Aluminum alloy articles having improved bond durability and inert surface aluminum alloy articles and methods of making and using the same

Abstract

The present disclosure generally provides aluminum alloy articles having improved bond durability at certain surfaces of the article. The disclosure also provides methods of making such materials, for example, via a selective etching process, as well as methods of using such articles in applications that involve bonding the article to other articles, such as other aluminum articles. The disclosure also provides articles of manufacture made from such articles, including bonded aluminum articles. The disclosure also provides aluminum alloy articles having an inert or neutralized surface. The inert or neutralized surfaces described herein are characterized by surfaces containing oxidized copper. Also described herein are methods including etching a surface of the aluminum alloy articles with an oxidant. The resulting aluminum alloy articles exhibit desirable bond durability properties and exceptional corrosion resistance. The disclosure also provides various end uses of such articles, such as in automotive, transportation, electronics, and industrial applications.

What is claimed is: 
     
         1 . An aluminum alloy article, comprising an aluminum alloy material that comprises Cu and Mg as alloying elements,
 wherein the aluminum alloy article comprises a subsurface portion and a bulk portion; and   wherein an atomic concentration ratio of Cu to Mg in the subsurface portion is from about 0.2 to about 5.0.   
     
     
         2 . The aluminum alloy article of  claim 1 , wherein the aluminum alloy material comprises a 5xxx series aluminum alloy, a 6xxx series aluminum alloy, or a 7xxx series aluminum alloy. 
     
     
         3 . The aluminum alloy article of  claim 1 , wherein the aluminum alloy material comprises:
 from 0.2 to 1.4 wt. % Si;   from 0.4 to 5.0 wt. % Mg;   from 0.01 to 2.0 wt. % Cu;   from 0.05 to 0.50 wt. % Fe;   up to 0.25 wt. % Mn;   up to 0.25 wt. % Cr;   up to 0.15 wt. % Zn;   up to 0.20 wt. % Ti;   up to 0.05 wt. % Zr;   up to 0.05 wt. % Pb; and   up to 0.15 wt. % impurities;   
       with the remainder being Al. 
     
     
         4 . The aluminum alloy article of  claim 3 , wherein the aluminum alloy material comprises:
 from 0.6 to 0.95 wt. % Si;   from 0.55 to 0.75 wt. % Mg;   from 0.05 to 0.60 wt. % Cu;   from 0.20 to 0.35 wt. % Fe;   from 0.05 to 0.20 wt. % Mn;   up to 0.15 wt. % Cr;   up to 0.15 wt. % Zn;   up to 0.15 wt. % Ti;   up to 0.05 wt. % Zr;   up to 0.05 wt. % Pb; and   up to 0.15 wt. % impurities;   
       with the remainder being Al. 
     
     
         5 . The aluminum alloy article of  claim 1 , further comprising up to 0.10 wt. % of one or more elements selected from the group consisting of Ni, Sc, Sn, Be, Mo, Li, Bi, Sb, Nb, B, Co, Sr, V, In, Hf, Ag, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. 
     
     
         6 . The aluminum alloy article of  claim 1 , wherein the aluminum alloy article is a rolled aluminum alloy shate or a rolled aluminum alloy sheet, wherein the aluminum alloy article has a thickness of no more than 15 mm, or no more than 14 mm, or no more than 13 mm, or no more than 12 mm, or no more than 11 mm, or no more than 10 mm, or no more than 9 mm, or no more than 8 mm, or no more than 7 mm, or no more than 6 mm, or no more than 5 mm, or no more than 4 mm, or no more than 3 mm, or no more than 2 mm, or no more than 1 mm, or no more than 0.5 mm, or no more than 0.3 mm, or no more than 0.1 mm. 
     
     
         7 . The aluminum alloy article of  claim 1 , wherein the subsurface portion extends from an external surface of the aluminum alloy article to a depth of up to 5 μm. 
     
     
         8 . The aluminum alloy article of  claim 1 , wherein the atomic concentration ratio of Cu to Mg in the aluminum alloy material of the subsurface portion is at least 20%, or at least 40%, or at least 60%, or at least 80%, or at least 100%, or at least 150%, or at least 200%, greater than the atomic concentration ratio of Cu to Mg in the aluminum alloy material of the bulk portion, based on the atomic concentration ratio of Cu to Mg in the aluminum alloy material of the bulk portion. 
     
     
         9 . The aluminum alloy article of  claim 1 , wherein the atomic concentration ratio of Cu to Mg in the aluminum alloy material of the subsurface portion is at least 20%, or at least 40%, or at least 60%, or at least 80%, or at least 100%, or at least 150%, or at least 200%, greater than an atomic concentration ratio of Cu to Mg in the aluminum alloy material of a subsurface portion of an untreated aluminum alloy material. 
     
     
         10 . The aluminum alloy article of  claim 1 , wherein the atomic concentration ratio of Cu to Mg in the aluminum alloy material of the subsurface portion ranges from 0.2 to 4.5, or from 0.2 to 4.0, or from 0.2 to 3.5, or from 0.2 to 3.0, or from 0.2 to 2.5, or from 0.2 to 2.0, or from 0.2 to 1.5, or from 0.2 to 1.0, or from 0.2 to 0.5. 
     
     
         11 . A method of making a surface-modified aluminum alloy article, the method comprising:
 providing an aluminum alloy article having a subsurface portion and a bulk portion, wherein the aluminum alloy article comprises an aluminum alloy material that comprises Mg and Cu as alloying elements; and   contacting a surface of the subsurface portion with a surface-modifying composition,   wherein an atomic concentration ratio of Cu to Mg in the subsurface portion is from about 0.2 to about 5.0.   
     
     
         12 . The method of  claim 11 , wherein the providing comprises:
 casting a molten aluminum alloy to form an aluminum alloy cast product;   optionally homogenizing the aluminum alloy cast product to form a homogenized aluminum alloy cast product;   rolling the homogenized aluminum alloy cast product or the aluminum alloy cast product to form a rolled aluminum alloy product; and   solutionizing the rolled aluminum alloy product to form the aluminum alloy article.   
     
     
         13 . The method of  claim 12 , wherein the aluminum alloy material comprises:
 from 0.2 to 1.4 wt. % Si;   from 0.4 to 5.0 wt. % Mg;   from 0.01 to 2.0 wt. % Cu;   from 0.05 to 0.50 wt. % Fe;   up to 0.25 wt. % Mn;   up to 0.25 wt. % Cr;   up to 0.15 wt. % Zn;   up to 0.20 wt. % Ti;   up to 0.05 wt. % Zr;   up to 0.05 wt. % Pb; and   up to 0.15 wt. % impurities;   
       with the remainder being Al. 
     
     
         14 . The method of  claim 12 , wherein the aluminum alloy material comprises:
 from 0.6 to 0.95 wt. % Si;   from 0.55 to 0.75 wt. % Mg;   from 0.05 to 0.60 wt. % Cu;   from 0.20 to 0.35 wt. % Fe;   from 0.05 to 0.20 wt. % Mn;   up to 0.15 wt. % Cr;   up to 0.15 wt. % Zn;   up to 0.15 wt. % Ti;   up to 0.05 wt. % Zr;   up to 0.05 wt. % Pb; and   up to 0.15 wt. % impurities;   
       with the remainder being Al. 
     
     
         15 . The method of  claim 11 , further comprising up to 0.10 wt. % of one or more elements selected from the group consisting of Ni, Sc, Sn, Be, Mo, Li, Bi, Sb, Nb, B, Co, Sr, V, In, Hf, Ag, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. 
     
     
         16 . The method of  claim 11 , wherein the aluminum alloy article has a thickness of no more than 15 mm, or no more than 14 mm, or no more than 13 mm, or no more than 12 mm, or no more than 11 mm, or no more than 10 mm, or no more than 9 mm, or no more than 8 mm, or no more than 7 mm, or no more than 6 mm, or no more than 5 mm, or no more than 4 mm, or no more than 3 mm, or no more than 2 mm, or no more than 1 mm, or no more than 0.5 mm, or no more than 0.3 mm, or no more than 0.1 mm. 
     
     
         17 . The method of  claim 11 , wherein the subsurface portion extends from an external surface of the aluminum alloy article to a depth of up to 5 μm. 
     
     
         18 . The method of  claim 11 , wherein the surface-modifying composition comprises a strong oxidizing agent at a concentration of no more than 1000 ppm, or no more than 500 ppm, or no more than 300 ppm, or no more than 100 ppm, or no more than 50 ppm, or no more than 25 ppm, or no more than 10 ppm. 
     
     
         19 . An aluminum alloy article, wherein the aluminum alloy article is the surface-modified aluminum alloy article formed by the method of  claim 11 . 
     
     
         20 . The aluminum alloy article of  claim 19 , wherein the aluminum alloy article is an automobile, a truck, a trailer, a train, a railroad car, an airplane, a body panel or part for any of the foregoing, a bridge, a pipeline, a pipe, a tubing, a boat, a ship, a storage container, a storage tank, a an article of furniture, a window, a door, a railing, a functional or decorative architectural piece, a pipe railing, an electrical component, a conduit, a beverage container, a food container, or a foil. 
     
     
         21 . An aluminum alloy article comprising a surface, a subsurface portion and a bulk portion, wherein the subsurface portion comprises an oxidized copper-containing layer. 
     
     
         22 . The aluminum alloy article of  claim 21 , wherein the oxidized copper-containing layer comprises at least one of copper (I) oxide (i.e., Cu 2 O), copper (II) oxide (CuO), copper peroxide (CuO 2 ), and copper (III) oxide (Cu 2 O 3 ). 
     
     
         23 . The aluminum alloy article of  claim 21 , wherein the oxidized copper-containing layer comprises oxidized copper particles including an atomic ratio of a copper ion concentration to an elemental copper concentration of from about 0.5 to about 1. 
     
     
         24 . The aluminum alloy article of  claim 21 , wherein the subsurface portion comprises an area from a surface of the aluminum alloy article to a depth of about 5 μm. 
     
     
         25 . The aluminum alloy article of  claim 24 , wherein the subsurface portion comprises an area from the surface of the aluminum alloy article to a depth of about 2 μm. 
     
     
         26 . A method of treating a surface of an aluminum alloy article, comprising:
 providing an aluminum alloy article having a subsurface portion and a bulk portion, wherein the subsurface portion comprises Cu; and   etching a surface of the aluminum alloy article with an etch solution comprising an oxidizing agent.   
     
     
         27 . The method of  claim 26 , wherein the providing step comprises providing an aluminum alloy article comprising at least about 0.001 wt. % Cu. 
     
     
         28 . The method of  claim 27 , wherein the providing step comprises providing an aluminum alloy article comprising from about 0.001 wt. % to about 10 wt. % Cu. 
     
     
         29 . The method of  claim 26 , wherein the providing step comprises providing an aluminum alloy article comprising a 1xxx series aluminum alloy, a 2xxx series aluminum alloy, a 3xxx series aluminum alloy, a 4xxx series aluminum alloy, a 5xxx series aluminum alloy, a 6xxx series aluminum alloy, a 7xxx series aluminum alloy, or an 8xxx series aluminum alloy. 
     
     
         30 . The method of  claim 26 , wherein the etching step comprises oxidizing at least a portion of the Cu present in the subsurface portion. 
     
     
         31 . The method of  claim 26 , wherein the etching step comprises oxidizing at least 30 at. % of the Cu present in the subsurface portion. 
     
     
         32 . The method of  claim 26 , wherein the oxidizing agent comprises nitric acid, perchloric acid, chromic acid, ammonium perchlorate, ammonium permanganate, barium peroxide, calcium chlorate, calcium hypochlorite, hydrogen peroxide, magnesium peroxide, potassium bromate, potassium chlorate, potassium peroxide, sodium chlorate, sodium chlorite, sodium perchlorate, sodium peroxide, or any combination thereof. 
     
     
         33 . The method of  claim 26 , wherein the etch solution further comprises one or more additional acids. 
     
     
         34 . The method of  claim 33 , wherein the one or more additional acids comprises phosphoric acid, sulfuric acid, hydrofluoric acid, acetic acid, and/or hydrochloric acid. 
     
     
         35 . The method of  claim 26 , wherein the etch solution comprises nitric acid, phosphoric acid, and sulfuric acid. 
     
     
         36 . The method of  claim 35 , wherein a volumetric concentration of nitric acid, phosphoric acid and sulfuric acid comprises from about 5 vol. % to about 30 vol. % nitric acid, from about 0 vol. % to about 75 vol. % phosphoric acid, and from about 7 vol. % to about 25 vol. % sulfuric acid. 
     
     
         37 . The method of  claim 26 , wherein the etch solution in the etching step is heated to a temperature of from about 90° C. to about 110° C. 
     
     
         38 . The method of  claim 26 , wherein the etching step is performed for a dwell time of from about 2 seconds to about 2 minutes. 
     
     
         39 . An aluminum alloy article prepared according to the method of  claim 26 . 
     
     
         40 . The aluminum alloy article of  claim 39 , wherein the aluminum alloy article comprises a motor vehicle body part.