくなる。
また、均質化処理を高温で長時間実施するほど、粗大なＳｉ粒子が生成され、低温で短時間実施することで微細なＳｉ粒子となる。
また、熱間圧延時の圧下率は、一度の圧下率が大きいほど化合物が微細に破砕される。
これらの条件を複合的に制御することで同じ成分でもＳｉの分布（大きさ、個数比）を変えることができる。
The distribution of the Si particles can be controlled by thermal management when manufacturing the aluminum alloy brazing material.
For example, the size of the Si particles can be controlled by the solidification rate during casting, the temperature and time of the homogenization treatment, the maximum rolling rate during hot rolling, etc. Can be controlled.
That is, coarser Si particles are generated as the solidification rate during casting is slower, and finer Si particles are generated as the solidification rate is higher. Further, the faster the solidification rate, the larger the number of Si particles, and the slower the solidification rate, the smaller the number of Si particles.
Further, as the homogenization treatment is performed at a high temperature for a long time, coarse Si particles are generated, and when the homogenization treatment is performed at a low temperature for a short time, fine Si particles are obtained.
Moreover, as for the rolling reduction at the time of hot rolling, the compound is finely crushed as the rolling reduction at one time is larger.
By controlling these conditions in a complex manner, the distribution (size, number ratio) of Si can be changed even for the same component.
２．芯材
本発明に用いるアルミニウムクラッド材の芯材組成は、接合を得るにあたって特に限定されるものではないが、フラックスレスろう付けを実現したことにより、高強度化を狙ったＭｇ添加が積極的に行える。
芯材成分としては、質量比でＳｉ：０．１〜１．２％、Ｍｇ：０．０１〜２．０％を含有し、残部がＡｌと不可避不純物からなるものが示される。
また、質量比で、Ｍｎ：０．２〜２．５％、Ｃｕ：０．０５〜１．０％、Ｓｉ：０．１〜１．２％、Ｆｅ：０．１〜１．０％、を含有し、残部Ａｌと不可避不純物とからなるものが示される。
また、芯材成分としては、Ｍｎ：０．２〜２．５％、Ｃｕ：０．０５〜１．０％、Ｆｅ：０．１〜１．０％の内１種または２種以上を含有し、さらに所望によりＺｒ：０．０１〜０．３％、Ｔｉ：０．０１〜０．３％、Ｃｒ：０．０１〜０．５％、Ｂｉ：０．０１〜１．０％の内１種または２種以上を含有し、残部がＡｌと不可避不純物からなるものが示される。各元素の作用及び限定理由は以下の通りである。
2. Core material The core material composition of the aluminum clad material used in the present invention is not particularly limited in obtaining a bond, but by realizing fluxless brazing, Mg addition aiming at high strength is actively added. Yes.
As a core component, what contains Si: 0.1-1.2% and Mg: 0.01-2.0% by mass ratio, and the remainder consists of Al and an unavoidable impurity are shown.
Moreover, by mass ratio, Mn: 0.2-2.5%, Cu: 0.05-1.0%, Si: 0.1-1.2%, Fe: 0.1-1.0%, Containing the balance Al and inevitable impurities.
As the core material component, one or more of Mn: 0.2 to 2.5%, Cu: 0.05 to 1.0%, and Fe: 0.1 to 1.0% are contained. If desired, Zr: 0.01 to 0.3%, Ti: 0.01 to 0.3%, Cr: 0.01 to 0.5%, Bi: 0.01 to 1.0% One or two or more types are contained, and the balance is composed of Al and inevitable impurities. The action of each element and the reasons for limitation are as follows.
