The present application claims the benefit of priority of Norwegian patent application NO20151653, filed on Dec. 2, 2015 with the Norwegian Patent Office with the title “Aluminium extrusion alloy suitable for etched and anodized components”, the entire content of which is incorporated herein by reference.
The present invention relates to an aluminum alloy suitable for etched and anodized components. More particularly the present invention relates mainly to extrusion alloys of the types MgSi, 6060 and 6063 which after being extruded to any wide variety of forms for different applications such as house buildings and other building applications, is subjected to etching and subsequent anodizing.
Due to environmental issues, it is foreseen that there will be an increased demand for re-melting post consumed aluminium products in the future. This may lead to somewhat higher levels of trace elements, like Zn in the re-melted metal, i.e. an enrichment over time.
Customers sometimes explicitly ask for recirculated aluminium, likely due to concern for the environment and reduced carbon footprint. It is therefore a prerequisite for metal suppliers to be able to handle such requests.
During normal alkaline etching prior to anodizing, it is experienced that some grains can be etched deeper than others, called “preferential grain etching” or “grainy” or “spangle appearance”. Further, the gloss that is created by etching usually increases with increased Zn content in alloy.
Due to the etching of such materials, the Zn-content in the etching bath may be enriched and influence on the etching response as well. This may be avoided by using additives that precipitate the accumulated Zn-ions. There are several suppliers, promoting different proprietary additives (different amounts and types of chemicals) and they may give varying results.
Preferential grain etching (PGE) is caused by Zn in the alloy and/or in the etching bath as indicated above. Thus, it has been found that when alloys containing zinc with an amount in excess of 0.03 wt % are etched in a solution alkaline etching bath, these alloys tend to yield a “grainy” surface appearance.
Reliable measurement of free Zn-ions in the etching bath is normally done by ICP (Inductively Coupled Plasma Mass Spectrometry) which is a time consuming procedure and which has to be carried out by specialists. An easy and reliable measuring technique has not been established so far. An alternative remedy is to increase the use of additives on a regular basis for instance by adding sufficient Na2S in the etching tanks one day and then the etching tank is ready for use the next day or day thereafter.
An alternative method is to carry out mechanical pretreatment of the profile surface (shot blasting) such that the necessary time in the etch tank is reduced and the risk of preferential grain etching is reduced.
Still another alternative method that may be possible is the use of acid etch instead of alkaline etching bath. However, the use of acid in etch baths is encumbered with high risk of hazardous impact on the environments and persons involved in the etching bath operation and is not permitted in most western countries.
From U.S. Pat. No. 3,594,133 is known an etched article being made from an Al—Mg—Si alloy where the Cu/Zn ratio is required to be 1:1 on a weight basis ratio when the zinc content is in the range 0.03-0.10 wt % and 2:1 when the zinc content is above 0.10 wt %. Tests performed by the inventors of the present invention has proved, however, that the high content of copper does not prevent formation of PGE. Besides, the patent suggests high Cu content, which is harmful in relation to the corrosion resistance of the alloy and high Zn content which increases the Zn content of the etching bath and which in turn causes increased PGE.
The 6060 alloys contain according to the international AA standard 0.30-0.6 wt % Si, 0.10-0.30 wt % Fe, max 0.10 wt % Cu, max 0.10 wt % Mn, 0.35-0.6 wt % Mg, max 0.05 wt % Cr, max 0.15 wt % Zn and max 0.10 wt % Ti, others each max 0.05 wt % and others total max 0.15 wt %. The 6063 alloys contains according to the AA standard on the other hand 0.20-0.6 wt % Si, max 0.35 wt % Fe, max 0.10 wt % Cu, max 0.10 wt % Mn, 0.45-0.9 wt % Mg, max 0.10 wt % Cr, max 0.10 wt % Zn and max 0.10 wt % Ti, others each max 0.05 wt % and others total max 0.15 wt %.
With the present invention is provided a selection alloy solution where the Zn and Cu alloying elements of the 6060 and 6063 types of alloys, based on extensive testing in many experiments, are controlled to obtain the desired and consistent, optimal gloss and PGE appearance of such alloys.
