JP4547032B1 - Fluxless brazing method of aluminum material and aluminum clad material for fluxless brazing - Google Patents
Fluxless brazing method of aluminum material and aluminum clad material for fluxless brazing Download PDFInfo
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Abstract
【課題】フラックスや真空設備を必要とすることなく大気圧下でのフラックスレスろう付けを可能にする。
【解決手段】質量％で、Ｍｇを０．１〜５．０％、Ｓｉを３〜１３％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て、減圧を伴わない非酸化性雰囲気で加熱温度５５９〜６２０℃において、前記Ａｌ−Ｓｉ系ろう材によりろう付け対象部材との接触密着部を接合する。フラックスや真空設備を必要とせずに大気圧下でのフラックスレスろう付けが可能になり、ろう材以外の被ろう付け構成部材へＭｇを添加した場合にもろう付け阻害要因とはならない。減圧を伴わない雰囲気での加熱となるため、ＭｇやＺｎの蒸発による炉内壁等の汚染も殆ど生じない。
【選択図】なしAn object of the present invention is to enable fluxless brazing at atmospheric pressure without requiring flux or vacuum equipment.
SOLUTION: Using an aluminum clad material in which an Al-Si brazing material containing 0.1% to 5.0% Mg and 3% to 13% Si is located on the outermost surface without mass reduction. At a heating temperature of 559 to 620 ° C. in a non-oxidizing atmosphere, the contact adhesion portion with the brazing target member is joined by the Al—Si brazing material. Fluxless brazing at atmospheric pressure is possible without the need for flux or vacuum equipment, and when Mg is added to brazed components other than the brazing material, brazing is not a hindering factor. Since the heating is performed in an atmosphere without decompression, the contamination of the inner wall of the furnace due to the evaporation of Mg and Zn hardly occurs.
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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クラッド材、及びそのろう付け方法に関する。 The present invention relates to an aluminum clad material that can be brazed without using a flux in a non-oxidizing atmosphere, and a brazing method thereof.
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 generate 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 inhibition factor, is destroyed. 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. is 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, Patent Document 2 proposes a mechanism in which a brazing member (cover) heated in the brazing furnace in advance is used to cover the brazed member in the furnace, thereby improving the decrease in the heating rate. Yes. However, in this method, it is necessary to provide a mechanism for controlling the operation of the windbreaker in the furnace, and there is a problem that it takes cost and labor to introduce and maintain equipment.
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 Patent Document 3, Mg is added to a brazing material of a clad material, and the inside of the heat exchanger tube formed by the clad material is set to atmospheric pressure in an inert atmosphere. A fluxless brazing method has been proposed below.
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 Patent Document 5, if the surface of the core material is clad with a brazing material made of an Al—Si—Mg alloy, and the material surface is acid-washed before brazing to reduce the thickness of the oxide film to 20 mm or less, There is a proposal that enables fluxless brazing in an oxidizing atmosphere.
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, Patent Documents 3 to 5 that enable brazing under atmospheric pressure without requiring a cover also have the following problems.
In the method proposed in Patent Document 3, a flux is used to join the outer surface of the tube and the fin, and there is a problem that the disadvantages of using the flux are not completely eliminated.
Moreover, 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, which reduces the material cost. 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 Patent Document 5 has a problem that the process management of the acid cleaning becomes complicated and the cost for the acid cleaning process increases.
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方法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 It was developed for the purpose of finding a general-purpose fluxless brazing method under atmospheric pressure that does not depend on the shape of a heat exchanger or the like.
上記目的を達成するため、本発明者らは鋭意研究を進めた結果、クラッド材のろう材に添加するＭｇ量を適正な範囲に収めることで、密着した接合継手を、減圧を伴うことなく非酸化性雰囲気中で、Ｍｇ蒸気を逃がさないようにする為の覆いを用いなくとも、良好なろう付け状態が得られることを見出した。この際、ろう付け前材料表面の初期酸化膜をあえて除去する必要はなく、通常に生産されているアルミニウム材が使用可能である。 In order to achieve the above object, the present inventors have conducted intensive research, and as a result, by keeping the amount of Mg added to the brazing material of the clad material within an appropriate range, the closely joined joint joint can be removed without depressurization. It has been found that a good brazing state can be obtained without using a cover for preventing Mg vapor from escaping in an oxidizing atmosphere. At this time, it is not necessary to dare to remove the initial oxide film on the surface of the material before brazing, and a commonly produced aluminum material can be used.
