JP4216779B2 - High corrosion resistance aluminum clad material for heat exchanger - Google Patents
High corrosion resistance aluminum clad material for heat exchanger Download PDFInfo
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Description
本発明は、熱交換器とくに自動車熱交換器に使用されるアルミニウムクラッド材、とくに、熱交換器と接続される配管材（押出クラッド管材）、真空ろう付けやフッ化物系フラックスやセシウム化物系フラックスを用いた不活性ガス雰囲気ろう付けにより接合されるエバポレータ、コンデンサ、ラジエータ、ヒータコア、インタークーラ、オイルクーラなどのアルミニウム合金製自動車熱交換器用のチューブ材、接着、溶接、はんだ付けなどの非ろう付け方式で接続される熱交換器用チューブ材として好適な熱交換器用高耐食アルミニウムクラッド材に関する。 The present invention relates to aluminum clad materials used in heat exchangers, particularly automobile heat exchangers, in particular piping materials (extruded clad pipe materials) connected to heat exchangers, vacuum brazing, fluoride fluxes and cesium fluoride fluxes. Non-brazing such as tubes, bonding, welding, soldering, etc. for aluminum alloy automotive heat exchangers such as evaporators, condensers, radiators, heater cores, intercoolers, oil coolers that are joined by brazing in an inert gas atmosphere The present invention relates to a highly corrosion-resistant aluminum clad material for a heat exchanger suitable as a tube material for a heat exchanger to be connected in a system.
自動車熱交換器、例えばラジエータは、外面にフィンを有し、内面が作動流体（不凍液）の通路となるチューブおよびヘッダーから構成されている。このような自動車のラジエータまたはヒータコアなどのチューブ材、ヘッダープレート材としては、ＪＩＳ Ａ３００３などのＡｌ−Ｍｎ系合金を芯材とし、芯材の片面にＡｌ−Ｓｉ系合金ろう材をクラッドした二層構造のアルミニウム合金クラッド材、芯材の一方の面にろう材をクラッドし、他方の面にＡｌ−Ｚｎ系合金またはＡｌ−Ｚｎ−Ｍｇ系合金の犠牲陽極材をクラッドした三層構造のアルミニウム合金クラッド材が用いられている。 An automobile heat exchanger, for example, a radiator, includes a tube and a header that have fins on the outer surface and the inner surface serves as a passage for a working fluid (antifreeze). As a tube material and header plate material such as a radiator or a heater core of such an automobile, a two-layer in which an Al-Mn alloy alloy such as JIS A3003 is used as a core material and an Al-Si alloy brazing material is clad on one side of the core material. Aluminum alloy clad material with a three-layer structure in which a brazing material is clad on one surface of the core material and a sacrificial anode material of Al-Zn alloy or Al-Zn-Mg alloy is clad on the other surface A clad material is used.
クラッド材のＡｌ−Ｓｉ系ろう材は、アルミニウム合金製熱交換器を製作するとき、チューブとフィンとの接合、チューブとヘッダープレートとの接合、またはクラッド板からろう付けによりチューブを製造する場合のろう付け接合のためにクラッドされている。また、犠牲陽極材は、たとえばチューブの内面側に使用され、作動流体と接して犠牲陽極作用を発揮し、芯材の孔食や隙間腐食の発生を防止する。 When manufacturing an aluminum alloy heat exchanger, the clad Al-Si brazing material is used when a tube is manufactured by joining a tube and a fin, joining a tube and a header plate, or brazing a clad plate. It is clad for brazing. The sacrificial anode material is used, for example, on the inner surface side of the tube, and exerts a sacrificial anode action in contact with the working fluid to prevent the occurrence of pitting corrosion and crevice corrosion of the core material.
近年、自動車の軽量化の要請に伴い、自動車熱交換器においても省エネルギー、省資源の観点から構成材料の薄肉化が要請され、チューブ材についても薄肉化が進行している。チューブ材を薄肉化するためには、材料の強度をさらに高める必要があり、芯材に多量のＣｕ、Ｓｉ、Ｍｎなどが含有されるが、これらの元素の含有により芯材の耐食性が低下するため、犠牲陽極材に多量のＺｎを添加して芯材との電位差を確保し、確実に犠牲陽極効果が得られるようにした材料構成が提案されている。 In recent years, with the demand for lighter automobiles, automobile heat exchangers are also required to be made thinner from the viewpoint of energy saving and resource saving, and the tube materials are also becoming thinner. In order to make the tube material thinner, it is necessary to further increase the strength of the material, and the core material contains a large amount of Cu, Si, Mn, etc., but the inclusion of these elements reduces the corrosion resistance of the core material. Therefore, a material configuration has been proposed in which a large amount of Zn is added to the sacrificial anode material to ensure a potential difference from the core material and to ensure the sacrificial anode effect.
