JP5188115B2 - High strength aluminum alloy brazing sheet - Google Patents
High strength aluminum alloy brazing sheet Download PDFInfo
- Publication number
- JP5188115B2 JP5188115B2 JP2007188856A JP2007188856A JP5188115B2 JP 5188115 B2 JP5188115 B2 JP 5188115B2 JP 2007188856 A JP2007188856 A JP 2007188856A JP 2007188856 A JP2007188856 A JP 2007188856A JP 5188115 B2 JP5188115 B2 JP 5188115B2
- Authority
- JP
- Japan
- Prior art keywords
- brazing
- core material
- sacrificial anode
- density
- intermetallic compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000005219 brazing Methods 0.000 title claims description 112
- 229910000838 Al alloy Inorganic materials 0.000 title claims description 28
- 239000011162 core material Substances 0.000 claims description 55
- 239000000463 material Substances 0.000 claims description 46
- 229910000765 intermetallic Inorganic materials 0.000 claims description 37
- 239000010405 anode material Substances 0.000 claims description 26
- 238000005098 hot rolling Methods 0.000 claims description 24
- 239000013078 crystal Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 11
- 238000005096 rolling process Methods 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910018125 Al-Si Inorganic materials 0.000 claims description 4
- 229910018520 Al—Si Inorganic materials 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 description 18
- 238000005260 corrosion Methods 0.000 description 18
- 239000000956 alloy Substances 0.000 description 16
- 229910045601 alloy Inorganic materials 0.000 description 15
- 230000000694 effects Effects 0.000 description 15
- 238000005728 strengthening Methods 0.000 description 11
- 230000003628 erosive effect Effects 0.000 description 10
- 239000006104 solid solution Substances 0.000 description 10
- 229910019018 Mg 2 Si Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000000137 annealing Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000003507 refrigerant Substances 0.000 description 5
- 229910018131 Al-Mn Inorganic materials 0.000 description 4
- 229910018461 Al—Mn Inorganic materials 0.000 description 4
- 238000003483 aging Methods 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910018643 Mn—Si Inorganic materials 0.000 description 3
- 238000005097 cold rolling Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000005304 joining Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910021364 Al-Si alloy Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 229910018473 Al—Mn—Si Inorganic materials 0.000 description 1
- 229910018580 Al—Zr Inorganic materials 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 208000014451 palmoplantar keratoderma and congenital alopecia 2 Diseases 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Pressure Welding/Diffusion-Bonding (AREA)
Description
本発明は、自動車用熱交換器に使用されるアルミニウム合金ブレージングシート、特にラジエータ、コンデンサなどの熱交換器の冷却水や冷媒の通路構成材として好適に使用される高強度アルミニウム合金ブレージングシートに関する。 TECHNICAL FIELD The present invention relates to an aluminum alloy brazing sheet used for a heat exchanger for automobiles, and more particularly to a high-strength aluminum alloy brazing sheet suitably used as a coolant or refrigerant passage constituent material for heat exchangers such as radiators and condensers.
アルミニウム合金は軽量かつ高熱伝導性を備えているため、自動車用熱交換器、例えば、ラジエータ、コンデンサ、エバポレータ、ヒーター、インタークーラなどに用いられている。自動車用熱交換器は主にろう付法によって製造される。通常、ろう付はＡｌ−Ｓｉ系合金のろう材を用い、６００℃程度の高温で行われる。
ろう付を用いて製造するアルミニウム合金製熱交換器は、主に放熱を担うコルゲート成形したフィンと、冷却水や冷媒を循環させるためのチューブとで構成される。チューブが破壊することで貫通すれば、内部を循環している冷却水や冷媒の漏洩が生じる。そのため、製品寿命を向上させるために、ろう付後の強度に優れたアルミニウム合金ブレージングシートが必要不可欠とされている。
Aluminum alloys are lightweight and have high thermal conductivity, and are therefore used in automotive heat exchangers such as radiators, condensers, evaporators, heaters, and intercoolers. Automotive heat exchangers are mainly manufactured by the brazing method. Usually, brazing is performed at a high temperature of about 600 ° C. using a brazing material of an Al—Si alloy.
An aluminum alloy heat exchanger manufactured by brazing is composed of corrugated fins that mainly perform heat dissipation and tubes for circulating cooling water and refrigerant. If the tube penetrates due to destruction, cooling water and refrigerant circulating inside the tube will leak. Therefore, in order to improve the product life, an aluminum alloy brazing sheet having excellent strength after brazing is indispensable.
ところで、近年は自動車の軽量化に対する要求が高まり、それに対応するため自動車用熱交換器の軽量化も求められている。そのため、熱交換器を構成する各部材の薄肉化が検討されており、アルミニウム合金ブレージングシートのろう付け後の強度をさらに向上させることが必要とされている。
従来、自動車用のラジエータやヒーターのように、冷却水がチューブ内面を循環する熱交換器のチューブ材として、ＪＩＳ３００３合金に代表されるようなＡｌ−Ｍｎ系合金などの心材の内面側にＡｌ−Ｚｎ系合金などの犠牲陽極材をクラッドし、大気側にＡｌ−Ｓｉ系合金などのろう材をクラッドした３層チューブ材が一般に用いられてきた。
By the way, in recent years, demands for weight reduction of automobiles have increased, and in order to meet such demands, weight reduction of automobile heat exchangers has also been demanded. Therefore, thinning of each member constituting the heat exchanger has been studied, and it is necessary to further improve the strength of the aluminum alloy brazing sheet after brazing.
Conventionally, as a heat exchanger tube material in which cooling water circulates on the inner surface of a tube, such as a radiator or heater for automobiles, an Al-Mn alloy such as an Al-Mn alloy typified by JIS3003 alloy is formed on the inner surface side. A three-layer tube material is generally used in which a sacrificial anode material such as a Zn-based alloy is clad and a brazing material such as an Al—Si alloy is clad on the atmosphere side.
しかしながら、ＪＩＳ３００３合金心材を使用したクラッド材のろう付け後強度は１１０ＭＰａ（１１０Ｎ／ｍｍ２）程度であり、強度が不十分である。
心材の均質化処理条件を規定し、熱間圧延前の加熱を５００℃以下とすることで、析出粒子の粗大化を抑制し、強度を向上させたアルミニウム合金ブレージングシートが提案されている（たとえば、特許文献１参照）。しかしながら、この製造工程では、熱間圧延時の開始温度と終了温度については考慮されておらず、ろう付後のＭｇ２Ｓｉによる時効硬化に悪影響を及ぼす金属間化合物が析出する可能性があるため、ろう付後強度が不十分となる問題がある。
An aluminum alloy brazing sheet has been proposed that regulates the homogenization treatment conditions of the core material and suppresses the coarsening of the precipitated particles and improves the strength by setting the heating before hot rolling to 500 ° C. or less (for example, , See Patent Document 1). However, in this manufacturing process, the start temperature and end temperature during hot rolling are not considered, and there is a possibility that an intermetallic compound that adversely affects age hardening by Mg 2 Si after brazing may precipitate. There is a problem that the strength after brazing becomes insufficient.