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け方法のうち、第１の本発明は、質量％で、Ｍｇを０．１〜５．０％、Ｓｉを３〜１３％含有し、残部がＡｌと不可避不純物からなるＡｌ−Ｓｉ系ろう材が芯材にクラッドされて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、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、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系ろう材とろう付け対象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ろう付け対象部材とを接合することを特徴とする。 That is, in the fluxless brazing method of the aluminum material of the present invention, the first present invention contains, by mass%, 0.1 to 5.0% Mg, 3 to 13% Si, and the balance being Al. And a brazing method using an aluminum clad material that is clad on the core material and is located on the outermost surface. The Si particles contained in the Al-Si braze material are: In the observation in the layer surface direction, among the number of equivalent circle diameters having a diameter of 0.8 μm or more, the number of those having a diameter of 1.75 μm or more is 25% or more, and in the non-oxidizing atmosphere without decompression, The Al-Si brazing material and the member to be brazed are brought into contact and intimate contact with each other, and the core material and the brazing are formed on the contact surface of the contact adhesion portion with the Al-Si brazing material at a heating temperature of 559 to 620 ° C. without flux. versus It is characterized by joining an elephant member.
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け方法は、前記第１の本発明において、前記アルミニウムクラッド材、及び、前記ろう付け対象部材の少なくとも接触密着部表面の表面粗さが、Ｒａ０．３μｍ以下であることを特徴とする。 The fluxless brazing method of the aluminum material of the second aspect of the present invention is the method according to the first aspect of the present invention, wherein the surface roughness of at least the contact adhesion portion surface of the aluminum clad material and the member to be brazed is Ra0. It is characterized by being 3 μm or less.
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け方法は、前記第１または第２の本発明のいずれかにおいて、前記Ａｌ−Ｓｉ系ろう材に質量％で、０．０１〜１．０％のＢｉを含有することを特徴とする。
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け方法は、前記第１〜第３の本発明のいずれかにおいて、前記Ａｌ−Ｓｉ系ろう材に質量％で、０．１〜５．０％のＺｎを含有することを特徴とする。
A fluxless brazing method for an aluminum material according to a third aspect of the present invention is the method according to any one of the first and second aspects, wherein the Al-Si brazing material is 0.01% to 1.0% by mass. Bi is contained.
A fluxless brazing method for an aluminum material according to a fourth aspect of the present invention is the method according to any one of the first to third aspects, wherein the Al-Si brazing material is 0.1% to 5.0% by mass. Zn is contained.
第５の本発明のアルミニウム材のフラックスレスろう付け方法は、前記第１〜第４の本発明のいずれかにおいて、前記Ａｌ−Ｓｉ系ろう材がクラッドされている芯材が、質量％で、Ｓｉ：０．１〜１．２％、Ｍｇ：０．０１〜２．０％を含有し、残部Ａｌと不可避不純物からなる組成を有することを特徴とする。 In the fluxless brazing method of the aluminum material of the fifth invention, the core material in which the Al-Si brazing material is clad in any one of the first to fourth inventions is in mass%, It contains Si: 0.1 to 1.2%, Mg: 0.01 to 2.0%, and has a composition composed of the balance Al and inevitable impurities.
第６の本発明のアルミニウム材のフラックスレスろう付け方法は、前記第１〜第４の本発明のいずれかにおいて、前記Ａｌ−Ｓｉ系ろう材がクラッドされている芯材が、質量％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組成を有することを特徴とする。 In the fluxless brazing method of the aluminum material of the sixth aspect of the present invention, in any one of the first to fourth aspects of the present invention, the core material on which the Al-Si brazing material is clad is in mass%, Mn: 0.2-2.5%, Cu: 0.05-1.0%, Si: 0.1-1.2%, Fe: 0.1-1.0%, the balance Al And a composition comprising inevitable impurities.