Ｓｉ：０．１〜１．２％
Ｓｉ単体でマトリックスに固溶して材料強度を向上させる他、本発明においては、Ｍｇの積極添加との相乗効果によって得られるＭｇ２Ｓｉの析出により、材料強度を向上させる。このＭｇ２Ｓｉ析出による硬化は、ろう付け熱処理後の時効析出により、飛躍的な材料強度向上に寄与する。従来のＡ３００３合金等をベースとした合金設計においては、Ａｌ−Ｍｎ−Ｓｉ化合物として分散して、材料強度を向上させる。下限未満では効果が不十分であり、上限を越えると、融点が低下し、芯材が溶融するので、上記範囲が望ましい。なお、Ｓｉ含有量の一層好ましい範囲は０．３〜１．０％である。Ｍｎ等の含有によりＳｉの積極的な含有を要しない場合、０．１％未満のＳｉを不純物として含有することは許容される。
Si: 0.1-1.2%
In addition to improving the material strength by dissolving Si in a matrix with a simple substance of Si, in the present invention, the material strength is improved by precipitation of Mg 2 Si obtained by a synergistic effect with the positive addition of Mg. This hardening by Mg 2 Si precipitation contributes to a dramatic improvement in material strength by aging precipitation after brazing heat treatment. In an alloy design based on the conventional A3003 alloy or the like, it is dispersed as an Al—Mn—Si compound to improve the material strength. If the amount is less than the lower limit, the effect is insufficient. If the upper limit is exceeded, the melting point decreases and the core material melts, so the above range is desirable. In addition, the more preferable range of Si content is 0.3 to 1.0%. When positive inclusion of Si is not required due to inclusion of Mn or the like, it is allowed to contain less than 0.1% of Si as an impurity.
Ｍｇ：０．０１〜２．０％
Ｍｇは、Ｓｉと同時に添加されることでろう付後に微細な金属間化合物Ｍｇ２Ｓｉとして析出し、時効硬化により著しく強度が向上する効果を有する。また、ろう付加熱中にろう材から拡散してきたＳｉとも反応し、同様の強度効果を有する。さらに一部はろう材中に拡散し、ろう材表面の酸化皮膜破壊、酸化皮膜成長抑制作用に寄与する。下限未満では効果不十分であり、上限を超えると融点が低下し、芯材が溶融する。このため、Ｍｇ含有量は上記範囲が望ましい。
Mg: 0.01-2.0%
When Mg is added simultaneously with Si, it precipitates as a fine intermetallic compound Mg 2 Si after brazing and has the effect of significantly improving strength by age hardening. Moreover, it reacts with Si diffused from the brazing material during the brazing heat and has the same strength effect. Further, some of them diffuse into the brazing material and contribute to the action of inhibiting the oxide film destruction and oxide film growth on the surface of the brazing material. Below the lower limit, the effect is insufficient, and when the upper limit is exceeded, the melting point decreases and the core material melts. For this reason, the above range is desirable for the Mg content.
Ｍｎ：０．２〜２．５％
Ｍｎは、金属間化合物として晶出または析出し、ろう付後の強度を向上させる。また、芯材の電位を貴にして耐食性も向上させる。下限未満では効果が不十分であり、上限を超えると、圧延などの加工性が低下する。また、一層の効果は得られない。これら理由によりＭｎ含有量は上記範囲が望ましい。なお、Ｍｎ含有量の一層好ましい範囲は０．５〜１．５％である。
Mn: 0.2 to 2.5%
Mn crystallizes or precipitates as an intermetallic compound, and improves the strength after brazing. In addition, the corrosion resistance is improved by making the potential of the core material noble. If it is less than the lower limit, the effect is insufficient, and if it exceeds the upper limit, workability such as rolling deteriorates. In addition, further effects cannot be obtained. For these reasons, the Mn content is preferably within the above range. In addition, the more preferable range of Mn content is 0.5 to 1.5%.
Ｃｕ：０．０５〜１．０％
Ｃｕは、固溶してろう付後の強度を向上させると共に、芯材の電位を貴にして耐食性を向上させる。下限未満では効果が不十分であり、上限を超えると、融点が低下し、芯材が溶融する。このため、Ｃｕ含有量は上記範囲が望ましい。なお、Ｃｕ含有量の一層好ましい範囲は０．１〜０．７％である。
Cu: 0.05 to 1.0%
Cu is dissolved to improve the strength after brazing and to improve the corrosion resistance by making the potential of the core material noble. Below the lower limit, the effect is insufficient, and when the upper limit is exceeded, the melting point decreases and the core material melts. For this reason, the above range is desirable for the Cu content. In addition, the more preferable range of Cu content is 0.1 to 0.7%.