アルミニウム合金ブレージングシートの薄肉化の要求を満たすべく、ろう付後強度等の特性を向上させる必要がある。従来技術では、肉薄でありながらさらなる強度向上を達成するに至る特性を得ることは困難であった。
本発明は、この問題点を解消するべく行われたものであって、アルミニウム合金ブレージングシートにおいて、ろう付時のろう拡散もなくろう付は良好であり、且つろう付後に優れた強度を有するアルミニウム合金ブレージングシート、特に自動車用熱交換器の流体通路構成材として好適に使用できるアルミニウム合金ブレージングシートを提供することを目的とするものである。
In order to satisfy the demand for thinning the aluminum alloy brazing sheet, it is necessary to improve properties such as strength after brazing. In the prior art, it has been difficult to obtain characteristics that achieve a further improvement in strength while being thin.
The present invention has been made to solve this problem, and in an aluminum alloy brazing sheet, aluminum has good brazing without brazing and diffusion during brazing, and has excellent strength after brazing. An object of the present invention is to provide an alloy brazing sheet, in particular, an aluminum alloy brazing sheet that can be suitably used as a fluid passage component of a heat exchanger for automobiles.
本発明者らは上記課題について研究した結果、特定の合金組成と合金組織を有するクラッド材がその目的に適合することを見出し、これに基づき本発明をなすに至った。
すなわち本発明は、
心材の片面にＡｌ−Ｓｉ系ろう材をクラッドし、心材の他方の面には犠牲陽極材をクラッドしたアルミニウム合金ブレージングシートであって、前記心材が、Ｓｉ：０．５〜１．０％（質量％、以下同じ）、Ｆｅ：０．１〜０．３％、Ｃｕ：０．３〜１．０％、Ｍｎ：１．０〜１．６％、Ｍｇ：０．１〜０．４％を含有し、さらにＴｉ：０．０５〜０．２％、Ｚｒ：０．０５〜０．２％、Ｖ：０．０５〜０．２％のうち1種以上を含有し、残部Ａｌと不可避的不純物からなるＡｌ合金であり、そのろう付後の心材の金属組織は、粒径０．１μｍ以上の金属間化合物の密度が１０個／μｍ２以下であり、且つろう付後の結晶粒径が１００μｍ以上であるＡｌ合金であり、前記犠牲陽極材が、Ｚｎ：２．０〜５．０％を含有し、さらにＳｉ：０．０５〜１．０％、Ｍｎ：０．０５〜１．６％、Ｔｉ：０．０５〜０．２％、Ｖ：０．０５〜０．２％のうち１種以上を含有し、残部Ａｌと不可避的不純物からなるＡｌ合金であり、心材、犠牲陽極材は、ろう材と共に組み合わせ、この組み合わせ材を熱間圧延の開始温度を４８０℃以下、熱間圧延の終了温度を２８０℃以下として熱間圧延することによりクラッド材を作製したことを特徴とする高強度アルミニウム合金ブレージングシート。
（但し、粒径０．１μｍ以上の金属間化合物の密度は、心材のＬ−ＬＴ面（圧延方向（Ｌ方向）と、圧延面に対して平行でＬ方向に対して垂直な方向（ＬＴ方向）で形成される面）を研磨で面出し、心材の透過型電子顕微鏡（ＴＥＭ）観察を以下のように行うことで調べた。等厚干渉縞から観察部の膜厚を測定し、膜厚が０．１〜０．３μｍの箇所でのみＴＥＭ観察を行い、ＴＥＭ写真を画像解析することで、ろう付後の金属間化合物の密度であり、この金属間化合物の密度は、１０視野についての値の平均値をとる。）
を提供するものである。
As a result of studying the above problems, the present inventors have found that a clad material having a specific alloy composition and alloy structure is suitable for the purpose, and based on this, the present invention has been made.
That is, the present invention
An aluminum alloy brazing sheet in which an Al—Si brazing material is clad on one side of a core material and a sacrificial anode material is clad on the other side of the core material, wherein the core material contains Si: 0.5 to 1.0% ( % By mass, the same applies hereinafter), Fe: 0.1 to 0.3%, Cu: 0.3 to 1.0%, Mn: 1.0 to 1.6%, Mg: 0.1 to 0.4% In addition, Ti: 0.05-0.2%, Zr: 0.05-0.2%, V: 0.05-0.2%, containing at least one of the remaining, inevitable with the remaining Al The metal structure of the core material after brazing is an Al alloy composed of mechanical impurities, the density of intermetallic compounds having a particle size of 0.1 μm or more is 10 pieces / μm 2 or less, and the crystal grain size after brazing In which the sacrificial anode material contains Zn: 2.0-5.0%, and Si: 0.0 -1.0%, Mn: 0.05-1.6%, Ti: 0.05-0.2%, V: One or more of 0.05-0.2% are contained, and the balance is Al. It is an Al alloy composed of inevitable impurities, and the core material and sacrificial anode material are combined with the brazing material, and this combined material is hot with a hot rolling start temperature of 480 ° C. or lower and a hot rolling end temperature of 280 ° C. or lower. A high-strength aluminum alloy brazing sheet characterized by producing a clad material by rolling .
(However, the density of the intermetallic compound having a particle size of 0.1 μm or more is determined by the L-LT plane of the core material (the rolling direction (L direction) and the direction parallel to the rolling plane and perpendicular to the L direction (LT direction)). The surface formed by polishing) was surfaced by polishing, and the core material was examined by observation with a transmission electron microscope (TEM) as follows: The film thickness of the observation part was measured from the equal thickness interference fringes, and the film thickness was measured. Is a density of the intermetallic compound after brazing by performing TEM observation only at a location of 0.1 to 0.3 μm and analyzing the image of the TEM photograph. The density of the intermetallic compound is about 10 fields of view. (The average value is taken.)
Is to provide.
本発明によれば、肉薄でありながらフィン接合率、耐エロージョン性などろう付性に優れ、且つろう付後の強度が高いアルミニウム合金ブレージングシートを得ることができる。そして、このブレージングシートは肉薄であり、自動車用の熱交換器として軽量で熱伝導性に優れ、ろう付後強度が高いことにより、熱交換器の寿命をさらに長くさせることができる。 According to the present invention, it is possible to obtain an aluminum alloy brazing sheet that is thin but has excellent brazing properties such as a fin joining rate and erosion resistance and high strength after brazing. And this brazing sheet is thin, is lightweight as a heat exchanger for automobiles, is excellent in thermal conductivity, and has high strength after brazing, so that the life of the heat exchanger can be further extended.
本発明のアルミニウム合金ブレージングシートの好ましい実施の態様について、詳細に説明する。
本発明のアルミニウム合金ブレージングシートを構成する心材、犠牲陽極材の成分元素の添加理由および添加範囲について説明し、ろう材について述べる。
A preferred embodiment of the aluminum alloy brazing sheet of the present invention will be described in detail.
The reason for addition and the range of addition of the constituent elements of the core material and sacrificial anode material constituting the aluminum alloy brazing sheet of the present invention will be described, and the brazing material will be described.