The invention provides an alloy according to claim 1. Further embodiments of the invention are described in the dependent claims, which describe preferred sub-ranges that result in alloys with favorable properties.
The Cu and Zn ranges in the claims are described by an area/polygon in the Cu—Zn diagram. The claimed ranges lie within the area that is obtained by drawing straight lines between the points in ascending order (e.g. a straight line from a1 to a2, a straight line from a2 to a3, etc.) and further a straight line between the last and the first point (e.g. a straight line from a6 to a1). The points and lines itself limit the area and are not a part of the claimed area. That is, the alloys according to the invention comprise at least a small amount of Zn and a small amount of Cu. Further, if for example an area is partially defined by a straight line drawn from a point corresponding to 0.025 wt-% Cu and 0.025 wt-% Zn to a point corresponding to 0.05 wt-% Cu and 0.05 wt-% Zn, said area does not include alloys having a ratio of Cu/Zn equal to 1, but for example only includes alloys having a ratio of Cu/Zn below 1. When a dependent claims refers to points (e.g. a1 and a5) mentioned in a claim to which said dependent claim refers (e.g. a1, a2, a3, a4, a5), these points are redefined by the dependent claim and the relevant area is formed by these redefined points (e.g. a1 and a5) together with the points mentioned in the claim from which said dependent claim is dependent and which are not redefined (e.g. a2, a3, a4). When a dependent claim introduces a new set of points (points with a new index letter such as b1, b2, b3, b4), said claim is directed to said smaller/narrower area defined by said new set of points (such as b1, b2, b3, b4) unless it is indicated otherwise.
A particularly robust alloy resistant to PGE and having good properties may be obtained when the Cu—Zn content of an alloy according to claim 1 is held within the composition window defined by points f1, f2, f3 and f4 in a Cu—Zn diagram, wherein f1 corresponds to 0.017 wt-% Cu and 0.025 wt-% Zn, f2 corresponds to 0.04 wt-% Cu and 0.07 wt-% Zn, f3 corresponds to 0.03 wt-% Cu and 0.07 wt-% Zn, and f4 corresponds to 0.007 wt-% Cu and 0.025 wt-% Zn. As is described herein (see e.g. also
The invention will be further described in the following by way of example and with reference to the figures where;
As stated above the present invention relates to aluminum alloys and particularly aluminium extrusion alloys of the types containing Magnesium and Silicon, 6060 and 6063 which after being extruded to any wide variety of forms for different applications such as house buildings and other building applications, is subjected to etching and subsequent anodizing. During normal alkaline etching prior to anodizing, it is experienced that some grains can be etched deeper than others, called “preferential grain etching” (PGE) or “grainy” or “spangle appearance”.
Extensive testing has been performed to arrive at an alloy composition where the Zn and Cu alloying elements are controlled to obtain the desired gloss and PGE. The alloy according to an embodiment of the invention may contain as follows in wt %: Si: 0.20-0.90, Mg: 0.30-0.90, Fe: 0.10-0.40, Mn: max 0.20, Zn: 0.025-0.10, Cu: 0.005-0.05, Ti: max 0.10, Cr: max 0.10, where the relation between Cu and Zn is controlled to avoid preferential grain etching and the ratio of Cu/Zn is below 1, including others or incidental impurities each in the amount of 0.05 wt % max, the total of others and impurities being in the amount of 0.15 wt % max and balance Al.
In this respect, the invention may according to a first exemplary aspect provide an aluminium alloy suitable for etched and anodized components, in particular aluminum extrusion alloys of the types containing Magnesium and Silicon, which after being extruded to any wide variety of forms for different applications such as house buildings and other building applications is subjected to etching in a conventional alkaline etching bath and subsequent anodizing, consisting of in wt %: Si: 0.20-0.90, Mg: 0.30-0.90, Fe: 0.10-0.40, Mn: max 0.20, Zn: 0.025-0.10, Cu: 0.005-0.05,Ti: max 0.10, Cr: max 0.10, where the relation between Cu and Zn is controlled to avoid preferential grain etching and the ratio of Cu/Zn is below 1, including others or incidental impurities each in the amount of 0.05 wt % max, the total of others and impurities being in the amount of 0.15 wt % max and balance Al.
