KR20220124242A - Heat-deformed oxide-based pretreatment of metal and method for manufacturing the same - Google Patents

Abstract

The present invention provides a corrosion-resistant metal substrate and a method for manufacturing the same by thermal deformation. The present invention provides a method of manufacturing a corrosion-resistant substrate by forming a pretreatment film on the surface of the metal substrate and heating the pretreated metal substrate. In particular, the metal substrate and/or the pretreated metal substrate according to the method of the present invention is one subjected to F heat treatment, T4 heat treatment, or T6 heat treatment.

Description

Heat-deformed oxide-based pretreatment of metal and method for manufacturing the same

This application claims priority to and claims the benefit of U.S. Provisional Patent Application No. 63/015,056, filed on April 24, 2020, the entire contents of which are incorporated herein by reference.

FIELD OF THE INVENTION The present invention relates generally to processing of metal substrates such as aluminum alloys. More particularly, the present invention relates to thermal modification of pretreated metal substrates.

Certain metallic articles, such as aluminum alloys, may benefit from pretreatment, for example, the application or manufacture of a pretreatment film on the surface of the metallic article. These advantages include bonding durability, color stability, ease of maintenance, aesthetics, health and safety, and low cost. However, it is difficult to fabricate an aluminum alloy coil with a pretreated film that meets the flexibility, durability and/or surface property requirements for downstream processing including bonding of aluminum alloy products. Moreover, conventional methods require, for example, to limit the high temperature exposure of the pretreated metal in order to avoid loss of the above-mentioned advantages. This limits the types of products that can be pretreated, such as the temper of aluminum alloys.

All embodiments of the invention are defined by the claims rather than this summary. This summary is a high-level overview of various aspects of the invention and introduces some of the concepts further described in the Detailed Description section below. This Summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used in isolation to determine the scope of the claimed subject matter. This subject matter should be understood with reference to the entire specification, some or all drawings, and the appropriate portion of each claim.

In one aspect, the present invention describes a method of making a corrosion resistant (corrosion resistant, 耐蝕性) substrate, the method comprising: providing a pretreated metal substrate by making a pretreatment film on the surface of the metal substrate; and heating the pretreated metal substrate at a first temperature to provide a corrosion-resistant substrate, wherein the first temperature is greater than 300° C., and the metal substrate and/or the pretreated metal substrate are subjected to F heat treatment, T4 heat treatment, or T6 heat treatment.

In some cases, the metal substrate comprises an aluminum alloy (eg, a 5xxx series aluminum alloy, a 6xxx series aluminum alloy, or a 7xxx series aluminum alloy). In some cases, the corrosion resistant substrate is T6 heat treated. In some cases, the pretreatment film includes an oxide layer. In some cases, the oxide layer includes aluminum oxide, silicon oxide, titanium oxide, chromium oxide, manganese oxide, nickel oxide, yttrium oxide, zirconium oxide, molybdenum oxide, or combinations thereof. In some cases, the process of making the pretreatment film includes applying an inorganic pretreatment composition to the surface of the metal substrate. In some cases, the process of making the pretreatment film includes anodizing the surface of the metal substrate. In some cases, the process of making the pretreatment film includes flame hydrolyzing the surface of the metal substrate. In some cases, the first temperature is between 300°C and 550°C. In some cases, the heating process includes heating the pretreated metal substrate at the first temperature for less than 30 minutes. Optionally, the heating process comprises further heating the pretreated metal substrate at the second temperature. In some cases, the second temperature is lower than the first temperature. In some cases, the second temperature is between 75°C and 250°C. In some cases, the heating process includes heating the pretreated metal substrate at the second temperature from 1 hour to 48 hours. In some cases, the metal substrate is a continuous coil.

In another aspect, the present invention describes a corrosion resistant coil comprising an aluminum alloy continuous coil, wherein the surface of the aluminum alloy continuous coil comprises an inorganic pretreatment film, and wherein the aluminum alloy continuous coil is F heat treated, T4 heat treated, or T6 heat treated. it has been heat treated. In some cases, the aluminum alloy continuous coil comprises a 5xxx series aluminum alloy, a 6xxx series aluminum alloy, or a 7xxx series aluminum alloy. In some cases, the inorganic pretreatment film includes an oxide layer. In some cases, the oxide layer includes aluminum oxide, silicon oxide, titanium oxide, chromium oxide, manganese oxide, nickel oxide, yttrium oxide, zirconium oxide, molybdenum oxide, or combinations thereof.