［１．心材］
Ｓｉは、Ｆｅ、ＭｎとともにＡｌ−Ｆｅ−Ｍｎ−Ｓｉ系の化合物を形成し、分散強化として作用し、或いはマトリクスに固溶して固溶強化により強度を向上させる。また、Ｍｇと反応してＭｇ２Ｓｉ化合物を形成することで強度が向上する。Ｓｉの含有量は、０．５〜１．０％（組成の％は質量％を表す、以下同じ）の範囲であり、０．５％未満ではその効果が小さく、１．０％を超えると心材の融点が低下し、溶融が起こる可能性が高くなる。好ましくは、０．６〜０．９％である。
Ｆｅは、再結晶核となり得るサイズの金属間化合物を作りやすい。ろう付後の結晶粒径を粗大にしてろう拡散を抑制するためには、Ｆｅの含有量は、０．１〜０．３％であり、０．１％未満では高純度アルミニウム地金を使用しなければならずコスト高となり、０．３％を超えるとろう付後の結晶粒径が微細となり、ろう拡散が生じる恐れがある。好ましくは、０．１〜０．２％である。
[1. Heartwood]
Si forms an Al—Fe—Mn—Si compound together with Fe and Mn, and acts as dispersion strengthening, or is dissolved in a matrix to improve strength by solid solution strengthening. Further, the strength is improved by reacting with Mg to form a Mg 2 Si compound. The content of Si is in the range of 0.5 to 1.0% (% of composition represents mass%, the same shall apply hereinafter), and if less than 0.5%, the effect is small, and exceeding 1.0% The melting point of the core material is lowered, and the possibility of melting is increased. Preferably, it is 0.6 to 0.9%.
Fe tends to make an intermetallic compound of a size that can be a recrystallization nucleus. In order to suppress the brazing diffusion by making the crystal grain size after brazing coarse, the Fe content is 0.1 to 0.3%, and if it is less than 0.1%, high-purity aluminum metal is used. If the content exceeds 0.3%, the crystal grain size after brazing becomes fine and brazing diffusion may occur. Preferably, it is 0.1 to 0.2%.
Ｃｕは、固溶強化により強度を向上させ、また電位を貴にして犠牲陽極材、フィン材との電位差を大きくし、犠牲陽極効果による防食効果を向上させる。Ｃｕの含有量は、０．３〜１．０％の範囲であり、０．３％未満ではその効果が小さく、１．０％を超えると粒界腐食が発生する可能性が高くなる。好ましくは、０．３〜０．９％である。
Ｍｎは、強度とろう付性、耐食性を向上させ、また電位を貴にする効果がある。Ｍｎの含有量は、１．０〜１．６％であり、１．０％未満ではその効果が小さく、１．６％を超えると鋳造時に巨大金属間化合物が形成されやすくなり、塑性加工性を低下させる。好ましくは、１．１〜１．５％である。
Ｍｇは、Ｍｇ２Ｓｉ析出による強度向上に効果がある。Ｍｇの含有量は、０．１〜０．４％であり、０．１％未満ではその効果が小さく、０．４％を超えるとろう付性が低下する。好ましくは、０．１５〜０．４％である
Cu improves the strength by solid solution strengthening, increases the potential difference between the sacrificial anode material and the fin material by making the potential noble, and improves the anticorrosion effect by the sacrificial anode effect. The Cu content is in the range of 0.3 to 1.0%. If the content is less than 0.3%, the effect is small. If the content exceeds 1.0%, the possibility of occurrence of intergranular corrosion increases. Preferably, it is 0.3 to 0.9%.
Mn has the effects of improving strength, brazing and corrosion resistance and making the potential noble. The content of Mn is 1.0 to 1.6%. If the content is less than 1.0%, the effect is small, and if it exceeds 1.6%, a giant intermetallic compound is easily formed during casting, and plastic workability is increased. Reduce. Preferably, it is 1.1 to 1.5%.
Mg is effective in improving the strength due to Mg 2 Si precipitation. The content of Mg is 0.1 to 0.4%. If the content is less than 0.1%, the effect is small, and if it exceeds 0.4%, the brazing property decreases. Preferably, it is 0.15-0.4%
本発明における心材には、さらにＴｉ、ＺｒおよびＶのうち１種以上を所定量含有させる。
Ｔｉは、固溶強化により強度を向上させ、また耐食性の向上が図れる。好ましい含有量は、０．０５〜０．２％であり、０．０５％未満ではその効果は得られず、０．２％を超えると巨大金属間化合物を形成しやすくなり、塑性加工性を低下させる。より好ましくは、０．１〜０．１５％である。
Ｚｒは、固溶強化により強度を向上させ、またＡｌ−Ｚｒ系の微細化合物が析出し、ろう付後の結晶粒粗大化に作用する。好ましい含有量は、０．０５〜０．２％であり、０．０５％未満ではその効果は得られず、０．２％を超えると巨大金属間化合物を形成しやすくなり、塑性加工性を低下させる。より好ましくは、０．１〜０．１５％である。
Ｖは、固溶強化により強度を向上させ、また耐食性の向上が図れる。好ましい含有量は、０．０５〜０．２％であり、０．０５％未満ではその効果は得られず、０．２％を超えると巨大金属間化合物を形成しやすくなり、塑性加工性を低下させる。より好ましくは、０．１〜０．１５％である。
The core material in the present invention further contains a predetermined amount of one or more of Ti, Zr and V.
Ti improves strength by solid solution strengthening and can improve corrosion resistance. The preferable content is 0.05 to 0.2%, and if it is less than 0.05%, the effect cannot be obtained, and if it exceeds 0.2%, it becomes easy to form a giant intermetallic compound, and the plastic workability is reduced. Reduce. More preferably, it is 0.1 to 0.15%.
Zr improves the strength by solid solution strengthening, and Al-Zr-based fine compounds precipitate, which acts on the coarsening of crystal grains after brazing. The preferable content is 0.05 to 0.2%, and if it is less than 0.05%, the effect cannot be obtained, and if it exceeds 0.2%, it becomes easy to form a giant intermetallic compound, and the plastic workability is reduced. Reduce. More preferably, it is 0.1 to 0.15%.
V improves strength by solid solution strengthening and can improve corrosion resistance. The preferable content is 0.05 to 0.2%, and if it is less than 0.05%, the effect cannot be obtained, and if it exceeds 0.2%, it becomes easy to form a giant intermetallic compound, and the plastic workability is reduced. Reduce. More preferably, it is 0.1 to 0.15%.