第７の本発明のアルミニウム材のフラックスレスろう付け方法は、前記第１〜第４の本発明のいずれかにおいて、前記Ａｌ−Ｓｉ系ろう材がクラッドされている芯材が、質量％で、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、残部Ａｌと不可避不純物とからなる組成を有することを特徴とする。 The fluxless brazing method of the aluminum material of the seventh aspect of the present invention is the flux material brazing method according to any one of the first to fourth aspects of the present invention, wherein the core material on which the Al-Si brazing material is clad is in mass%, Si: 0.1 to 1.2%, Mg: 0.01 to 2.0%, Mn: 0.2 to 2.5%, Cu: 0.05 to 1.0%, Fe: It is characterized by containing one or more of 0.1 to 1.0% and having a composition composed of the balance Al and inevitable impurities.
第８の本発明のアルミニウム材のフラックスレスろう付け方法は、前記第１〜第４の本発明のいずれかにおいて、前記Ａｌ−Ｓｉ系ろう材がクラッドされている芯材が、質量％で、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Ａｌと不可避不純物とからなる組成を有することを特徴とする。 The fluxless brazing method of the aluminum material according to the eighth aspect of the present invention, in any one of the first to fourth aspects of the present invention, the core material clad with the Al-Si brazing material is in mass%, Si: 0.1 to 1.2%, Mg: 0.01 to 2.0%, Mn: 0.2 to 2.5%, Cu: 0.05 to 1.0%, Fe: It contains one or more of 0.1 to 1.0%, Zr: 0.01 to 0.3%, Ti: 0.01 to 0.3%, Cr: 0.01 to 0 0.5%, Bi: 0.01 to 1.0% of one or more of them, and having a composition composed of the balance Al and inevitable impurities.
第９の本発明のフラックスレスろう付け用アルミニウムクラッド材は、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前記Ａｌ−Ｓｉ系ろう材が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系ろう材をろう付け対象部材に接触密着させて前記Ａｌ−Ｓｉ系ろう材により前記接触密着面において前記ろう付け対象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。 An aluminum clad material for fluxless brazing according to a ninth aspect of the present invention is an Al-Si based brazing material obtained by cladding the Al-Si based brazing material according to any one of the first to fourth aspects of the present invention on a core material. The material is located on the outermost surface, and the Al-Si brazing material is brought into contact and contact with the brazing target member in a non-oxidizing atmosphere without decompression, and the Al-Si brazing material is used to bring the Al-Si brazing material into contact with the contact surface. It is used for fluxless brazing so as to join the member to be brazed.
第１０の本発明のフラックスレスろう付け用アルミニウムクラッド材は、前記第９の本発明において、前記芯材が前記第５〜８のいずれかの本発明に記載された組成を有することを特徴とする。 Fluxless brazing of aluminum clad material of the present invention of a 10 and characterized by the present invention of the ninth, having a composition wherein the core material according to any one of the present invention of the fifth to eighth To do.
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
本発明で用いるアルミニウムクラッド材では、ろう材としてＡｌ−Ｓｉ系合金をベースに、Ｍｇを添加したものを用いる。
1. Brazing material In the aluminum clad material used in the present invention, a brazing material based on an Al-Si alloy and added with Mg is used.
Ｓｉの含有量は特に限定されるものではないが、一般的にろう材として用いられる３〜１３％程度が好適であり、さらに６〜１２％が好適である。６％未満ではろう付け時の液相量が不足する傾向にあり、１２％を越えると、Ａｌ−Ｓｉ系合金の過共晶Ｓｉ領域となり、アルミニウム板製造時の加工性が悪くなる傾向にあるためである。 Although content of Si is not specifically limited, About 3 to 13% generally used as a brazing material is suitable, and 6 to 12% is more suitable. If it is less than 6%, the amount of liquid phase at the time of brazing tends to be insufficient, and if it exceeds 12%, it becomes a hypereutectic Si region of an Al—Si based alloy, and the workability at the time of producing an aluminum plate tends to deteriorate. Because.
Ｍｇの含有量は０．１〜５．０％がよく、０．１％未満では本発明の効果であるろう付け時接合面の再酸化防止効果が得られず、５％を越えると効果が飽和し、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によるゲッター作用との相乗効果により、より良好なろう付け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℃以上でろう付けができるようになる。 The content of Mg is preferably 0.1 to 5.0%. If it is less than 0.1%, the effect of the present invention, which is the effect of the present invention, cannot be obtained by the effect of preventing reoxidation of the joint surface at the time of brazing. Saturates and causes difficulty in workability of the aluminum material. In the present invention, brazing properties can be secured only by the oxide film destruction 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 a solder | brazing | wax will fully be acquired, and it becomes possible to obtain a more favorable brazing property by the synergistic effect with the getter action by Mg. Specifically, brazing can be performed at the lowest solidus temperature of 559 ° C. or higher with an Al—Si—Mg alloy.