In another aspect, the present invention describes a method for manufacturing a corrosion-resistant substrate, the method comprising: providing a pretreated metal substrate by preparing a pretreatment film on the surface of the metal substrate; and heating the pretreated metal substrate at a first temperature to provide a corrosion resistant substrate, wherein the metal substrate and/or the pretreated metal substrate are F heat treated, and the corrosion resistant substrate is T5 heat treated, T6 heat treated, T61 heat treated, T7 heat treatment, T8x heat treatment, or T9 heat treatment.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
1 illustrates results from glow discharge optical emission spectroscopy (GDOES) analysis of corrosion-resistant substrates in accordance with certain aspects of the present invention.

A method of making a corrosion-resistant metal substrate, such as a corrosion-resistant aluminum alloy substrate, is described herein. The corrosion-resistant metal substrates described herein can be used, for example, to produce corrosion-resistant products with excellent surface quality and minimal surface disadvantages when compared to products made from metal substrates that have not been treated with the method according to the invention.

Various pretreatments are often applied to conventional processing of metal substrates such as aluminum alloys. In some conventional processing processes, a pretreatment film is prepared on one or more surfaces of a metal substrate by chemical or electrolytic modification. The pretreatment film can change the properties of the metal substrate, such as bond durability, adhesion, and corrosion rate. In the conventional method, the metal substrate is not subjected to thermal deformation after pretreatment. In particular, the conventional method avoids exposing the pretreatment film on the surface of the metal substrate to high temperatures (eg, temperatures higher than 400° C.). For example, conventional methods dry the pretreated surface at a temperature lower than 100°C. This is due to the common belief of those skilled in the art that exposure to high temperatures degrades the pretreatment film by, for example, burning the pretreatment film or otherwise reducing the effectiveness of the pretreatment film. Moreover, because of the commonly held belief that exposure to high temperatures provides no benefit, thermal deformation of metal substrates after pretreatment has been regarded as an unnecessary additional cost to be avoided.

Notwithstanding otherwise claimed prior beliefs, the methods herein intentionally include exposing the pretreatment film to high temperatures. The present invention provides a method of manufacturing a corrosion-resistant metal substrate by preparing a pretreatment film on the surface of the metal substrate, and heating the pretreated metal substrate to a temperature higher than 400°C. Exposure of the pretreatment film to high temperatures (eg, greater than 400° C.) according to the methods described herein does not degrade or adversely affect the pretreatment film. On the contrary, high temperature improves (ie, enhances) the properties of the pretreatment film. Heating the pretreated metal substrate according to the present invention results in drying and/or densification of the pretreatment film to improve the bonding durability, adhesion and/or corrosion resistance imparted by the pretreatment film.

Therefore, the corrosion-resistant substrate manufactured by the method described herein exhibits excellent physical properties such as bonding durability. Moreover, the method described herein is also suitable for coil-to-coil line and batch processing.

Definition and Description

As used herein, the terms “invention”, “this invention” and “invention” are intended to refer broadly to all subject matter of this patent application and the claims that follow. It is to be understood that statements containing these terms are not intended to limit the subject matter described herein or to limit the meaning or scope of the claims below.

In the present invention, reference is made to alloys identified by aluminum industry designations such as "series" or "7xxx". To understand the most commonly used numbering systems for naming and identifying aluminum and its alloys, see "International Alloy Designations and Chemical Composition Limits for Wrought Aluminum and Wrought Aluminum Alloys" or "Registration Record of See "Aluminum Association Alloy Designations and Chemical Compositions Limits for Aluminum Alloys in the Form of Castings and Ingot".

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

As used herein, a sheet (also referred to as a sheet plate) generally has a thickness of from about 4 mm to about 15 mm. For example, the sate may have a thickness of 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 11 mm, 12 mm, 13 mm, 14 mm or 15 mm.