［２．犠牲陽極材］
Ｚｎは、電位を卑にすることができ、心材との電位差を形成することで犠牲陽極効果により耐食性を向上できる。Ｚｎの含有量は、２．０〜５．０％であり、２．０％未満ではその効果が十分ではなく、５．０％を超えると、腐食速度が速くなり早期に犠牲陽極材が消失し、耐食性が低下する。好ましくは、３．０〜５．０％である。
Ｓｉは、Ｆｅ、ＭｎとともにＡｌ−Ｆｅ―Ｍｎ−Ｓｉ系の化合物を形成し、分散強化として作用し、或いはマトリクスに固溶して固溶強化により強度を向上させる。また、ろう付時に心材から拡散してくるＭｇと反応してＭｇ２Ｓｉ化合物を形成することで強度が向上する。好ましいＳｉ含有量は０．０５〜１．０％、より好ましくは０．１〜０．８％である。１．０％を超えると犠牲陽極材の融点が低下し、溶融が起こる可能性が高くなる。また犠牲陽極材の電位を貴にするため、犠牲陽極効果を阻害し、耐食性が低下する。０．０５％未満では、強度の向上に対して不十分である。
Ｍｎは、強度と耐食性を向上させる。好ましい含有量は０．０５〜１．６％、より好ましくは０．１〜１．０％である。１．６％を超えると鋳造時に巨大金属間化合物が形成されやすくなり、塑性加工性を低下させる。また犠牲陽極材の電位を貴にするため、犠牲陽極効果を阻害し、耐食性が低下する。０．０５％未満では、強度の向上に対して不十分である。
[2. Sacrificial anode material]
Zn can lower the potential, and can improve the corrosion resistance by the sacrificial anode effect by forming a potential difference with the core material. The Zn content is 2.0 to 5.0%. If the content is less than 2.0%, the effect is not sufficient. If the content exceeds 5.0%, the corrosion rate increases and the sacrificial anode material disappears early. In addition, the corrosion resistance decreases. Preferably, it is 3.0 to 5.0%.
Si forms an Al—Fe—Mn—Si compound together with Fe and Mn and acts as dispersion strengthening, or improves the strength by solid solution strengthening by solid solution. Further, the strength is improved by reacting with Mg diffused from the core material during brazing to form a Mg 2 Si compound. A preferable Si content is 0.05 to 1.0%, more preferably 0.1 to 0.8%. If it exceeds 1.0%, the melting point of the sacrificial anode material is lowered and the possibility of melting is increased. Moreover, since the potential of the sacrificial anode material is made noble, the sacrificial anode effect is hindered and the corrosion resistance is lowered. If it is less than 0.05%, it is insufficient for improving the strength.
Mn improves strength and corrosion resistance. The preferred content is 0.05 to 1.6%, more preferably 0.1 to 1.0%. If it exceeds 1.6%, a huge intermetallic compound is likely to be formed during casting, and the plastic workability is lowered. Moreover, since the potential of the sacrificial anode material is made noble, the sacrificial anode effect is hindered and the corrosion resistance is lowered. If it is less than 0.05%, it is insufficient for improving the strength.
Ｔｉは、固溶強化により強度を向上させ、また耐食性の向上が図れる。好ましい含有量は、０．０５〜０．２％以下である。０．２％を超えると巨大金属間化合物を形成しやすくなり、塑性加工性を低下させる。より好ましくは、０．１〜０．１５％である。
Ｖは、固溶強化により強度を向上させ、また耐食性の向上が図れる。好ましい含有量は、０．０５〜０．２％であり、０．０５％未満ではその効果は得られず、０．２％を超えると巨大金属間化合物を形成しやすくなり、塑性加工性を低下させる。より好ましくは、０．１〜０．１５％である。
これら、Ｓｉ、Ｍｎ、Ｔｉ、Ｖは、犠牲陽極材中に必要により少なくとも１種が添加されていればよい。
なお、犠牲陽極材中には、不可避的不純物として０．０５〜０．２％程度のＦｅが含有されていてもかまわない。
Ti improves strength by solid solution strengthening and can improve corrosion resistance. A preferable content is 0.05 to 0.2% or less. If it exceeds 0.2%, it becomes easy to form a giant intermetallic compound, and the plastic workability is lowered. More preferably, it is 0.1 to 0.15%.
V improves strength by solid solution strengthening and can improve corrosion resistance. The preferable content is 0.05 to 0.2%, and if it is less than 0.05%, the effect cannot be obtained, and if it exceeds 0.2%, it becomes easy to form a giant intermetallic compound, and the plastic workability is reduced. Reduce. More preferably, it is 0.1 to 0.15%.
These Si, Mn, Ti, and V may be added in the sacrificial anode material if necessary.
The sacrificial anode material may contain about 0.05 to 0.2% Fe as an inevitable impurity.
［３．ろう材］
ろう材は通常使用されているＡｌ−Ｓｉ系合金ろう材を使用することができ、特に制限されるものではなく、例えば、ＪＩＳ４３４３、４０４５、４０４７合金（Ａｌ−７〜１３ｗｔ％Ｓｉ）が好ましい。
[3. Brazing material]
As the brazing material, a commonly used Al—Si based alloy brazing material can be used, and is not particularly limited. For example, JIS 4343, 4045, 4047 alloy (Al-7 to 13 wt% Si) is preferable.
本発明のブレージングシートは、ろう付後の心材の金属組織は、粒径０．１μｍ以上の金属間化合物、例えばＡｌ−Ｍｎ、Ａｌ−Ｍｎ−Ｓｉ、Ａｌ−Ｆｅ−Ｍｎ―Ｓｉ等、の密度が１０個／μｍ２以下、より好ましくは、５個／μｍ２以下とする。本発明におけるアルミニウム合金ブレージングシートは、Ｍｇ２Ｓｉの時効硬化による強化をメインに強度アップを図っているが、粒径０．１μｍ以上の金属間化合物がろう付終了後に存在すると、ろう付後の冷却の過程において、Ｍｇ２Ｓｉがそれら金属間化合物の表面に析出し、時効硬化に寄与しないＭｇ２Ｓｉ量が増える。その結果、心材に添加したＭｇおよびＳｉが強度向上に有効に作用せず、十分なろう付後の強度が得られない可能性がある。そこで、Ｍｇ２Ｓｉの時効硬化を効果的に作用させるため、ろう付後心材中に存在する粒径０．１μｍ以上の金属間化合物の密度が１０個／μｍ２以下とした。好ましくは、５個／μｍ２以下である。粒径０．１μｍ以上の金属間化合物の密度は、心材のＬ−ＬＴ面（圧延方向（Ｌ方向）と、圧延面に対して平行でＬ方向に対して垂直な方向（ＬＴ方向）で形成される面）を研磨で面出しし、心材の透過型電子顕微鏡（ＴＥＭ）観察を行うことで調べた。等厚干渉縞から観察部の膜厚を測定し、膜厚が０．１〜０．３μｍの箇所でのみＴＥＭ観察を行った。ＴＥＭ写真を画像解析することで、ろう付後の金属間化合物の密度を求めた。ここで、金属間化合物の粒径は円相当径のことである。 In the brazing sheet of the present invention, the metal structure of the core material after brazing has a density of an intermetallic compound having a particle size of 0.1 μm or more, such as Al—Mn, Al—Mn—Si, Al—Fe—Mn—Si, and the like. Is 10 pieces / μm 2 or less, more preferably 5 pieces / μm 2 or less. The aluminum alloy brazing sheet in the present invention is intended to increase the strength mainly by strengthening by age hardening of Mg 2 Si, but if an intermetallic compound having a particle size of 0.1 μm or more is present after brazing, In the cooling process, Mg 2 Si is deposited on the surface of these intermetallic compounds, and the amount of Mg 2 Si that does not contribute to age hardening increases. As a result, there is a possibility that Mg and Si added to the core material do not effectively work to improve the strength and sufficient strength after brazing cannot be obtained. Therefore, in order to effectively cause age hardening of Mg 2 Si, the density of intermetallic compounds having a particle size of 0.1 μm or more present in the core material after brazing is set to 10 / μm 2 or less. Preferably, it is 5 pieces / μm 2 or less. The density of the intermetallic compound having a particle size of 0.1 μm or more is formed in the L-LT surface of the core (the rolling direction (L direction) and the direction parallel to the rolling surface and perpendicular to the L direction (LT direction). The surface to be surfaced was polished and examined by observing the core material with a transmission electron microscope (TEM). The film thickness of the observation part was measured from the equal-thickness interference fringes, and TEM observation was performed only at locations where the film thickness was 0.1 to 0.3 μm. The density of the intermetallic compound after brazing was determined by image analysis of the TEM photograph. Here, the particle diameter of the intermetallic compound is the equivalent circle diameter.