Ｆｅ：０．１〜１．０％
Ｆｅは金属間化合物として晶出または析出し、ろう付後の強度を向上させる。また、最終焼鈍時とろう付時の再結晶を促進する。下限未満では効果が不十分であり、上限を超えると、腐食速度が速くなりすぎる。また、最終焼鈍後の結晶粒径が細かくなりすぎて成形時に加工の導入されない部分でろうの侵食が著しく大きくなる。これら理由によりＦｅ含有量が上記範囲が望ましい。なお、Ｆｅ含有量の一層好ましい範囲は０．２〜０．５％である。
Fe: 0.1 to 1.0%
Fe crystallizes or precipitates as an intermetallic compound, and improves the strength after brazing. It also promotes recrystallization during final annealing and brazing. If it is less than the lower limit, the effect is insufficient, and if it exceeds the upper limit, the corrosion rate becomes too fast. Further, the crystal grain size after the final annealing becomes too fine, and the erosion of the wax becomes remarkably large at the portion where the processing is not introduced at the time of molding. For these reasons, the above range is desirable for the Fe content. In addition, the more preferable range of Fe content is 0.2 to 0.5%.
Ｚｒ、Ｔｉ：０．０１〜０．３％、Ｃｒ：０．０１〜０．５％
Ｚｒ、ＴｉまたはＣｒは、ろう付後に微細な金属間化合物として分散し、強度を向上させる。下限未満では効果不十分であり、上限を超えると加工性が低下する。このため、これら成分の含有量は上記範囲が望ましい。
Zr, Ti: 0.01 to 0.3%, Cr: 0.01 to 0.5%
Zr, Ti or Cr is dispersed as a fine intermetallic compound after brazing to improve the strength. If it is less than the lower limit, the effect is insufficient, and if it exceeds the upper limit, the workability decreases. Therefore, the content of these components is preferably in the above range.
Ｂｉ：０．０１〜１．０％
Ｂｉは、材料表面の再酸化を抑制し、ろう材の濡れ拡がり性を向上させる。下限未満では効果が不十分であり、上限を超えても一層の効果は得られない。このため、Ｂｉの含有量は、上記範囲が望ましい。
Bi: 0.01 to 1.0%
Bi suppresses re-oxidation of the material surface and improves the wetting and spreading property of the brazing material. If it is less than the lower limit, the effect is insufficient, and even if the upper limit is exceeded, no further effect can be obtained. For this reason, the above range is desirable for the Bi content.
３．クラッド材
本発明に使用する上記クラッド材においては、少なくとも片面に上記Ａｌ−Ｓｉ系ろう材がクラッドされていればよく、適宜、片面と両面クラッド材を使い分けることができる。両面クラッド材では、芯材の両面にろう材がクラッドされているものであってもよく、また片面に上記ろう材がクラッドされ、他の片面に犠牲材等のその他の材料がクラッドされているものであってもよい。
3. Clad material In the clad material used in the present invention, it is sufficient that the Al-Si brazing material is clad on at least one side, and one side and a double sided clad material can be properly used. In the double-sided clad material, the both sides of the core material may be clad with a brazing material, the brazing material is clad on one side, and other materials such as a sacrificial material are clad on the other side. It may be a thing.
４．被ろう付け部材の材質
ろう材以外の被ろう付け部材としては、一般的に用いられているアルミニウム合金であれば何れも問題なく使用可能である。なお、被ろう付け部材にはろう材がクラッドされてるものであってもよい。
4). Material of Brazed Member As the brazed member other than the brazing material, any commonly used aluminum alloy can be used without any problem. Note that the brazing member may be clad with a brazing material.