また、本ろう材には製品の耐食性を向上させる目的で、Ｚｎを適宜含有できるものとする。この成分は、例えば、０．１〜５．０％の含有量で含有させることができる。さらに、本発明で接合を得るにあたり、Ｂｉの含有は必須ではないが、Ｂｉを含有させることにより、よりろう材の濡れ性を向上させることが可能となる。
Ｂｉの含有量は０．０１〜１．０％がよい。０．０１％未満では効果が十分でなく、１．０％を越えると効果の飽和、材料コストの増大を招くため好ましくない。
The brazing material can contain Zn as appropriate for the purpose of improving the corrosion resistance of the product. This component can be contained at a content of 0.1 to 5.0%, for example. Further, in order to obtain a bond in the present invention, Bi is not essential, but by incorporating Bi, the wettability of the brazing material can be further improved.
The Bi content is preferably 0.01 to 1.0%. If it is less than 0.01%, the effect is not sufficient, and if it exceeds 1.0%, the effect is saturated and the material cost is increased.
そして、本発明を実施するにあたっては、ろう材表面に比較的粗大なＳｉ粒子が存在していることが好ましい。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。酸化膜の厚みが増すほど、酸化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。本発明では、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膜が成長せず、この部位がアルミニウム材料表面の酸化膜欠陥として働く。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膜破壊作用が進んでいくものと考えられる。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。本発明においてＳｉ粒子の密度には言及していないが、本発明で用いる合金組成と製造条件範囲、及び材料の仕上げ板厚寸法によって、１００００μｍ２視野における０．８μｍ以上のＳｉ粒子数は数十〜数千個の範囲に及ぶと考えられ、その規定は難しいことから、本発明においては、このＳｉ粒子数範囲で、１．７５μｍ径以上のものが２５％以上の個数存在すれば、効果を得られることを確認し上記規定を望ましいものとした。 In carrying out the present invention, it is preferable that relatively coarse Si particles exist on the surface of the brazing material. Usually, a dense oxide film such as Al 2 O 3 is present on the surface of the aluminum material, and this further grows to become a thick film in the brazing heat treatment process. The general view is that the greater the thickness of the oxide film, the stronger the tendency to inhibit the destruction of the oxide film. In the present invention, since coarse Si particles are present 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 thick during the brazing heat treatment, the brazing material oozes out from the Si particle portion, and the oxide film destruction action proceeds from this site. Conceivable. 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. Although the density of the Si particles is not mentioned in the present invention, the number of Si particles of 0.8 μm or more in the 10000 μm 2 field of view is several tens depending on the alloy composition used in the present invention, the manufacturing condition range, and the finished plate thickness of the material. In the present invention, if the number of particles having a diameter of 1.75 μm or more is 25% or more, the effect is obtained. After confirming that it was obtained, the above regulations were made desirable.
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、ろう材表面の酸化膜破壊、酸化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, a part of it diffuses into the brazing material and contributes to the action of suppressing 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．ろう付け対象部材の材質
ろう材以外の被ろう付け構成部材としては、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。
4). Material of brazing target member Any commonly used aluminum alloy can be used as the brazing constituent member other than the brazing material without any problem.
５．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機密性が得られないためろう付け性が低下する。
5). Surface roughness of the brazing member In carrying out the present invention, it is difficult to supply oxygen from the outside to the contact adhesion portion which is the junction portion by increasing the contact adhesion state of the junction portion. Increases the ability to suppress oxidation of the material surface. 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 deteriorated because sufficient confidentiality cannot be obtained even if the pressure adhesion is increased.
６．被ろう付け構成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 brazed component 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 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 required, 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、被ろう付け物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 a non-oxidizing gas such as an inert gas or 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℃超ではろう浸食が顕著となり、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 remarkable, which causes a problem in maintaining the product shape and the like, which is not preferable. 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.