また、本発明ではろう付後の心材の結晶粒径を１００μｍ以上とする。ろう付時に溶融したろうは、結晶粒界を経路として心材側へ拡散し、エロージョンが生じることがある。ろう付後の心材の結晶粒径が微細であれば、溶融ろうの経路が増えるため、心材側へ拡散するろうが多くなり、エロージョンが発生する。エロージョンが発生すると、強度、耐食性等のろう付後の特性が低下し、接合に使用される有効ろう量が少なくなってろう付性の低下をまねく。そのため、ろう付後の心材の結晶粒径は１００μｍ以上であり、より好ましくは１５０μｍ以上とする。
心材の結晶粒径は、心材のＬ−ＬＴ面を研磨で面出しし、その後バーカーエッチングを行い、光学顕微鏡で写真撮影し、面積法にて平均結晶粒径を求めたものである。
Moreover, in this invention, the crystal grain diameter of the core material after brazing shall be 100 micrometers or more. The solder melted at the time of brazing may diffuse to the core material side through the crystal grain boundary and cause erosion. If the crystal grain size of the core material after brazing is fine, the number of brazing wax paths increases, so that the amount of wax that diffuses toward the core material side increases, and erosion occurs. When erosion occurs, properties after brazing such as strength and corrosion resistance are lowered, and the amount of brazing used for joining is reduced, resulting in a reduction in brazing. Therefore, the crystal grain size of the core material after brazing is 100 μm or more, more preferably 150 μm or more.
The crystal grain size of the core material is obtained by polishing the L-LT surface of the core material, then performing Barker etching, taking a photograph with an optical microscope, and obtaining the average crystal grain size by the area method.
次に、本発明のアルミニウム合金ブレージングシートの製造方法について説明する。
本発明のアルミニウム合金ブレージングシートは、上記記載の合金からなる心材の片面にＡｌ−Ｓｉ系ろう材をクラッドし、心材の他方の面には犠牲陽極材をクラッドすることで製造される。
心材、犠牲陽極材用として、前記した所望の成分組成を有するアルミニウム合金をそれぞれ溶解し、鋳造し、面削して仕上げ、熱間圧延前に、心材に対しては、鋳塊の均質化処理を行わないか、または５５０℃以上で行い、熱間圧延により所望の厚さまで圧延し、それぞれ心材および犠牲陽極材を作製する。心材の均質化処理を５５０℃以上で行うことで、心材中のＡｌ−Ｍｎ系化合物の分布を疎にすることができ、ろう付後の心材の金属間化合物密度を下げることができる。或いは、心材の均質化処理を行わないことで、熱間圧延前の心材の固溶度を高い状態に維持できるため、熱間圧延時に微細な金属間化合物を析出させ、これらの微細な金属間化合物はろう付時に再固溶するため、ろう付後の心材の金属間化合物密度を下げることができる。
Next, the manufacturing method of the aluminum alloy brazing sheet of this invention is demonstrated.
The aluminum alloy brazing sheet of the present invention is manufactured by clad an Al—Si brazing material on one side of a core material made of the above-described alloy and clad a sacrificial anode material on the other side of the core material.
For the core material and sacrificial anode material, the above-mentioned aluminum alloys having the desired component composition are respectively melted, cast, chamfered and finished, and the ingot is homogenized before hot rolling. Or is performed at 550 ° C. or higher and rolled to a desired thickness by hot rolling to produce a core material and a sacrificial anode material, respectively. By performing the homogenization treatment of the core material at 550 ° C. or more, the distribution of the Al—Mn compound in the core material can be made sparse, and the intermetallic compound density of the core material after brazing can be lowered. Alternatively, since the solid solution of the core material before hot rolling can be maintained in a high state by not homogenizing the core material, fine intermetallic compounds are precipitated during hot rolling, Since the compound is re-dissolved during brazing, the density of intermetallic compounds in the core material after brazing can be lowered.
得られた心材、犠牲陽極材は、公知のろう材と共に組み合わせ、この組み合わせ材を熱間圧延の開始温度を４８０℃以下、熱間圧延の終了温度を２８０℃以下として熱間圧延することによりクラッド材を作製する。熱間圧延の開始温度を４８０℃以下とすることで、熱間圧延終了後の心材中の金属間化合物の分布を微細とすることができる。開始温度が４８０℃を超えると、金属間化合物の粗大な分布が得られる。熱間圧延時の析出物を微細にしておくことで、ろう付中に微細な金属化合物がマトリクスに再固溶し、ろう付後の金属間化合物の密度を低くすることができる。熱間圧延の開始温度は、より好ましくは４６０℃以下である。また、熱間圧延の終了温度を２８０℃以下とすることで、熱間圧延終了後にコイルに巻いた後の析出を抑制することができる。終了温度が２８０℃を超えると、コイルに巻いた後も心材で金属間化合物の析出或いは粗大化が起こり、適正な金属間化合物の分布が得られない。熱間圧延の終了温度は、より好ましくは２６０℃以下である。 The obtained core material and sacrificial anode material are combined with a known brazing material, and this combined material is clad by hot rolling at a hot rolling start temperature of 480 ° C. or lower and a hot rolling end temperature of 280 ° C. or lower. Make the material. By setting the hot rolling start temperature to 480 ° C. or less, the distribution of the intermetallic compound in the core material after the hot rolling can be made fine. When the starting temperature exceeds 480 ° C., a coarse distribution of intermetallic compounds is obtained. By making the precipitates during hot rolling fine, the fine metal compound is re-dissolved in the matrix during brazing, and the density of the intermetallic compound after brazing can be lowered. The starting temperature of hot rolling is more preferably 460 ° C. or less. Moreover, the precipitation after winding to a coil after completion | finish of hot rolling can be suppressed because the completion | finish temperature of hot rolling shall be 280 degrees C or less. When the end temperature exceeds 280 ° C., the intermetallic compound is precipitated or coarsened in the core material even after being wound around the coil, and an appropriate intermetallic compound distribution cannot be obtained. The end temperature of hot rolling is more preferably 260 ° C. or lower.