５．被ろう付け部材の表面粗さ
本発明を実施するに当たっては、接合部の接触密着状態を高めることで、接合部である接触密着部への外部からの酸素供給がされにくくなり、ろう付け昇温過程での材料表面の酸化抑制力が高まる。ここで言う酸素供給とは、大気雰囲気中での酸素を意味するのではなく、非酸化性雰囲気中に僅かに含まれる酸素によるものを示す。本発明者らが調べた結果、接合部における接合部材両者の表面粗さがＲａ０．３μｍ以下であれば、より良好な接合が得られることが判り、さらに好ましくは、Ｒａ０．２５μｍ以下で安定して良好な接合状態が得られることも判った。表面粗さがＲａ０．３μｍを超える場合は加圧密着力を高めても十分な気密性が得られないためろう付け性が低下する。
5. Surface roughness of brazed member In carrying out the present invention, it is difficult to supply oxygen from the outside to the contact adhesion portion which is a junction portion by increasing the contact adhesion state of the junction portion. The ability to suppress oxidation of the material surface during the process is increased. The oxygen supply here does not mean oxygen in the air atmosphere, but indicates that oxygen is slightly contained in the non-oxidizing atmosphere. As a result of investigations by the present inventors, it has been found that if the surface roughness of both joining members in the joint portion is Ra 0.3 μm or less, better joining can be obtained, and more preferably, Ra 0.25 μm or less is stable. It was also found that a good bonding state can be obtained. When the surface roughness exceeds Ra 0.3 μm, brazing performance is lowered because sufficient airtightness cannot be obtained even if the pressure adhesion is increased.
６．ろう材および被ろう付け部材の初期酸化膜厚
本発明の実施に当たっては、特に材料表面の初期酸化皮膜を抑制するような材料製作は必要としない為、通常、アルミニウムの量産コイル材として作製され得る、初期酸化膜厚２０〜５００Å程度のアルミニウム材料を使用できる。２０Å未満では、従来技術に示したような酸洗浄等が必要となり、５００Åを越えるものはＭｇによる酸化皮膜破壊作用が十分に得られず、良好な接合状態が得られにくくなる。
6). Initial oxide film thickness of brazing material and brazed member In carrying out the present invention, since it is not necessary to produce a material that suppresses the initial oxide film on the surface of the material in particular, it can usually be produced as a mass production coil material of aluminum. An aluminum material having an initial oxide film thickness of about 20 to 500 mm can be used. If it is less than 20 mm, acid cleaning or the like as shown in the prior art is necessary, and if it exceeds 500 mm, the oxide film destruction action by Mg cannot be sufficiently obtained, and it becomes difficult to obtain a good bonding state.
７．炉内雰囲気
本発明の実施にあたっては、炉内雰囲気を不活性ガス、或いは還元性ガス等の非酸化性ガスとすることで、雰囲気中の酸素濃度や露点を低下させ、被ろう付け部材の再酸化を抑制する必要がある。使用する置換ガスの種類としては、接合を得るにあたり特に限定されるものではないが、コストの観点で、不活性ガスとしては窒素、アルゴン、還元性ガスとしては水素、アンモニア、一酸化炭素を用いることが好適である。雰囲気中の酸素濃度管理範囲としては、５〜５００ｐｐｍがよい。５ｐｐｍ未満の場合は、接合に不具合は生じないが、雰囲気の管理に多量のガスを使用する等、製造コストの増大懸念が生じるためである。５００ｐｐｍ超では被ろう付け部材の再酸化が進みやすくなり、特にろう材が表面にないベア構成部材とろう材間の接合が十分に得られない為である。
7). In-furnace atmosphere In carrying out the present invention, the atmosphere in the furnace is changed to an inert gas or a non-oxidizing gas such as a reducing gas, thereby reducing the oxygen concentration and dew point in the atmosphere, and It is necessary to suppress oxidation. The type of replacement gas to be used is not particularly limited in obtaining bonding, but from the viewpoint of cost, nitrogen, argon, and hydrogen, ammonia, and carbon monoxide are used as the inert gas and the reducing gas, respectively. Is preferred. The oxygen concentration management range in the atmosphere is preferably 5 to 500 ppm. If it is less than 5 ppm, there is no problem in the joining, but there is a concern that the manufacturing cost will increase, such as using a large amount of gas for managing the atmosphere. If the content exceeds 500 ppm, the reoxidation of the brazed member is likely to proceed, and in particular, it is not possible to sufficiently obtain a bond between the bare component member having no brazing material on the surface and the brazing material.