例えば、ラジエータなど自動車用熱交換器のチューブ材として、Ｍｎ：０．２〜１．５％、Ｓｉ：０．３〜１．３％を含有するＡｌ−Ｍｎ系合金の芯材の一方の面にＡｌ−Ｓｉ系合金ろう材をクラッドし、他方の面に５％以下のＺｎを含有するＡｌ−Ｚｎ合金をクラッドし、芯材のＣｕ量を０．６％以下に規定してなり、ろう付け後の芯材と犠牲陽極材との電位差が３０〜１２０ｍＶであり、とくに当該熱交換器がフッ化物系フラックスを用いる不活性ガス雰囲気ろう付けに組み立てられる場合に優れた耐食性が得られるアルミニウム合金複合材が提案されている（特許文献１参照）。 For example, one surface of a core material of an Al-Mn alloy containing Mn: 0.2 to 1.5% and Si: 0.3 to 1.3% as a tube material of an automotive heat exchanger such as a radiator Clad with an Al—Si alloy brazing material, clad with an Al—Zn alloy containing 5% or less of Zn on the other surface, and the Cu content of the core material is defined as 0.6% or less. Aluminum alloy having a potential difference between the core material after sacrificing and the sacrificial anode material of 30 to 120 mV, and particularly excellent corrosion resistance when the heat exchanger is assembled in an inert gas atmosphere brazing using a fluoride-based flux A composite material has been proposed (see Patent Document 1).
また、Ａｌ−Ｍｎ系合金からなる芯材にクラッドされる犠牲陽極材について、犠牲陽極材のＺｎ含有量（１〜５％）と犠牲陽極材の厚さ（５〜５０μｍ）を組み合わせてなり、犠牲陽極材中のＣｕ量を０．０５％以下に規制して、薄肉化を可能としながらも、ろう付け後に優れた耐食性が得られる自動車用熱交換器のチューブ材として好適なアルミニウムクラッド材も提案されている（特許文献２参照）。 Further, for the sacrificial anode material clad on the core material made of an Al-Mn alloy, the Zn content (1-5%) of the sacrificial anode material and the thickness (5-50 μm) of the sacrificial anode material are combined, There is also an aluminum clad material suitable as a tube material for automotive heat exchangers that can provide excellent corrosion resistance after brazing while regulating the amount of Cu in the sacrificial anode material to 0.05% or less and enabling thinning. It has been proposed (see Patent Document 2).
しかしながら、犠牲陽極材への多量のＺｎの添加は、犠牲陽極効果が達成される反面、犠牲陽極材の自己腐食速度が大きくなり犠牲陽極材の消耗を早めることがある。また、犠牲陽極材には、犠牲陽極材中に不純物として含まれているＦｅ、ＳｉなどがＡｌ−Ｓｉ系化合物やＡｌ−Ｆｅ系化合物として分散しており、これらの化合物のうち表面に露出している化合物は耐食性を保持するための酸化皮膜の欠陥となり、この欠陥が腐食の起点となって腐食が生じ、腐食が生じた後は、これら化合物がカソードとなって化合物の周囲が優先的に腐食し、腐食速度を高める。 However, when a large amount of Zn is added to the sacrificial anode material, the sacrificial anode effect is achieved, but the sacrificial anode material has a high self-corrosion rate, and the sacrificial anode material may be consumed quickly. In the sacrificial anode material, Fe, Si and the like contained as impurities in the sacrificial anode material are dispersed as Al-Si compounds and Al-Fe compounds, and these compounds are exposed on the surface. These compounds become defects in the oxide film to maintain corrosion resistance, and these defects become the starting point of corrosion, causing corrosion. After corrosion occurs, these compounds become cathodes and the surroundings of the compounds are preferentially used. Corrodes and increases the corrosion rate.