本発明の方法は、この後このクラッド材を冷間圧延するが、冷間圧延の間に中間焼鈍を少なくとも１回行うものである。その後、最終板厚まで冷間圧延を行う。ここで中間焼鈍には、バッチ式焼鈍炉、或いは連続焼鈍炉（ＣＡＬ）のいずれを用いてもよい。
なお、本発明のアルミニウム合金ブレージングシートの厚さ、各層のクラッド率には特に制限はないが、通常冷却水や冷媒を循環させるチューブ材として使う場合では、約０．３ｍｍ程度以下の薄肉ブレージングシートとすることができる。犠牲陽極材層、ろう材層のクラッド率は通常７〜２０％程度である。
このアルミニウム合金ブレージングシートは、肉薄でありながら強度に優れ、ろう付性も良好であるので、軽量の自動車用熱交換器の作製に好適である。
In the method of the present invention, the clad material is then cold-rolled, and intermediate annealing is performed at least once during the cold-rolling. Thereafter, cold rolling is performed to the final thickness. Here, either a batch-type annealing furnace or a continuous annealing furnace (CAL) may be used for the intermediate annealing.
In addition, although there is no restriction | limiting in particular in the thickness of the aluminum alloy brazing sheet of this invention, and the clad rate of each layer, When using as a tube material which circulates cooling water or a refrigerant | coolant normally, a thin brazing sheet of about 0.3 mm or less It can be. The clad rate of the sacrificial anode material layer and the brazing material layer is usually about 7 to 20%.
Although this aluminum alloy brazing sheet is thin, it has excellent strength and brazing properties, and is therefore suitable for production of a lightweight automotive heat exchanger.
次に、本発明を実施例に基づいてさらに詳細に説明するが、本発明はこれに制限されるものではない。
表１、２に示す金属成分および組成をもつ心材、犠牲陽極材合金をそれぞれＤＣ鋳造により鋳造して各々両面を面削して仕上げた。ろう材には、ＪＩＳ４０４５合金を用い、ろう材、犠牲陽極材を熱間圧延によりそれぞれ所望の厚さまで圧延した。これらの合金材をろう材―心材―犠牲陽極材の組み合わせで表３に示すように組み合わせて、その際のろう材、犠牲陽極材のクラッド率を全て１５％とし、熱間圧延の開始温度を４６０℃、熱間圧延の終了温度を２６０℃として熱間圧延を行い、３．５ｍｍの３層クラッド材とした。その後、中間焼鈍、最終冷間圧延を実施し、Ｈ１ｎ調質の板厚０．２５ｍｍの板材とした。
Next, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.
A core material and a sacrificial anode material alloy having the metal components and compositions shown in Tables 1 and 2 were each cast by DC casting, and each side was chamfered and finished. JIS4045 alloy was used for the brazing material, and the brazing material and the sacrificial anode material were each rolled to a desired thickness by hot rolling. These alloy materials are combined as shown in Table 3 with a combination of brazing material, core material, and sacrificial anode material. The clad rate of the brazing material and sacrificial anode material at that time is 15%, and the hot rolling start temperature is Hot rolling was performed at 460 ° C. and the end temperature of hot rolling was 260 ° C. to obtain a 3.5 mm three-layer clad material. Thereafter, intermediate annealing and final cold rolling were performed to obtain a plate material of H1n tempered plate thickness of 0.25 mm.
次に、前記作製した板材の一部を供試材とし、供試材のろう付後の金属間化合物の密度、ろう付後の結晶粒径、およびろう付後強度、ろう付性の評価を下記に示す方法で行い、それらの結果を表４に示した。 Next, a part of the prepared plate material is used as a test material, and the density of the intermetallic compound after brazing of the test material, the crystal grain size after brazing, the strength after brazing, and the evaluation of brazing properties are evaluated. The results are shown in Table 4 and the results are shown below.
（１）ろう付後の金属間化合物の密度：
６００℃×３分のろう付加熱後、心材のＬ−ＬＴ面を研磨で面出しし、心材の透過型電子顕微鏡（ＴＥＭ）観察を行うことで調べた。具体的には、等厚干渉縞から観察部の膜厚を測定し、膜厚が０．１〜０．３μｍの箇所でのみＴＥＭ観察を行った。各サンプル１０視野ずつ観察を行い、それぞれの視野のＴＥＭ写真を画像解析することで、ろう付後の粒径０．１μｍ以上の金属間化合物の密度を求めた。表記したろう付後の金属間化合物の密度は、各１０視野より求めた値の平均値とした。
（２）ろう付加熱後の結晶粒径：
６００℃×３分のろう付加熱後、心材のＬ−ＬＴ面を研磨して面出しし、その後バーカーエッチングを行い、面積法にて平均結晶粒径の算出を行った。（参考文献；金属学会会報 第１０巻（１９７１）、ｐ.２７９−２８９）
(1) Density of intermetallic compound after brazing:
After brazing heat at 600 ° C. for 3 minutes, the L-LT surface of the core material was surfaced by polishing, and the core material was examined by observation with a transmission electron microscope (TEM). Specifically, the film thickness of the observation part was measured from the equal-thickness interference fringes, and TEM observation was performed only at locations where the film thickness was 0.1 to 0.3 μm. Ten samples of each field of view were observed, and TEM photographs of each field of view were subjected to image analysis to determine the density of intermetallic compounds having a particle size of 0.1 μm or more after brazing. The density of the intermetallic compound after brazing represented was an average value obtained from 10 fields of view.
(2) Crystal grain size after heat of brazing addition:
After heat addition at 600 ° C. for 3 minutes, the L-LT surface of the core material was polished and surfaced, then Barker etching was performed, and the average crystal grain size was calculated by the area method. (Reference: The Japan Institute of Metals, Vol. 10 (1971), p. 279-289)
（３）ろう付後の引張強度：
６００℃×３分のろう付加熱後、２００℃／ｍｉｎの冷却速度で冷却し、その後室温で１週間放置した。このサンプルを引張速度１０ｍｍ／ｍｉｎ、ゲージ長５０ｍｍの条件で、ＪＩＳ Ｚ２２４１に従って、常温にて引張試験を実施した。
（４）フィン接合率：
ＪＩＳ ３００３合金に１．５％のＺｎを添加した合金のフィン材をコルゲート成形し、供試材のろう材面とあわせた後、これを５％のフッ化物フラックス懸濁液中に浸漬し、２００℃で乾燥後に６００℃×３分のノコロックろう付加熱を行った。この試験コアのフィンの全山数に対する接合したフィンの山数の割合をフィン接合率とした。
フィン接合率が９５％以上のものはろう付性が良好「○」、９５％未満のものはろう付性が不十分「×」とした。
（５）耐エロージョン性：
上記と同様の条件で試験コアを作製後、断面ミクロ観察を行い、エロージョン発生の有無を確認した。エロージョン無しは「○」、エロージョン有りは「×」とした。
(3) Tensile strength after brazing:
After the brazing heat of 600 ° C. × 3 minutes, it was cooled at a cooling rate of 200 ° C./min, and then allowed to stand at room temperature for 1 week. This sample was subjected to a tensile test at room temperature according to JIS Z2241 under the conditions of a tensile speed of 10 mm / min and a gauge length of 50 mm.
(4) Fin joint rate:
After corrugating a fin material of an alloy obtained by adding 1.5% Zn to JIS 3003 alloy and combining it with the brazing material surface of the test material, this was immersed in a 5% fluoride flux suspension, After drying at 200 ° C., nocollock brazing heat was applied at 600 ° C. for 3 minutes. The ratio of the number of fins joined to the total number of fins of the test core was defined as the fin joining rate.
Those with a fin joint ratio of 95% or more were rated as “Good” with a good brazing property, and those with a fin bonding rate of less than 95% were evaluated as “B” with an insufficient brazing property.