８．ろう付け温度
本発明においては、ろう材Ａｌ−Ｓｉ−Ｍｇ合金の最も低い固相線温度の５５９℃以上でろう付けができ、当然、従来からのＡｌ−Ｓｉろう材によるろう付け温度範囲も使用可能である。具体的には５５９〜６２０℃が良い。５５９℃未満ではろうの溶融が得られずろう付けが得られない。６２０℃超ではろう侵食が顕著となり、製品形状の維持等に問題が生じるため好ましくない。但し、この温度範囲においても、ろうの合金組成によって固相線温度が低い場合には、ろう侵食が顕著になる場合もあり、その際は、この温度範囲の中で合金組成にあったろう付け温度を選択するのが好ましい。
8). Brazing temperature In the present invention, brazing can be performed at the lowest solidus temperature of 559 ° C. of the brazing material Al—Si—Mg alloy, and naturally, the brazing temperature range by the conventional Al—Si brazing material is also used. Is possible. Specifically, 559-620 degreeC is good. If it is less than 559 degreeC, the melting | fusing of a brazing cannot be obtained and brazing cannot be obtained. If it exceeds 620 ° C., the wax erosion becomes prominent, and there is a problem in maintaining the product shape. However, even in this temperature range, if the solidus temperature is low due to the alloy composition of the brazing, brazing erosion may become prominent. In this case, the brazing temperature suitable for the alloy composition within this temperature range. Is preferably selected.
以上説明したように、本発明のアルミニウム材のフラックスレスろう付方法、フラックスレスろう付用アルミニウム合金ブレージングシートおよびフラックスレスろう付用アルミニウム合金ろう材によれば、フラックスや真空設備を必要としない、大気圧下のフラックスレスろう付が可能となり、従来よりも安定した接合状態を容易かつ確実に得ることができる。また、減圧を伴わない雰囲気での加熱となるため、アルミニウム材料からのＭｇやＺｎの蒸発はほとんど発生せず、炉内壁等の汚染を生じないというメリットが得られる。 As explained above, according to the fluxless brazing method of the aluminum material of the present invention, the aluminum alloy brazing sheet for fluxless brazing and the aluminum alloy brazing material for fluxless brazing, no flux or vacuum equipment is required. Fluxless brazing at atmospheric pressure is possible, and a more stable joining state than before can be obtained easily and reliably. In addition, since heating is performed in an atmosphere without decompression, there is an advantage that Mg and Zn are hardly evaporated from the aluminum material, and the inner wall of the furnace is not contaminated.
以下に、本発明の一実施形態を説明する。
質量％で、少なくともＭｇを０．１〜５．０％、Ｓｉを３〜１３％、Ｃａ：０．００１〜１．０％を含有するＡｌ−Ｓｉ系ろう材と、芯材とは常法により製造することができる。両者またはこれに犠牲材などの他の材料とを重ねてクラッド圧延する。各層のクラッド率は本発明として特定されるものではない。
Hereinafter, an embodiment of the present invention will be described.
Al-Si based brazing material containing at least 0.1 to 5.0% Mg, 3 to 13% Si, and Ca: 0.001 to 1.0% in mass% and a core material are ordinary methods. Can be manufactured. Both or another material such as a sacrificial material is overlapped and clad rolled. The clad rate of each layer is not specified as the present invention.
なお、上記ろう材では、鋳造時の凝固速度や均質化処理の温度と時間、熱間圧延時の最大圧延率等によってＳｉ粒子の分布を制御する。
これらの条件を複合的に制御することでＳｉ粒子の分布（大きさ、粗大な粒子の個数比）を調整し、円相当径０．８μｍ以上のＳｉ粒子の個数のうち、１．７５μｍ以上のものの個数が２５％以上となるようにする。
In the above brazing material, the distribution of Si particles is controlled by the solidification rate during casting, the temperature and time of the homogenization treatment, the maximum rolling rate during hot rolling, and the like.