According to a second exemplary aspect, the alloy according to the first aspect may be a 6060 or 6063 alloy according to the International AA alloy standard but where the concentration of Cu is between 0.005 and 0.05 wt % and the concentration of Zn is between 0.025 and 0.10 wt %.
According to a third exemplary aspect, the alloy according to the first or second aspect may be characterized in that the minimum concentration of Cu is 0.010 wt %.
According to a fourth aspect, the alloy according to any of the first to third aspect may be characterized in that the maximum concentration of Cu is 0.04 wt %.
According to a fifth exemplary aspect, the alloy according to any of the first to third aspect may be characterized in that the maximum concentration of Cu is 0.03 wt %.
According to a sixth aspect, the alloy according to any of the first to third aspect may be characterized in that the maximum concentration of Cu is 0.025 wt %.
According to a seventh exemplary aspect, the alloy according to any of the first to sixth aspect may be characterized in that the minimum concentration of Zn is 0.030 wt %. According to an eight exemplary aspect, the alloy according to any of the first to seventh aspect may be characterized in that the maximum concentration of Zn is 0.08 wt %.
According to a ninth exemplary aspect, the alloy according to any of the first to seventh aspect may be characterized in that the maximum concentration of Zn is 0.06 wt %.
According to a tenth exemplary aspect, the alloy according to any of the first to seventh aspect may be characterized in that the maximum concentration of Zn is 0.055 wt %. According to an eleventh exemplary aspect, the alloy according to any of the first to seventh aspect may be characterized in that the maximum concentration of Zn is 0.05 wt %. According to a twelfth exemplary aspect, the alloy according to any of the first to seventh aspect may be characterized in that the maximum concentration of Zn is 0.050 wt %.
According to a thirteenth exemplary aspect, the alloy according to any of the first to twelfth aspect may be characterized in that the ratio of Cu/Zn is between 0.8 and 0.2.
According to a fourteenth exemplary aspect, the alloy according to any of the first to twelfth aspect may be characterized in that the ratio of Cu/Zn is between 0.5 and 0.2.
According to a fifteenth exemplary aspect, the alloy according to any of the first to fourteenth aspect may be characterized in that the concentration of Fe is between 0.22 and 0.37 wt %.
According to a sixteenth exemplary aspect, the alloy according to any of the first to fifteenth aspect may be characterized in that the concentration of Mn is between 0.03 and 0.06 wt %.
According to a seventeenth exemplary aspect, the alloy according to any of the first to sixteenth aspect may be characterized in that the concentration of Mg is between 0.30 and 0.50 wt % and the concentration of Si is between 0.35 and 0.50 wt %.
The tests were initially carried out with alloys having a chemistry as defined in table 1 below. The concentrations of Si, Mg and Mn in these tested alloys are kept close to constant, while the concentrations of Fe and Zn are varied. To alloys 11, 12 and 17 it was added 0.05 wt % Cu.
One log/billet of each alloy was, after casting, homogenized together (at the same time) with the following specified time-temperature path:
After homogenisation the billets were extruded in an 800 tons vertical press with a container diameter of 100 mm and a billet length of 200 mm. Prior to extrusion the billets were preheated by induction heating at approximately 100° C./min to an average temperature 520° C. The container temperature was approximately 430° C. and the extrusion ratio was 78.5. The ram speed was 4.4 mm/s, while the profile speed was 22 m/m in. After extrusion, the profiles were air cooled to room temperature and then stretched to approximately 0.5% plastic strain. The extruded profiles were further aged (dual rate) as follows:
The 18 newly extruded profiles were mounted horizontally and etched in an industrial 15000 litres NaOH etching bath with A18000 additive (commercially available product). The temperature was 70° C. and the etching time was 15 minutes. Finally, the etched profile samples were anodized, also in normal production.
Evaluation of Anodized Surfaces.
From
The effect of Cu on PGE and gloss is, however, remarkable when being added to the alloy containg 0.05 wt % Zn and 0.30 wt % Fe, as can be seen in
Gloss was measured at an angle of 60° along the extrusion direction using a handheld measurement device.