上記の現象は、薄肉化された犠牲陽極材においてとくに顕著となる。従って、クラッド材を薄肉化するために犠牲陽極材を低減した場合には、上記の現象によって短期間で犠牲陽極材が消耗する。クラッド材の薄肉化に際し、犠牲陽極材は薄肉化せず芯材のみを薄くした場合には、クラッド材の剛性の維持が困難となる。
発明者らは、熱交換器のチューブ材における前記従来の問題点を解消するために、犠牲陽極材の自己耐食性を向上させるとともに、犠牲陽極効果も得られるチューブ材用アルミニウムクラッド材の構成について試験、検討を重ねた結果、犠牲陽極材をＭｇを含有するＡｌ−Ｍｇ合金で構成し、Ｍｇの添加により犠牲陽極材の表面に均一なＭｇＯの酸化皮膜を形成させ、且つＭｇとＡｌとの合計含有量を多くしてＦｅ、Ｓｉの濃度を低め、Ａｌ−Ｆｅ系化合物、Ａｌ−Ｓｉ系化合物の生成を少なくすることによって、クラッド材の薄肉化に伴って犠牲陽極材の厚さを低減した場合にも、犠牲陽極材の自己耐食性と犠牲陽極効果の両特性を維持することが可能であることを見出した。 The inventors tested the configuration of an aluminum clad material for a tube material that improves the self-corrosion resistance of the sacrificial anode material and also provides the sacrificial anode effect in order to eliminate the above-mentioned conventional problems in the tube material of the heat exchanger. As a result of repeated studies, the sacrificial anode material is composed of an Al-Mg alloy containing Mg, and by adding Mg, a uniform oxide film of MgO is formed on the surface of the sacrificial anode material, and the total of Mg and Al The thickness of the sacrificial anode material was reduced along with the thinning of the cladding material by increasing the content and decreasing the concentration of Fe and Si and reducing the generation of Al-Fe compounds and Al-Si compounds. In some cases, it has been found that both the self-corrosion resistance and the sacrificial anode effect of the sacrificial anode material can be maintained.
本発明は、上記の知見に基づいてさらに検討を加えた結果としてなされたものであり、その目的は、熱交換器とくに自動車用熱交換器のチューブ材、例えば、熱交換器と接続される配管材（押出クラッド管材）、真空ろう付けやフッ化物系フラックスやセシウム化物系フラックスを用いた不活性ガス雰囲気ろう付けにより接合されるエバポレータ、コンデンサ、ラジエータ、ヒータコア、インタークーラ、オイルクーラなどのアルミニウム合金製自動車熱交換器のチューブ材、接着、溶接、はんだ付けなどの非ろう付け方式で接続される熱交換器用チューブ材として好適に使用される熱交換器用高耐食アルミニウムクラッド材を提供することにある。 The present invention has been made as a result of further investigation based on the above-described knowledge, and the object thereof is a tube material of a heat exchanger, particularly an automobile heat exchanger, for example, a pipe connected to the heat exchanger. Aluminum alloys such as evaporators, condensers, radiators, heater cores, intercoolers, and oil coolers that are joined together by brazing materials (extruded clad pipe materials), vacuum brazing, and inert gas atmosphere brazing using fluoride or cesium fluxes To provide a highly corrosion-resistant aluminum clad material for a heat exchanger that is suitably used as a tube material for a heat exchanger to be connected by a non-brazing method such as a tube material of an automobile heat exchanger, bonding, welding, soldering, etc. .
上記の目的を達成するための請求項１による熱交換器用高耐食アルミニウムクラッド材は、アルミニウム（アルミニウム合金を含む）からなる芯材の少なくとも一方の面に犠牲陽極材をクラッドしたアルミニウムクラッド材であって、犠牲陽極材が、少なくともＭｇを含有し、ＡｌとＭｇとの合計含有量が９９．９９％以上のアルミニウム合金で構成されることを特徴とする。 In order to achieve the above object, a highly corrosion-resistant aluminum clad material for a heat exchanger according to claim 1 is an aluminum clad material in which a sacrificial anode material is clad on at least one surface of a core material made of aluminum (including an aluminum alloy). The sacrificial anode material is characterized by comprising an aluminum alloy containing at least Mg and a total content of Al and Mg of 99.99 % or more.