By controlling these conditions in a complex manner, the distribution of Si particles (size, number ratio of coarse particles) is adjusted, and the number of Si particles having an equivalent circle diameter of 0.8 μm or more is 1.75 μm or more. The number of objects should be 25% or more.
また、芯材の組成は、Ｓｉ：０．１〜１．２％、Ｍｇ：０．０１〜２．０％を含有するもの、Ｍｎ：０．２〜２．５％、Ｃｕ：０．０５〜１．０％、Ｓｉ：０．１〜１．２％、Ｆｅ：０．１〜１．０％を含有するもの、あるいはＳｉ：０．１〜１．２％、Ｍｇ：０．０１〜２．０％を含有し、さらにＭｎ：０．２〜２．５％、Ｃｕ：０．０５〜１．０％、Ｆｅ：０．１〜１．０％の内１種または２種以上を含有し、さらに所望によりＺｒ：０．０１〜０．３％、Ｔｉ：０．０１〜０．３％、Ｃｒ：０．０１〜０．５％の内１種または２種以上を含有などが望ましい。 The composition of the core material is Si: 0.1 to 1.2%, Mg: 0.01 to 2.0%, Mn: 0.2 to 2.5%, Cu: 0.05 -1.0%, Si: 0.1-1.2%, Fe: 0.1-1.0%, or Si: 0.1-1.2%, Mg: 0.01- 2.0%, and Mn: 0.2 to 2.5%, Cu: 0.05 to 1.0%, Fe: 0.1 to 1.0%, or one or more of them Containing Zr: 0.01 to 0.3%, Ti: 0.01 to 0.3%, Cr: 0.01 to 0.5%, or more if desired. desirable.
上記によって得られるアルミニウムクラッド材１は、図１に示すように芯材２の片面または両面にクラッドされた上記Ａｌ−Ｓｉ系ろう材３が最表面に位置しており、初期酸化膜厚として２０〜５００Åの酸化皮膜が形成されている。
上記アルミニウムクラッド材１は、前記Ａｌ−Ｓｉ系ろう材３が、ベアフィン、無垢材コネクタなどの被ろう付け部材４に接触密着するように組み付けられて、好適には熱交換器組立体などを構成する。なお、被ろう付け部材としては種々の組成のアルミニウム材料を用いることができ、本発明としては特定のものに限定されるものではない。
As shown in FIG. 1, the aluminum clad material 1 obtained as described above has the Al—
The aluminum clad material 1 is assembled so that the Al—
上記組立体は、減圧を伴うことなく非酸化性雰囲気とされた加熱炉内に配置される。該非酸化性雰囲気は、窒素、アルゴンなどの不活性ガスまたは水素、アンモニア、一酸化炭素などの還元性ガス、あるいはこれらの混合ガスを用いて構成することができる。非酸化性雰囲気は、ろう付加熱時には減圧を伴わず、通常は大気圧とされる。なお、非酸化性雰囲気を得る前に、置換などの目的で減圧工程を含むものであってもよい。加熱炉は密閉した空間を有することを必要とせず、ろう付材の搬入口、搬出口を有するものであってもよい。このような加熱炉でも、不活性ガスを炉内に吹き出し続けることで非酸化性雰囲気が維持される。該非酸化性雰囲気としては、酸素濃度として体積比で５〜５００ｐｐｍが望ましい。上記雰囲気下で５５９〜６２０℃で加熱をしてろう付を行う。ろう付においては、被ろう付け部材４との接触密着部５がフラックスレスで良好に接合される。
なお、上記ろう材は、クラッド材として提供される他、単独の材料として提供されるものであってもよい。
The assembly is placed in a heating furnace having a non-oxidizing atmosphere without decompression. The non-oxidizing atmosphere can be configured using an inert gas such as nitrogen or argon, or a reducing gas such as hydrogen, ammonia or carbon monoxide, or a mixed gas thereof. The non-oxidizing atmosphere is not at reduced pressure during brazing addition heat, and is usually at atmospheric pressure. In addition, before obtaining a non-oxidizing atmosphere, you may include a pressure reduction process for the purpose of substitution. The heating furnace does not need to have a sealed space, and may have a brazing material carry-in port and a carry-out port. Even in such a heating furnace, the non-oxidizing atmosphere is maintained by continuously blowing the inert gas into the furnace. The non-oxidizing atmosphere preferably has an oxygen concentration of 5 to 500 ppm by volume. It brazes by heating at 559-620 degreeC under the said atmosphere. In brazing, the
The brazing material may be provided as a single material in addition to being provided as a clad material.