As used herein, a sheet generally refers to an aluminum article having a thickness of less than about 4 mm, for example, a sheet is less than 4 mm, less than 3 mm, less than 2 mm, less than 1 mm, less than 0.5 mm; It may have a thickness of less than 0.3 mm or less than 0.1 mm.

As used herein, "bond durability" refers to the ability of an adhesive to bond two articles together to withstand cyclic mechanical stress after exposure to environmental conditions that initiate failure of the adhesive. Bonded products are exposed to environmental conditions until the bonding fails, whereas bonding durability is characterized by the number of cycles of mechanical stress applied to the bonded product.

As used herein, terms such as “cast metal product”, “cast product”, “cast aluminum alloy product”, etc. are interchangeable and refer to direct chill casting (direct cooling cavity- casting) or semi-continuous casting, continuous casting (including, for example, by use of twin belt casters, twin roll casters, twin block casters or other continuous casters), electromagnetic casting, hot top casting, or Refers to products made by the use of other casting methods.

As used herein, "coil to coil" line or "coil to coil processing" refers to a method of processing continuously on a continuous line, whereby the alloy processed in the processing method, such as an aluminum alloy, is processed from a coil. After being fed into the process, the coils are unwound during the treatment process and re-coiled after the treatment process is complete. Alloys processed by this treatment method are referred to herein as "continuous coils" or "aluminum alloy continuous coils".

In this application, reference is made to alloy conditions or heat treatment. For an understanding of the most commonly used alloy heat treatment theory, refer to "American National Standards (ANSI) H35 on Alloy and Temper Designation Systems". F Condition or heat treatment refers to the aluminum alloy as manufactured. The zero condition or heat treatment refers to an aluminum alloy after annealing. The T1 condition or heat treatment refers to an aluminum alloy that is cooled in hot working and aged naturally (eg, at room temperature). The T2 condition or heat treatment refers to an aluminum alloy cooled from hot working, cold working and natural aging. T3 condition or heat treatment refers to an aluminum alloy solution that has been heat treated, cold worked and naturally aged. T4 condition or heat treatment refers to an aluminum alloy solution that has been heat treated and subjected to natural aging. The T5 condition or heat treatment refers to an aluminum alloy cooled in hot working and artificially aged (at high temperature). The T6 condition or heat treatment refers to an aluminum alloy solution that has been heat treated and artificially aged. The T7 condition or heat treatment refers to an aluminum alloy solution that has been heat treated and artificially overaged. The T8x condition or heat treatment refers to an aluminum alloy solution that has been heat treated, cold worked and artificially aged. The T9 condition or heat treatment refers to an aluminum alloy solution that has been heat treated and artificially aged and cold worked.

As used herein, the meaning of the English article "a", "an", or "the" includes the singular and the plural unless the context clearly dictates otherwise.

As used herein, the modifier "about" is intended to include terms described without the word "about" (eg, "about 10" is intended to include "10").

As used herein, “room temperature” means from about 15°C to about 30°C, such as 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.

All ranges disclosed herein are to be understood to include any and all subranges subsumed therein. For example, a specified range from "1 to 10" should be considered to include all subranges between the minimum value of 1 and the maximum value of 10; That is, it is intended to include all subranges beginning with a minimum value of 1 or greater, such as 1 to 6.1, and ending with a maximum value of 10 or less, such as 5.5 to 10.

metal substrate

As mentioned, the present invention provides a method of making a corrosion-resistant metal substrate. More specifically, the present invention forms a pretreatment film on the surface of a metal substrate. The configuration of the metal substrate on which the pretreatment film is formed is not particularly limited. The pretreatment film can be applied to any suitable aluminum alloy, for example, a continuous coil of aluminum alloy. Suitable aluminum alloys include, for example, 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, 8xxx series aluminum alloys. .

By way of non-limiting example, exemplary 1xxx series aluminum alloys for use as metal substrates 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. In some cases, the aluminum alloy comprises at least 99.9% pure aluminum (e.g., at least 99.91%, at least 99.92%, at least 99.93%, at least 99.94%, at least 99.95%, at least 99.96%, at least 99.97%, at least 99.98%, more than 99.99% pure aluminum).