The positive test results from the experiments that were done under Example 1 relating to the effect of Cu on alloys containg Zn led to the conclusion that further test should be done with alloys containing different ranges of Cu in relation to Zn. Such test were carried out under the following example.
Additional test were carried out on alloys with varying ranges of Cu and Zn concentrations as defined in the table below:
As can be seen from Table 2, the concentrations of Si, Mg, Fe and Mn are basically kept the same for all of the alloys, while the concentrations of Cu and Zn are varied. The alloys as defined in table 2 were cast, heat treated, extruded to profiles, stretched, aged, etched and anodized the same way and under the same conditions as under example 1 above.
The initial three alloys in Table 2, B1, B2 and B3, correspond respectively to alloys A4, A10 and A11 in Table 1 above from example 1 and are included in the alloy matrix as reference material.
Based on the tests under the examples above it has been possible to optimize the addition of Cu in relation to Zn to obtain the desired reduced gloss and PGE as defined in the claims. On the other hand, the content of Cu should be as low as possible to reduce the possibility of corrosion, even below 0.010 wt %. Further, the content of Zn should not be too high, since for example it may result in accumulation of Zn in the etching bath, which in turn results in higher risk for PGE.
Further experiments have been carried out on alloys with varying ranges of Cu and Zn concentrations as defined in the table shown in
The samples were then analyzed as described above and the results are shown in
As can be seen, there are slight variations for the same samples depending on the location in which the trial was conducted. There are further slight variations for the same sample and the same location when a trial was repeated. It is assumed that these differences are caused by slight process variations that cannot be accounted for by current process control, such as variations of conditions in the etching bath. Environmental conditions such as humidity and temperature may also influence the results.
Accordingly, embodiments of the present invention define composition ranges that allow an efficient production of efficient alloys for etching and/or anodizing and give consistent results even when the process parameters, that cannot be efficiently controlled by production means, fluctuate.
Further tests have been carried out with alloys in different temper conditions as shown in
Number | Date | Country | Kind |
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20151653 | Dec 2015 | NO | national |
Filing Document | Filing Date | Country | Kind |
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PCT/EP2016/079257 | 11/30/2016 | WO |
Publishing Document | Publishing Date | Country | Kind |
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WO2017/093304 | 6/8/2017 | WO | A |
Number | Name | Date | Kind |
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3594133 | Cote et al. | Jul 1971 | A |
20020112797 | Parson | Aug 2002 | A1 |
Number | Date | Country |
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2 251 337 | Oct 1997 | CA |
3738940 | Jan 2006 | JP |
Entry |
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Holme et al., Preferential Grain Etching of AlMgSi(Zn) Model Alloys, Oct. 14, 2010, Journal of the Electrochemical Society, 157 URL: <http://jes.ecsdl.org/content/157/12/C424.full.pdf>, pp. C424-C427 (Year: 2010). |
The Aluminum Association, International Alloy Designations and Chemical Composition Limits for Wrought Aluminum and Wrought Aluminum Alloys, Jan. 2015, URL: <https://www.aluminum.org/sites/default/files/Teal%20Sheets.pdf>, pp. Title, Copyright, Table of Contents, i-iii, 1-32 (Year: 2015). |
Atsuo et al., JP3738940 B2 machine translation, Oct. 19, 1999, entire machine translation (Year: 1999). |
Nedal Aluminium, “Alloy Data Sheet EN-AW6060 [AlMgSi]”, Nov. 2017, URL: <https://web.archive.org/web/*/https://www.nedal.com/wp-content/uploads/2017/11/Nedal-alloy-Datasheet-EN-AW-6060.pdf>, entire document (Year: 2017). |
ASM Aerospace Specification Metals Inc., “Aluminum 6063-T6”, Oct. 1, 2015, URL:<https://web.archive.org/web/20151001202453/http://asm.matweb.com/search/SpecificMaterial.asp?bassnum=MA6063T6>, entire document (Year: 2015). |
International Search Report dated Feb. 13, 2017 in International Application No. PCT/EP2016/079257. |
Number | Date | Country | |
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20190256954 A1 | Aug 2019 | US |