請求項２による熱交換器用高耐食アルミニウムクラッド材は、アルミニウムからなる芯材の一方の面に犠牲陽極材をクラッドし、他方の面にろう材をクラッドしたアルミニウムクラッド材であって、犠牲陽極材が、少なくともＭｇを含有し、ＡｌとＭｇとの合計含有量が９９．９９％以上のアルミニウム合金で構成されることを特徴とする。 A highly corrosion-resistant aluminum clad material for a heat exchanger according to claim 2 is an aluminum clad material in which a sacrificial anode material is clad on one surface of a core material made of aluminum and a brazing material is clad on the other surface. Is composed of an aluminum alloy containing at least Mg and having a total content of Al and Mg of 99.99 % or more.
請求項３による熱交換器用高耐食アルミニウムクラッド材は、請求項１または２において、前記犠牲陽極材を構成するアルミニウム合金のＭｇ含有量が０．０１〜５．０％であることを特徴とする。 The highly corrosion-resistant aluminum clad material for heat exchanger according to claim 3 is characterized in that, in claim 1 or 2, the Mg content of the aluminum alloy constituting the sacrificial anode material is 0.01 to 5.0%. .
本発明によれば、熱交換器とくに自動車用熱交換器のチューブ材、例えば、熱交換器と接続される配管材（押出クラッド管材）、真空ろう付けやフッ化物系フラックスやセシウム化物系フラックスを用いた不活性ガス雰囲気ろう付けにより接合されるエバポレータ、コンデンサ、ラジエータ、ヒータコア、インタークーラ、オイルクーラなどのアルミニウム合金製自動車熱交換器のチューブ材、接着、溶接、はんだ付けなどの非ろう付け方式で接続される熱交換器用チューブ材として好適に使用される熱交換器用高耐食アルミニウムクラッド材が提供される。 According to the present invention, a tube material of a heat exchanger, in particular, an automotive heat exchanger, for example, a piping material (extruded clad tube material) connected to the heat exchanger, vacuum brazing, fluoride-based flux, or cesium-based flux is used. Non-brazing methods such as tubes, bonding, welding, and soldering for aluminum alloy automotive heat exchangers such as evaporators, condensers, radiators, heater cores, intercoolers, and oil coolers that are joined by brazing in an inert gas atmosphere. A highly corrosion-resistant aluminum clad material for a heat exchanger that is suitably used as a tube material for a heat exchanger that is connected in the above is provided.
以下、本発明のアルミニウム合金クラッド材の構成について説明する。
（犠牲陽極材）
本発明においては、犠牲陽極材が、少なくともＭｇを含有し、ＭｇとＡｌとの合計含有量が９９．９９％以上のアルミニウム合金で構成される。例えば、犠牲陽極材をＭｇを含有するＡｌ−Ｍｇ合金で構成し、ＭｇとＡｌの合計含有量を９９．９９％以上とする。Ｍｇの含有により、犠牲陽極材の表面に均一な酸化皮膜（ＭｇＯ）が形成されるとともに、ＭｇとＡｌとの合計含有量を９９．９９％以上とすることによりＦｅおよびＳｉの濃度が低くなって、Ａｌ−Ｆｅ化合物やＡｌ−Ｓｉ化合物の生成が低減され、且つＭｇＯ皮膜は通常のアルミニウム合金の表面に形成されるＡｌ２Ｏ３皮膜より防食効果が優れており、表面の酸化皮膜が保護皮膜となって安定に保持されるため、腐食の起点となる表面欠陥がほとんど存在せず、腐食の発生が抑制される。一旦腐食が発生しても、カソードとして作用するマトリックス中のＡｌ−Ｆｅ系化合物やＡｌ−Ｓｉ系化合物が少ないため、自己腐食速度が遅くなる。
Hereinafter, the structure of the aluminum alloy clad material of the present invention will be described.
(Sacrificial anode material)
In the present invention, the sacrificial anode material is made of an aluminum alloy containing at least Mg and a total content of Mg and Al of 99.99 % or more. For example, the sacrificial anode material is made of an Al—Mg alloy containing Mg, and the total content of Mg and Al is 99.99 % or more. By containing Mg, a uniform oxide film (MgO) is formed on the surface of the sacrificial anode material, and by making the total content of Mg and Al 99.99 % or more, the concentration of Fe and Si is lowered. In addition, the production of Al-Fe compounds and Al-Si compounds is reduced, and the MgO film has a better anticorrosion effect than the Al 2 O 3 film formed on the surface of a normal aluminum alloy, and the surface oxide film is protected. Since it becomes a film and is held stably, there are almost no surface defects that become the starting point of corrosion, and the occurrence of corrosion is suppressed. Once corrosion occurs, the self-corrosion rate is slowed because there are few Al—Fe compounds or Al—Si compounds in the matrix acting as the cathode.