以下に、本発明の実施例を説明する。
表１、２に示す組成（残部Ａｌと不可避不純物）のＡｌ−Ｓｉ系ろう材と、Ａｌ−０．５Ｍｇ−０．５Ｓｉ−１．０Ｍｎ−０．３Ｆｅからなる組成（残部不可避不純物）の芯材とを熱間圧延および冷間圧延によってクラッドしたアルミニウムクラッド材を用意した。各合金の鋳造時の凝固速度は一般的な半連続鋳造の条件である０．１〜２．０℃／ｓｅｃの範囲に制御した。なお、ろう材は鋳造時の凝固速度と均質化処理条件、熱間圧延時の最大圧延率を種々変化させることによって、Ｓｉ粒子の分布を制御した。
なお、均質化処理は、３００〜５９５℃×１〜４８時間の範囲内で調整し、熱間圧延の最大圧延率は、１５〜５０％の範囲内で調整した。
上記アルミニウムクラッド材は、各種組成のろう材と芯材とを選択し、ろう材クラッド率１０％、Ｈ１４相当調質で０．５ｍｍ厚に仕上げた。
Examples of the present invention will be described below.
A core of the composition (the balance unavoidable impurities) consisting of an Al-Si brazing material having the composition shown in Tables 1 and 2 (the balance Al and inevitable impurities) and Al-0.5Mg-0.5Si-1.0Mn-0.3Fe An aluminum clad material was prepared by cladding the material with hot rolling and cold rolling. The solidification rate during casting of each alloy was controlled within a range of 0.1 to 2.0 ° C./sec, which is a general semi-continuous casting condition. In the brazing filler metal, the distribution of Si particles was controlled by variously changing the solidification speed and homogenization treatment conditions during casting and the maximum rolling rate during hot rolling.
In addition, the homogenization process was adjusted within the range of 300-595 degreeC x 1-48 hours, and the maximum rolling rate of hot rolling was adjusted within the range of 15-50%.
As the aluminum clad material, brazing materials and core materials having various compositions were selected and finished to a thickness of 0.5 mm with a brazing material clad rate of 10% and H14 equivalent tempering.
Ｓｉ粒子の測定
作製したアルミニウムクラッド材について、ろう材最表面を０．１μｍの砥粒で研磨し、０．５％フッ酸水溶液で６０秒エッチングした後、表面方向からＥＰＭＡ（電子線マイクロアナライザ）を用いた全自動粒子解析により粒子サイズと個数を測定した。測定は各サンプルについて２５０μｍ角相当の観察視野で任意部５ヶ所について測定し、Ｓｉ粒子の分布（０．８μｍ以上のうち１．７５μｍ以上の個数比率）を求め、その結果を表１、２に示した。
また、被ろう付け部材としてＪＩＳ Ａ３００３合金、Ｈ１４相当調質のアルミニウム
ベア材（０．１ｍｍ厚）のコルゲートフィン材を用意した。
Measurement of Si Particles For the prepared aluminum clad material, the outermost surface of the brazing material was polished with 0.1 μm abrasive grains, etched with 0.5% hydrofluoric acid aqueous solution for 60 seconds, and then EPMA (electron beam microanalyzer) from the surface direction. Particle size and number were measured by fully automatic particle analysis using Measurements were made at 5 arbitrary portions in an observation field corresponding to 250 μm square for each sample to obtain Si particle distribution (number ratio of 1.75 μm or more out of 0.8 μm or more). Indicated.