本発明では、ろう材に添加された適量のＭｇが接合部接触密着表面の酸化膜を破壊し、再酸化を抑制することで、良好な接合を得られる。この機構自体は、真空ろう付けや、大気圧下でのフラックスレスろう付け等を提案している従来技術と同様であるが、真空ろう付けでは、部材の再酸化防止のため真空の維持が必須であり、また、大気圧下の従来技術では、ろう材の表面に酸化防止層を設けたり、被ろう付け部材を覆いで囲ったりする等して、材料の再酸化やＭｇ蒸気の拡散防止を行う必要がある。一方、本発明においては、接合せしめる構成部材同士を確実に接触密着させた上で、ある一定以上のＭｇをろう材に添加し、さらに、ろう付けを非酸化性雰囲気中で行うことで、材料表面の再酸化力よりもＭｇによる酸化膜破壊活動が上回る条件を見出し、ろう材がろう付け構成物の最表面に位置する場合においても、接合を成立させている。このとき、ろう材に添加されたＭｇはろうの融点を低下させ、Ｍｇのゲッター作用とろうの溶融（局部溶融を含む）がほぼ同じ温度域で生じる効果も得られ、ろう付性を向上させている。 In the present invention, an appropriate amount of Mg added to the brazing material breaks down the oxide film on the contact surface of the joint portion and suppresses reoxidation, so that good bonding can be obtained. This mechanism itself is the same as the conventional technology that proposes vacuum brazing, fluxless brazing under atmospheric pressure, etc. However, in vacuum brazing, it is essential to maintain a vacuum to prevent reoxidation of members. In addition, in the prior art under atmospheric pressure, an anti-oxidation layer is provided on the surface of the brazing material, or the brazed member is covered and surrounded to prevent re-oxidation of the material and diffusion of Mg vapor. There is a need to do. On the other hand, in the present invention, the component members to be bonded are reliably brought into contact with each other, then a certain amount or more of Mg is added to the brazing material, and further brazing is performed in a non-oxidizing atmosphere. A condition has been found in which the oxide film destruction activity by Mg exceeds the surface reoxidation power, and even when the brazing material is located on the outermost surface of the brazing component, the bonding is established. At this time, Mg added to the brazing material lowers the melting point of the brazing, and the effect that the getter action of Mg and the melting of the brazing (including local melting) occur in almost the same temperature range can be obtained, thereby improving the brazing property. ing.
以上のように、本発明によるろう付け法を用いれば、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けが可能となり、また、ろう材以外の被ろう付け構成部材へＭｇを添加した場合にもろう付け阻害要因とはならないことから、Ｍｇを構造部材に添加した、熱交換器用アルミニウム高強度部材への用途展開も図れることになる。その他、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の蒸発は製品周辺に止まり、炉内壁等の汚染は殆ど生じないというメリットも得られる。 As described above, if the brazing method according to the present invention is used, fluxless brazing at atmospheric pressure is possible without the need for flux and vacuum equipment, and Mg is added to brazed components other than the brazing material. When added, it does not become a brazing-inhibiting factor, so that it is possible to develop applications for high-strength aluminum members for heat exchangers in which Mg is added to the structural member. In addition, since heating is performed in an atmosphere without decompression, Mg and Zn evaporation from the aluminum material stops around the product, and there is an advantage that contamination of the furnace inner wall and the like hardly occurs.
以下に、本発明の一実施形態を説明する。
質量％で、Ｍｇを０．１〜５．０％、Ｓｉを３〜１３％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、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。該クラッド圧延での製造条件は本発明としては特に限定されるものではない。また、各層のクラッド率も本発明としては特定されるものではない。
なお、上記のように芯材の組成は、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％、Ｂｉ：０．０１〜１．０％の内１種または２種以上を含有などが望ましい。
本発明では、前記Ａｌ−Ｓｉ系ろう材に含まれるＳｉ粒子で、円相当径で０．８μｍ以上の径をもつものの数の内、１．７５μｍ以上の径のものの数が２５％以上とするのが望ましい。本材料を得るには、ろう材の鋳造スラブを製造するにあたり、その冷却速度を１０℃/ｓｅｃよりも遅い範囲とし、凝固冷却で生じるＳｉ粒子サイズを粗大にすることで、その後の圧延工程でのＳｉ粒子破砕を経ても、上記条件を満たすことが可能となる。但し、この冷却速度が１０℃/ｓｅｃより速くなった場合においても、鋳造後に均質化処理として、例えば５００℃以上の条件で数時間の熱処理を加えれば、Ｓｉ粒子の粗大化が図れ、上記同様に、圧延後には本発明条件のＳｉ粒子サイズを得ることが可能である。
また、本発明では前記アルミニウムクラッド材、及び、前記ろう付け対象部材の少なくとも接触密着部表面の表面粗さを、Ｒａ０．３μｍ以下とするのが望ましい。この表面粗さは、材料の最終圧延時のロール表面粗度に依存し、そのロール表面粗度を、Ｒａで０．４５μｍ以下とすることで得られる。尚、ろう付け接合部がプレス等の熱交換器部材加工表面となる場合には、そのプレス等金型表面粗度を同様に管理することで目的の表面粗度が得られる。
Hereinafter, an embodiment of the present invention will be described.