また、電位を卑にするＦｅ、Ｓｉの濃度が低く、さらに電位を卑にするＭｇが添加されているため、犠牲陽極材の電位は卑に維持され、犠牲陽極効果が長期間持続する。ＭｇとＡｌとの合計含有量が９９．９％未満ではその効果が十分でなく耐食性が低下する。ＭｇとＡｌとのより好ましい含有範囲は９９．９９％以上であり、ＭｇとＡｌとのさらに好ましい含有範囲は９９．９９９％以上である。 In addition, since the Fe and Si concentrations that lower the potential are low and Mg that lowers the potential is added, the potential of the sacrificial anode material is maintained at a lower level, and the sacrificial anode effect lasts for a long time. If the total content of Mg and Al is less than 99.9%, the effect is not sufficient and the corrosion resistance is lowered. A more preferable content range of Mg and Al is 99.99% or more, and a more preferable content range of Mg and Al is 99.999% or more.
犠牲陽極材中のＭｇは、犠牲陽極材の表面に防食作用を有する均一な酸化皮膜（ＭｇＯ）を形成し、腐食の発生を抑制するよう機能する。また、犠牲陽極材の電位を卑にし、芯材に対する犠牲陽極効果を発揮させ、芯材の孔食や隙間腐食を防止する。Ｍｇの好ましい含有量は０．０１〜５．０％の範囲であり、０．０１％未満ではＭｇＯの生成が不十分となり易く、５．０％を越えると圧延性が劣り、健全なクラッド材が製造し難くなる。 Mg in the sacrificial anode material functions to form a uniform oxide film (MgO) having an anticorrosive action on the surface of the sacrificial anode material and suppress the occurrence of corrosion. Further, the potential of the sacrificial anode material is made lower, the sacrificial anode effect on the core material is exhibited, and pitting corrosion and crevice corrosion of the core material are prevented. The preferred Mg content is in the range of 0.01 to 5.0%. If it is less than 0.01%, MgO formation tends to be insufficient, and if it exceeds 5.0%, the rollability is inferior and the clad material is sound. Is difficult to manufacture.
（芯材）
芯材としてはアルミニウムまたはアルミニウム合金が適用され、芯材用アルミニウムまたはアルミニウム合金は、熱交換器において必要とされる強度に応じて選択される。芯材として、一般的には３０００系（Ａｌ−Ｍｎ系）合金、より強度が要求される場合には２０００系（Ａｌ−Ｃｕ系）合金、５０００系（Ａｌ−Ｍｇ系）合金、６０００系（Ａｌ−Ｍｇ−Ｓｉ系）合金を使用することができ、８０００系合金を用いることもできる。
(Core material)
Aluminum or aluminum alloy is applied as the core material, and the aluminum or aluminum alloy for the core material is selected according to the strength required in the heat exchanger. As a core material, a 3000 series (Al-Mn series) alloy is generally used, and when a higher strength is required, a 2000 series (Al-Cu series) alloy, a 5000 series (Al-Mg series) alloy, a 6000 series ( Al—Mg—Si based alloy can be used, and 8000 based alloy can also be used.
（ろう材）
ろう材としては、通常用いられているＡｌ−Ｓｉ系合金ろう材、例えば、Ｓｉ：６〜１３％を含有するＡｌ−Ｓｉ系合金ろう材が使用される。熱交換器の接合を真空ろう付けによって行う場合には、Ｍｇを含有するＡｌ−Ｓｉ−Ｍｇ系合金ろう材が適用される。これらＡｌ−Ｓｉ系合金ろう材、Ａｌ−Ｓｉ−Ｍｇ系合金ろう材には、例えば、０．００５〜０．１％のＳｒ、０．２％以下のＢｉ、０．１％以下のＢｅ、０．００１〜０．０５％のＩｎ、０．００１〜０．０５％のＳｎ、１〜１００ｐｐｍのＮａ、２％以下のＦｅ、８％以下のＺｎ、５％以下のＣｕの１種または２種以上が含有されていてもよい。
(Brazing material)
As the brazing material, a commonly used Al—Si based brazing material, for example, an Al—Si based brazing material containing 6 to 13% of Si is used. When the heat exchanger is joined by vacuum brazing, an Al—Si—Mg alloy brazing material containing Mg is applied. These Al—Si alloy brazing material and Al—Si—Mg alloy brazing material include, for example, 0.005 to 0.1% Sr, 0.2% or less Bi, 0.1% or less Be, One or two of 0.001 to 0.05% In, 0.001 to 0.05% Sn, 1 to 100 ppm Na, 2% or less Fe, 8% or less Zn, 5% or less Cu More than one species may be contained.
本発明のアルミニウムクラッド材は、芯材、犠牲陽極材およびろう材を構成するアルミニウム材料を、たとえば、連続鋳造により造塊し、必要に応じて均質化処理後、犠牲陽極材およびろう材の鋳塊については、それぞれ所定厚さまで熱間圧延し、ついで、芯材の鋳塊と犠牲陽極材の熱間圧延材を組み合わせ、あるいは芯材の鋳塊、犠牲陽極材の熱間圧延材、ろう材の熱間圧延材を組み合わせて、常法に従って熱間圧延によりクラッド材とし、その後冷間圧延、中間焼鈍、冷間圧延により所定の厚さとすることによって製造される。 The aluminum clad material of the present invention is formed by agglomerating the aluminum material constituting the core material, the sacrificial anode material and the brazing material, for example, by continuous casting, and after homogenizing treatment as necessary, casting of the sacrificial anode material and the brazing material. The ingots are each hot-rolled to a predetermined thickness, and then a core ingot and a sacrificial anode material hot-rolled material are combined, or a core ingot, sacrificial anode material hot-rolled material, brazing material These hot-rolled materials are combined into a clad material by hot rolling according to a conventional method, and then made into a predetermined thickness by cold rolling, intermediate annealing, and cold rolling.
以下、本発明の実施例を比較例と対比して説明する。これらの実施例は、本発明の一実施態様を示すものであり、本発明はこれらに限定されるものではない。 Examples of the present invention will be described below in comparison with comparative examples. These examples show one embodiment of the present invention, and the present invention is not limited to these examples.
実施例１
連続鋳造によって表１に示す組成を有する芯材用合金、表２に示す組成を有する犠牲陽極材用合金を造塊し、得られた鋳塊を均質化処理した。なお、犠牲陽極材用合金Ｂ１、Ｂ４、Ｂ７、Ｂ１０およびＢ１１は参考として示す。
Example 1
A core material alloy having the composition shown in Table 1 and a sacrificial anode material alloy having the composition shown in Table 2 were ingoted by continuous casting, and the resulting ingot was homogenized. The sacrificial anode material alloys B1, B4, B7, B10 and B11 are shown for reference.
ついで、犠牲陽極材用合金の鋳塊を所定の厚さまで熱間圧延し、得られた熱間圧延板と芯材用合金の鋳塊を組み合わせて熱間圧延した後、冷間圧延、中間焼鈍、冷間圧延によって厚さ０．２０ｍｍのクラッド材（調質Ｈ１４）を得た。クラッド材の構成は、犠牲陽極材を０．０１０〜０．０２０ｍｍ厚さとした。 Next, the ingot of the sacrificial anode material alloy is hot-rolled to a predetermined thickness, and the obtained hot-rolled sheet and the core alloy ingot are hot-rolled in combination, followed by cold rolling and intermediate annealing. Then, a clad material (tempered H14) having a thickness of 0.20 mm was obtained by cold rolling. The structure of the clad material was 0.010 to 0.020 mm thick for the sacrificial anode material.
得られたクラッド材を試験材として、以下の方法により、犠牲陽極材の耐食性を評価した。結果を表３〜６に示す。なお、犠牲陽極材用合金Ｂ１、Ｂ４、Ｂ７、Ｂ１０およびＢ１１をクラッドした試験材Ｎｏ．１、１７、３３、５５および５６は参考として示す。 Using the obtained clad material as a test material, the corrosion resistance of the sacrificial anode material was evaluated by the following method. The results are shown in Tables 3-6. In addition, the test material No. which clad alloy B1, B4, B7, B10, and B11 for sacrificial anode materials was carried out. 1, 17, 33, 55 and 56 are shown for reference.
犠牲陽極材の耐食性：得られたクラッド材（試験材）を、単板のままフッ化物系フラックスを塗布して窒素ガス雰囲気中で６００℃（材料温度）のろう付け温度に加熱した後、犠牲陽極材面について下記の条件で腐食試験を行った。
腐食液：Ｃｌ- ：３００ｐｐｍ、ＳＯ4 2- ：１００ｐｐｍ、Ｃｕ2+：１０ｐｍ
比液量：５ｍＬ／ｃｍ2
シール：芯材面と端面をシリコン樹脂でシールした。
試験方法：８８℃に加熱した腐食液中に８時間浸漬した後、冷却して２５℃で１６時間保持するサイクルを２か月間繰り返して、最大腐食深さを測定し、最大腐食深さ０．０３ｍｍ以下を耐食性良好とした。
Corrosion resistance of sacrificial anode material: The obtained clad material (test material) was applied as a single plate with fluoride-based flux and heated to a brazing temperature of 600 ° C. (material temperature) in a nitrogen gas atmosphere. A corrosion test was performed on the anode material surface under the following conditions.
Corrosion solution: Cl − : 300 ppm, SO 4 2− : 100 ppm, Cu 2+ : 10 pm
Specific liquid volume: 5 mL / cm 2
Seal: The core material surface and end surface were sealed with silicon resin.
Test method: After immersing in a caustic solution heated to 88 ° C. for 8 hours, a cycle of cooling and holding at 25 ° C. for 16 hours was repeated for 2 months, the maximum corrosion depth was measured, and the maximum corrosion depth was 0. The corrosion resistance was good at 03 mm or less.
表６にみられるように、本発明に従う試験材Ｎｏ．４９〜５４はいずれも、犠牲陽極材の腐食試験において、最大腐食深さはいずれも０．００８ｍｍ以下であり、優れた耐食性をそなえている。 As seen in Table 6 , the test material No. 49 to 54 all have a maximum corrosion depth of 0.008 mm or less in the corrosion test of the sacrificial anode material, and have excellent corrosion resistance.
比較例１
連続鋳造によって表７に示す組成を有する犠牲陽極材用合金を造塊し、得られた鋳塊を均質化処理した。
Comparative Example 1
An alloy for a sacrificial anode material having the composition shown in Table 7 was formed by continuous casting, and the resulting ingot was homogenized.
ついで、犠牲陽極材用合金の鋳塊を所定の厚さまで熱間圧延し、得られた犠牲陽極材の熱間圧延板と表１のＮｏ．Ａ３の芯材用合金の鋳塊を組み合わせて熱間圧延した後、冷間圧延、中間焼鈍、冷間圧延によって厚さ０．２０ｍｍのクラッド材（調質Ｈ１４）を得た。クラッド材の構成は、犠牲陽極材を０．０２０ｍｍ厚さとした。なお、表７において、本発明の条件を外れたものには下線を付した。 Subsequently, the ingot of the alloy for sacrificial anode material was hot-rolled to a predetermined thickness, and the obtained hot-rolled plate of the sacrificial anode material and No. 1 in Table 1 were used. A hot-rolling was performed by combining the ingots of the core alloy of A3, and then a clad material (tempered H14) having a thickness of 0.20 mm was obtained by cold rolling, intermediate annealing, and cold rolling. The structure of the clad material was such that the sacrificial anode material was 0.020 mm thick. In Table 7, those outside the conditions of the present invention are underlined.
得られたクラッド材を試験材として、実施例１と同じ方法で犠牲陽極材の耐食性を評価した。結果を表８に示す。 The corrosion resistance of the sacrificial anode material was evaluated by the same method as in Example 1 using the obtained clad material as a test material. The results are shown in Table 8.
表８に示すように、試験材Ｎｏ．５７は犠牲陽極材のＭｇとＡｌとの合計含有量が低いため、また、試験材Ｎｏ．５８は、犠牲陽極材が２％のＺｎを含有し、ＭｇとＡｌとの合計含有量が低くなっているため、いずれも犠牲陽極材の耐食性が劣っている。 As shown in Table 8, the test material No. No. 57 has a low total content of Mg and Al in the sacrificial anode material. In No. 58, since the sacrificial anode material contains 2% Zn and the total content of Mg and Al is low, the corrosion resistance of the sacrificial anode material is inferior.
Claims (3)
3. The highly corrosion-resistant aluminum clad material for heat exchanger according to claim 1, wherein Mg content of the aluminum alloy constituting the sacrificial anode material is 0.01 to 5.0%.
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