Metal alloy surface modification method and related metal alloy products having improved bond joint durability

Abstract

Methods for treating a surface of a metal alloy substrate and related metal alloy products are described. The methods may include providing an aluminum alloy product having a body and a surface, and scanning a high-energy beam across the surface. The methods may also include applying a liquid layer to the surface before scanning the high-energy beam. The high-energy beam may interact with the surface and / or the liquid layer to form a treated surface. The high-energy beam may interact with the surface and / or the liquid layer to physically modify at least a portion of the aluminum alloy product, thereby forming a treated subsurface layer.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of and priority to U.S. Provisional Application No. 62 / 978,767, filed February 19, 2020, U.S. Provisional Application No. 62 / 984,555, filed March 3, 2020, and U.S. Provisional Application No. 62 / 993,365, filed March 23, 2020, which are incorporated herein by reference in their entireties. Technical Field

[0003] The present disclosure relates generally to metallurgy and, more particularly, to techniques for modifying the surface properties of metal alloy products, such as the near-surface microstructure on the surface of the metal alloy products. Background Art

[0004] During the processing of aluminum alloy products, near-surface microstructures may be generated, which may include defects. These defects may include, for example, rolled-in oxides, rolled-in oils, transfer cracks, surface cracks, internal cracks, fissures, intermetallic particles, or high-density clusters of alloying elements, which may accumulate on the surface of the aluminum alloy product. Defects within the near-surface microstructure may affect the wettability and / or adhesion properties of the aluminum alloy product. Technologies for addressing surface defects, including near-surface microstructures, are lacking. Summary of the Invention

[0005] The terms "embodiment" and similar terms are intended to refer broadly to all subject matter of the present disclosure and the appended claims. Statements containing these terms should not be construed to limit the subject matter described herein, or to limit the meaning or scope of the appended claims. The embodiments of the present disclosure covered by this document are defined by the appended claims, not by this Summary. This Summary is a high-level overview of various aspects of the disclosure and introduces some concepts that are further described in the Detailed Description section below. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to determine the scope of the claimed subject matter in isolation. The subject matter should be understood by reference to the entire specification of the disclosure, any or all of the drawings, and appropriate portions of each claim.

[0006] In one aspect, the method for the surface of the processing metal alloy substrate is described. The method of this aspect may include providing an aluminum alloy product with a main body and a first surface. The method may also include scanning a high-energy beam across the first surface. The high-energy beam can interact with the first surface and can physically modify the first surface to form a treated first surface. In an embodiment, the method for the surface of the processing metal alloy substrate may include a treated first surface, and this treated first surface is tested according to FLTM BV 101-07 standard, and the stress durability test (StressDurability Test for Adhesive) (2017) of the adhesive lap shear bond head (bond) shows 45 cycles to 125 or more cycle bond head durability. In an embodiment, the aluminum alloy product may include 5xxx series aluminum alloy, 6xxx series aluminum alloy or 7xxx series aluminum alloy.

[0007] In various embodiments, the method may also include applying a first liquid layer to the first surface before scanning the high-energy beam. The scanning high-energy beam can be performed across the first liquid layer and / or through the first liquid layer. The high-energy beam can interact with the first liquid layer to form a treated first surface. The high-energy beam can interact with the first liquid layer to physically modify at least a portion of the body, thereby forming a treated subsurface layer. The body portion to be modified may include intermetallic particles and a matrix comprising aluminum alloy grains. In an exemplary embodiment, the treated subsurface layer may include a resolidified layer of aluminum alloy that has previously been melted by the high-energy beam. The subsurface layer may occupy a depth of 1 μm to 10 μm into the aluminum alloy product. In an embodiment, the first intermetallic particle concentration in the treated subsurface layer may be less than the second intermetallic particle concentration in the body. In some embodiments, the first liquid layer may have a thickness of 1 nm to 1 mm. In other embodiments, the first liquid layer may have a thickness of 1 mm to 5 mm.

[0008] In an embodiment, the method for treating the surface of a metal alloy substrate may further include applying a second liquid layer to the second surface. The second surface may be opposite to the first surface. In some embodiments, the second liquid layer may have a thickness of 1 nm to 1 mm. In other embodiments, the second liquid layer may have a thickness of 1 mm to 5 mm. The second liquid layer may be the same as the first liquid layer, or alternatively, the second liquid layer may be different from the first liquid layer. In some embodiments, at least one of the first liquid layer and the second liquid layer may comprise an aqueous solution. In some embodiments, at least one of the first liquid layer and the second liquid layer may comprise a non-aqueous solution. In some embodiments, at least one of the first liquid layer and the second liquid layer may comprise glycerol, an alcohol solution, steam, or any combination thereof. In an exemplary embodiment, at least one of the first liquid layer and the second liquid layer may comprise a pretreatment chemical configured to inhibit corrosion, texture the surface, and / or increase adhesion. The pretreatment chemical may be selected from organophosphonic acids, organophosphinic acids, silanes, coupling agents, polymers, copolymers, Zr / Mo pretreatment agents, Mn-based pretreatment agents, Ce-based pretreatment agents, adhesion promoters, corrosion inhibitors, any suitable pretreatment solution, or combinations thereof.

[0009] In various embodiments, the method for treating the surface of a metal alloy substrate may include applying a first liquid layer and a second liquid layer to the first surface and the second surface by two or more applicators. The two or more applicators may include a spray applicator with or without pulse emission, a low-pressure high-volume spray applicator, a low-pressure low-volume spray applicator, a rotary atomizer, an electrostatic applicator, a roller applicator, or any combination thereof. In an embodiment, the two or more applicators may be located in a continuous line. In an embodiment, the two or more applicators may be configured as two or more applicator baths.

[0010] In embodiments, scanning the high energy beam across the first surface or the first liquid layer may include directing the laser energy beam onto the first liquid layer. The laser energy beam may be provided by a continuous laser, a pulsed laser, a nanosecond pulsed laser, a picosecond pulsed laser, a femtosecond pulsed laser, a single pass configuration, a double pass configuration, a laser with a continuous wave, a laser without a continuous wave, or any combination thereof. The laser energy beam may be provided by an ytterbium laser, an Nd-YAG laser, a CO2 laser, an excimer laser, any beam or wave with an energy level that can interact and couple with a metal surface, or any combination thereof. In some instances, the laser energy beam may have a wavelength of about 200 nm to about 1500 nm.

[0011] In some embodiments, a method of treating a surface of a metal alloy substrate may include scanning a high energy beam across and / or through a first liquid layer. This may include directing at least one laser energy beam onto the first liquid layer. The method may also include directing at least one additional laser energy beam onto a second liquid layer.

[0012] In some embodiments, the method for treating the surface of a metal alloy substrate may include a first surface that is an untreated first surface. The untreated first surface may have one or more of organic matter, oil, hydrocarbons, dirt, or inorganic residues. The treated first surface may be free of or substantially free of one or more of organic matter, oil, hydrocarbons, dirt, or inorganic residues. In some embodiments, the untreated first surface may not have been subjected to one or more wet processing steps selected from the following: chemical etching, acidic or alkaline cleaning, solvent cleaning, vapor degreasing, mechanical surface treatment, brushing, polishing, mechanical surface polishing, electrochemical polishing, chemical polishing, surfactant cleaning, and conversion coating. In some embodiments, before the high-energy beam is directed onto the untreated first surface, the untreated first surface may not have been subjected to one or more wet processing steps. In some embodiments, the untreated first surface may correspond to a rolled surface having a rolling lubricant thereon. In an embodiment, directing the high-energy beam onto the untreated first surface may correspond to a dry cleaning process, and wherein the treated first surface corresponds to the cleaned surface. In an embodiment, directing a high energy beam onto an untreated first surface may correspond to a dry surface modification process, and the treated first surface may correspond to an activated surface suitable for bonding with an adhesive. The first surface may include near-surface microstructures. Directing the energy beam onto the first surface may remove or eliminate at least a portion of the near-surface microstructures. Directing the high energy beam onto the first surface may thermally modify the near-surface microstructures. In an embodiment, the treated first surface exhibits a dry static friction coefficient of 0.1 to 0.5, although surfaces having dry static friction coefficients outside of this range are also contemplated.

[0013] In another aspect, a metal alloy product having a treated surface is described. The metal alloy product, such as a rolled aluminum alloy substrate, may include a main body and a laser-treated region. The main body may include intermetallic particles and a matrix comprising aluminum alloy grains. The laser-treated region may cover a first portion of the main body. The laser-treated region may include a treated subsurface layer. The treated subsurface layer may include a resolidified layer of aluminum alloy that has previously been melted by a high-energy beam. The treated subsurface layer may occupy a depth of 1 μm to 10 μm into the aluminum alloy product. The first intermetallic particle concentration in the treated subsurface layer may be less than the second intermetallic particle concentration in the main body. The treated subsurface layer may be or may further include a laser-processed surface layer. The laser-processed surface layer may be free of or substantially free of near-surface microstructure. The laser-processed surface layer may be free of or substantially free of one or more of organic matter, oil, hydrocarbons, dirt, inorganic residues, rolled-in oxide, or anodic oxide. The laser-processed surface layer may include a first oxide layer having a thickness of 10 nm to 300 nm. In some embodiments, the laser treated area may exhibit a bond durability of 45 cycles to 125 cycles or more when tested according to the FLTM BV 101-07 standard.

[0014] In embodiments, the aluminum alloy may include a 5xxx series aluminum alloy, a 6xxx series aluminum alloy, or a 7xxx series aluminum alloy. In embodiments, the magnesium concentration in the aluminum alloy may be less than 10 weight %. The magnesium concentration in the main body may be greater than the magnesium concentration in the treated subsurface layer. The zinc concentration in the main body may be greater than the zinc concentration in the treated subsurface layer. In various embodiments, the aluminum alloy product may not include a functionalized layer. The example of the functionalized layer may include a phosphorus-containing organic acid coating or a pre-treater layer.

[0015] In some embodiments, the aluminum alloy may further include an untreated region covering the second portion of the body. The untreated region may not or may not have been subjected to a laser treatment process. In an embodiment, the first arithmetic mean height (Spk) of the laser-treated region may be less than the second arithmetic mean height of the untreated region. In an embodiment, the laser-treated region exhibits an arithmetic mean height (Sa) of 0.1 μm to 10 μm. In an embodiment, the laser-treated region may exhibit a complexity (Sdr) of 0.1% to 80%.

[0016] In various embodiments, the laser-treated area can exhibit surface stability for up to 3 months or up to 6 months, for example, which can indicate that the laser-treated area is suitable for bonding to another product during any period of time during which the surface is stable. In other words, the laser-treated area can be stable for up to 3 months or up to 6 months according to the FLTM BV101-07 standard test or other standard tests and exhibit bond durability of 45 cycles to 125 cycles or more, despite not initially being bonded for periods of up to 3 months or up to 6 months. This surface stability can allow for storage and / or a delay between preparation and bonding to another product without affecting the durability of the resulting bond or prematurely degrading it.

[0017] Other objects and advantages of the present invention will become apparent from the following detailed description given by way of non-limiting example. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The description refers to the following drawings, in which the same reference numerals are used in different drawings to indicate the same or similar components.

[0019] Figure 1 A schematic overview of a method of making a metal alloy product is provided.

[0020] Figure 2 Schematic illustrations of metal alloy products having a near-surface microstructure comprising one or more defects are provided.

[0021] Figure 3A A schematic illustration of a cross-section of a metal alloy product having an untreated surface and a near-surface microstructure comprising one or more defects is provided.

[0022] Figure 3B Provided Figure 3A Shown is a schematic diagram of a cross section with a high energy beam directed onto a surface to affect near-surface microstructure and provide a cleaned surface.

[0023] Figure 3C Provided Figure 3B Shown is a schematic illustration of a cross section with a high energy beam directed onto a cleaned surface to affect near-surface microstructure and provide a textured surface.

[0024] Figure 4A Schematic illustrations of a cross-section of a metal alloy product having an untreated surface and a near-surface microstructure comprising one or more defects including metal oxide particles and intermetallic particles are provided.

[0025] Figure 4B Provided Figure 4AShown is a schematic diagram of a cross section with a high energy beam directed onto an untreated surface to affect the near-surface microstructure and provide a cleaned surface.

[0026] Figure 4C Provided Figure 4B Shown is a schematic diagram of a cross section with a high energy beam directed onto a cleaned surface to affect the near-surface microstructure and provide an activated surface free of metal oxide particles and inter-metallic particles.

[0027] Figure 5 Schematic representations of a formed metal alloy product having a modified surface and joined to another product by an adhesive are provided.

[0028] Figure 6A Schematic illustrations of a cross-section of a metal alloy product having an untreated surface and a near-surface microstructure comprising one or more defects including metal oxide particles and intermetallic particles are provided.

[0029] Figure 6B Provided Figure 6A Schematic illustration of a cross section shown with a high thermal conductivity condensed vapor layer applied to an untreated surface.

[0030] Figure 6C Provided Figure 6B Shown is a schematic diagram of a cross section with a high energy beam directed onto a condensing vapor layer to affect the near-surface microstructure and provide an activated surface free of metal oxide particles and inter-metallic particles.

[0031] Figure 7 A schematic illustration of a continuous coil line process for producing an aluminum alloy product having a condensed vapor layer applied to each side prior to directing a high energy beam onto each side opposite each other is provided.

[0032] Figure 8 A schematic illustration of a continuous coil line process for making aluminum alloy products in another embodiment is provided in which a condensed vapor layer is simultaneously applied to each side of the product before a high energy beam is directed thereto.

[0033] Figure 9 A schematic diagram is provided of a continuous coil wire process for manufacturing an aluminum alloy product having a thicker layer, such as condensed vapor or an aqueous or non-aqueous solution, continuously applied or coupled to each side of the product before directing a high energy beam into the condensed vapor layer.

[0034] Figure 10AImages of a first example of a textured surface of an aluminum alloy product are provided.

[0035] Figure 10B Images of a second example of a textured surface of an aluminum alloy product are provided.

[0036] Figure 10C Images of a third example of a textured surface of an aluminum alloy product are provided.

[0037] Figure 10D Images of a fourth example of a textured surface of an aluminum alloy product are provided.

[0038] Figure 10E Images of a fifth example of a textured surface of an aluminum alloy product are provided.

[0039] Figure 11A A graph showing the contact angle of an aluminum alloy product at various laser energy densities is provided.

[0040] Figure 11B A graph showing the contact angle of another aluminum alloy product at various laser energy densities is provided.

[0041] Figure 12A A morphological analysis of an aluminum alloy product having an untreated surface is provided.

[0042] Figure 12B A topographic analysis of an aluminum alloy product having a surface treated with a laser with a 25% overlap between passes is provided.

[0043] Figure 12C A topographic analysis of an aluminum alloy product having a surface treated with a laser with a 50% inter-pass overlap is provided.

[0044] Figure 13 is an electron micrograph of a cross-section of an aluminum alloy product having an untreated surface and showing a near-surface microstructure including a metal oxide layer.

[0045] Figure 14 At a lower magnification Figure 13 Electron microscopy image of a cross section showing intermetallic particles in the near-surface microstructure.

[0046] Figure 15 is an electron micrograph of a cross-section of an aluminum alloy product having a surface treated with a laser with a 50% inter-pass overlap, showing the microstructure near the surface with less near-surface microstructure.

[0047] Figure 16 At a lower magnification Figure 15Electron microscopy image of a cross section showing fewer intermetallic particles in the near-surface microstructure. DETAILED DESCRIPTION

[0048] Described herein are metal and metal alloy products produced by casting and / or rolling processes, and methods for producing such products, in which the near-surface microstructure of a product having an untreated surface is subjected to a high-energy beam to provide a modified surface. The modified surface may be a cleaned, textured, activated, or otherwise prepared or treated surface. The untreated surface may exhibit a near-surface microstructure that may occupy a region deep into the bulk of the product and may contain one or more defects. In some cases, near-surface microstructures or defects can be reduced or eliminated by treatment with a high-energy beam. The high-energy beam may optionally be directed onto a liquid layer in contact with the surface of the metal alloy product, and the interaction between the high-energy beam, the optional liquid layer, and the surface may result in modification of the surface of the metal alloy product. The composition of the modified surface may differ from the composition of the near-surface microstructure of the product having the untreated surface. Benefits may include better weldability (e.g., spot weldability) and longer tip life as well as improved paint adhesion and / or corrosion resistance. The modified surface may have improved wettability and / or bond durability properties compared to a product having an untreated surface. For example, the modified surface may exhibit improved bond durability properties compared to an untreated surface.

[0049] Definition and Description:

[0050] As used herein, the terms "invention," "the described invention," "this invention," and "present invention" are intended to refer broadly to all subject matter of this patent application and the appended claims. Statements containing these terms should not be construed to limit the subject matter described herein, or to limit the meaning or scope of the appended patent claims.

[0051] In this specification, reference is made to alloys identified by AA numbers and other related designations, such as "Series" or "7xxx." For information on the numbering system most commonly used to name and identify aluminum and its alloys, see "International Alloy Designations and Chemical Composition Limits for Wrought Aluminum and Wrought Aluminum Alloys" or "Registration Record of Aluminum Association Alloy Designations and Chemical Compositions Limits for Aluminum Alloys in the Form of Castings and Ingots," published by The Aluminum Association.

[0052] As used herein, plate generally has a thickness greater than about 15 mm. For example, plate can refer to an aluminum product having a thickness greater than about 15 mm, greater than about 20 mm, greater than about 25 mm, greater than about 30 mm, greater than about 35 mm, greater than about 40 mm, greater than about 45 mm, greater than about 50 mm, or greater than about 100 mm.

[0053] As used herein, the thickness of Saudi plate (also referred to as sheet plate) is generally about 4mm to about 15mm.For example, the thickness of Saudi plate can be about 4mm, about 5mm, about 6mm, about 7mm, about 8mm, about 9mm, about 10mm, about 11mm, about 12mm, about 13mm, about 14mm or about 15mm.

[0054] As used herein, sheet generally refers to aluminum products having a thickness of less than about 4 mm. For example, the sheet can have a thickness of less than about 4 mm, less than about 3 mm, less than about 2 mm, less than about 1 mm, less than about 0.5 mm, or less than about 0.3 mm (e.g., about 0.2 mm).

[0055] Reference may be made to alloy tempers or conditions throughout this application. For descriptions of the most commonly used alloy tempers, see American National Standards (ANSI) H35 on Alloy and Temper Designation Systems. The F temper or temper refers to the aluminum alloy as fabricated. The O temper or temper refers to the aluminum alloy after annealing. The Hxx temper or temper, also referred to herein as the H temper, refers to a non-heat-treatable aluminum alloy with or without heat treatment (e.g., annealing) after cold rolling. Suitable H tempers include the HX1, HX2, HX3, HX4, HX5, HX6, HX7, HX8, or HX9 tempers. The T1 temper or temper refers to an aluminum alloy that has been cooled from hot working and naturally aged (e.g., at room temperature). The T2 temper or temper refers to an aluminum alloy that has been cooled from hot working, cold worked, and naturally aged. The T3 temper or temper refers to an aluminum alloy that has been cooled from hot working, cold worked, and naturally aged. Aluminum alloys that have been solution heat treated, cold worked, and naturally aged. The T4 temper or temper refers to aluminum alloys that have been solution heat treated and naturally aged. The T5 temper or temper refers to aluminum alloys that have been cooled from hot working and artificially aged (at elevated temperatures). The T6 temper or temper refers to aluminum alloys that have been solution heat treated and artificially aged. The T7 temper or temper refers to aluminum alloys that have been solution heat treated and artificially aged. The T8x temper or temper refers to aluminum alloys that have been solution heat treated, cold worked, and artificially aged. The T9 temper or temper refers to aluminum alloys that have been solution heat treated, artificially aged, and cold worked. The W temper or temper refers to aluminum alloys that have been solution heat treated.

[0056] As used herein, terms such as "cast metal product," "cast product," "cast aluminum alloy product" are interchangeable and refer to products produced by direct chill casting (including direct chill co-casting) or semi-continuous casting, continuous casting (including, for example, by using a twin-belt caster, a twin-roll caster, a block caster, or any other continuous casting machine), electromagnetic casting, hot top casting, or any other casting method.

[0057] As used herein, “room temperature” may include temperatures from about 15° C. to about 30° C., for example, about 15° C., about 16° C., about 17° C., about 18° C., about 19° C., about 20° C., about 21° C., about 22° C., about 23° C., about 24° C., about 25° C., about 26° C., about 27° C., about 28° C., about 29° C., or about 30° C. As used herein, “ambient conditions” may include temperatures of approximately room temperature, relative humidity of about 20% to about 100%, and an atmospheric pressure of about 975 millibars (mbar) to about 1050 mbar. For example, the relative humidity can be about 20%, about 21%, about 22%, about 23%, about 24%, about 25%, about 26%, about 27%, about 28%, about 29%, about 30%, about 31%, about 32%, about 33%, about 34%, about 35%, about 36%, about 37%, about 38%, about 39%, about 40%, about 41%, about 42%, about 43%, about 44%, about 45%, about 46%, about 47%, about 48%, about 49%, about 50%, about 51%, about 52%, about 53%, about 54%, about 55%, about 56%, about 57%, about 58%, about 59%, about 60%, about 61%, about 62%, about 63%, about 64%, about 65%, about 66%, about 67%, about 68%, about 69%, about 70%, about 71%, about 72%, about 73%, about 74%, about 75%, about 76%, about 77%, about 78%, about 79%, about 80%, about 81%, about 82%, about 83%, about 84%, about 85%, about 86%, about 87%, about 88%, about 89%, about 90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%, about 97%, about 98%, about 99%, about 100%, about 101%, about 102%, about 103%, about 104%, about 105%, about 106%, about 107%, about 108%, about 109%, about 110%, about 111%, about 112%, about 113%, about 114%, about 115%, about 116%, about %, about 94%, about 95%, about 96%, about 97%, about 98%, about 99%, about 100%, about 101%, about 102%, about 103%, about 104%, about 105%, about 106%, about 107%, about 108%, about 109%, about 110%, about 111%, about 112%, about 113%, about 114%, about 115%, about 116%, about 117%, about 118%, about 119%, about 120%, about 121%, about 122%, about 123%, about 124%, about 125%, about 126%, about 127%, about 128%, about 129%, about 130%, about 131%, about 132%, about 133%, about 134%, about 135%, about 136%, about 137%, about 138%, about 139%, about 200%, about 201%, about 202%, about 203%, about 204%, about 205%, about 206%, about 207%, about 208%, about 209%, about For example, the atmospheric pressure may be about 975 mbar, about 980 mbar, about 985 mbar, about 990 mbar, about 995 mbar, about 1000 mbar, about 1005 mbar, about 1010 mbar, about 1015 mbar, about 1020 mbar, about 1025 mbar, about 1030 mbar, about 1035 mbar, about 1040 mbar, about 1045 mbar, about 1050 mbar, or any value therebetween.

[0058] All ranges disclosed herein should be understood to encompass any and all subranges contained therein. For example, a specified range of "1 to 10" should be considered to include any and all subranges between a minimum of 1 and a maximum of 10 (and including 1 and 10); that is, all subranges start with a minimum of 1 or a larger number (such as 1 to 6.1) and end with a maximum of 10 or a smaller number (such as 5.5 to 10). Unless otherwise stated, when referring to the composition of an element, the expression "up to / up to" means that the element is optional and includes zero percent of the specific element. Unless otherwise stated, all composition percentages are weight percent (wt%).

[0059] As used herein, the meanings of “a,” “an,” and “the” include both singular and plural referents unless the context clearly dictates otherwise.

[0060] In this specification, aluminum alloy products and parts thereof may be described according to their elemental composition expressed in weight percent (wt%). In each alloy, the remainder is aluminum, with a maximum wt% of the sum of all impurities being 0.15%.

[0061] Incidental elements such as grain refiners and deoxidizers or other additives may be present in the present invention and may themselves add other properties without departing from or significantly changing the alloys described herein or the properties of the alloys described herein.

[0062] Small amounts of unavoidable impurities, including materials or elements, may be present in the alloy due to the inherent properties of aluminum or leaching from contact with processing equipment. Some alloys as described may contain no more than about 0.25% by weight of any element in addition to alloying elements, incidental elements, and unavoidable impurities.

[0063] Methods for producing alloys and aluminum alloy products

[0064] The alloys described herein can be cast using any suitable casting method known to those of ordinary skill in the art. As some non-limiting examples, the casting process can include a direct chill (DC) casting process or a continuous casting (CC) process. The continuous casting process can include a continuous casting system having a pair of moving relative casting surfaces (e.g., moving relative belts, rollers, or blocks), a casting cavity between the pair of moving relative casting surfaces, and a molten metal ejector. The molten metal ejector can have an end opening from which molten metal can exit the molten metal ejector and be ejected into the casting cavity.

[0065] Ingots, billets, or other cast products may be processed by any suitable means. Optional processing steps include, but are not limited to, homogenization, hot rolling, cold rolling, solution heat treatment, and optional pre-aging steps. Cast aluminum alloy products, such as ingots or other cast products, may be processed by any means known to those skilled in the art. Optionally, the processing steps may be used to produce sheet.

[0066] Cast product as herein described can be used for manufacturing the product or other suitable products in sheet, plate form.For example, can be by processing ingot in homogenizing step or cast product in continuous casting machine and carry out hot rolling step subsequently to prepare the plate comprising product as herein described.In hot rolling step, cast product can be hot rolled to 200mm thick or less specification (for example, from about 10mm to about 200mm).For example, cast product can be hot rolled to final specification thickness be about 10mm to about 175mm, about 15mm to about 150mm, about 20mm to about 125mm, about 25mm to about 100mm, about 30mm to about 75mm, or about 35mm to about 50mm plate.In some cases, plate may be rolled into thinner metal product, such as sheet.

[0067] Figure 1 An overview of an exemplary method of making a metal alloy product is provided. Figure 1 The method begins at step 105, in which a metal alloy 106 is cast to produce a cast metal alloy product 107, such as an ingot or other cast product. At optional step 110, the cast metal alloy product 107, which may be a cast aluminum alloy product, is homogenized to produce a homogenized metal alloy product 111. At step 115, the homogenized metal alloy product 111 is subjected to one or more hot rolling passes and / or one or more cold rolling passes to produce a rolled metal alloy product 112, which may correspond to an aluminum alloy article, such as an aluminum alloy plate, aluminum alloy slat, or aluminum alloy sheet. Optionally, the rolled metal alloy product 112 is subjected to one or more forming or stamping processes to form the metal alloy article.

[0068] The metals or metal alloys described herein (which may be aluminum alloys) may be cast using any suitable casting method. Exemplary casting processes include direct chill casting (including direct chill co-casting), semi-continuous casting, continuous casting (including, for example, by using a twin-belt caster, a twin-roll caster, a block caster, or any other continuous casting machine), electromagnetic casting, hot top casting, or any other casting method. As some non-limiting examples, the casting process may include a direct chill (DC) casting process or a continuous casting (CC) process. For example, Figure 1 A schematic diagram of a DC casting process is depicted at 105. A continuous casting system may include a pair of moving opposing casting surfaces (e.g., moving opposing belts, rollers, or blocks), a casting cavity located between the pair of moving opposing casting surfaces, and a molten metal ejector. The molten metal ejector may have an end opening from which molten metal may exit the molten metal ejector and be ejected into the casting cavity.

[0069] Figure 2A metal alloy product 200 is schematically shown. For example, the metal alloy product 200 may be a plate, a slat, or a sheet. The metal alloy product 200 may include or correspond to a rolled product. The rolled product may be a cold-rolled or hot-rolled product, depending on the casting process and / or the application of the metal alloy product 200. The metal alloy product 200 may be produced by any suitable casting and / or rolling process as described above. In an embodiment, the cross-section of the rolled product may be relatively rectangular, and its width and thickness may be selected based on the application of the metal alloy product 200. For example, the metal alloy product 200 may be a rolled aluminum alloy product in the form of a plate, a slat, or a sheet.

[0070] The rolled product may include a near-surface microstructure 220 and a body 230. During the rolling process, the near-surface microstructure 220 may be generated as part of the rolled product. The near-surface microstructure 220 may appear in a subsurface layer of the rolled product and may occupy a portion or substantially all of the subsurface layer. The subsurface layer, also referred to as a "surface layer" or "Beilby layer", may include a portion of the rolled product that occupies a space from the surface of the rolled product to a depth into the thickness of the rolled product. In an embodiment, the rolled product may include more than one surface and / or have more than one subsurface layer. In such embodiments, the near-surface microstructure 220 may appear in each subsurface layer. For example, the rolled product may have a thickness such that two surfaces are generated: a surface at the top of the rolled product and a surface at the bottom of the rolled product, each surface directly opposite each other. The other four sides of the rolled product extending circumferentially around the sides of the rolled product may not be thick enough to form a subsurface layer and / or may not have been subjected to sufficient rolling processes to produce a rolled near-surface microstructure, at least not to the same extent as the top and bottom surfaces. In such an example, each of the two surfaces may have a corresponding subsurface layer. A near-surface microstructure 220 may be present in each of the corresponding subsurface layers. Thus, in various embodiments, the rolled product may have a near-surface microstructure 220 on multiple surfaces or in multiple regions on one surface.

[0071] In an embodiment, the near-surface microstructure 220 may occupy the entire subsurface layer, but in some cases, the near-surface microstructure 220 may occupy only a portion of the subsurface layer. The near-surface microstructure 220 may occupy a space from the surface of the rolled product to a depth into the product up to the body 230. The depth of the near-surface microstructure 220 into the metal alloy product 200 may be in the range of 200 nm to 400 nm, 300 nm to 500 nm, 400 nm to 600 nm, 200 nm to 600 nm, 500 nm to 700 nm, 500 nm to 800 nm, 200 nm to 800 nm, 800 nm to 1 μm, 1 μm to 5 μm, 5 μm to 10 μm, 10 μm to 15 μm, 15 μm to 20 μm, 200 nm to 20 μm, or any subrange thereof.

[0072] A boundary 225 may exist between the near-surface microstructure 220 and the bulk 230. The boundary 225 may indicate the depth at which the composition of the metal alloy product 200 transitions to the composition of the bulk 230 (also referred to as the bulk composition). The boundary 225 may exist at a depth within the metal alloy product 200 at which the near-surface microstructure 220 exists. The boundary 225 may extend parallel or approximately parallel to the surface of the metal alloy product 200 and extend across the entire width of the metal alloy product 200, although this is not required. In some embodiments, the boundary 225 may occur at discrete depths or may occur within a range of depths. In embodiments, the boundary 225 may be a grain boundary between the surface microstructure 220 and the bulk 230, occur at a grain boundary between the surface microstructure 220 and the bulk 230, or represent a grain boundary between the near-surface microstructure 220 and the bulk 230. A grain boundary may be a boundary demarcated between two different grain structures, one corresponding to the grain structure of the near-surface microstructure 220 and the other corresponding to the bulk 230. For example, the near-surface microstructure 220 may have a non-homogeneous grain structure, such as an uneven distribution of large and small grain sizes. In contrast, the main body 230 may have a homogeneous (e.g., evenly distributed) grain structure, such as an even distribution of grain sizes that may be large or small. In such an example, the boundary 225 may be a grain boundary between the non-homogeneous grain structure of the near-surface microstructure 220 and the homogeneous grain structure of the main body 230. In an embodiment, the main body 230 may occur at a depth of between 10 μm and 45 μm from the surface into the metal alloy product 200, depending on the alloy and processing history. In some cases, a homogeneous grain structure may mean that a certain percentage of any given volume of the main body 230 may have the same or approximately the same grain size. For example, a homogeneous grain structure may mean that approximately 70% or more of any given volume of the main body 230 have approximately the same grain size, such as an average grain size in the range of 5 nm to 200 nm. Different grain structure homogeneity can be achieved by different filling patterns of the near-surface microstructure 220 and the main body 230. Figure 2 and other figures indicated.

[0073] The composition of the near-surface microstructure 220 may differ from the composition of the bulk. For example, the composition of the near-surface microstructure 220 may include one or more defects 240a to 240g (collectively, defects 240). The one or more defects 240 may affect the mechanical and / or chemical properties of the aluminum alloy product 212. For example, the one or more defects 240 may increase the corrosion susceptibility of the aluminum alloy product 212, reduce the bond joint durability performance of the aluminum alloy product, and / or reduce the tensile and shear strength of the aluminum alloy product.

[0074] like Figure 2As illustrated, the one or more defects 240 may include a variety of defects. For example, the defects 240 may include one or more internal cracks 240a or surface cracks 240d. The internal cracks 240a and surface cracks 240d may include transfer cracks, cracks, and microcracks. The internal cracks 240a and surface cracks 240d may occur due to stress or strain conditions applied to the rolled product during the rolling process, such as vertical shear stress applied to the rolled product by the rolls. Figure 2 As illustrated, surface cracks 240d may occur on the surface of the near-surface microstructure 220, resulting in surface unevenness or irregularity. In contrast, internal cracks 240a may occur within the near-surface microstructure 220. In embodiments, the internal cracks 240a may extend horizontally through the near-surface microstructure 220, parallel to the surface of the near-surface microstructure 220, or in any other direction relative to the surface of the near-surface microstructure 220.

[0075] In embodiments, voids 240b can induce the development of internal cracks 240a and surface cracks 240d. Weak sites created by defects 240, such as voids 240b, can provide more active sites for crack initiation. Voids 240b may include or consist of spaces within the near-surface microstructure 220 that are devoid of any material. The absence of any material may be the result of vapor incorporation into the near-surface microstructure 220 during processing, or may be the result of the mechanical structure and / or grain composition of the rolled product material.

[0076] The one or more defects 240 may also include rolled-in material 240c. For example, the rolled-in material 240c may include hot mill pickup, such as rolled-in oxides and / or rolled-in oils. The rolled-in material 240c may include entrained oxides and lubricants that are incorporated into the near-surface microstructure 220 during the rolling process, and optionally other rolled-in impurities. For example, during the rolling of the rolled product 212, a rolling lubricant may be incorporated into the near-surface microstructure 220. Entrained amorphous carbon and / or aluminum carbide in the near-surface microstructure 220 may indicate or correspond to the rolled-in lubricant. For example, the rolled-in oxide may include a metal oxide, such as aluminum oxide or magnesium oxide. Metal oxides may be generated when a metallic element at or near the surface of the rolled product is oxidized during processing and subsequently incorporated into the rolled product. The rolled-in material 240c may also include other contaminants such as dust, dirt, water, organic matter, inorganic matter, or other materials that may be present or deposited on the surface or contact surface of the metal alloy product 200 (e.g., the roll surface) and incorporated into the near-surface microstructure 220, such as during hot rolling or cold rolling.

[0077] The presence of voids 240b and / or rolled-in material 240c near the boundary 225 may induce crack propagation. Weak points at the boundary 225, such as voids 240b and rolled-in material 240c, may provide crack propagation paths between the near-surface microstructure 220 and the main body 230. Because the path between such defects may be a preferential crack propagation path, any stress condition may induce internal cracks 240a between the near-surface microstructure 220 and the main body 230. Stress exposure may cause the near-surface microstructure 220 to partially or completely shear from the main body 230. In addition, any internal cracks 240a may nucleate further cracks. Therefore, the presence of the defect 240 may produce a chain reaction of destructive defects within the near-surface microstructure 220 and potentially into the main body 230.

[0078] In an embodiment, the body 230 may have a composition referred to herein as a "body composition," which may primarily include aluminum and alloying elements 250. Exemplary alloying elements 250 for non-limiting examples of the aluminum alloy product 200 may include zinc, magnesium, copper, chromium, silicon, iron, and / or manganese, and may be dependent on or limited to the particular alloy. Figure 2 As illustrated, the alloying elements 250 may be spatially homogeneously (eg, evenly) distributed within the body 230 . Figure 2 The homogeneous distribution of alloying elements 250 depicted in may not imply or require that an array of alloying elements 250 be present, or that alloying elements 250 exist as particles or agglomerates of material. Figure 2 The distribution of alloying elements 250 illustrated in FIG. 1 is intended to be a schematic representation of a homogeneous distribution of alloying elements 250, such as an aluminum solid solution in which the alloying elements are homogeneously distributed throughout. A homogeneous distribution of alloying elements 250 may mean that a certain percentage of any given volume of the bulk composition may contain the same or substantially the same amount of alloying elements 250 as any other sample of the same volume.

[0079] In various embodiments, one of the defects 240 may include a non-uniform distribution of alloying elements 250. During the casting and / or rolling process, high density groups 240e of alloying elements 250 may appear within the near-surface microstructure 220. Some of the alloying elements 250 may exhibit different diffusion coefficients from one another, resulting in different alloying elements having different diffusion rates. That is, some of the alloying elements 250 may diffuse at a different rate than another alloying element 250. Therefore, during the casting and / or rolling of the rolled product, certain alloying elements may diffuse from the body 230 to the surface or into the near-surface microstructure 220 at a faster rate than other elements present in the body 230. The faster diffusion rates of certain alloying elements 250 may result in a non-uniform distribution of alloying elements 250 within the near-surface microstructure 220. For example, in some embodiments, high density groups 240e of zinc may appear within the near-surface microstructure 220 because zinc may diffuse at a higher rate than other alloying elements under processing conditions. Again, it should be understood that Figure 2 The illustrated high-density clusters 240e are merely pictorial representations and do not limit the high-density clusters of alloying elements 250 to clusters of alloying elements as illustrated, although in some cases there may be clusters of alloying elements 250. Rather, the presence of high-density clusters 240e in the near-surface microstructure 220 may indicate that the concentration of the alloying element in the near-surface microstructure 220 is, on average, different (e.g., higher) than in the bulk 230.

[0080] The inhomogeneous distribution of alloying elements and other defects 240 may affect the chemical properties of the metal alloy product 212. For example, the presence of defects 240 within the near-surface microstructure 220 may result in incomplete coverage or incomplete pretreatment application. Defects 240 may also interfere with etch pretreatment because the inhomogeneous distribution of defects 240 and alloying elements 250 may result in an inconsistent medium for the etch process.

[0081] High-density clusters 240e may also or alternatively increase the corrosion susceptibility of the metal alloy product 212. At or near the surface, the diffusion rate of alloying elements 250 may be increased by a factor of one or two due to the low activation energy and the presence of other defects 240. Consequently, high-density clusters 240e may expand reactive pockets or regions with the potential to initiate corrosion within the near-surface microstructure 220. Certain aluminum alloys may be more susceptible to corrosion susceptibility due to high-density clusters 240e of alloying elements 250. For example, 7xxx series aluminum alloys may be more susceptible to high-density clusters 240e due to their higher alloying element 250 composition. While other aluminum alloy series may contain 3% to 4% alloying elements, 7xxx series aluminum alloys may contain, for example, more than 10% alloying elements.

[0082] The one or more defects 240 may also include intermetallic particles 240f. During the casting process, aluminum alloy products containing iron (Fe) and manganese (Mn) may produce intermetallic particles 240f comprising aluminum and one or more of iron or manganese, which, for example, may be referred to herein as Al-(Fe,Mn) intermetallic particles or β-phase intermetallic particles for the rolled aluminum alloy product 212. When silicon (Si) is present, intermetallic particles comprising aluminum, silicon, and one or more of iron or manganese may also be produced, which are also referred to herein as Al-(Fe,Mn)-Si intermetallic particles or α-phase intermetallic particles. Since a certain amount of iron and silicon are generally present in almost all aluminum alloys, many aluminum alloys may contain such intermetallic particles after casting.

[0083] Each of these particle types exhibits different properties and contributes to the structure of aluminum alloys in different ways. For example, in general, beta-phase particles tend to be larger, blockier, or more geometric than alpha-phase particles, while alpha-phase particles are harder and tend to be smaller than beta-phase particles. For example, during hot and cold rolling, intermetallic particles can break apart, affecting their size, distribution, and number density.

[0084] The presence of intermetallic particles in cast aluminum alloy products can be beneficial. For example, aluminum alloys containing intermetallic particles can be beneficial in the manufacture of aluminum beverage containers because the intermetallic particles can be significantly harder than the rest of the aluminum alloy product. During drawing, ironing, and necking, hard intermetallic particles can reduce wear by cleaning the die surfaces. For example, intermetallic particles can wear drawing, ironing, and necking dies and reduce or remove metal buildup on the die surfaces. In other metal alloy products, it may be desirable to not have intermetallic particles 240f in the near-surface microstructure 220.

[0085] The one or more defects 240 may also include organic matter, oil and hydrocarbons and other contaminants 240g. During the casting process and / or rolling process, organic matter, oil and hydrocarbons and other contaminants 240g may be introduced into the casting process and / or rolling process. Figure 2 20 and / or the body 230. This is due to lubricants typically used in the processes associated with manufacturing the metal alloy product 200. In a metal alloy product, it may be desirable to be free of organics, oils, and hydrocarbons and other contaminants 240g in the near-surface microstructure 220.

[0086] The presence of defect 240 may result in poor bonding performance, such as when an adhesive (such as an epoxy adhesive) is used to bond an aluminum alloy product to another product or material. The bond head durability test evaluates the strength of the bond head produced between the bonded products and can indicate the ability of the near-surface microstructure of the aluminum alloy product to firmly bond with the adhesive under long-term use and corrosion conditions or under conditions that are otherwise different from environmental conditions. During the test, a bond head is produced between two aluminum alloy products by, for example, an epoxy adhesive. The bonded aluminum alloy products are then subjected to strain and / or other conditions. For example, the bonded aluminum alloy products can be immersed in a salt solution, subjected to wet conditions or dry conditions. After a series of cycles under one or more conditions, the chemical and mechanical failure of the bond head between the aluminum alloy products is evaluated. The bond head durability performance of the aluminum alloy product can indicate the reactivity and corrosion sensitivity of the near-surface microstructure of the product, or can be a function of the reactivity and corrosion sensitivity of the near-surface microstructure of the product.

[0087] Methods of using the disclosed aluminum alloy products

[0088] The aluminum alloy products described herein can be used in automotive applications and other transportation applications, including aircraft and railroad applications. For example, the disclosed aluminum alloy products can be used to prepare formed metal products and automotive structural parts, such as bumpers, side sills, roof beams, cross beams, pillar reinforcements (e.g., A-pillars, B-pillars, and C-pillars), interior panels, exterior panels, side panels, inner covers, outer covers, or trunk lids. The aluminum alloy products and methods described herein can also be used in applications in aircraft or railroad vehicles to prepare, for example, exterior and interior panels.

[0089] The aluminum alloy products and methods described herein can also be used in electronic applications. For example, the aluminum alloy products and methods described herein can be used to make housings for electronic devices, including mobile phones and tablet computers. In some examples, the aluminum alloy products can be used to make housings for mobile phones (e.g., smartphones), tablet chassis, and other portable electronic devices.

[0090] The aluminum alloy products and methods described herein may be used in any other desired application.

[0091] Methods for treating metals and metal alloys

[0092] Methods for treating metals and metal alloys (including aluminum, aluminum alloys, magnesium, magnesium alloys, magnesium composites, and steel, among others) and the resulting treated metals and metal alloys are described herein. In some instances, the metals used in the methods described herein include aluminum alloys, such as 1xxx series aluminum alloys, 2xxx series aluminum alloys, 3xxx series aluminum alloys, 4xxx series aluminum alloys, 5xxx series aluminum alloys, 6xxx series aluminum alloys, 7xxx series aluminum alloys, and 8xxx series aluminum alloys. In some instances, the materials used in the methods described herein include nonferrous materials, including aluminum, aluminum alloys, magnesium, magnesium-based materials, magnesium alloys, magnesium composites, titanium, titanium-based materials, titanium alloys, copper, copper-based materials, composites, sheets used in composites, or any other suitable metal, non-metal, or material combination. Monolithic and non-monolithic materials, such as rolled bonded materials, clad alloys, claddings, composites (such as, but not limited to, materials containing carbon fibers), or various other materials may also be used in the methods described herein. In some instances, ferrous aluminum alloys may be used in conjunction with the methods described herein.

[0093] As non-limiting examples, exemplary 1xxx series aluminum alloys for use in the methods described herein may include AA1100, AA1100A, AA1200, AA1200A, AA1300, AA1110, AA1120, AA1230, AA1230A, AA1235, AA1435, AA1145, AA1345, AA1445, AA1150, AA1350, AA1350A, AA1450, AA1370, AA1275, AA1185, AA1285, AA1385, AA1188, AA1190, AA1290, AA1193, AA1198, or AA1199.

[0094] Non-limiting exemplary 2xxx series aluminum alloys for use in the methods described herein may include AA2001, A2002, AA2004, AA2005, AA2006, AA2007, AA2007A, AA2007B, AA2008, AA2009, AA2010, AA2011, AA2011A, AA2111, AA2111A, AA2111B, AA2012, AA2013, AA2014, AA2015, AA2016, AA2017, AA2018, AA2019, AA2020, AA2021, AA2022, AA2023, AA2024, AA2025, AA2026, AA2027, AA2028, AA2029, AA2030, AA2031, AA2032 4A, AA2214, AA2015, AA2016, AA2017, AA2017A, AA2117, AA2018, AA2218, AA2618, AA2618A, AA2219, AA2 319, AA2419, AA2519, AA2021, AA2022, AA2023, AA2024, AA2024A, AA2124, AA2224, AA2224A, AA2324, AA2 424, AA2524, AA2624, AA2724, AA2824, AA2025, AA2026, AA2027, AA2028, AA2028A, AA2028B, AA2028C, A A2029, AA2030, AA2031, AA2032, AA2034, AA2036, AA2037, AA2038, AA2039, AA2139, AA2040, AA2041, AA2 044, AA2045, AA2050, AA2055, AA2056, AA2060, AA2065, AA2070, AA2076, AA2090, AA2091, AA2094, AA209 5. AA2195, AA2295, AA2196, AA2296, AA2097, AA2197, AA2297, AA2397, AA2098, AA2198, AA2099 or AA2199.

[0095] Non-limiting exemplary 3xxx series aluminum alloys for use in the methods described herein may include AA3002, AA3102, AA3003, AA3103, AA3103A, AA3103B, AA3203, AA3403, AA3004, AA3004A, AA3104, AA3204, AA3304, AA3005, AA3005A, AA3105, AA3105A, AA3105B, AA300 07, AA3107, AA3207, AA3207A, AA3307, AA3009, AA3010, AA3110, AA3011, AA3012, AA3012A, AA3013, AA3014, AA3015, AA3016, AA3017, AA3019, AA3020, AA3021, AA3025, AA3026, AA3030, AA3130, or AA3065.

[0096] Non-limiting exemplary 4xxx series aluminum alloys for use in the methods described herein may include AA4045, AA4004, AA4104, AA4006, AA4007, AA4008, AA4009, AA4010, AA4013, AA4014, AA4015, AA4015A, AA4115, AA4016, AA4017, AA4018, AA4019, AA4020, AA4021, AA4026, AA4032, AA4043, AA4043A, AA4143, AA4343, AA4643, AA4943, AA4044, AA4145, AA4145A, AA4046, AA4047, AA4047A, or AA4147.

[0097] Non-limiting exemplary 5xxx series aluminum alloys for use in the methods described herein may include AA5182, AA5183, AA5005, AA5005A, AA5205, AA5305, AA5505, AA5605, AA5006, AA5106, AA5010, AA5110, AA5110A, AA5210, AA5310, AA5016, AA5017, AA5018, AA5018A, AA5019, AA5019A, AA5119, AA5110A, AA5210, AA5310, AA5016, AA5017, AA5018, AA5018A, AA5019, AA5019A, AA5110, AA5111A, AA5111A, AA5111A, AA5111B, AA5111C, AA5111C, AA5111A, AA5111B, AA5111C, AA5111A 19A, AA5021, AA5022, AA5023, AA5024, AA5026, AA5027, AA5028, AA5040, AA5140, AA5041, AA5042, AA5043, AA5049, A A5149, AA5249, AA5349, AA5449, AA5449A, AA5050, AA5050A, AA5050C, AA5150, AA5051, AA5051A, AA5151, AA5251, AA 5251A, AA5351, AA5451, AA5052, AA5252, AA5352, AA5154, AA5154A, AA5154B, AA5154C, AA5254, AA5354, AA5454, AA5 554, AA5654, AA5654A, AA5754, AA5854, AA5954, AA5056, AA5356, AA5356A, AA5456, AA5456A, AA5456B, AA5556, AA55 56A, AA5556B, AA5556C, AA5257, AA5457, AA5557, AA5657, AA5058, AA5059, AA5070, AA5180, AA5180A, AA5082, AA518 2. AA5083, AA5183, AA5183A, AA5283, AA5283A, AA5283B, AA5383, AA5483, AA5086, AA5186, AA5087, AA5187 or AA5088.

[0098] Non-limiting exemplary 6xxx series aluminum alloys for use in the methods described herein may include AA6101, AA6101A, AA6101B, AA6201, AA6201A, AA6401, AA6501, AA6002, AA6003, AA6103, AA6005, AA6005A, AA6005B, AA6005C, AA6105, AA6205, AA6305, AA6006, AA6106, AA6206, AA6306, AA6007, AA6108, AA6209, AA6310, AA6320, AA6330, AA6340, AA6350, AA6360, AA6370, AA6371, AA6372, AA6373, AA6374, AA6375, AA6376, AA6377, AA6378, AA6379, AA6380, AA6390, AA6401, AA6402, AA6403, AA6404, AA6410 08. AA6009, AA6010, AA6110, AA6110A, AA6011, AA6111, AA6012, AA6012A, AA6013, AA6113, AA6014, AA6015, AA60 16. AA6016A, AA6116, AA6018, AA6019, AA6020, AA6021, AA6022, AA6023, AA6024, AA6025, AA6026, AA6027, AA6028 ,AA6031,AA6032,AA6033,AA6040,AA6041,AA6042,AA6043,AA6151,AA6351,AA6351A,AA6451,AA6951,AA6053, AA6055, AA6056, AA6156, AA6060, AA6160, AA6260, AA6360, AA6460, AA6460B, AA6560, AA6660, AA6061, AA6061A, AA6261, AA6361, AA6162, AA6262, AA6262A, AA6063, AA6063A, AA6463, AA6463A, AA6763, A6963, AA6064, AA6064A, AA6065, AA6066, AA6068, AA6069, AA6070, AA6081, AA6181, AA6181A, AA6082, AA6082A, AA6182, AA6091, or AA6092.

[0099] Non-limiting exemplary 7xxx series aluminum alloys for use in the methods described herein may include AA7011, AA7019, AA7020, AA7021, AA7039, AA7072, AA7075, AA7085, AA7108, AA7108A, AA7015, AA7017, AA7018, AA7019A, AA7024, AA7025, AA7028, AA 7030, AA7031, AA7033, AA7035, AA7035A, AA7046, AA7046A, AA7003, AA7004, AA7005, AA7009 ,AA7010,AA7011,AA7012,AA7014,AA7016,AA7116,AA7122,AA7023,AA7026,AA7029,AA712 9. AA7229, AA7032, AA7033, AA7034, AA7036, AA7136, AA7037, AA7040, AA7140, AA7041, AA70 49. AA7049A, AA7149, 7204, AA7249, AA7349, AA7449, AA7050, AA7050A, AA7150, AA7250, AA7 AA7055, AA7155, AA7255, AA7056, AA7060, AA7064, AA7065, AA7068, AA7168, AA7175, AA7475, AA7076, AA7178, AA7278, AA7278A, AA7081, AA7181, AA7185, AA7090, AA7093, AA7095, or AA7099.

[0100] Non-limiting exemplary 8xxx series aluminum alloys for use in the methods described herein may include AA8005, AA8006, AA8007, AA8008, AA8010, AA8011, AA8011A, AA8111, AA8211, AA8112, AA8014, AA8015, AA8016, AA8017, AA8018, AA8019, AA8021, AA8021A, AA8021B, AA8022, AA8023, AA8024, AA8025, AA8026, AA8030, AA8130, AA8040, AA8050, AA8150, AA8076, AA8076A, AA8176, AA8077, AA8177, AA8079, AA8090, AA8091, or AA8093.

[0101] The methods of the present disclosure modify the surface of an aluminum alloy product, such as to remove or alter near-surface microstructures present on the surface, without requiring the use of standard techniques, including any mechanical surface preparation (such as micro-blasting, macro-blasting, carbon dioxide dry ice shock and blasting, or any combination thereof), such as chemical or wet etching techniques, conversion coating, and dry cleaning processes. Advantageously, the disclosed methods can produce modified (such as cleaned and / or activated) surfaces on aluminum alloy products that are ready for use and exhibit good coating deposition and adhesion, paint adhesion, highly durable adhesive bonds, and the like. Further, the disclosed methods can achieve such conditions without the use of wet sections typically used for chemical etching, cleaning, and / or conversion coating, thereby simplifying aluminum alloy product processing and also reducing or eliminating the use of undesirable, expensive, and / or, in some cases, hazardous or toxic chemicals. In some cases, wet sections typically used for chemical etching, cleaning, mechanical surface preparation, and / or conversion coating can still be utilized. In some cases, only dry processing or no chemical pretreatment techniques are utilized.

[0102] Figures 3A to 3C 3 illustrates a method for modifying the near-surface microstructure present on a metal alloy substrate 300. The substrate 300 may be a metal alloy product as described above, such as a rolled aluminum alloy product. In FIG3 , the substrate 300 has a near-surface microstructure 320 and a bulk microstructure 330, such as Figure 2 The near-surface microstructure 320 includes an untreated surface 305. The untreated surface may correspond to an as-rolled surface that has not been subjected to any surface treatment or modification, including but not limited to chemical or wet etching techniques, mechanical surface preparation techniques, and / or pretreatment (e.g., conversion coating) techniques. In some embodiments, at least one surface 305 or some or all exposed surfaces of the substrate 300 is untreated. The near-surface microstructure 320 of the substrate 300 includes an untreated surface 305. Figure 2 Defects 240a to 240g are similar to those described above. Figure 3A At least some of the defects 340a to 340g are shown.

[0103] like Figure 3B The high energy beam 355 is shown directed onto the untreated surface 305 ( Figure 3A) to physically modify the surface 305 and provide a cleaned surface 306 that is free of at least some of the defects 340. In embodiments, the cleaned surface 306 may still include near-surface microstructures 321 but may be substantially free of defects 340. Specifically, for example, the cleaned surface 306 may be substantially free of organic matter, oils, and hydrocarbons 340g.

[0104] Figure 3A The near-surface microstructure 320 has a thickness t1. Figure 3B Near-surface microstructure 321 has thickness t2. High-energy beam 355 can remove at least a portion of near-surface microstructure 320. In other words, after high-energy beam 355 is directed onto untreated surface 305, thickness t2 of near-surface microstructure 321 coupled to cleaned surface 306 can be reduced relative to thickness t1 of near-surface microstructure 320 coupled to untreated surface 305.

[0105] The high energy beam 355 may be directed onto the cleaned surface 306 ( Figure 3B ) to further modify the surface, thereby providing Figure 3C Textured surface 307 is shown. Figure 3C The near-surface microstructure 322 has a thickness t3 together with the textured surface 307. After the high-energy beam 355 is directed onto the cleaned surface 306, the thickness t3 of the near-surface microstructure 322 associated with the textured surface 307 can be further reduced relative to the thickness t2 of the near-surface microstructure 321 associated with the cleaned surface 306. Optionally, the near-surface microstructure 322 can be completely removed or modified, such as to provide a zero thickness t3, so that the body 330 can be exposed as a top surface and can include the textured surface 307 or be associated with the textured surface. In some embodiments, thickness t3 ≤ thickness t2 ≤ thickness t1. The textured surface 307 can include at least one of a grid, stripes, wavy lines, pits, surface relief of texture elements, or a combination thereof. Variables used to modify / optimize the textured surface 307 can include laser parameters such as spot size, overlap, beam energy, raster pattern, raster speed, and pulse frequency. Texture can be defined by Sa (3D surface roughness measurement), Sdr (complexity defined as the ratio between the area of the actual developed surface and the projected surface area or the developed interface area ratio), Spk (3D surface peak height measurement), Spc peak count, Sv or Sz (texture depth), skewness, etc.

[0106] Advantageously, modifying the surface 305 by exposure to the high-energy beam 355 to create the cleaned surface 306 or the textured surface 307 can change the wettability characteristics of the surface from being relatively non-wettable to being relatively more wettable. Additionally or alternatively, modifying the surface 305 by exposure to the high-energy beam 355 to create the cleaned surface 306 or the textured surface 307 can strengthen the bond of the adhesive to the surface from a relatively weak bond to a relatively strong bond. Additionally or alternatively, modifying the surface 305 by exposure to the high-energy beam 355 to create the cleaned surface 306 or the textured surface 307 can reduce the corrosion potential of the surface from a relatively high level of corrosion activity to a relatively low level of corrosion activity. Additionally or alternatively, modifying the surface 305 by exposure to the high-energy beam 355 to create the cleaned surface 306 or the textured surface 307 can reduce the corrosion potential of the surface from a relatively high level of corrosion activity to a relatively low level of corrosion activity. Additionally or alternatively, modifying the surface 305 by exposure to the high energy beam 355 to generate a cleaned surface 306 or a textured surface 307 can change the bond durability of a bond between the surface and another product from a relatively small bond durability to a relatively large or high performing bond durability. In embodiments, as Figure 3C The textured surface 307 in the may exhibit a bond durability of at least 35 cycles, or at least 40 cycles, or at least 45 cycles, or at least 50 cycles, or at least 55 cycles, or at least 60 cycles, or at least 65 cycles, or at least 70 cycles, or at least 75 cycles, or at least 80 cycles, or at least 85 cycles, or at least 90 cycles, or at least 95 cycles, or at least 100 cycles, or at least 105 cycles, or at least 110 cycles, or at least 115 cycles, or at least 120 cycles, or at least 125 cycles or more, such as according to the FLTM BV 101-07 standard test or other standard test.

[0107] The substrate 300 may comprise a non-ferrous material, including aluminum, an aluminum alloy, magnesium, a magnesium-based material, a magnesium alloy, a magnesium composite material, titanium, a titanium-based material, a titanium alloy, copper, a copper-based material, a composite material, a sheet material used in a composite material, or any other suitable metal, non-metal, or material combination, depending on the specific alloy or metal used. In some embodiments, the substrate 300 comprises an aluminum alloy, a magnesium alloy, a magnesium composite material, steel, or any combination thereof. In some embodiments, the substrate 400 is an aluminum alloy. Useful aluminum alloys include any of the aluminum alloys previously described in detail, for example, 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.

[0108] High energy beam 355 (such as Figure 3B and 3C The energy density (in) can be provided by a laser. The laser can be at least one selected from a continuous laser, a pulsed laser, a nanosecond pulsed laser, a picosecond pulsed laser, and / or a femtosecond pulsed laser. The laser can be at least one selected from an ytterbium laser, an Nd-YAG laser, a CO2 laser, or an excimer laser, or can be any suitable laser that provides the desired energy density.

[0109] like Figure 3B and 3C The energy density of the high energy beam 355 shown may be, for example, 10 mJ / mm 2 Up to 150mJ / mm 2 The energy density can be optionally within the following range: 10 mJ / mm 2 Up to 30mJ / mm 2 , 20mJ / mm 2 Up to 40mJ / mm 2 、30mJ / mm 2 Up to 50mJ / mm 2 、40mJ / mm 2 Up to 60mJ / mm 2 、50mJ / mm 2 Up to 70mJ / mm 2 、60mJ / mm 2 Up to 80mJ / mm 2 、70mJ / mm 2 Up to 90mJ / mm 2 、80mJ / mm 2 Up to 100mJ / mm 2 、90mJ / mm 2 Up to 110mJ / mm 2 、100mJ / mm 2 Up to 120mJ / mm 2 、110mJ / mm 2 Up to 130mJ / mm 2 、120mJ / mm 2 Up to 140mJ / mm 2 、130mJ / mm 2 Up to 150mJ / mm 2 or any subrange thereof.

[0110] The contact angle between the surface and the liquid (such as water, liquid adhesive or organic or inorganic lubricant) can be determined, and the contact angle can optionally change based on the energy density of the energy beam for treating the surface, such as to evaluate wettability. The contact angle mentioned herein is generally represented by the contact angle of water and the surface. In some cases, as the energy density of the high-energy beam increases, the contact angle decreases relative to the original surface. For example, the original substrate can have a contact angle of about 75 degrees, and as the surface is treated by being exposed to a high-energy beam (such as a laser), this angle can be reduced. The lower contact angle reflects the improved surface wettability, and can also reflect the improvement of the bonding durability characteristics for bonding the modified surface to another substrate or product. In embodiments, the energy density of the high-energy beam is enough to reduce the contact angle of the surface after being exposed to the high-energy beam. In some embodiments, the contact angle of the modified surface is at most 20 degrees, at most 15 degrees or at most 10 degrees. In some embodiments, the contact angle of the textured surface is at most 20 degrees, at most 15 degrees or at most 10 degrees. Optionally, the contact angle of the water droplet with the surface can be from 0 to 20 degrees, such as from 0 to 5 degrees, from 0 to 10 degrees, from 0 to 15 degrees, from 5 to 10 degrees, from 5 to 15 degrees, from 5 to 20 degrees, from 10 to 15 degrees, from 10 to 20 degrees, or from 15 to 20 degrees, or any value therebetween.

[0111] Another method according to the present disclosure modifies near-surface microstructures without the use of chemical or wet etching techniques, mechanical surface preparation techniques, and / or conversion coating. Figures 4A to 4C The method of modifying the near-surface microstructure is shown in FIG. Figure 4A As shown, a metal alloy substrate 400 is provided. The substrate 400 may be a metal alloy product as previously described, such as an aluminum alloy product. The substrate 400 has a near-surface microstructure 420 and a bulk microstructure 430, as described for Figure 2 and Figure 3A The near-surface microstructure 420 includes an untreated surface 405. The untreated surface 405 has not been subjected to any surface treatment or modification including, but not limited to, chemical or wet etching techniques, mechanical surface preparation techniques, and / or conversion coating. In some embodiments, at least one surface 405 or some or all exposed surfaces of the substrate 400 is untreated. The near-surface microstructure 420 of the substrate 400 includes a surface 405 that is not treated with respect to the substrate 400. Figure 2 Defects 240a to 240g are similar to those described above. Figure 4A At least some of the defects 440a to 440g shown. Figure 4AAs shown, the near-surface microstructure 420 includes defects 440. Defects 440 include rolled-in materials, including various metal oxides 440c, various intermetallic particles 440f, and organic matter, oil, and hydrocarbons 440g. Defects 440 may also include defects including internal cracks 440a, voids 440b, surface cracks 440d, and high-density clusters of alloying elements 440e.

[0112] like Figure 4B The high energy beam 455 is shown directed onto the untreated surface 405 ( Figure 4A ) to physically modify the surface, thereby providing a cleaned surface 406 that is free of at least some of the defects 440. In embodiments, the cleaned surface 406 may still include near-surface microstructures 421 but may be substantially free of defects 440g. Specifically, the cleaned surface 406 may be substantially free of organic matter, oil, and hydrocarbons 440g.

[0113] Figure 4A The near-surface microstructure 420 has a thickness t4. Figure 4B The near-surface microstructure 421 has a thickness t5. The high-energy beam 455 can remove at least a portion of the near-surface microstructure 420. In other words, after the high-energy beam 455 is directed onto the untreated surface 405, the thickness t5 of the near-surface microstructure 420 coupled to the cleaned surface 406 can be reduced relative to the thickness t4 of the near-surface microstructure 420 coupled to the untreated surface 405.

[0114] The high energy beam 455 may be directed onto the cleaned surface 406 ( Figure 4B ) to further modify the surface, thereby providing Figure 4C Activated surface 407 is shown, optionally having near-surface microstructure 422. The high-energy beam directed onto cleaned surface 406 affects the near-surface microstructure by melting at least one of the plurality of metal oxides 440c and the plurality of intermetallic particles 440f. The melted particles may be incorporated into the bulk composition. The activated surface 407 associated with the near-surface microstructure 422 is substantially free of at least one of the plurality of metal oxides 440c and the plurality of intermetallic particles 440f. In an embodiment, the activated surface 407 associated with the near-surface microstructure 422 is substantially free of metal oxides 440c and intermetallic particles 440f. In an embodiment, Figure 4CThe near-surface microstructure 422, together with the activated surface 407, has a thickness t6. After directing the high-energy beam 455 onto the cleaned surface 406, the thickness t6 of the near-surface microstructure 422 associated with the activated surface 407 can be further reduced relative to the thickness t5 of the near-surface microstructure 421 associated with the cleaned surface 406. Optionally, the near-surface microstructures 420, 421, 422 can be completely removed or modified, such as to provide a zero thickness t6, so that the body 430 can be exposed as a top surface and can include or be associated with the activated surface 407. In some embodiments, thickness t6 ≤ thickness t5 ≤ thickness t4. In embodiments, the near-surface microstructure is removed to a depth of up to about 10 μm. In other embodiments, the near-surface microstructure is removed to a depth of up to about 5 μm. In other words, thickness t6 is less than thickness t4 by up to about 10 μm or by up to about 5 μm, as a result of directing the high-energy beam 455 onto the substrate surface.

[0115] Advantageously, modifying the surface 405 by exposure to the high-energy beam 455 to create the cleaned surface 406 or the activated surface 407 can change the wettability characteristics of the surface from being relatively non-wettable to being relatively more wettable. Additionally or alternatively, modifying the surface 405 by exposure to the high-energy beam 455 to create the cleaned surface 406 or the activated surface 407 can strengthen the bond between the adhesive and the surface from a relatively weak bond to a relatively strong bond. Additionally or alternatively, modifying the surface 405 by exposure to the high-energy beam 455 to create the cleaned surface 406 or the activated surface 407 can reduce the corrosion potential of the surface from a relatively high level of corrosion activity to a relatively low level of corrosion activity. Additionally or alternatively, modifying the surface 405 by exposure to the high-energy beam 455 to create the cleaned surface 406 or the activated surface 407 can reduce the corrosion potential of the surface from a relatively high level of corrosion activity to a relatively low level of corrosion activity, thereby making the surface more electrochemically superior. Additionally or alternatively, modifying the surface 405 by exposure to the high energy beam 455 to generate a cleaned surface 406 or an activated surface 407 can change the bond durability of the bond between the surface and another product from a relatively small bond durability to a relatively large or high performing bond durability. Figure 4CThe activated surface 407 in the can exhibit a bond durability of at least 35 cycles, or at least 40 cycles, or at least 45 cycles, or at least 50 cycles, or at least 55 cycles, or at least 60 cycles, or at least 65 cycles, or at least 70 cycles, or at least 75 cycles, or at least 80 cycles, or at least 85 cycles, or at least 90 cycles, or at least 95 cycles, or at least 100 cycles, or at least 105 cycles, or at least 110 cycles, or at least 115 cycles, or at least 120 cycles, or at least 125 cycles or more, such as according to the FLTM BV 101-07 standard test or other standard test.

[0116] The substrate 400 may comprise a non-ferrous material, including aluminum, an aluminum alloy, magnesium, a magnesium-based material, a magnesium alloy, a magnesium composite material, titanium, a titanium-based material, a titanium alloy, copper, a copper-based material, a composite material, a sheet material used in a composite material, or any other suitable metal, non-metal, or material combination, depending on the specific alloy or metal used. In some embodiments, the substrate 400 comprises an aluminum alloy, magnesium, a magnesium alloy, a magnesium composite material, steel, or any combination thereof. In some embodiments, the substrate 400 is an aluminum alloy. Useful aluminum alloys include any of the aluminum alloys previously described in detail, for example, 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.

[0117] High energy beam 455 (such as Figure 4B and 4C The laser may be provided by a laser. The laser may be at least one selected from a continuous laser, a pulsed laser, a nanosecond pulsed laser, a picosecond pulsed laser, or a femtosecond pulsed laser. The laser may be at least one selected from an ytterbium, Nd-YAG, CO2, and an excimer laser, or may be any suitable laser that provides the desired energy density. The laser may have any suitable wavelength, such as from about 200 nm to about 1500 nm. In some cases, treatment performed by laser may be referred to as laser ablation therapy.

[0118] like Figure 4B and 4C The energy density of the high energy beam 455 shown may be at least 10 mJ / mm 2 Up to 200mJ / mm 2 The energy density can be within the following range: 10mJ / mm 2 Up to 30mJ / mm 2 , 20mJ / mm 2 Up to 40mJ / mm 2 、30mJ / mm2 Up to 50mJ / mm 2 、40mJ / mm 2 Up to 60mJ / mm 2 、50mJ / mm 2 Up to 70mJ / mm 2 、60mJ / mm 2 Up to 80mJ / mm 2 、70mJ / mm 2 Up to 90mJ / mm 2 、80mJ / mm 2 Up to 100mJ / mm 2 、90mJ / mm 2 Up to 110mJ / mm 2 、100mJ / mm 2 Up to 120mJ / mm 2 、110mJ / mm 2 Up to 130mJ / mm 2 、120mJ / mm 2 Up to 140mJ / mm 2 、130mJ / mm 2 Up to 150mJ / mm 2 、140mJ / mm 2 Up to 160mJ / mm 2 、150mJ / mm 2 Up to 170mJ / mm 2 、160mJ / mm 2 Up to 180mJ / mm 2 、170mJ / mm 2 Up to 190mJ / mm 2 、180mJ / mm 2 Up to 200mJ / mm 2 or any subrange thereof. In an embodiment, the power of the high energy beam may be in the range of at least 7 W to at most 1000 W. The power of the high energy beam may be in the range of 7 W to 100 W, 50 W to 150 W, 100 W to 200 W, 150 W to 250 W, 200 W to 300 W, 250 W to 350 W, 300 W to 400 W, 350 W to 450 W, 400 W to 500 W, 450 W to 550 W, 500 W to 600 W, 550 W to 650 W, 600 W to 700 W, 650 W to 750 W, 700 W to 800 W, 750 W to 850 W, 800 W to 900 W, 850 W to 950 W, 900 W to 1000 W, or any subrange thereof. In some embodiments, the high energy beam power is about 300W.

[0119] Figure 5A schematic illustration of a metal alloy product 500 is provided in which a surface has been modified according to the methods disclosed above, such as to provide a modified surface, such as, for example, a cleaned surface, a textured surface, or an activated surface. As illustrated, a first product 500 is a formed metal alloy product having a surface 510. Surface 510 may be similar to any of the cleaned surfaces, textured surfaces, or activated surfaces described above. A second product 550 having a surface 560 may optionally comprise another material, and surface 560 may or may not be an untreated surface, a modified surface, a cleaned surface, a textured surface, or an activated surface. Although the metal alloy product 500 and the second product 550 are Figure 5 500 and the second product 550 are shown in a formed configuration, but one or both of the metal alloy product 500 and the second product 550 may optionally be in an unformed (e.g., planar) configuration. Advantageously, the adhesive 545 can securely bond the surface 510 to the surface 560 and provide a high-strength joint between the metal alloy product 500 and the second product 550. Example adhesives for joining a metal alloy product to another product may include epoxy adhesives, acrylate adhesives, phenolic adhesives, polyurethane adhesives, and the like.

[0120] Surfaces according to the present disclosure, namely, cleaned surface 306, textured surface 307, and activated surface 407, may be formed as Figure 55. The bonding surface is advantageously not required to be immediately bonded to another surface, substrate, or product and can be characterized by a surface stability or wait period corresponding to a duration during which the bonding surface can be bonded to another product using an adhesive and the resulting bonded product will exhibit high bond durability, such as a bond durability of at least 45 cycles when subjected to FLTM BV 101-07 Standard Test, Stress Durability of Adhesive Lap Shear Bonds (2017), which is incorporated herein by reference, or some other standard test. Thus, the bonding surface may be associated with a wait period before being bonded to another surface, substrate, or product.For example, the surface stability and / or waiting period can be from 1 minute to 6 months, e.g., 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, up to or about 1 day, up to or about 3 days, up to or about 1 week, up to or about 2 weeks, up to or about 3 weeks, up to or about 4 weeks, up to or about 1 month, up to or about 15 months ... months, up to or about 2 months, up to or about 3 months, up to or about 4 months, up to or about 5 months, up to or about 6 months or longer, 1 hour to 6 months, 8 hours to 6 months, 12 hours to 6 months, 1 day to 6 months, 3 days to 6 months, 1 week to 6 months, 2 weeks to 6 months, 1 month to 6 months, 2 months to 6 months, 3 months to 6 months, 4 months to 6 months, 5 months to 6 months, 1 hour to 5 months, 8 hours to 5 months, 12 hours to 5 months, 1 day to 5 months, 3 days to 5 months, 1 week to 5 months, 2 weeks to 5 months, 1 month to 5 months, 2 months to 5 months, 3 months to 5 months, 4 months to 5 months, 1 hour to 4 months, 8 hours to 4 months, 12 hours to 4 months, 1 day to 4 months, 3 days to 4 months, 1 week to 4 months, 2 weeks to 4 months, 1 month to 4 months, 2 months to 4 months, 3 months to 4 months, 1 hour to 3 months, 8 hours to 3 months, 12 hours to 3 months, 1 day to 3 months, 3 days to 3 months, 1 week to 3 months, 2 weeks to 3 months, 1 month to 3 months, 2 months to 3 months, 1 hour to 2 months, 8 hours to 2 months, 12 hours to 2 months, 1 day to 2 months, 3 days to 2 months, 1 week to 2 months, 2 weeks to 2 months, 1 month to 2 months, 1 hour to 1 month, 8 hours to 1 month, 12 hours to 1 month, 1 day to 1 month, 3 days to 1 month, 1 week to 1 month, 2 weeks to 1 month, 1 hour to 2 weeks, 8 hours to 2 weeks, 12 hours to 2 weeks, 1 day to 2 weeks, 3 days to 2 weeks, 1 week to 2 weeks, 1 hour to 1 week, 8 hours to 1 week, 12 hours to 1 week, 1 day to 1 week, or 3 days to 1 week.

[0121] For a waiting period of, for example, 3 months or longer, before applying adhesives, paints or weld adhesives (weld-bonding), the surface can be activated alternatively with air plasma, vacuum plasma or other known plasma technologies. After or before the high-energy beam is applied, the plasma reactor can generate ions and chemically reactive species and release them onto hard surfaces such as metals, plastics, ceramics, etc. Such ions and substances on the surface can utilize etching and / or enhanced surface energy to induce deep cleaning to improve wetting. Although it is preferably desired to generate low-energy plasma (cold plasma) at near room temperature and ambient pressure in order to keep the substrate surface temperature low during cleaning, according to the present disclosure, high-energy plasma (hot plasma) such as those used for plasma torches, fusion plasmas, plasma sprays, arc discharge plasmas, etc. is also contemplated. Low-energy plasma can also be used to deposit organic, inorganic or mixed adhesion promoters during or after the cleaning step. According to the present disclosure, any plasma discharge source is contemplated, such as ambient pressure plasma, corona discharge, low pressure plasma (DC plasma, DC glow discharge), low to medium frequency (RF - capacitive or inductive coupling), high frequency (microwave - electron cyclotron resonance), and flame.

[0122] Similarly, other dry cleaning methods (such as vacuum arc) may be used alone or in combination with another high energy beam, laser, plasma system, or any combination thereof, after or before the high energy beam application. The dry cleaning process may include any mechanical surface preparation, such as micro-blasting, macro-blasting, carbon dioxide dry ice shock and blasting, or any combination thereof. It is worth noting that vacuum arc systems are expensive and are more conducive to batch processes, during which the entire coil can be loaded into the vacuum chamber, and may have a significant adverse impact on the operation of a plant running continuous rolled products. For example, the continuous movement of the coil from the ambient environment into the vacuum chamber requires enormous pumping capacity, even to achieve relatively moderate vacuum levels, so the benefits generally obtained from vacuum processing may be greatly limited.

[0123] Any combination of the surface preparation and treatment processes described herein can be used to tailor surface properties to provide the desired surface properties for a given end product or process. For example, a carbon dioxide spray treatment can be used to remove fine particles and other loose debris, as well as hydrocarbon contaminants, before directing a high-energy beam onto the metal or metal alloy surface. Ultrasonic or radio frequency (RF) activation of the surface is contemplated in accordance with the present disclosure as being suitable for enhancing any of the effects described in using the dry cleaning methods described.

[0124] In some cases, the ablation efficiency or surface modification efficiency may be improved compared to the products and methods detailed above. Another method according to the present disclosure uses a liquid or condensed vapor layer applied to a metal alloy substrate to modify the near-surface microstructure of the alloy described herein, wherein the layer increases the interaction of the high-energy beam with the substrate surface, thereby advantageously improving the ablation efficiency. By utilizing the interaction of a high-energy beam (e.g., a laser) with a layer of liquid intentionally applied to the substrate surface, for example, the durability performance of the bond joint before failure can be increased to at least 75 or more cycles compared to 5 cycles without laser treatment. The methods described herein advantageously provide a treated metal or metal alloy surface that is clean and / or deposited with a chemically reactive substance to provide a stronger bond with an adhesive used down the line in the manufacturing process (such as in automotive manufacturing). Compared to untreated surfaces, the improved bond joint durability strength can produce improved weldability, paintability and other application-related requirements, including smoother surface roughness and smoother surface morphology. The methods described herein can also improve ablation efficiency by introducing a liquid layer having a higher thermal conductivity than air to reduce the heat-affected (or treated) zone and reduce residual thermal damage resulting from high-energy beam treatment of a metal or metal alloy surface covered with a liquid layer. Ablation efficiency can be indirectly characterized by cleanliness measurements performed using an optically stimulated electron emission (OSEE) tool. In some embodiments, the presence of a liquid layer is demonstrated to provide a relatively cleaner surface as measured by OSEE compared to a surface that does not have a liquid layer prior to directing a high-energy beam such as with laser ablation.

[0125] Figures 6A to 6C Methods of modifying the surface of a metal alloy product, such as a surface including a near-surface microstructure, are exemplified. Figure 6A As shown, a metal alloy substrate 600 is provided. The substrate 600 may be a metal alloy product as previously described, such as an aluminum alloy product. The substrate 600 has a near-surface microstructure 620 and a bulk microstructure 630, as described for Figure 2 、 Figure 3A and Figure 4A The near-surface microstructure 620 includes or comprises an untreated surface 605. The untreated surface 605 has not been subjected to any surface treatment or modification including, but not limited to, chemical or wet etching techniques and / or conversion coating. Optionally, the surface 605 may be subjected to chemical cleaning, water washing (at room temperature or elevated temperature), mechanical surface cleaning, activation or texturing, or any other cleaning method as desired. In some embodiments, at least one surface 605 or some exposed surfaces or all exposed surfaces of the substrate 600 are untreated. The near-surface microstructure 620 of the substrate 600 includes, for example, Figure 6AAt least some of the defects 640a to 640g shown are related to the defects Figure 2 The defects 240a to 240g described and Figure 4A Defects 440a to 440g are shown to be similar. Figure 6A As shown, the near-surface microstructure 620 includes defects 640. Defects 640 include rolled-in material, which includes various metal oxides 640c, various intermetallic particles 640f, and organic matter, oil, and hydrocarbons 640g. Defects 640 may also include defects including internal cracks 640a, voids 640b, surface cracks 640d, and high-density clusters of alloying elements 640e.

[0126] Apply liquid to Figure 6A The untreated surface 605 is formed as Figure 6B In some embodiments, the other surface opposite surface 606 also has a liquid applied so that both sides of the metal alloy substrate 600 include a liquid layer 635. The liquid can be a condensed vapor to form a liquid layer 635 or a film. In some embodiments, a first liquid layer is applied to surface 605 and a second liquid layer is applied to surface 685, where the first and second liquid layers can be the same or different. The presence of liquid layer 635 can, in embodiments, enhance the efficiency of energy coupling with the directed energy beam (e.g., compared to air or the absence of a liquid layer). Figure 6C As shown). Figure 6BThe liquid layer 635 shown may include an aqueous solution or a non-aqueous solution. Suitable solutions may include glycerol, an alcoholic solution, steam, or a combination thereof, or may be generated using glycerol, an alcoholic solution, steam, or a combination thereof. The solution may optionally include pretreatment chemicals, anodic and / or cathodic corrosion inhibitors, or a combination thereof. The pretreatment chemicals may be configured to have at least one of the following functions: inhibiting corrosion, texturing the surface, and increasing adhesion by changing the surface chemistry and / or mechanical state. Suitable pretreatment chemicals for addition to the solution may be selected from organic phosphonic acids, organic phosphinic acids, silanes, coupling agents, polymers, copolymers, pretreatment agents containing zirconium / molybdenum (Zr / Mo), pretreatment agents containing manganese (Mn), pretreatment agents containing cerium (Ce), adhesion promoters, or any suitable chemical or mechanical technique for changing and / or functionalizing the surface by chemical, mechanical, and / or electrochemical methods, or any combination thereof. By incorporating optional pretreatment chemicals, the metal or metal alloy surface can be cleaned simultaneously while further providing a surface tailored for improved bond durability and coating adhesion performance. In some embodiments, the metal or metal alloy surface can be treated without any prior cleaning steps, including simultaneous cleaning, activation, and functionalization, while texturing the surface by dry techniques or using vapor, aqueous, or non-aqueous films present on the metal or metal alloy. In some embodiments, the interaction of the metal surface with the high-energy beam and the liquid layer is further enhanced by depositing a chemically reactive species onto the treated surface. Coatings such as from slurries, gels, or pastes are also contemplated. Suitable coatings may include or be selected from metals, polymers, or ceramics to enhance the interaction of the high-energy beam with layer 635.

[0127] like Figure 6B The application of the layer 635 in can be provided by an applicator or by two or more applicators. By using two or more applicators, the speed at which one or more substrate surfaces are covered with a liquid layer or film on one or both substrate surfaces can be greatly increased. The use of two or more applicators is suitable for applications such as Figures 7 to 9 The one or more applicators may be at least one selected from a spray applicator with or without pulse emission, a low pressure high volume spray applicator, a low pressure low volume spray applicator, a rotary atomizer, an electrostatic applicator, a roller applicator, or any combination thereof.

[0128] like Figure 6C A high energy beam 655 is shown directed onto a surface 606 ( Figure 6B to modify the surface physically and chemically to provide Figure 6C The activated surface 607 in FIG. 5 is free of at least some of the defects 640 .

[0129] Figure 6A The near-surface microstructure 620 has a thickness t7. Figure 6B Liquid layer 635 has a thickness t8. High-energy beam 655 can remove at least a portion of near-surface microstructure 620. In other words, after high-energy beam 655 is directed onto surface 606, thickness t9 of near-surface microstructure 620 associated with cleaned surface 607 can be reduced relative to thickness t7 of near-surface microstructure 620 associated with untreated surface 605.

[0130] is directed to surface 606 ( Figure 6B The high energy beam 655 on the middle) can provide Figure 6C The activated surface 607 shown may optionally have a near-surface microstructure 622. The high-energy beam directed onto the liquid layer 635 having the surface 606 may affect the near-surface microstructure through interaction between the high-energy beam and the liquid layer, which interaction may melt at least one of the plurality of metal oxides 640c and the plurality of intermetallic particles 640f. The molten particles may be incorporated into the bulk composition. The activated surface 607 associated with the near-surface microstructure 622 is substantially free of at least one of the plurality of metal oxides 640c and the plurality of intermetallic particles 640f. In an embodiment, the activated surface 607 associated with the near-surface microstructure 622 is substantially free of metal oxides 640c and intermetallic particles 640f. In an embodiment, Figure 6C The near-surface microstructure 622 has a thickness t9 together with the activated surface 607. After directing the high-energy beam 655 onto the surface 606, the near-surface microstructure 620 having a thickness t7 has a thickness t8, and the thickness t9 is reduced relative to the thickness t7. Optionally, the near-surface microstructure 620 or 622 can be completely removed or modified, such as to provide a zero thickness t9, so that the body 630 can be exposed as a top surface and can include the activated surface 607 or be coupled to the activated surface. In some embodiments, the thickness t9 is less than or equal to the thickness t7. In an embodiment, the near-surface microstructure is removed to a depth of up to about 10 μm or up to about 5 μm. In some examples, a 2 mm thick layer of deionized water can be applied to the 6xxx series aluminum alloy for surface treatment according to the method of the present invention, thereby removing a near-surface microstructure layer of about 5 μm or about 10 μm. In other words, thickness t9 is about 10 μm or about 5 μm less than thickness t7 as a result of directing high energy beam 655 onto the substrate surface.

[0131] Advantageously, modifying the surface 605 to generate an activated surface 607 by exposing it to a high energy beam 655 in the presence of a liquid layer 635 can change the bond durability of a bond between the surface and another product from a relatively short bond durability to a relatively long or high performing bond durability. In embodiments, as Figure 6C The activated surface 607 in the embodiment can exhibit a bond tip durability of at least 35 cycles, at least 40 cycles, at least 45 cycles, at least 50 cycles, or more. Furthermore, the laser and metal or metal alloy surface coupling provides a cleaner and smoother surface compared to an ablated surface that does not include a liquid layer. During the strong coupling between the high-energy laser beam and the metal or metal alloy surface, efficient debris removal is achieved through induced thermal convection and bubble motion, thereby improving the surface.

[0132] In addition, the method described herein can substantially or completely ablate surface and near-surface microstructure to remove the surface and at least partially remove any subsurface layer. This may produce a clean surface formed with enriched oxide and functionalized with hydroxyl chemicals. This can be carried out in air so that the oxygen in the air reacts with the metal surface under the high temperature generated by the laser to form an enriched oxide layer, which is significantly different from the near-surface microstructure of the untreated surface. The enriched oxide layer can be hydrated by any residual water on the surface or by moist air. The metal or metal alloy surface formed with enriched oxide and functionalized with hydroxyl chemicals can easily react with an adhesive and provide bonding with an adhesive, thereby providing extended BD performance.

[0133] The substrate 600 may comprise a non-ferrous material, including aluminum, an aluminum alloy, magnesium, a magnesium-based material, a magnesium alloy, a magnesium composite material, titanium, a titanium-based material, a titanium alloy, copper, a copper-based material, a composite material, a sheet material used in a composite material, or any other suitable metal, non-metal, or material combination, depending on the specific alloy or metal used. In some embodiments, the substrate 600 comprises an aluminum alloy, magnesium, a magnesium alloy, a magnesium composite material, steel, or any combination thereof. In some embodiments, the substrate 600 is an aluminum alloy. Useful aluminum alloys include any of the aluminum alloys previously described in detail, for example, 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.

[0134] like Figure 6C The high energy beam 655 in the embodiment can be provided by one laser or by two or more lasers. By using two or more laser units, the speed at which one or more substrate surfaces having a liquid layer on one or both substrate surfaces can be processed can be greatly increased. The use of two or more lasers is suitable for example Figures 7 to 9 The non-limiting continuous line embodiment shown. The one or more lasers can be selected from a continuous laser, a pulsed laser, a nanosecond pulsed laser, a picosecond pulsed laser, or a femtosecond pulsed laser, a single and / or double pass configuration, and at least one of a laser with or without a continuous wave. The laser can be selected from at least one of ytterbium, Nd-YAG, CO2 or an excimer laser, or can be any suitable laser that provides a desired energy density. The laser can have any suitable wavelength, such as from about 200nm to about 1500nm. According to some embodiments, the wavelength, frequency, working distance, laser incident angle and energy level can be customized.

[0135] like Figure 6C The energy density of the high energy beam 655 can be at least 10mJ / mm 2 Up to 200mJ / mm 2 The energy density can be within the following range: 10mJ / mm 2 Up to 30mJ / mm 2 , 20mJ / mm 2 Up to 40mJ / mm 2 、30mJ / mm 2 Up to 50mJ / mm 2 、40mJ / mm 2 Up to 60mJ / mm 2 、50mJ / mm 2 Up to 70mJ / mm 2 、60mJ / mm 2 Up to 80mJ / mm 2 、70mJ / mm 2 Up to 90mJ / mm 2 、80mJ / mm 2 Up to 100mJ / mm 2 、90mJ / mm 2 Up to 110mJ / mm 2 、100mJ / mm 2 Up to 120mJ / mm 2 、110mJ / mm 2 Up to 130mJ / mm 2 、120mJ / mm 2 Up to 140mJ / mm 2 、130mJ / mm 2 Up to 150mJ / mm 2 、140mJ / mm 2 Up to 160mJ / mm 2 、150mJ / mm 2 Up to 170mJ / mm 2 、160mJ / mm2 Up to 180mJ / mm 2 、170mJ / mm 2 Up to 190mJ / mm 2 、180mJ / mm 2 Up to 200mJ / mm 2 or any subrange thereof. In an embodiment, the power of the high energy beam may be in the range of at least 7 W to at most 1000 W. The power may be in the range of 7 W to 100 W, 50 W to 150 W, 100 W to 200 W, 150 W to 250 W, 200 W to 300 W, 250 W to 350 W, 300 W to 400 W, 350 W to 450 W, 400 W to 500 W, 450 W to 550 W, 500 W to 600 W, 550 W to 650 W, 600 W to 700 W, 650 W to 750 W, 700 W to 800 W, 750 W to 850 W, 800 W to 900 W, 850 W to 950 W, 900 W to 1000 W, or any subrange thereof.

[0136] Optionally, steam or another gas or method may be used after directing the high energy beam to the surface to prepare the surface for the adhesive joint. Advantageously, metal byproducts may be generated and may include metal nanopowders formed during laser ablation of the aluminum alloy substrate or sheet according to some embodiments disclosed herein. These metal nanopowders can be captured by filtering and drying for use in metal powder processes or other processes. Reference Figures 7 to 9 , a continuous line embodiment is shown according to the methods disclosed herein. Figure 7 One embodiment of a continuous line process for applying a first liquid and a second liquid from applicators 765A and 765B to both sides of a substrate (as shown in sheet form) is schematically illustrated. The continuous line process moves the substrate or substrate sheet 700 in a direction as indicated by flow arrows F. The application of at least one liquid 735A and 735B is performed simultaneously with directing high energy beams from a first laser 755A and a second laser 755B to one or more substrate surfaces. For example, applicator 765A applies liquid 735A to substrate surface 705, while applicator 765B applies liquid 735B to substrate surface 785. Simultaneously, the high energy beam is delivered to substrate surface 705 by laser 755A, and the high energy beam is delivered to substrate surface 785 by laser 755B. The interaction between the laser energy and the liquids 735A and 735B at surfaces 705 and 785, respectively, produces treated surfaces 707A and 707B along the continuous line process as indicated by the flow arrows. For Figure 7In the embodiment shown, the thickness of layers 735A and 735B ranges from the molecular level of condensed vapor to a liquid layer of up to 5 mm for complete sheet surface coverage. Liquid layers 735A and 735B may be the same or different.

[0137] Figure 8 The schematic diagram shows another embodiment of a continuous line process. Both sides of the substrate 800 are applied with a first liquid and a second liquid (e.g., 835A and 835B) from applicators 865A and 865B. Optionally, at box 899, the substrate is cleaned by chemical, water washing, or other cleaning or washing methods known in the art. Cleaning can be carried out at room temperature or at an elevated temperature of up to about 90°C. In some embodiments, cleaning is carried out at a temperature below 50°C to minimize and control any evaporation loss of aqueous detergents. Similar temperatures can be used for non-aqueous detergents. Vapor degreasing may be useful before laser functionalization and texturing the coil surface. The continuous line process moves the substrate or substrate sheet 800 in the direction indicated by arrow 890. Application of at least one liquid 835 can be performed before directing the high-energy beams from lasers 855A and 855B. For example, applicator 865A applies liquid 835A to substrate surface 805, while applicator 865B applies liquid 835B to substrate surface 885. A high energy beam can be delivered to substrate surface 805 by laser 855A, and a high energy beam can be delivered to substrate surface 885 by laser 855B. The interaction between the laser energy and the liquids 835A and 835B covering surfaces 805 and 885 produces treated surfaces 807A and 807B, respectively. Figure 8 In the embodiment shown, the thickness of layers 835A and 835B ranges from the molecular level of condensed vapor to a liquid layer of up to 5 mm for complete sheet surface coverage. Liquid layers 835A and 835B may be the same or different.

[0138] Figure 9 A further embodiment of a continuous line process is schematically illustrated. Figure 9 In the embodiment shown, the thickness of layers 935A and 935B is up to 5 mm. In some embodiments, the thickness of the layer can be greater than 5 mm, provided that the film thickness is consistent and allows interaction and coupling between the laser and the metal or metal alloy surface to functionalize and texturize to obtain the desired properties. The first liquid and the second liquid (e.g., 935A and 935B) are applied to the substrate 900 from applicator baths 995A and 995B at a temperature below 90°C, preferably below 50°C, and more preferably at room temperature. The continuous line process moves the substrate or substrate sheet 900 in a direction as indicated by arrow 990. The application of at least one liquid 935 can be performed while directing the high energy beams from the lasers 955A and 955B by adjusting the position of the lasers (e.g., Figure 9 ) or before. For example, applicator bath 995A applies liquid 935A to substrate surface 905, while applicator bath 995B applies liquid 935B to substrate surface 985. A high energy beam may be delivered to substrate surface 905 by laser 955A, and a high energy beam may be delivered to substrate surface 985 by laser 955B. The interaction between the laser energy and the liquids 935A and 935B covering surfaces 905 and 985 produces treated surfaces 907A and 907B, respectively. The liquid layers 935A and 935B may be the same or different. In some embodiments, the liquid layers 935A and 935B of baths 995A and 995 may provide coverage of both sides 905 and 985. For Figure 9 In the embodiment shown, the thickness of layers 935A and 935B is up to about 5 mm. In some embodiments, the thickness of the layer can be greater than 5 mm, provided that the film thickness is consistent and allows interaction and coupling between the laser and the metal or metal alloy surface to perform functionalization and texturing to obtain the desired properties.

[0139] like Figures 7 to 9 The treated surfaces 707A, 707B, 807A, 807B, 907A, and 907B in FIG. 1 are suitable for bonding and can be used, for example, as automotive sheet products. Automotive sheet products may include, but are not limited to, 5xxx series aluminum alloys, 6xxx series aluminum alloys, or 7xxx series aluminum alloys. The automotive sheet products may be DC cast, CC cast, or clad, among others.

[0140] The following examples will be used to further illustrate the present invention, but do not constitute any limitation of the present invention. On the contrary, it should be clearly understood that after reading the description herein, those skilled in the art can think of making various other embodiments, modifications and equivalents thereof without departing from the spirit of the present invention. In the research process described in the following examples, unless otherwise stated, conventional procedures are followed. Below for illustrative purposes, some procedures are described.

[0141] Example 1

[0142] Aluminum alloy product samples were prepared by direct chill (DC) casting, hot rolling, cold rolling, and solution heat treatment to produce AA5182 sheet samples (tested in O temper) and AA6451 sheet samples (tested in T4 temper) with final gauge thicknesses of 0.9 mm to 2.0 mm. The sheet samples were then positioned so that the surface was exposed to a nanosecond ytterbium laser (model YLPN, 1064 nm, IPG Photonics) with a pulse duration of 40 ns, a 30% overlap rate, up to 1000 W, a spot size of 0.85 mm or 1.4 mm, and a frequency of 10 kHz or 20 kHz, and the laser beam settings and surface customization parameters were adjusted to obtain different surface textures, such as for the AA5182 sample. Figure 10A 、 Figure 10B 、 Figure 10C And for AA6451 samples Figure 10D and Figure 10E shown. Figure 10A shows the surface texture evolution of AA5182 alloy treated with 100W to 1000W at 10kHz with a spot size of 0.85mm. Similarly, Figure 10B Shown is the surface texture evolution of AA5182 alloy treated with 100 W to 1000 W at 10 kHz with a spot size of 1.4 mm. Figure 10C The surface texture evolution of AA5182 alloy treated with 100W to 1000W at 20kHz with a spot size of 1.4mm is shown. Figures 10D to 10E The evolution of surface texture is shown at 10 kHz and 20 kHz, respectively, with a 1.4 mm spot at ten different power states, starting from 100 W at the top and ending at 1000 W at the bottom. The texturing of the surface shown increases with increasing power. The contact angle of water with the resulting surface as a function of laser beam energy was obtained using standard techniques for sessile drop contact angle measurement.

[0143] Figure 11A The energy density (mJ / mm) of the Yb laser is shown. 2 ) on the x-axis and the y-axis corresponding to the contact angle of the resulting sample surface (expressed in degrees). The original AA5182 surface was measured to have a contact angle of 76 degrees. As the energy density of the laser increased from 0 to about 15 mJ / mm 2 , the contact angle drops sharply to less than 10 degrees. The lower contact angle indicates improved wettability and good bond durability behavior. Further increasing the energy density to about 15mJ / mm 2 Above, the results show that at about 15mJ / mm 2 Up to more than 100mJ / mm 2 The contact angle remains stable at a low energy density of about 5 degrees.

[0144] Figure 11B The energy density (mJ / mm) of the Yb laser is shown. 2 ) on the x-axis and the y-axis corresponding to the contact angle of the resulting sample surface (expressed in degrees). The original AA6451 surface was measured to have a contact angle of 75 degrees. As the energy density of the laser increased from 0 to about 15 mJ / mm 2 The contact angle drops sharply to about 10 degrees. The energy density is further increased to about 15mJ / mm 2 The above results show that the contact angle is about 52mJ / mm 2 The lower one decreases to about 5 degrees.

[0145] At 15mJ / mm 2 、23.1mJ / mm 2 and 57.8mJ / mm 2 AA5182 sheet samples, each treated and surface textured with a 1.4 mm spot size, were adhesively bonded and subjected to a bond durability test according to the example standard test for determining bond durability: FLTM BV 101-07 standard test, stress durability test of adhesive lap shear joints (2017). During the bond durability test, each sample consisted of two aluminum alloy product sheets prepared and processed under the same conditions and then bonded together at six bonding sites using an epoxy adhesive. Next, each sample was subjected to various test conditions including being immersed in a salt solution, exposed to wet conditions, exposed to dry conditions, and / or applying one or more of the forces inducing stress or strain. Under such test conditions, each sample was subjected to multiple bond durability cycles. The number of cycles the sample was subjected to was the number of cycles to mechanical failure, or 60 or more cycles. The results were analyzed using a 15 mJ / mm 2 The durability test of the bond head on the treated AA5182 sample surface was an average of 60 cycles, while the 23.1mJ / mm 2 The treated and textured AA5182 alloy sample surface gave an increased bond durability performance of 115 cycles. 2 The AA5182 samples prepared with high energy levels resulted in early failure in less than 10 cycles.

[0146] Example 2

[0147] Aluminum alloy product samples were prepared by DC casting, hot rolling, cold rolling, laboratory heat treatment at 480°C for 5 minutes to simulate hot forming temperature, and artificial aging to T6 tempering at 125°C for 24 hours to produce AA7075 sheet samples with a final specification of about 2.8 mm. The surface of the sheet sample was then exposed to a CL300 watt high intensity laser (Adapt Laser, LLC) with a frequency range of 15 kHz to 40 kHz. The laser fired pulses across the surface at 300 W and a spot size of 428 μm with different levels of overlap (25% and 50%) for each subsequent pulse. The morphology of the sample surface before and after laser treatment was measured, as shown in FIG. Figures 12A to 12C As shown. For comparison, Figure 12A Shown is the topography as measured on the original mill finish or 'untreated' surface of an AA7075 sheet sample. Figure 12B Shown is the topography as measured on the surface of an AA7075 sheet sample, where a high-energy beam of laser light emitted in pulses was directed to the exposed surface with a 25% pulse-to-pulse overlap. Figure 12C The topography as measured on the surface of an AA7075 sheet sample is shown, where a high-energy laser beam emitted in pulses was directed to the exposed surface with a 50% pulse-to-pulse overlap. Increasing the overlap from 25% to 50% resulted in a rougher surface topography, as indicated by the range of color output across the measured topography. The results show that increasing the overlap percentage results in a higher surface roughness (as measured in 3D). The untreated surface (as measured in 3D) Figure 12A The Sa value of the laser treated surface (shown as Figure 12B The Sa value of the laser treated surface (shown in FIG) is about 1.1 μm, and the laser treated surface (shown in FIG) with a 50% pulse overlap rate is about 1.1 μm. Figure 12C The Sa value of the quartz crystal (shown) is about 1.4 μm.

[0148] The sample was adhesively bonded and subjected to a bond head durability test according to the standard test method FLTM BV101-07 as described in Example 1 above. During the bond head durability test, each sample was made of two aluminum alloy products that were prepared and processed using the same conditions and then bonded together using an epoxy resin adhesive via six bonding sites. Next, each sample was subjected to various test conditions. For example, the test conditions included being immersed in a salt solution, exposed to wet conditions, exposed to dry conditions, or applying one or more of the forces that induce stress or strain. Each sample was subjected to multiple cycles of these test conditions. The number of cycles the sample was subjected to was the number of cycles that reached mechanical failure, or 60 cycles, the maximum number of cycles used in this particular standard test. Mechanical failure includes bond head failure or adhesive fracture. The bond head durability performance test of AA7075 with temper T6 included obtaining a maximum of 60 cycles for all twelve test samples at 15kHz using a laser CL300 with a 50% overlap rate for the sample surface. The AA7075 (T6) sample surfaces treated with a CL300 laser at 15 kHz at 20% overlap achieved a maximum of 60 cycles for five test samples, with the sixth sample failing at 43 cycles. After three months of aging, the same AA7075 (T6) at 50% overlap achieved an average bond durability of 95 cycles for twelve test samples. After six months of aging, the same AA7075 (T6) at 50% overlap achieved a maximum bond durability of 60 cycles for ten of the twelve test samples, with the eleventh sample failing at 51 cycles and the twelfth sample failing at 60 cycles.

[0149] Figure 13 This is an image of a comparative example of AA7075 with a milled finish (no surface treatment) obtained using a scanning electron microscope (SEM) at a full-width field of view of 20 μm and a magnification of 20KX. Near-surface microstructure 1320, such as rolled-in oxides, intermetallic particles, and voids, is evident from the micrograin morphology beneath surface 1305. Surface 1305 is coated with gold (Au) for SEM imaging purposes. Intermetallic particles 1340f appear brightly colored and distributed throughout near-surface microstructure 1320. Figure 14 , which is an image obtained with an SEM at a lower 10KX magnification with a full width field of view of 40 μm, shows the proximity of the inter-metallic particle 1440 f relative to the surface of the untreated milled finish surface 1405 .

[0150] Figure 15 The image was obtained using SEM at a full width field of view of 20 μm and a magnification of 20K X, and Figure 16This is an image obtained with a SEM at a full width field of view of 40 μm and a magnification of 10KX, for example, of AA7075, where the surface was laser ablated with a 50% pulse-to-pulse overlap (CL300W high intensity laser, 50% overlap per subsequent pulse, 300W, and a spot size of 428 μm). Figure 15 As shown, for the laser treated surface, below the surface 1505, near-surface microstructures such as rolled-in oxides, intermetallic particles 1540f, and voids are less or not evident at all due to the lack of micro-grain morphology. Figure 16 As shown, Figure 14 Compared to the polished surface of the comparative example shown, fewer intermetallic particles 1640f are clearly visible from the surface 1605 to a depth of about 5 μm.

[0151] Illustrative aspects

[0152] As used below, any reference to a series of aspects (e.g., aspects 1 to 4) or an unlisted group of aspects (e.g., "any previous or subsequent aspect") should be understood as a reference to each of those aspects separately (e.g., "Aspects 1 to 4" should be understood as "Aspect 1, 2, 3, or 4").

[0153] Aspect 1 is a method comprising: providing an aluminum alloy product having a body and a first surface, scanning a high-energy beam across the first surface, wherein the high-energy beam interacts with the first surface to physically modify the first surface, thereby forming a treated first surface.

[0154] Aspect 2 is the method of any preceding or subsequent aspect, further comprising applying a first liquid layer onto the first surface prior to scanning the high-energy beam, wherein the scanning high-energy beam is performed across the first liquid layer and the high-energy beam interacts with the first liquid layer to form the treated first surface.

[0155] Aspect 3 is the method of any preceding or subsequent aspect, wherein the treated first surface exhibits a bond durability of 45 cycles to 125 cycles or more when tested according to the FLTM BV101-07 standard.

[0156] Aspect 4 is the method of any preceding or subsequent aspect, wherein the aluminum alloy product comprises a 5xxx series aluminum alloy, a 6xxx series aluminum alloy, or a 7xxx series aluminum alloy.

[0157] Aspect 5 is the method of any preceding or subsequent aspect, wherein the high-energy beam interacts with the first liquid layer to physically modify at least a portion of the body, wherein the body comprises intermetallic particles and a matrix comprising aluminum alloy grains, to form a treated subsurface layer.

[0158] Aspect 6 is the method of any previous or subsequent aspect, wherein the treated subsurface layer comprises a resolidified layer of aluminum alloy that had previously been melted by the high-energy beam, wherein the subsurface layer occupies a depth of 1 μm to 10 μm into the aluminum alloy product, and wherein the first intermetallic particle concentration in the treated subsurface layer is less than the second intermetallic particle concentration in the body.

[0159] Aspect 7 is the method of any preceding or subsequent aspect, wherein the thickness of the first liquid layer is from 1 nm to 1 mm.

[0160] Aspect 8 is the method of any preceding or subsequent aspect, wherein the thickness of the first liquid layer is 1 mm to 5 mm.

[0161] Aspect 9 is the method of any preceding or subsequent aspect, further comprising applying a second liquid layer to a second surface, wherein the second surface is opposite the first surface.

[0162] Aspect 10 is the method of any preceding or subsequent aspect, wherein the second liquid layer has a thickness of 1 nm to 1 mm.

[0163] Aspect 11 is the method of any preceding or subsequent aspect, wherein the second liquid layer has a thickness of 1 mm to 5 mm.

[0164] Aspect 12 is the method of any preceding or subsequent aspect, wherein the second liquid layer is the same as the first liquid layer.

[0165] Aspect 13 is the method of any preceding or subsequent aspect, wherein the second liquid layer is different from the first liquid layer.

[0166] Aspect 14 is the method of any preceding or subsequent aspect, wherein at least one of the first liquid layer and the second liquid layer comprises condensed vapor.

[0167] Aspect 15 is the method of any preceding or subsequent aspect, wherein at least one of the first liquid layer and the second liquid layer comprises an aqueous solution.

[0168] Aspect 16 is the method of any preceding or subsequent aspect, wherein at least one of the first liquid layer and the second liquid layer comprises a non-aqueous solution.

[0169] Aspect 17 is the method of any preceding or subsequent aspect, wherein at least one of the first liquid layer and the second liquid layer comprises glycerol, an alcohol solution, steam, or any combination thereof.

[0170] Aspect 18 is the method of any previous or subsequent aspect, wherein at least one of the first liquid layer and the second liquid layer comprises a pretreatment chemical configured to have at least one of the following functions: inhibiting corrosion, texturing the surface, and increasing adhesion, the pretreatment chemical being selected from an organic phosphonic acid, an organic phosphinic acid, a silane, a coupling agent, a polymer, a copolymer, a Zr / Mo pretreatment agent, a Mn-based pretreatment agent, a Ce-based pretreatment agent, or a combination thereof.

[0171] Aspect 19 is the method of any preceding or subsequent aspect, wherein the first liquid layer and the second liquid layer are applied to the first surface and the second surface by two or more applicators.

[0172] Aspect 20 is the method of any preceding or subsequent aspect, wherein the two or more applicators comprise a spray applicator with or without pulse emission, a low pressure high volume spray applicator, a low pressure low volume spray applicator, a rotary atomizer, an electrostatic applicator, a roller applicator, or any combination thereof.

[0173] Aspect 21 is the method of any previous subsequent aspect, wherein the two or more applicators are located in a continuous line.

[0174] Aspect 22 is the method of any preceding or subsequent aspect, wherein the two or more applicators are configured as two or more applicator baths.

[0175] Aspect 23 is the method of any preceding or subsequent aspect, wherein scanning the high energy beam across the first liquid layer comprises directing a beam of laser energy onto the first liquid layer.

[0176] Aspect 24 is the method of any preceding or subsequent aspect, wherein the laser energy beam is provided by a continuous laser, a pulsed laser, a nanosecond pulsed laser, a picosecond pulsed laser, a femtosecond pulsed laser, a single-pass configuration, a dual-pass configuration, a laser with a continuous wave, a laser without a continuous wave, or any combination thereof.

[0177] Aspect 25 is the method of any preceding or subsequent aspect, wherein the laser energy beam is provided by an ytterbium laser, an Nd-YAG laser, a CO2 laser, an excimer laser, or any combination thereof.

[0178] Aspect 26 is the method of any preceding or subsequent aspect, wherein the laser energy beam has a wavelength of about 200 nm to about 1500 nm.

[0179] Aspect 27 is the method of any preceding or subsequent aspect, wherein scanning the high energy beam across the first liquid layer comprises directing at least one laser energy beam onto the first liquid layer, and wherein the method further comprises directing at least one additional laser energy beam onto the second liquid layer.

[0180] Aspect 28 is the method of any preceding or subsequent aspect, wherein the first surface is an untreated first surface.

[0181] Aspect 29 is a method according to any preceding or subsequent aspect, wherein the untreated first surface has one or more of organic matter, oil, hydrocarbons, dirt, or inorganic residues, and wherein the treated first surface is free of or substantially free of one or more of organic matter, oil, hydrocarbons, dirt, or inorganic residues.

[0182] Aspect 30 is the method of any preceding or subsequent aspect, wherein the untreated first surface has not been subjected to one or more wet processing steps selected from chemical etching, acidic or alkaline cleaning, solvent cleaning, vapor degreasing, mechanical surface treatment, brushing, lapping, mechanical surface polishing, electrochemical polishing, chemical polishing, surfactant cleaning, and conversion coating.

[0183] Aspect 31 is the method of any preceding or subsequent aspect, wherein the untreated first surface has not been subjected to the one or more wet processing steps prior to directing the high energy beam onto the untreated first surface.

[0184] Aspect 32 is the method of any preceding or subsequent aspect, wherein the untreated first surface corresponds to a rolled surface having a rolling lubricant thereon.

[0185] Aspect 33 is the method of any preceding or subsequent aspect, wherein directing a high energy beam onto the untreated first surface corresponds to a dry cleaning process, and wherein the treated first surface corresponds to a cleaned surface.

[0186] Aspect 34 is the method of any preceding or subsequent aspect, wherein directing the high-energy beam onto the untreated first surface corresponds to a dry surface modification process, and wherein the treated first surface corresponds to an activated surface suitable for bonding with an adhesive.

[0187] Aspect 35 is the method of any preceding or subsequent aspect, wherein the first surface includes near-surface microstructures, and wherein directing the energy beam onto the first surface removes or eliminates at least a portion of the near-surface microstructures.

[0188] Aspect 36 is the method of any preceding or subsequent aspect, wherein directing the high-energy beam onto the first surface thermally modifies the near-surface microstructure.

[0189] Aspect 37 is the method of any preceding or subsequent aspect, wherein the treated first surface exhibits a dry static coefficient of friction of 0.1 to 0.5.

[0190] Aspect 38 is an aluminum alloy product comprising: a rolled aluminum alloy substrate, the rolled aluminum alloy substrate comprising: a body, wherein the body comprises intermetallic particles and a matrix comprising aluminum alloy grains; a laser-treated region covering a first portion of the body, wherein the laser-treated region comprises: a treated subsurface layer, wherein the treated subsurface layer comprises a resolidified layer of aluminum alloy that had previously been melted by a high-energy beam, wherein the treated subsurface layer occupies a depth of 1 μm to 10 μm into the aluminum alloy product, and wherein the first intermetallic particle concentration in the treated subsurface layer is less than the second intermetallic particle concentration in the body; and a laser-processed surface layer, wherein the laser-processed surface layer is substantially free of near-surface microstructure and one or more of organic matter, oil, hydrocarbons, dirt, inorganic residues, rolled-in oxides, or anodized oxides, and wherein the laser-processed surface layer comprises a first oxide layer having a thickness of 10 nm to 300 nm.

[0191] Aspect 39 is the aluminum alloy product of any preceding or subsequent aspect, wherein the aluminum alloy comprises a 5xxx series aluminum alloy, a 6xxx series aluminum alloy, or a 7xxx series aluminum alloy.

[0192] Aspect 40 is the aluminum alloy product of any preceding or subsequent aspect, wherein the magnesium concentration in the aluminum alloy is less than 10 weight percent.

[0193] Aspect 41 is the aluminum alloy product of any preceding or subsequent aspect, wherein the magnesium concentration in the bulk is greater than the magnesium concentration in the treated subsurface layer, or wherein the zinc concentration in the bulk is greater than the zinc concentration in the treated subsurface layer.

[0194] Aspect 42 is the aluminum alloy product of any preceding or subsequent aspect, wherein the laser treated area exhibits a bond joint durability of 45 cycles to 125 cycles or more when tested according to FLTM BV 101-07 standard.

[0195] Aspect 43 is the aluminum alloy product of any preceding or subsequent aspect, wherein the aluminum alloy product does not include a functionalized layer thereon, such as a phosphorus-containing organic acid coating.

[0196] Aspect 44 is the aluminum alloy product of any preceding or subsequent aspect, further comprising an untreated region covering the second portion of the body, wherein the untreated region is not or has not been subjected to a laser treatment process.

[0197] Aspect 45 is the aluminum alloy product of any preceding or subsequent aspect, wherein a first arithmetic mean height (Spk) of the laser-treated areas is less than a second arithmetic mean height of the untreated areas.

[0198] Aspect 46 is the aluminum alloy product of any preceding or following aspect, wherein the laser-treated region exhibits an arithmetic mean height (Sa) of 0.1 μm to 10 μm.

[0199] Aspect 47 is the aluminum alloy product of any preceding or following aspect, wherein the laser-treated region exhibits a complexity (Sdr) of 0.1% to 80%.

[0200] Aspect 48 is the aluminum alloy product of any preceding or following aspect, wherein the laser treated area exhibits surface stability for up to 3 months.

[0201] All patents, publications, and abstracts cited above are incorporated herein by reference in their entirety. The foregoing description of the embodiments (including the illustrated embodiments) is presented for purposes of illustration and description only and is not intended to be exhaustive or to limit the precise forms disclosed. Various modifications, variations, and uses thereof will be apparent to those skilled in the art.

Claims

1. A method for modifying the surface of a metal alloy, comprising: providing an aluminum alloy product having a body and a first surface, applying a first liquid layer onto the first surface, A high energy beam is scanned across the first liquid layer and the first surface, wherein the high energy beam interacts with the first surface and the first liquid layer to physically modify the first surface to form a treated first surface, and the first liquid layer comprises glycerol, an alcohol solution, vapor, or any combination thereof, and wherein the high energy beam interacts with the first liquid layer to physically modify at least a portion of the body, wherein the body comprises intermetallic particles and a matrix comprising aluminum alloy grains, to form a treated subsurface layer, wherein the treated subsurface layer comprises a resolidified layer of aluminum alloy that was previously melted by the high energy beam, wherein the subsurface layer occupies a depth of 1 μm to 10 μm into the aluminum alloy product, and wherein the concentration of first intermetallic particles in the treated subsurface layer is less than the concentration of second intermetallic particles in the body.

2. The method of claim 1, wherein the treated first surface exhibits a bond durability of 45 cycles to 125 cycles tested according to FLTM BV 101-07 standard.

3. The method of claim 1, wherein the aluminum alloy product comprises a 5xxx series aluminum alloy, a 6xxx series aluminum alloy, or a 7xxx series aluminum alloy. The method of claim 1 , wherein the thickness of the first liquid layer is 1 nm to 1 mm. The method of claim 1 , wherein the thickness of the first liquid layer is 1 mm to 5 mm.

6. The method of claim 1, further comprising applying a second liquid layer to a second surface, wherein the second surface is opposite the first surface. The method of claim 6 , wherein the second liquid layer has a thickness of 1 nm to 1 mm. The method of claim 6 , wherein the second liquid layer has a thickness of 1 mm to 5 mm.

9. The method of claim 6, wherein the second liquid layer is the same as the first liquid layer.

10. The method of claim 6, wherein the second liquid layer is different from the first liquid layer.

11. The method of claim 6, wherein at least one of the first liquid layer and the second liquid layer comprises condensed vapor.

12. The method of claim 6, wherein at least one of the first liquid layer and the second liquid layer comprises an aqueous solution.

13. The method of claim 6, wherein at least one of the first liquid layer and the second liquid layer comprises a non-aqueous solution.

14. The method of claim 6, wherein at least one of the first liquid layer and the second liquid layer comprises glycerol, an alcohol solution, steam, or any combination thereof.

15. The method of claim 6, wherein at least one of the first liquid layer and the second liquid layer comprises a pretreatment chemical configured to have at least one of the following functions: inhibiting corrosion, texturing the first surface or the second surface, and increasing adhesion, the pretreatment chemical being selected from an organophosphonic acid, an organophosphinic acid, a coupling agent, a polymer, or a combination thereof.

16. The method of claim 6, wherein at least one of the first liquid layer and the second liquid layer comprises a pretreatment chemical configured to have at least one of the following functions: inhibiting corrosion, texturing the first surface or the second surface, and increasing adhesion, the pretreatment chemical being selected from an organophosphonic acid, an organophosphinic acid, a silane, a copolymer, or a combination thereof.

17. The method of claim 6, wherein the first liquid layer and the second liquid layer are applied to the first surface and the second surface by two or more applicators.

18. The method of claim 17, wherein the two or more applicators comprise a spray applicator with or without pulse emission, a rotary atomizer, an electrostatic applicator, a roller applicator, or any combination thereof.

19. The method of claim 17, wherein the two or more applicators comprise low pressure, high volume spray applicators or low pressure, low volume spray applicators.

20. The method of claim 17, wherein the two or more applicators are positioned in a continuous line.

21. The method of claim 17, wherein the two or more applicators are configured as two or more applicator baths.

22. The method of claim 1, wherein scanning a high energy beam across the first liquid layer comprises directing a beam of laser energy onto the first liquid layer.

23. The method of claim 22, wherein the laser energy beam is provided by a continuous laser or a pulsed laser.

24. The method of claim 22, wherein the beam of laser energy is provided by a single-pass structuring laser or a dual-pass structuring laser.

25. The method of claim 22, wherein the laser energy beam is provided by a nanosecond pulsed laser, a picosecond pulsed laser, or a femtosecond pulsed laser.

26. The method of claim 22, wherein the laser energy beam is provided by a laser having a continuous wave or a laser not having a continuous wave.

27. The method of claim 22, wherein the laser energy beam is provided by an ytterbium laser, an Nd-YAG laser, a CO2 laser, an excimer laser, or any combination thereof.

28. The method of claim 22, wherein the laser energy beam has a wavelength of 200 nm to 1500 nm.

29. The method of claim 6, wherein scanning the high energy beam across the first liquid layer comprises directing at least one beam of laser energy onto the first liquid layer, and wherein the method further comprises directing at least one additional beam of laser energy onto the second liquid layer.

30. The method of claim 1, wherein the first surface is an untreated first surface, wherein the untreated first surface has not been subjected to a wet processing step prior to directing the high energy beam onto the first surface.

31. The method of claim 30, wherein the untreated first surface has one or more of organic matter or inorganic residue thereon, and wherein the treated first surface is free of one or more of organic matter or inorganic residue.

32. The method of claim 30, wherein the untreated first surface has not been subjected to one or more wet processing steps selected from the group consisting of chemical etching, solvent cleaning, vapor degreasing, mechanical surface treatment, painting, and conversion coating.

33. The method of claim 30, wherein the untreated first surface has not been subjected to acidic or alkaline cleaning.

34. The method of claim 30, wherein the untreated first surface has not been subjected to polishing.

35. The method of claim 30, wherein the untreated first surface has not been subjected to one or more wet processing steps selected from mechanical surface polishing and chemical polishing.

36. The method of claim 30, wherein the untreated first surface has not been subjected to electrochemical polishing.

37. The method of claim 30, wherein the untreated first surface has not been subjected to surfactant cleaning.

38. The method of claim 30, wherein the untreated first surface corresponds to a rolled surface having a rolling lubricant thereon.

39. The method of claim 30, wherein directing a high energy beam onto the untreated first surface is a dry cleaning process, and wherein the treated first surface is a cleaned surface.

40. The method of claim 30, wherein directing a high energy beam onto the untreated first surface is a dry surface modification process, and wherein the treated first surface is an activated surface suitable for bonding with an adhesive.

41. The method of claim 1, wherein the first surface includes near-surface microstructure, and wherein directing the high-energy beam onto the first surface removes at least a portion of the near-surface microstructure.

42. The method of claim 41, wherein directing the high energy beam onto the first surface thermally modifies the near-surface microstructure.

43. The method of claim 1, wherein the treated first surface exhibits a dry static coefficient of friction of 0.1 to 0.

5.

44. An aluminum alloy product comprising: A rolled aluminum alloy substrate, comprising: a body, wherein the body comprises intermetallic particles and a matrix comprising aluminum alloy grains; a laser and liquid treated area covering the first portion of the body, wherein the laser and liquid treated area comprises: a laser and liquid treated subsurface layer, wherein the laser and liquid treated subsurface layer comprises a resolidified layer of an aluminum alloy that has been previously melted by a high energy beam, wherein the laser and liquid treated subsurface layer occupies a depth of 1 μm to 10 μm into the aluminum alloy product, and wherein a first intermetallic particle concentration in the laser and liquid treated subsurface layer is less than a second intermetallic particle concentration in the bulk; and A laser and liquid processed surface, wherein the laser and liquid processed surface is free of near-surface microstructure, and one or more of organic matter, inorganic residue, rolled-in oxide, or anodic oxide, and wherein the laser and liquid processed surface comprises a first oxide layer having a thickness of 10 nm to 300 nm, and the liquid comprises glycerol, an alcohol solution, vapor, or any combination thereof.

45. The aluminum alloy product of claim 44, wherein the aluminum alloy comprises a 5xxx series aluminum alloy, a 6xxx series aluminum alloy, or a 7xxx series aluminum alloy.

46. The aluminum alloy product of claim 44, wherein the concentration of magnesium in the aluminum alloy is less than 10 weight percent.

47. The aluminum alloy product of claim 44, wherein the magnesium concentration in the bulk is greater than the magnesium concentration in the laser and liquid treated subsurface layer, or wherein the zinc concentration in the bulk is greater than the zinc concentration in the laser and liquid treated subsurface layer.

48. The aluminum alloy product of claim 44, wherein the laser and liquid treated area exhibits a bond joint durability of from 45 cycles to 125 cycles tested according to FLTM BV 101-07 standard.

49. The aluminum alloy product of claim 44, wherein the aluminum alloy product does not include a functionalized layer thereon.

50. The aluminum alloy product of claim 44, wherein the aluminum alloy product does not include a phosphorus-containing organic acid coating thereon.

51. The aluminum alloy product of claim 44, further comprising a non-laser and liquid treated area covering the second portion of the body, wherein the non-laser and liquid treated area has not been subjected to a laser and liquid treatment process.

52. The aluminum alloy product of claim 51, wherein a first arithmetic mean height Spk of the laser and liquid treated areas is less than a second arithmetic mean height of the non-laser and liquid treated areas.

53. The aluminum alloy product of claim 44, wherein the laser and liquid treated areas exhibit an arithmetic mean height Sa of 0.1 μm to 10 μm.

54. The aluminum alloy product of claim 44, wherein the laser and liquid treated region exhibits a complexity Sdr of 0.1% to 80%.

55. The aluminum alloy product of claim 44, wherein the laser and liquid treated areas exhibit a surface stability of 3 months.

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