An Al—Si brazing material containing 0.1 to 5.0% Mg and 3 to 13% Si and a core material can be manufactured by a conventional method, and both or a sacrificial material. Clad rolling with other materials. The production conditions in the clad rolling are not particularly limited as the present invention. Further, the cladding ratio of each layer is not specified as the present invention.
As described above, 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 to 1.0%, Si: 0.1 to 1.2%, Fe: 0.1 to 1.0%, or Si: 0.1 to 1.2%, Mg: 0.01-2.0%, Mn: 0.2-2.5%, Cu: 0.05-1.0%, Fe: 0.1-1.0% 2 or more types, and 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 It is desirable to contain one or more of 0.0%.
In the present invention, among the number of Si particles contained in the Al—Si brazing material having an equivalent circle diameter of 0.8 μm or more, the number of particles having a diameter of 1.75 μm or more is 25% or more. Is desirable. In order to obtain this material, in producing a cast slab of brazing filler metal, the cooling rate is set to a range slower than 10 ° C./sec, and the Si particle size generated by solidification cooling is coarsened. Even if the Si particles are crushed, the above conditions can be satisfied. However, even when this cooling rate is higher than 10 ° C./sec, Si particles can be coarsened by applying a heat treatment for several hours under conditions of 500 ° C. or higher as a homogenization treatment after casting, as described above. In addition, it is possible to obtain the Si particle size of the present invention after rolling.
In the present invention, it is desirable that the surface roughness of at least the contact adhesion portion surface of the aluminum clad material and the brazing target member is Ra 0.3 μm or less. This surface roughness depends on the roll surface roughness at the time of final rolling of the material, and can be obtained by setting the roll surface roughness to Ra of 0.45 μm or less. In addition, when the brazed joint portion is a heat exchanger member processed surface such as a press, the target surface roughness can be obtained by similarly controlling the die surface roughness of the press.
常法により得られるアルミニウムクラッド材は、上記Ａｌ−Ｓｉ系ろう材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は、ベアフィン、無垢材コネクタなどのろう付け対象部材と組み付けられて、好適には熱交換器組立体などを構成する。なお、ろう付け対象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。
In the aluminum clad material obtained by a conventional method, the Al—Si brazing material is located on the outermost surface, and an oxide film having an initial oxide film thickness of 20 to 500 mm is formed.
The aluminum clad material is assembled with a member to be brazed such as a bare fin or a solid material connector, and preferably constitutes a heat exchanger assembly or the like. Note that aluminum materials having various compositions can be used as the brazing target member, and the present invention is not limited to a specific one.
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、ろう付け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、ろう付け材の搬入口、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けを行う。ろう付けにおいては、ろう付け対象部材との接触密着部がフラックスレスで良好に接合される。
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 heating 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 property 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 contact and adhesion portion with the brazing target member is satisfactorily joined without flux.
表１〜表３に示す組成（残部Ａｌと不可避不純物）のＡｌ−Ｓｉ系ろう材と、同じく表１〜表３に示す組成（残部Ａｌと不可避不純物）の芯材とをクラッドしたアルミニウムクラッド材として用意した。ろう材中のＳｉ粒子径は、鋳造時の冷却速度を０．５〜１０℃／ｓｅｃの範囲で変化させ、また、材料表面粗さは最終圧延時のロール表面粗度をＲａ０．０５〜０．９０の範囲で変えることによって変化させた。 An aluminum clad material clad with an Al-Si brazing material having the composition shown in Tables 1 to 3 (remainder Al and inevitable impurities) and a core material having the composition shown in Tables 1 to 3 (remainder Al and inevitable impurities) Prepared as. The Si particle diameter in the brazing material changes the cooling rate during casting in the range of 0.5 to 10 ° C./sec, and the material surface roughness indicates the roll surface roughness during final rolling by Ra 0.05 to 0. .Varying by changing in the range of 90.