(5) Erosion resistance:
After producing a test core under the same conditions as described above, cross-sectional micro observation was performed to confirm the presence or absence of erosion. “○” indicates no erosion, and “×” indicates erosion.
（６）外部耐食性評価：
上記と同様の条件で試験コアを作製後、犠牲陽極材側をシールし、ＣＡＳＳ試験（ＪＩＳ Ｈ８６８１）５００ｈを実施し、最大孔食深さを測定した。
（７）内部耐食性評価：
引張試験試料と同様、６００℃×３分のろう付加熱を行った後、ろう材側をシールし、Ｃｌ−５００ｐｐｍ、ＳＯ４ ２−１００ｐｐｍ、Ｃｕ２＋１０ｐｐｍを含む８８℃の高温水中で８ｈ、室温放置で１６ｈのサイクル浸漬試験を３ヶ月実施し、最大孔食深さを測定した。
(6) External corrosion resistance evaluation:
After producing a test core under the same conditions as described above, the sacrificial anode material side was sealed, a CASS test (JIS H8681) 500 h was performed, and the maximum pitting depth was measured.
(7) Internal corrosion resistance evaluation:
Similar to the tensile test specimen, after brazing heating of 600 ° C. × 3 minutes, to seal the brazing material side, Cl - 500ppm, SO 4 2- 100ppm, 8h in high-temperature water of 88 ° C. containing Cu 2+ 10 ppm, A 16-hour cycle immersion test was conducted for 3 months at room temperature, and the maximum pitting corrosion depth was measured.
表４から明らかなように、本発明例である試験材Ｎｏ．１〜４は、ろう付後の引張強さが１８５Ｎ／ｍｍ２以上と高く、またフィン接合率、耐エロージョン性などのろう付性が優れており、さらに外側（熱交換器の大気側に相当）、内側（冷媒側に相当）共に耐食性が良好である。
それに対して、比較例である試験材Ｎｏ．５、６は、ろう付後の引張強さが１８０Ｎ／ｍｍ２未満であり、本発明例よりも低かった。試験材Ｎｏ．５、６、７については、フィン接合率の低下、或いはエロージョンの発生により、ろう付性が低下した。試験材Ｎｏ．５、８、９については、外側もしくは内側で貫通腐食が生じた。試験材Ｎｏ．６、８、９については、心材或いは犠牲材において鋳造時に巨大金属間化合物が生成した。
As is apparent from Table 4, the test material No. 1-4 have a high tensile strength of 185 N / mm 2 or more after brazing, excellent brazing properties such as fin joint ratio and erosion resistance, and the outside (corresponding to the atmosphere side of the heat exchanger) ) And inside (corresponding to the refrigerant side) have good corrosion resistance.
On the other hand, test material No. which is a comparative example. In Nos. 5 and 6, the tensile strength after brazing was less than 180 N / mm 2 , which was lower than the examples of the present invention. Test material No. As for 5, 6, and 7, the brazing performance was lowered due to the decrease in the fin joint ratio or the occurrence of erosion. Test material No. For 5, 8, and 9, penetration corrosion occurred outside or inside. Test material No. For 6, 8, and 9, giant intermetallic compounds were formed in the core material or sacrificial material during casting.
Claims (1)
（但し、粒径０．１μｍ以上の金属間化合物の密度は、心材のＬ−ＬＴ面（圧延方向（Ｌ方向）と、圧延面に対して平行でＬ方向に対して垂直な方向（ＬＴ方向）で形成される面）を研磨で面出し、心材の透過型電子顕微鏡（ＴＥＭ）観察を以下のように行うことで調べた。等厚干渉縞から観察部の膜厚を測定し、膜厚が０．１〜０．３μｍの箇所でのみＴＥＭ観察を行い、ＴＥＭ写真を画像解析することで、ろう付後の金属間化合物の密度であり、この金属間化合物の密度は、１０視野についての値の平均値をとる。）
An aluminum alloy brazing sheet in which an Al—Si brazing material is clad on one side of a core material and a sacrificial anode material is clad on the other side of the core material, wherein the core material contains Si: 0.5 to 1.0% ( % By mass, the same applies hereinafter), Fe: 0.1 to 0.3%, Cu: 0.3 to 1.0%, Mn: 1.0 to 1.6%, Mg: 0.1 to 0.4% In addition, Ti: 0.05-0.2%, Zr: 0.05-0.2%, V: 0.05-0.2%, containing at least one of the remaining, inevitable with the remaining Al The metal structure of the core material after brazing is an Al alloy composed of mechanical impurities, the density of intermetallic compounds having a particle size of 0.1 μm or more is 10 pieces / μm 2 or less, and the crystal grain size after brazing In which the sacrificial anode material contains Zn: 2.0-5.0%, and Si: 0.0 -1.0%, Mn: 0.05-1.6%, Ti: 0.05-0.2%, V: One or more of 0.05-0.2% are contained, and the balance is Al. It is an Al alloy composed of inevitable impurities, and the core material and sacrificial anode material are combined with the brazing material, and this combined material is hot with a hot rolling start temperature of 480 ° C. or lower and a hot rolling end temperature of 280 ° C. or lower. A high-strength aluminum alloy brazing sheet characterized by producing a clad material by rolling .