Further, a JIS A3003 alloy and a corrugated fin material made of H14-equivalent aluminum bare material (thickness: 0.1 mm) were prepared as brazing members.
ろう付性
本発明の上記アルミニウムクラッド材を用いて幅２０ｍｍの扁平電縫管を製作し、前記コルゲートフィンと組合せてコア形状とした。コアサイズは、チューブ１５段、長さ３００ｍｍの構成とした。
上記コアを窒素雰囲気中（酸素含有量５０ｐｐｍ）にて、５６０〜６２０℃まで加熱するろう付熱処理を行った後、チューブとフィンの接合率を測定することでろう付性を評価した。フィンの接合率は、以下の式で求め、その結果を表１、２に示した。
フィン接合率＝（フィンとチューブの総ろう付接合長さ／フィンとチューブの総接触長さ）×１００（％）
Brazing property Using the aluminum clad material of the present invention, a flat electric sewn tube having a width of 20 mm was manufactured and combined with the corrugated fin to form a core shape. The core size was a tube with 15 steps and a length of 300 mm.
After performing the brazing heat treatment which heats the said core to 560-620 degreeC in nitrogen atmosphere (oxygen content 50ppm), brazing property was evaluated by measuring the joining rate of a tube and a fin. The bonding rate of the fins was obtained by the following formula, and the results are shown in Tables 1 and 2.
Fin joint rate = (total brazed joint length of fin and tube / total contact length of fin and tube) × 100 (%)
材料強度
製作した上記アルミニウムクラッド材（０．５ｍｍ厚）をＪＩＳ５号試験片とし、上記条件によるろう付熱処理後、９０℃×７日間時効処理後に引張試験に供した。得られた材料強度測定値を評価し、その結果を表１、２に示した。
Material Strength The manufactured aluminum clad material (0.5 mm thickness) was used as a JIS No. 5 test piece, and subjected to a tensile test after brazing heat treatment under the above conditions and after aging treatment at 90 ° C. for 7 days. The obtained material strength measurements were evaluated, and the results are shown in Tables 1 and 2.
本発明の実施例は従来例に比べ良好なろう付性を示したのに対し、比較例では十分な接合が得られなかった。また、実施例では材料の高強度化とろう付性との両立が得られたが、比較材でその効果は得られなかった。 The examples of the present invention showed better brazing properties than the conventional examples, whereas the comparative examples did not provide sufficient bonding. Further, in the examples, it was possible to achieve both high strength and brazability of the material, but the effect was not obtained with the comparative material.
１ アルミニウムクラッド材
２ 芯材
３ Ａｌ−Ｓｉ系ろう材
４ 被ろう付け部材
５ 接触密着部
DESCRIPTION OF SYMBOLS 1 Aluminum clad
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| JP6188511B2 (en) * | 2013-09-20 | 2017-08-30 | 株式会社Uacj | Aluminum alloy brazing sheet for fluxless brazing and manufacturing method thereof |
| JP2016203193A (en) * | 2015-04-17 | 2016-12-08 | 株式会社Uacj | Aluminum alloy sheet and manufacturing method of the same, aluminum brazing sheet using the aluminum alloy sheet |
| WO2020129268A1 (en) * | 2019-01-23 | 2020-06-25 | 三菱アルミニウム株式会社 | Aluminum alloy for brazing and aluminum brazing sheet |
| CN110719965B (en) * | 2019-01-23 | 2021-01-08 | 三菱铝株式会社 | Aluminum brazing sheet for fluxless brazing |
| CN115243883A (en) * | 2020-01-21 | 2022-10-25 | 诺维尔里斯公司 | Aluminum alloy and coated aluminum alloy having high corrosion resistance and method for producing the same |
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| JPS53123354A (en) * | 1977-04-04 | 1978-10-27 | Mitsubishi Aluminium | Fluxless brazing method of al and al alloy parts |
| JPS6137395A (en) * | 1984-07-31 | 1986-02-22 | Sumitomo Light Metal Ind Ltd | Aluminum alloy brazing filler metal for aluminum heat exchanger |
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