上記アルミニウムクラッド材は、各種組成ろう材と各種組成芯材とを、ろう材クラッド率１０％とし、Ｈ１４相当調質の０．５ｍｍ厚に仕上げた。
また、ろう付け対象部材としてＪＩＳＡ３００３合金、Ｈ１４のアルミニウムベア材（０．１ｍｍ厚）のフィン材を用意した。
The aluminum clad material was prepared by brazing various composition brazing materials and various composition core materials to a brazing material clad rate of 10% and a tempering equivalent to H14 to a thickness of 0.5 mm.
Further, as a brazing target member, a fin material made of JIS A3003 alloy and H14 aluminum bare material (thickness: 0.1 mm) was prepared.
○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、ＪＩＳ Ａ３００３ベア材の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のコアである。
コアを窒素雰囲気中（酸素含有量１５ｐｐｍ）のろう付け炉にて、５６０〜６００℃まで加熱し、そのろう付け状態でろう付性を評価した。ろう付性は、以下式にて接合率を求め、その接合率の優劣で評価した。
O Brazing property A flat electro-sewn tube having a width of 20 mm was manufactured using the aluminum clad material of the present invention, and combined with a corrugated fin of JIS A3003 bare material to form a core shape. The core size is a core having 15 tubes and a length of 300 mm.
The core was heated to 560 to 600 ° C. in a brazing furnace in a nitrogen atmosphere (oxygen content: 15 ppm), and brazing properties were evaluated in the brazed state. The brazing property was evaluated based on the superiority or inferiority of the joining rate obtained by the following formula.
フィン接合率＝（フィンとチューブの総ろう付け長さ／フィンとチューブの総接触長さ）×１００
ろう付け性判定は、ろう付け後のフィン接合率（◎：９５％以上、○：８５％以上、△：８０％以上、×：８０％未満）によって行い、その結果を表１〜表３に示した。
Fin joint rate = (total brazing length of fin and tube / total contact length of fin and tube) × 100
The brazing performance is determined by the fin joint rate after brazing (◎: 95% or more, ○: 85% or more, Δ: 80% or more, ×: less than 80%), and the results are shown in Tables 1 to 3. Indicated.
○材料強度
製作したクラッド材（０．５ｍｍ厚）をＪＩＳ５号試験片とし、ろう付け熱処理後、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〜表３に示した。
Material Strength The manufactured clad material (0.5 mm thickness) was a JIS No. 5 test piece, and subjected to a tensile test after brazing heat treatment and after aging treatment at 90 ° C. for 7 days. The obtained material strength measurement values were evaluated, and the results are shown in Tables 1 to 3.
作製したクラッド材について、ろう材最表面を＃１０００のエメリー紙で研削後、０．１μｍの砥粒で鏡面処理し、表面方向１００００μｍ２（１００μｍ角相当）の観察視野において、ＥＰＭＡ（電子線マイクロアナライザ）を用いた全自動粒子解析を行った。測定した０．８μｍ以上の総粒子数中で、１．７５μｍ以上のものの割合を表に示した About the produced clad material, the outermost surface of the brazing material is ground with # 1000 emery paper, then mirror-finished with 0.1 μm abrasive grains, and EPMA (electron beam micrometer) is observed in the observation field of surface direction of 10,000 μm 2 (equivalent to 100 μm square). Fully automatic particle analysis using an analyzer was performed. The ratio of particles with a particle size of 1.75 μm or more out of the total number of particles of 0.8 μm or more measured is shown in the table.
実施例の何れも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、比較材でその条件は得られなかった。
また、芯材の成分が好適範囲を外れる参考例では、種々の不具合が認められた。
While all of the examples showed good brazing properties, the comparative example did not provide sufficient bonding. Further, in the examples, it was possible to achieve both high material strength and brazing, but the conditions were not obtained with the comparative material.
Further, in the reference example in which the core component deviated from the preferred range, various problems were observed.
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