(However, the density of the intermetallic compound having a particle size of 0.1 μm or more is determined by the L-LT plane of the core material (the rolling direction (L direction) and the direction parallel to the rolling plane and perpendicular to the L direction (LT direction)). The surface formed by polishing) was surfaced by polishing, and the core material was examined by observation with a transmission electron microscope (TEM) as follows: The film thickness of the observation part was measured from the equal thickness interference fringes, and the film thickness was measured. Is a density of the intermetallic compound after brazing by performing TEM observation only at a location of 0.1 to 0.3 μm and analyzing the image of the TEM photograph. The density of the intermetallic compound is about 10 fields of view. (The average value is taken.)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007188856A JP5188115B2 (en) | 2007-07-19 | 2007-07-19 | High strength aluminum alloy brazing sheet |
| US12/218,440 US8142907B2 (en) | 2007-07-19 | 2008-07-15 | Aluminum alloy brazing sheet having high-strength and production method therefor |
| EP08075642.2A EP2017032B2 (en) | 2007-07-19 | 2008-07-17 | Aluminum alloy brazing sheet having high-strength and production method therefor |
| DE102008034031.6A DE102008034031B4 (en) | 2007-07-19 | 2008-07-17 | High strength aluminum alloy brazing sheet and manufacturing method thereof |
| CN 200810161188 CN101358311B (en) | 2007-07-19 | 2008-07-18 | Aluminum alloy brazing sheet having high-strength and production method therefore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007188856A JP5188115B2 (en) | 2007-07-19 | 2007-07-19 | High strength aluminum alloy brazing sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2009024221A JP2009024221A (en) | 2009-02-05 |
| JP5188115B2 true JP5188115B2 (en) | 2013-04-24 |
Family
ID=40330908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007188856A Active JP5188115B2 (en) | 2007-07-19 | 2007-07-19 | High strength aluminum alloy brazing sheet |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5188115B2 (en) |
| CN (1) | CN101358311B (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5944088B2 (en) * | 2008-02-12 | 2016-07-05 | 株式会社神戸製鋼所 | Aluminum alloy laminate with excellent fatigue characteristics |
| US8343635B2 (en) | 2008-02-12 | 2013-01-01 | Kobe Steel, Ltd. | Multi-layered sheet of aluminum alloys |
| JP5917786B2 (en) * | 2008-02-12 | 2016-05-18 | 株式会社神戸製鋼所 | Aluminum alloy laminate with excellent fatigue characteristics |
| EP2540848B1 (en) * | 2010-02-26 | 2018-05-23 | Furukawa Electric Co., Ltd. | Aluminum alloy conductor |
| JP5537256B2 (en) * | 2010-05-18 | 2014-07-02 | 株式会社神戸製鋼所 | Aluminum alloy brazing sheet |
| JP5466080B2 (en) * | 2010-05-18 | 2014-04-09 | 株式会社神戸製鋼所 | Aluminum alloy brazing sheet |
| CN102773626B (en) * | 2012-07-11 | 2014-12-03 | 东莞市闻誉实业有限公司 | Corrosion-resistant aluminum alloy soldering material |
| CN103255324B (en) * | 2013-04-19 | 2017-02-08 | 北京有色金属研究总院 | Aluminum alloy material suitable for manufacturing car body panel and preparation method |
| DE112014003155T5 (en) * | 2013-07-05 | 2016-03-24 | Uacj Corporation | Aluminum alloy brazing sheet and process for its production |
| CN103572100A (en) * | 2013-10-21 | 2014-02-12 | 姚富云 | Aluminum alloy material for heat exchanger |
| CN103572078A (en) * | 2013-10-21 | 2014-02-12 | 姚富云 | Refining method of aluminum alloy for heat exchangers |
| CN103572099A (en) * | 2013-10-21 | 2014-02-12 | 姚富云 | Aluminum alloy material for heat exchangers and refining method thereof |
| JP6228500B2 (en) * | 2014-03-28 | 2017-11-08 | 株式会社神戸製鋼所 | Aluminum alloy brazing sheet |
| JP6942449B2 (en) * | 2016-08-30 | 2021-09-29 | 株式会社Uacj | Aluminum alloy brazing sheet |
| CN107090557A (en) * | 2017-03-13 | 2017-08-25 | 北京工业大学 | A kind of aluminium alloy and preparation method for being used to prepare inexpensive high temperature resistant brazed aluminum/steel composite strip |
| CN109554571B (en) * | 2018-12-27 | 2019-10-22 | 吉林大学 | A kind of preparation method of two-way vertical controlled rolling trace Ti C REINFORCED Al-Cu-Mg sheet alloy |
| CN109943796A (en) * | 2019-03-21 | 2019-06-28 | 珠海弘德表面技术有限公司 | A kind of thermal spraying material and preparation method thereof of resistance to molten aluminum etch |
| CN112577336B (en) * | 2019-09-30 | 2022-06-21 | 杭州三花微通道换热器有限公司 | Fin for heat exchanger and heat exchanger |
| CN114346518A (en) * | 2021-12-03 | 2022-04-15 | 中车永济电机有限公司 | Application of flux-cored solder and brazing method |
| CN114752819A (en) * | 2022-04-19 | 2022-07-15 | 中国第一汽车股份有限公司 | Nano ceramic particle reinforced aluminum alloy and preparation method thereof |
| CN117230348B (en) * | 2023-09-18 | 2024-04-26 | 华北铝业新材料科技有限公司 | 1100B high-strength battery foil and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0790454A (en) * | 1993-09-08 | 1995-04-04 | Furukawa Electric Co Ltd:The | Production of aluminum alloy brazing sheet for heat exchanger and heat exchanger made of aluminum alloy |
| EP0718072B1 (en) * | 1994-12-19 | 2003-07-09 | Corus Aluminium Walzprodukte GmbH | Brazing sheet |
| JP4030006B2 (en) * | 2002-07-05 | 2008-01-09 | 住友軽金属工業株式会社 | Aluminum alloy clad material and manufacturing method thereof |
| JP4181607B2 (en) * | 2007-03-29 | 2008-11-19 | 株式会社神戸製鋼所 | Aluminum alloy brazing sheet and method for producing the same |
-
2007
- 2007-07-19 JP JP2007188856A patent/JP5188115B2/en active Active
-
2008
- 2008-07-18 CN CN 200810161188 patent/CN101358311B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN101358311A (en) | 2009-02-04 |
| CN101358311B (en) | 2013-03-06 |
| JP2009024221A (en) | 2009-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5188115B2 (en) | High strength aluminum alloy brazing sheet | |
| JP5793336B2 (en) | High strength aluminum alloy brazing sheet and method for producing the same | |
| JP5049488B2 (en) | Method for producing aluminum alloy brazing sheet | |
| US11408690B2 (en) | Method for producing aluminum alloy clad material | |
| JP4825507B2 (en) | Aluminum alloy brazing sheet | |
| JP5188116B2 (en) | High strength aluminum alloy brazing sheet and method for producing the same | |
| JP5339560B1 (en) | Aluminum alloy brazing sheet and method for producing the same | |
| WO2015001725A1 (en) | Aluminum alloy brazing sheet and method for producing same | |
| JP2004084060A (en) | Aluminum alloy fin material for heat exchanger and heat exchanger including the fin material | |
| WO2017141921A1 (en) | Aluminum alloy brazing sheet, manufacturing method therefor, and manufacturing method for vehicle heat exchanger using said brazing sheet | |
| JP6047304B2 (en) | High strength aluminum alloy brazing sheet and method for producing the same | |
| JP2016522311A (en) | Brazing sheet core alloy for heat exchanger | |
| JP4916333B2 (en) | Aluminum alloy clad material for heat exchangers with excellent strength and brazing | |
| JP4916334B2 (en) | Aluminum alloy clad material for heat exchangers with excellent strength and brazing | |
| JP2013216935A (en) | Aluminum alloy fin material for heat exchanger, method for producing the same, and method for producing the heat exchanger | |
| JP4996909B2 (en) | Aluminum alloy brazing sheet and method for producing the same | |
| JP5543119B2 (en) | Method for producing high heat resistant aluminum alloy brazing sheet | |
| JP6758281B2 (en) | Aluminum alloy brazing sheet fin material for heat exchanger and its manufacturing method | |
| JP5396042B2 (en) | Aluminum alloy brazing sheet with excellent brazeability | |
| WO2018110320A1 (en) | Aluminum alloy brazing sheet and method for manufacturing same | |
| JP2005232507A (en) | Aluminum alloy clad material for heat exchanger | |
| JP5952995B2 (en) | Aluminum alloy fin material for heat exchanger | |
| JP2010209444A (en) | Brazing sheet of highly heat-resistant aluminum alloy and method for manufacturing the same | |
| JP2009149936A (en) | Aluminum alloy clad material for heat-exchanger for brazed-making pipe excellent in strength and brazing property, and aluminum alloy tube for heat-exchanger | |
| JP5306836B2 (en) | Aluminum alloy brazing sheet with excellent strength and corrosion resistance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100609 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20120509 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120619 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120816 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130115 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130122 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160201 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5188115 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |