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    • 专利摘要:

    公开号:SE0950340A1
    申请号:SE0950340
    申请日:2009-05-14
    公开日:2010-11-15
    发明作者:Linda Ahl；Stefan Norgren
    申请人:Sapa Heat Transfer Ab；
    IPC主号:
    专利说明:

    The present invention relates to soldered aluminum sheet comprising a core and a plating material on one side of the core consisting of an aluminum alloy of 0.2-2.0 wt% Mg, but more preferably 0.7-1.4 wt% Mg, and most preferably 0.8-1.3 wt% Mg, 0.5 to 1.5 wt% Si, 1.0-2.0 wt%, most preferably 1.4 to 1.8 wt% Mn, s 0.1 wt% Cu, and s 4 wt% Zn, s 0.3 wt% each of Zr, Ti, Ni, Hf, V, Cr, ln, Sn and s 0.5 wt% total of Zr, Ti, Ni, Hf, V, Cr, ln, Sn, and the residue consisting of Al and unavoidable impurities.
    Detailed Description It has been found that the Mg content of solder plated sheet, for example that described in US7387844 (see above), is not high enough to provide the required strength and corrosion resistance. The presence of Cr and Cu and the high content of Zn also contribute to the material being unsuitable for plating on the water side. High levels of Zn lower the melting point of the plating material, which can make the material more brittle and cause problems when rolling.
    The solder plated sheet in the present invention has a core of an aluminum alloy with a solder plating on the side which in a heat exchanger is in direct contact with the coolant, and possibly also a solder plating on the opposite side. The plating on the coolant side is hereinafter referred to as plating on the water side, or the plating on the water side; this is the outermost layer of the soldered plate, and the layer which is in direct contact with the coolant.
    The plating on the water side consists of an aluminum alloy with a corrosion potential which is lower than that of the core and which constitutes the outermost layer on the water side of a solder-plated sheet. The plating on the water side consists of an aluminum alloy with 0.2 to 2.0 wt% Mg, 0.5 to 1.5 wt% Si, 1.0 to 2.0 wt%, preferably 1.4-1.8% Mn , s0.7 wt% Fe, s0.1 wt% Cu, and s4 wt% Zn, s0.3 wt% each of Zr, Ti, Ni, Hf, V, Cr, ln, Sn and s0.5 wt% total of Zr, Ti, Ni, Hf, V, Cr, ln, Sn, and the residue consisting of Al and unavoidable impurities.
    The plating material should be an aluminum alloy containing essentially 0.7 to 1.4% by weight of Mg, 0.5 to 1.5% by weight of Si, 1.4 to 1.8% by weight of Mn, s0.7% by weight of Fe, s0.1 wt% Cu, and s4 wt% Zn, s0.3 wt% each of Zr, Ti, Ni, Hf, V, Cr, ln, Sn and s0.5 wt% total of Zr, Ti, Ni, Hf, V, Cr, ln, Sn, and the residue consisting of Al and unavoidable impurities. The plating on the water side can also consist of an aluminum alloy which mainly consists of 0.8 to 1.3% by weight of Mg, 0.5 to 1.5% by weight of Si, 1.4 to 1.8% by weight. % Mn, s0.7 wt% Fe, s 0.1 wt% Cu, and 54 wt% Zn, 50.3 wt% each of Zr, Ti, Ni, Hf, V, Cr, ln, Sn, and 50, 5% by weight in total of Zr, Ti, Ni, Hf, V, Cr, ln, Sn, and the remainder consisting of Al and unavoidable impurities. The plating material may contain s0.05-0.3 wt% Zr.
    Mn is a substance that increases both the strength of the water-side plating material and its erosion-corrosion resistance in, for example, pipes in a heat exchanger. An Mn content below 1.0% by weight is not high enough to be able to increase either particle-induced strength or the erosion corrosion resistance of the material, whereby the strength cannot be guaranteed. When the Mn content is higher than 2.0% by weight, the formability of the plating material deteriorates and excessive intermetallic particles can also be formed, which can adversely affect the fatigue properties of the material. An Mn content between 1.4 and 1.8% by weight Mn gives the desired amount of small dispersoids (<0.5 μm), and in addition larger eutectic particles are obtained, which improves the erosion corrosion resistance. Therefore, the Mn content of plating material for the water side has been set at between 1.0 and 2.0, but preferably between 1, 4 and 1.8% by weight.
    Si reacts with Mn, which improves the strength of the plating material on the water side.
    When the Si content is lower than 0.5% by weight, too few AlMnSi dispersoids are formed and the strength does not increase sufficiently. Si also helps to lower the melting point of the plating and the Si content must therefore not be higher than 1.5% by weight. The Si content of plating material for the water side has thus been determined to be 0.5-1.5% by weight.
    If the Si content is reduced, the corrosion potential of the material is affected; the plating becomes nobler and the sacrificial anodic effect diminishes, which is not desirable. The Si content in the plating on the water side should also be balanced against the Si content in the core to obtain the desired sacrificial anodic effect. When the Mn content is high (1, 4-1, 8%), the Si content may have to be higher in the plating material because some Si disappears into the core by diffusion, where a reaction with Mn occurs and AlMnSi particles are formed. Even during soldering, Si diffuses from the plating of the water side and into the core where AlMnSi dispersoids are formed, which means that the corrosion attacks are limited to the outermost layer of the core.
    Zn is added to the plating material to reduce the corrosion potential of the plating material. In this case, where the Cu content is virtually negligible, the required sacrificial anodic effect is obtained and high corrosion resistance is maintained, even if the Zn content of the plating material is less than 4% by weight. With thinner material in the core, or with a soldering process with high temperature or long holding time at high temperature, Zn in the plating on the water side tends to diffuse deep into the core, which can lead to deteriorated corrosion properties of the solder plated sheet. The upper limit of the Zn content has therefore been set at 4% by weight.
    Mg is added to the plating material to improve both strength and corrosion and erosion resistance. A Mg content below 0.2% by weight does not have a sufficiently large effect on either corrosion resistance or strength. A Mg content above 2.0% impairs the processing properties of the material during rolling and lowers the melting point. With a Mg content between 0.7 and 1.4% by weight, or more preferably between 0.8 and 1.3% by weight, the criteria for strength and workmanship are met, and in addition the corrosion properties are improved.
    To facilitate the recycling of the material, the plating should not contain Ni. In the plating of the water side, the Cu level must be low as Cu impairs the corrosion resistance by increasing the risk of pitting corrosion. The Cu level has therefore been set to a maximum of 0.1%, but preferably <0.04% by weight.
    The core material of the solder-plated sheet in an aluminum alloy contains 50.1% by weight of Si, but preferably 0.06% by weight of Si, 50.35% by weight of Mg, from 1.0 to 2.0, but preferably 1.4 to 1.8% by weight. % Mn, from 0.2 to 1.0, but most preferably 0.6 to 1.0% by weight of Cu, 50.7% by weight of Fe, and 50.3% by weight each of Zr, Ti, Ni, Hf, V, Cr, ln, Sn, and 50.5% by weight in total of Zr, Ti, Ni, Hf, V, Cr, ln, Sn, and the remainder consisting of aluminum and unavoidable impurities.
    The material in the core should contain 50.1% by weight of Si, but preferably 50.06% by weight of Si, 50.35% by weight of Mg, from 1.4 to 1.8% by weight of Mn, from 0.6 to 1.0% by weight. Cu, 50.7 wt% Fe, 0.05 to 0.3 wt% Zr, and 50.3 wt% each of Ti, Ni, Hf, V, Cr, ln, Sn and 50.5 wt% total of Zr , Ti, Ni, Hf, V, Cr, ln, Sn, and the remainder consisting of aluminum and unavoidable impurities. Both the material in the core and the plating should preferably be nickel-free.
    Mn in the core increases the strength, both in solid solution and in particles. At an Mn content in the core of at least 1.0% by weight, a large number of particles can be separated during preheating and subsequent hot rolling, and a significant potential gradient can be obtained between core and water side plating due to the large Mn difference in solid solution after soldering.
    The term preheating refers to the heating of the ingot before hot rolling at a temperature of not more than 550 ° C. At Mn contents above 2.0% by weight, large eutectic particles can be formed during the casting, which is something that should be avoided in the manufacture of thin tubes. An Mn content of 1.8% by weight or even less is desirable because the primary particles formed during casting then become smaller. With an Mn content of between 1.4 and 1.8% by weight, the desired amount of small dispersoids and larger eutectic particles is obtained. 0.2-1.0% by weight of Cu is added to further increase the strength, since copper is a reinforcing agent in aluminum in solid solution. In addition, a significantly increased aging response is expected through the heat treatment or use of the soldered products.
    But Cu also increases the risk of heat cracks during casting, the corrosion resistance decreases and the solidus temperature is lowered. The copper content should be between 0.6 and 1.0 in cases where the strength needs to be improved.
    If Zr is added, the number of very small particles is increased, which improves the deflection resistance.
    This also gives larger grains after soldering, which is good for corrosion resistance. Thus, in order to obtain a good deflection resistance and large grains, 0.05-0.3% by weight of Zr can be added to the core and / or the alloy on the water side.
    The silicon concentration in the core should be 50.1% by weight Si, however preferably 50.06% by weight, since pitting corrosion can then be avoided as the corrosion attacks instead go in the lateral direction. At concentrations above 0.1% by weight, the formation of a sacrificial anodic layer is significantly slowed down.
    In the manufacture of an aluminum alloy for a soldered sheet in accordance with the present invention, it is impossible to completely avoid contaminants. These contaminants are neither described nor avoided in the present invention but never exceed a total content of 0.15% by weight. In all embodiments and examples of the present invention, the remaining amount consists of aluminum.
    A solder plated sheet made according to the present invention provides high strength and superior corrosion resistance, both for the plating on the water side and for the solder plating on the other side. The cladding material intended for the water side is particularly well suited as corrosion protection on selected type of core material, thanks to a well-matched corrosion potential between core and plating. The alloy combination enables the production of thinner pipe materials with sufficiently high strength and good corrosion properties. A plated sheet metal should be 300 μm thick, but preferably 200 μm, and the plating on the water side should be S30 μm, but preferably less than 20 μm thick. 10 15 20 25 30 35 The composition and contents of the various alloying elements should be chosen with great care. Therefore, the present invention provides a method of, through extremely carefully tested levels of Mg, Mn, Si, Cu, Zr and optionally Zn, regulating potential gradients and corrosion properties in plated sheet metal. Thus, the plating on the water side can be made extremely thin without reducing the strength and the corrosion and erosion resistance. A well-balanced and improved corrosion resistance is required to meet both the external corrosion environment and vehicles exposed to due to the salting of roads, as well as a sometimes tough internal corrosion environment caused by poor quality coolant, in addition to the zinc effect in the sacrificial anodic plating on the water side.
    All aluminum alloys in the 4XXX series can be used within the scope of the invention.
    Thus, the types of plumbing and the thicknesses illustrated in the examples below illustrate the present invention are to be construed as examples only.
    Both the core and the water side plating have a high Mn content to give the solder plated sheet high strength. By carefully weighing the difference in Si content in the two materials, a potential gradient is obtained which means that the plating of the water side becomes sacrificial anodic to the core. During soldering, thanks to the silicon in the water side plating, the dissolved Mn content will be low, mainly in the water side plating, as Si stabilizes the alpha-AlMnSI dispersoids and possibly forms new ones - after the soldering there has thus been a difference of 1 Mn in solid solution between the core and the plating on the water side. The low Si content in the core enables a high content of dissolved Mn, since most of the finest AlMn dispersoids formed in the production of the sheet are dissolved during soldering.
    This allows a potential gradient to be formed; a property that is not affected by either soldering cycles or the thickness of the plating. It is desirable that the ratio between Si in the cladding and the Si in the core is at least 1: 5, but preferably at least 1021. Thus, with thin solder-plated sheet metal and even thinner cladding on the water side, the silicon content on the water side should preferably be 0.5% by weight or more. ensure that sufficient Si is available to maintain a high level of alpha-AlMnSi dispersoids during soldering. Zn can be added to the plating on the water side to, if necessary, further increase the potential gradient, so that the plating on the water side has an even higher sacrificial anodic effect. However, thanks to the present invention, the zinc content of the sacrificial anodic layer can be reduced, which means reduced risk of zinc diffusing deep into the core and reducing the overall corrosion resistance from the outside. Reduced zinc content also helps to make it easier to recycle heat exchanger components, and in addition, production can be made more flexible as different types of heat exchangers can be placed in the same CAB oven. 10 15 20 25 30 35 This, in combination with the effect of low copper content in the plating on the water side and high copper content in the core, further increases the difference in corrosion potential; this in turn further improves the corrosion resistance, in addition to the effect that silicon and manganese already provide.
    When Mg is added to the plating on the water side, the strength of the plating is improved, which in turn contributes to improving the overall strength of the plate. Thanks to the relatively high mechanical strength of the plating, it is thus possible to produce very thin solder-plated sheet metal. It has also emerged in the work with the present invention that Mg in the plating on the water side reduces the depth of the caustic pits in corrosive environments.
    In some applications, however, the solderability may be impaired by Mg. For geometries other than round welded pipes, for example folded pipes, it is possible that the solderability of B-shaped pipe joints can be negatively affected if there is Mg in the plating on the water side.
    The present invention therefore enables the use of several alloys, where the silicon content in the sacrificial anodic layer (ie the plating on the water side) and in the core plays an important role and is therefore balanced against each other in such a way that a high silicon content in the sacrificial anodic plating on the water side in combination with a very low silicon content in the core means that there is a difference in corrosion potential after a soldering process. A potential gradient is obtained mainly by the differences in the levels of dissolved Mn, Cu, and possibly Zn (if Zn is added) between plating and core. The Si content in the core and in the claddings has been determined with great accuracy in order to obtain optimum performance. The Si content in the core is as low as possible to avoid the formation of dispersoids containing alpha-AIMnSi during soldering. in combination with the effect of low copper levels in the plating on the water side and a high level of copper in the core, this further increases the differences in corrosion potential; this in turn further improves the corrosion resistance, in addition to the effect of silicon and manganese.
    The plating on the water side also has large grains and a large number of intermetallic particles, which means that it can withstand erosion caused by liquid flow. Both the high Mn content and the manufacturing process contribute to this. The ingot for both core and plating is produced in a process where the temperature during preheating after casting is at most 550 ° C. The erosion properties are important for pipes in systems with liquid de fate, for example a radiator or a heater. The plating on the water side according to the present invention has been tailored to provide high resistance to erosion. The resistance to erosion is closely related to particle fraction and size distribution; a controlled number of particles containing Al-Si-Fe-Mn helps to improve the erosion resistance of the material. The alloy on the water side according to the present invention has a carefully matched particle fraction. The fraction in the soldered state depends on the composition, process and soldering cycle. It is obtained according to the present invention for the production of AlMn sheet by the roll ingot for the water side plating is prepared from a melt containing (in% by weight) 0.5-1.5% Si, 1.0-2.0, but preferably 1.4 -1.8% Mn, 0.2-2.0% Mg, s 0.1% Cu, s 0.7% Fe, s1.4%, s4% Zn, s0.3% by weight each of Zr, Ti, Ni, Hf, V, Cr, ln, Sn, and sO, 5% by weight in total of Zr, Ti, Ni, Hf, V, Cr, ln, Sn, and the remainder consisting of aluminum and unavoidable impurities. All levels of alloying elements below are given in weight percent. The ingot is aggravated before hot rolling at a preheating temperature not exceeding 550 ° to control the number and size of the dispersoids (particles separated from supersaturated solid solution), after which the preheated ingot is hot rolled into a hot strip of the desired dimensions. Total height reduction during hot rolling of strips for the water side depends on the desired final thickness and the thickness of the water side plating but is normally> 70%. The output thickness for hot strip intended for plating on the water side is normally between 25 and 100 mm. It is welded to the sheet metal blank made from a melt containing <0.1, more preferably <0.06% Si, 1.0-2.0%, most preferably 1.4-1.8% Mn, s0.35 % Mg, s 0.2-1.0%, but preferably 0.6-1.0% Cu, s 0.7% Fe, s0.3% by weight each of Zr, Ti, Ni, Hf, V, Cr , ln, Sn, and sO, 5% by weight in total of Zr, Ti, Ni, Hf, V, Cr, ln, Sn, and the remainder consisting of aluminum and unavoidable impurities ..
    The plated ingot is preheated at a preheating temperature of not more than 550 ° C. It is hot rolled first and then cold rolled to final thickness. The roll should be heat treated at final thickness. the water side plating then has a microstructure after soldering with a particle structure between 0.5 and 20 x 105 particles per mm'2, but preferably between 1 and 12 x 105 particles per mmz, and most preferably between 2 and 9 x 105 particles per mmz , when the diameter of the particles is 50-500 nm, and a particle density between 1-20 x 103 particles per mm 2, however preferably between 7 and 15 x 103 particles per mm 2 when the particle diameter is> 50 nm.
    These fine particles are formed for the most part during preheating before hot rolling.
    Normal soldering conditions include heating to a temperature of 580-630 ° C, e.g. around 600 ° C, with a holding time of 2-5 minutes, usually around 3 minutes. How the particle density was measured is described in Example 2.
    An Al-Si solder plating containing 5-13% by weight of Si can be applied directly to the solder plated plate, on the opposite side seen from the water side plating. With a solder plating on the opposite side to the water side plating, thanks to the low silicon content in the core, a sacrificial anodic layer is obtained, which means that the corrosion goes in the lateral direction also on the solder plated side. The excellent corrosion resistance of this core material has been previously described in EP1580286. When a solder plated sheet is provided with solder plating, no intermediate layer is required on the solder plating side, which is an advantage in terms of cost. Recycling is also simplified when there is no intermediate layer with a composition other than the core.
    The corrosion protection in a solder-plated sheet metal with solder plating is very good thanks to the fact that potential gradients are created for both inner and outer sides. On the outside, ie the side facing the air side, a sacrificial anodic layer is created under the solder under the surface, a so-called "long-life" layer. Fine particles in the core containing Al, Mn and Si are separated right next to the surface of the solder plating, thanks to the inward diffusion of Si from the solder plating. This lowers the Mn content in solid solution in this range compared to in the core. At greater depths in the core, where the silicon does not reach, most of the fine AlMn dispersants dissolve during the soldering process and the amount of dissolved Mn increases. The difference in the amount of redeemed Mn in the sacrificial anodic layer below the surface before and after the soldering process results in a potential gradient between outer surface and core, which gives superior corrosion properties.
    Also the actual manufacturing process for the solder plated sheet has been optimized to obtain a solder plated sheet with the best possible properties. The final profile of Mn, Cu and Si in solid solution, and thus the anti-corrosion properties, after soldering, depends on the manufacturing process used.
    The ingot of the soldered plate is preheated to <550 ° C only before hot rolling. This is to obtain a core material with a large amount of Mn-containing dispersoids, which are small enough to be able to dissolve during the soldering process, so that the Mn content in solid solution becomes as high as possible. State H24 is preferred over state H14. It is clear that if the material is produced in state H24, the potential gradient from the outer solder-plated side becomes sharper.
    Therefore, condition H24 is preferred for the core of a soldered aluminum sheet made in accordance with the present invention, and ingots for both core and plating should be prepared in a process of preheating after casting to a maximum of 550 ° C.
    Embodiments of the present invention are described below by way of example.
    EXAMPLES Example 1 Material sheet samples A-D were made with a core whose composition is described in Table 1 below. Hot rolled material of said core material was used and was originally plated with 10% AA4343 solder plating and 10% plating thickness on the water side.
    The plating on the water side was removed if replaced with plating of other alloys intended for the water side, the compositions of which are described in Table 2. Samples A and C are reference specimens. The thickness of the material was further reduced by cold rolling in a laboratory environment to desired dimensions and finally heat treated to state H24.
    Table 1 Chemical composition of the core in% by weight, measured by OES.
    Si Fe Cu Mn Mg Zn Zr Ti Core 0.05 0.2 0.80 1.7 <0.01 <0.01 0.13 0.03 Table 2 Chemical composition of the water-side alloys in% by weight, measured by OES.
    Sample Si Fe Cu Mn Mg Zn Zr Ti A 0.8 0.2 <0.01 1.7 <0.01 <0.01 <0.01 <0.01 B 0.8 0.2 <0.01 1.7 1.1 <0.01 <0.01 <0.01 C 0.8 0.2 <0.01 1.6 <0.01 2.7 <0.01 <0.01 D 0, 8 0.2 <0.01 1.6 1.1 2.7 <0.01 <0.01 All test pieces were soldered in a CAB oven for batch insertion. The plates were placed in pairs with the water side plating against each other to minimize zinc evaporation. A heating cycle was used, where the temperature was raised from room temperature to 600 ° C in 20 minutes, 3 minutes holding time at the highest temperature with subsequent cooling to 200 ° C with one of the two cooling processes described in Table 3. The cooling environment was air or N2. Even if the cooling rate is not determined, it is desirable that the cooling is fast. The different material combinations and soldering processes are described in Table 4. As already stated, all samples have a core according to Table 1, a solder plating type AA 4343 and plating on the water side according to Table 2. Thickness and plating thickness were measured with a light optical microscope (LOM) on polished samples. 10 15 20 Table 3 Soldering cycles. 11. . Maximum Hold Time at Cooling Speed U h tt td. .
    Solder cycle fl m. Pp e: young l temperature temperature to 200 C Kym fi U-ö (mm) cc) (min) rclsek) I 20 600 2 2.4 air ll 20 600 2 1.4 Nz Table 4 Material combinations and solder scheme. plate - pj - t - Plumbing plumbing. water sludge on the water side (pm) (glue) A1 A 210 22 11 I B1 B 190 19 10 I C1 C 202 20 11 I D1 D 205 19 12 l A2 A 210 22 11 Il B2 B 190 19 10 Il D2 D 205 19 12 ll The corrosion behavior on the inside is analyzed using a glass beaker test. Samples of 40x80 mm were made in order of each material combination. They were degreased in a mild alkaline degreasing bath (Candoclene). The back of the samples was masked with tape. Samples were placed in glass beakers containing 400 ml of OY aqueous solution, four in each beaker. The composition of the OY water was 195 ppm Cl ", 60 ppm SO42", 1 ppm Cuz fl and 30 ppm Fe ". The mixture consisted of NaCl, Na 2 SO 4, CuCl 2 -2H 2 O, and FeCl 3 -6H 2 O added in deionized water. The beaker was placed on a magnetic plate with magnetic stirring that could be regulated with a timer.
    The temperature cycle was set at 88 ° C for 8 hours followed by room temperature for 16 hours. Stirring only during the heating periods of 8 hours. The test was performed over a two week period and the same solution was used throughout the test period. Duplicate specimens of each material combination were analyzed. After the test, the test pieces were placed in HNO 2 for 10-15 minutes and then rinsed in deionized water. The depth of attack was analyzed with the microscope method according to ISO 11463. Cross sections were studied in a light optical microscope for a more detailed analysis of the type of corrosion attack and the depth of the attack. Any holes were counted, but holes less than 5 mm from the edges were not included. Table 5 shows the results of corrosion tests of the inside. The number of holes (total of two test pieces) is stated. No holes were detected.
    Table 6 shows attack depth in samples A1-D1 and A3-D3. B1, B2, D1 and D2 are samples according to the present invention, and A1, A2 and C1 are reference materials.
    Table 5 Number of holes after two weeks of corrosion testing of the inside.
    Sample Plating on Thickness Plating thickness Number of perforations on the water side (pm) on the water side (um) A1 A 210 22 0 B1 B 190 19 0 C1 C 202 20 0 D1 D 205 19 0 A2 A 210 22 0 B2 B 190 19 0 D2 D 205 19 0 10 15 20 25 30 13 Table 6 Depth of corrosion attack according to the focusing method after two weeks of corrosion testing of the inside.
    Sample Plating on Average Std deviation water side pit depth (pm) (pm) A1 A 110 28 B1 B 78 20 C1 C 136 29 moi ro 11 A2 A 136 33 B2 B 70 17 D2 D 49 14 Table 6 shows that the corrosion attacks in B1 and B2 are not as deep as in A1 and A2.
    The attacks in D1 and D2 are not as deep as in C1. It is clear that if magnesium is added to the plating on the water side, the depth of attack is reduced. This is also evident from the cross-sections of Figures 1 and 2, which show materials C1 and D1 after corrosion testing of the inside. A potential gradient between the plating of the water side and the core according to the present invention is sufficient for the materials A and C to pass corrosion tests of the inside without holes occurring.
    However, the corrosion properties are significantly improved if Mg is added to the plating on the water side. A combination of a strong core and a water side plating with improved resistance to pitting corrosion means that thinner materials can be produced.
    The corrosion potential profiles were measured for materials in both H14 and H24 conditions. The measurements were made from the solder plating side, after CAB soldering, see above. Corrosion potential measurements were made at 6-8 different depths, starting at the outer surface of the remaining solder plating and further into the core. The samples were etched in hot NaOH to the various depths (with the back masked with tape). After etching, the samples were purified in concentrated HNO 3 and then rinsed in deionized water and ethanol. The thickness of the samples was measured with micrometers before and after etching to determine the depth.
    The back of the test pieces was masked with tape and the edges were covered with nail polish. Active area after masking was ~ 20x30 mm. Solartron lMP process log was used for the electrochemical measurements. A Standard Calomel Electrode (SCE) was used as the reference electrode. The samples were immersed in a SWAAT electrolyte solution (ASTM D1141 without heavy metals and with a pH of 2.95). 10 ml of HZOZ per liter of electrolyte solution was added when the measurements were started. OCP (Open Circuit Potential) was monitored as a function of depth by etching the samples before the measurement.
    The corrosion potential profiles are shown in Figure 3. It shows that materials in condition H24 give a steeper corrosion potential profile than materials in condition H14.
    Example 2 Another aspect of the present invention is the particle distribution. Materials whose core has a composition according to Table 1 and plating E from Table 7 on the water side were analyzed.
    It is unlikely that the Mg content will affect the particle density to any great extent. The ingot for the plating on the water side was preheated at a temperature between 450 and 550 ° C and then hot rolled with a total reduction of 90%. The ingot was then welded to the core ingot; on the opposite side, a roller casing of plating type AA4343 was welded. The temperature was <550 ° C and the hot rolling gave a total reduction of 99%, down to 3.9 mm. The ingot was then cold rolled to its final thickness of 0.270 mm. The roll was heat treated to state H24.
    Table 1 Chemical composition for water side plating in% by weight, measured with OES.
    Sample Si Fe Cu Mn Mg Zn Zr Ti E 0.9 0.3 <0.01 1.6 <0.01 1.6 0.1 <0.01 Material from the roll as above was solder simulated in a CAB oven. Two heating cycles were used: one involved raising the temperature from room temperature to 610 ° C in 20 minutes followed by a holding time of 3 minutes at the maximum temperature. The second heat cycle was similar to the first, but with a maximum temperature of 585 ° C. The cooling took place in an inert environment at a speed of ~ 0.50 ° C / s.
    In order to be able to measure the particle density of the material, sections were cut in the longitudinal direction of the belt (ND-RD). The sections were mechanically polished with Struer's OP-S suspension containing 0.04 μm colloidal silica in the final preparation step. The particle cross section was measured in a FEG-SEM, Philips XL3OS, with an image analysis system from Oxford Instruments llVlQuant / X. 10 15 20 15 Images for the measurements were recorded as backscatter images with so-called ln-lens detector in the microscope. To minimize the depth of information and get an image with good spatial resolution, low acceleration voltage, 3kV, was used. Normal gray level threshold was used to track the particles. To obtain a result that is representative of the number of particles and distribution in the sample, the picture frames were spread over the cross section. The measurements were made in two steps. The first stage occupied smaller dispersoids (particles with a diameter of <500 nm). More than 1000 dispersoids were measured. The area, A, of each particle was measured and a corresponding particle diameter was calculated as ~ / (4A / 1t). The second measurement was made on intermetallic particles (particles with a diameter> 500 nm). The measurements were made on an image field that comprised around 80% of the plating thickness. 100 such image fields were analyzed.
    After soldering at 610 ° C for 2 minutes, the specimen had a particle density of 3.9x105 dispersoids per mm 2 of particles in the size range of 50-500 nm. After soldering, the test pieces had a particle density for the intermetallic particles in the size range> 500 nm of 1.4x104 particles per mm 2. After soldering at 585 ° C for 2 minutes, the specimen had a particle density for dispersoids in the size range of 50-500 nm of 6.8x105 particles per mm 2. After soldering, the test pieces had a particle density for intermetallic particles in the size range> 500 nm of 1x104 particles per mm2.
    权利要求:
    Claims (15)
    [1]
    An iodine-plated aluminum sheet comprising: a core material of an aluminum alloy; and a plating material on at least one side of the core material made of an aluminum alloy having a lower corrosion potential than the core material, the plating being the outermost layer of the solder plated sheet, the plating material being an aluminum alloy having 0.8 to 1.3% by weight of Mg, 0, 5 to 1.5% by weight of Si, 1.0 to 2.0% by weight, but preferably 1.4-1.8% by weight of Mn, 50.7% by weight of Fe, 0.1% by weight of Cu, and 54% by weight of Zn, 50.3% by weight each of Zr, Ti, Ni, Hf, V, Cr, ln, Sn and 50.5% by weight in total of Zr, Ti, Ni, Hf, V, Cr, ln, Sn with the residue consisting of of Al and unavoidable pollutants.
    [2]
    A soldered aluminum sheet according to claim 1, wherein the plating material is made of an aluminum alloy consisting essentially of 0.7 to 1.4% by weight of Mg, 0.5 to 1.5% by weight of Si, 1.0-2.0% by weight. %, but preferably 1.4 to 1.8% by weight of Mn, 50.7% by weight of Fe, 0.1% by weight of Cu, and 54% by weight of Zn, 50.3% by weight each of Zr, Ti, Ni, Hf , V, Cr, ln, Sn and 50.5% by weight in total of Zr, Ti, Ni, Hf, V, Cr, ln, Sn, and the residue consisting of Al and unavoidable impurities.
    [3]
    Solder-plated aluminum sheet according to any one of claims 1-2, wherein the plating material contains 50.05-0.3% by weight of Zr.
    [4]
    Solder-plated aluminum sheet according to any one of claims 1-3, wherein the composition of the plating does not include Ni.
    [5]
    Solder-plated aluminum sheet according to any one of claims 1-4, wherein the copper content of the plating is <0.04% by weight.
    [6]
    Solder-plated aluminum sheet according to any one of claims 1-5, wherein the core material contains 50.1% by weight of Si, but preferably 0.06% by weight of Si, 50.35% by weight of Mg, from 1.0 to 2.0% by weight, however, preferably 1.4 to 1.8% by weight of Mn, from 0.2 to 1.0, however preferably 0.6 to 1.0% by weight of Cu, 50.7% by weight of Fe, and 50.3% by weight each of Zr, Ti, Ni, Hf, V, Cr, ln, Sn and 50.5% by weight in total of Zr, Ti, Ni, Hf, V, Cr, ln, Sn, the remainder consisting of aluminum and unavoidable impurities.
    [7]
    Solder-plated aluminum sheet according to any one of claims 1-6, wherein the core material contains 50.1% by weight of Si, but preferably 0.06% by weight of Si, 0.35% by weight of Mg, from 1.4 to 1.8% by weight % Mn, from 0.6 to 1.0% by weight of Cu, 50.7% by weight of Fe, 0.05 to 0.3% by weight of Zr, and 50.3% each of Ti, Ni, Hf, V, Cr, ln, Sn and 50.5% by weight in total of Zr, Ti, Ni, Hf, V, Cr, ln, Sn, and the remainder consisting of aluminum and unavoidable impurities.
    [8]
    Solder-plated aluminum sheet according to any one of claims 1 ~ 7, wherein both core material and plating material are nickel-free. 10 15 20
    [9]
    Solder-plated aluminum sheet according to any one of claims 1-8, wherein said plating material is intended for the water side, and wherein the core has an additional Al-Si solder plating applied directly to the plate on the opposite side, and wherein this solder plating comprises 5-13% by weight Si.
    [10]
    Solder-plated aluminum sheet according to any one of claims 1-9, wherein the ratio between Si in the water side plating and Si in the core is at least 5: 1, but preferably 1011.
    [11]
    Solder-plated aluminum sheet according to any one of claims 1-9, wherein the thickness of the solder-plated sheet is less than 300 μm, but preferably less than 200 μm.
    [12]
    Solder-plated aluminum sheet according to claim 11, wherein the thickness of the plating is S30 μm, but preferably less than 20 μm.
    [13]
    A soldered aluminum sheet according to any one of claims 1-12, wherein the condition of the core is H24.
    [14]
    Solder-plated aluminum sheet according to any one of claims 1-12, with roll ingot for core and plating produced in a process where the preheating after casting is at most 550 ° C.
    [15]
    Solder-plated aluminum sheet according to any one of claims 1-12, wherein the water-side plating after soldering has a microstructure with a particle density in the size range between 0.5 and 20x105 particles per mm 2, but more preferably between 1 and 12x105 particles per mm 2, and most preferably between 2 and 9x105 particles per mmz when the particles have a corresponding diameter in the order of 50-500 nm, and a particle density in the order of 1-2Ox103 particles per mmz, but preferably between 7 and 15x103 particles per mmz when the particles have a corresponding diameter> 500 nm .
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    同族专利:
    公开号 | 公开日
    US9096916B2|2015-08-04|
    CN102422118A|2012-04-18|
    KR101686497B1|2016-12-14|
    RU2011150793A|2013-06-20|
    JP2012526660A|2012-11-01|
    RU2553133C2|2015-06-10|
    EP2430386A4|2017-04-19|
    BRPI1012187A2|2016-04-05|
    KR20120024549A|2012-03-14|
    JP2015148013A|2015-08-20|
    WO2010132018A1|2010-11-18|
    US20120070681A1|2012-03-22|
    JP5948450B2|2016-07-06|
    CN102422118B|2013-09-11|
    PL2430386T3|2019-03-29|
    MX2011010869A|2011-11-02|
    EP2430386B1|2018-08-22|
    SE534693C2|2011-11-22|
    EP2430386A1|2012-03-21|
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    法律状态:
    2020-05-12| NUG| Patent has lapsed|
    优先权:
    申请号 | 申请日 | 专利标题
    SE0950340A|SE534693C2|2009-05-14|2009-05-14|Soldered aluminum sheet with high strength and excellent corrosion properties|SE0950340A| SE534693C2|2009-05-14|2009-05-14|Soldered aluminum sheet with high strength and excellent corrosion properties|
    RU2011150793/02A| RU2553133C2|2009-05-14|2010-05-12|Aluminium sheet for high temperature soldering with high strength and excellent corrosion characteristics|
    US13/262,843| US9096916B2|2009-05-14|2010-05-12|Aluminium brazing sheet with a high strength and excellent corrosion performance|
    EP10775170.3A| EP2430386B1|2009-05-14|2010-05-12|Aluminium brazing sheet with a high strength and excellent corrosion performance|
    KR1020117024661A| KR101686497B1|2009-05-14|2010-05-12|Aluminium brazing sheet with a high strength and excellent corrosion performance|
    MX2011010869A| MX2011010869A|2009-05-14|2010-05-12|Aluminium brazing sheet with a high strength and excellent corrosion performance.|
    BRPI1012187A| BRPI1012187A2|2009-05-14|2010-05-12|high strength aluminum brazing sheet and excellent corrosion result|
    CN2010800212096A| CN102422118B|2009-05-14|2010-05-12|Aluminium brazing sheet with a high strength and excellent corrosion performance|
    PL10775170T| PL2430386T3|2009-05-14|2010-05-12|Aluminium brazing sheet with a high strength and excellent corrosion performance|
    PCT/SE2010/050526| WO2010132018A1|2009-05-14|2010-05-12|Aluminium brazing sheet with a high strength and excellent corrosion performance|
    JP2012510779A| JP2012526660A|2009-05-14|2010-05-12|Aluminum brazing sheet with high strength and excellent corrosion resistance|
    JP2015032182A| JP5948450B2|2009-05-14|2015-02-20|Aluminum alloy sheet for brazing having high strength and excellent corrosion resistance and method for producing the same|
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