As a non-limiting example, 2xxx series aluminum alloys for use as metal substrates include AA2001, AA2002, AA2004, AA2005, AA2006, AA2007, AA2007A, AA2007B, AA2008, AA2009, AA2010, AA2011, AA2011A, AA2111, AA2111A, AA2111B, AA2012 , AA2013, AA2014, AA2014A, AA2214, AA2015, AA2016, AA2017, AA2017A, AA2117, AA2018, AA2218, AA2618, AA2618A, AA2219, AA2319, AA2419, AA2519, AA2021, AA2224, AA24, AA, AA2022, AA24, AA, AA2022, AA24, AA , AA2324, AA2424, AA2524, AA2624, AA2724, AA2824, AA2025, AA2026, AA2027, AA2028, AA2028A, AA2028B, AA2028C, AA2029, AA2030, AA2031, AA2032, AA1 AA 2039, AA 2038, AA2034, AA20 , AA2044, AA2045, AA2050, AA2055, AA2056, AA2060, AA2065, AA2070, AA2076, AA2090, AA2091, AA2094, AA2095, AA2195, AA2295, AA2196, AA2296, AA2097, AA2099, AA2197, AA2098, AA2197 AA2199.

By way of non-limiting example, 3xxx series aluminum alloys for use as metal substrates are AA3002, AA3102, AA3003, AA3103, AA3103A, AA3103B, AA3203, AA3403, AA3004, AA3004A, AA3104, AA3204, AA3304, AA3005, AA3005A, AA3105, AA3105A, AA3105, AA3005A , AA3105B, AA3007, AA3107, AA3207, AA3207A, AA3307, AA3009, AA3010, AA3110, AA3011, AA3012, AA3012A, AA3013, AA3014, AA3015, AA3016, AA3017, AA30, AA30 AA 30 AA 20 AA30, AA3026, AA 3025, AA3019, AA AA3065.

By way of non-limiting example, 4xxx series aluminum alloys for use as metal substrates include AA4004, AA4104, AA4006, AA4007, AA4008, AA4009, AA4010, AA4013, AA4014, AA4015, AA4015A, AA4115, AA4016, AA4017, AA4018, AA40 , AA4021, AA4026, AA4032, AA4043, AA4043A, AA4143, AA4343, AA4643, AA4943, AA4044, AA4045, AA4145, AA4145A, AA4046, AA4047, AA4047A, or AA4147.

As a non-limiting example, 5xxx series aluminum alloys for use as metal substrates include AA5182, AA5183, AA5005, AA5005A, AA5205, AA5305, AA5505, AA5605, AA5006, AA5106, AA5010, AA517110, AA5110A, AA5210, AA5310, AA5016, AA50 , AA5018, AA5018A, AA5019, AA5019A, AA5119, AA5119A, AA5021, AA5022, AA5023, AA5024, AA5026, AA5027, AA5028, AA5040, AA5140, AA5041, AA5450, AA 5049, AA5043, 249, AA 5054, AA5042, AA5043, 249 , AA5050A, AA5050C, AA5150, AA5051, AA5051A, AA5151, AA5251, AA5251A, AA5351, AA5451, AA5052, AA5252, AA5352, AA5154, AA5154A, AA5154B, AA5454 AA54, AA5554, AA54 AA54, AA5554, 5652 AA5154C, AA53 5652 , AA5954, AA5056, AA5356, AA5356A, AA5456, AA5456A, AA5456B, AA5556, AA5556A, AA5556B, AA5556C, AA5257, AA5457, AA5557, AA5657, AA5058, AA5657, AA5058, AA5180A, AA5059, AA18050 1835 70, AA5059, AA18050 , AA5283, AA5283A, AA5283B, AA5383, AA5483, AA5086, AA5186, AA5087, AA5187, or AA5088.

As a non-limiting example, a 6xxx series aluminum alloy for use as a metal substrate is AA6101, AA6101A, AA6101B, AA6201, AA6201A, AA6401, AA6501, AA6002, AA6003, AA6103, AA6005, AA6005A, AA6005B, 6305 AA6005C, AA6105. , AA6006, AA6106, AA6206, AA6306, AA6008, AA6009, AA6010, AA6110, AA6110A, AA6011, AA6111, AA6012, AA6012A, AA6013, AA6113, AA6014, AA6015, AA60, AA60, AA6019, 1860 AA60, AA6019, AA60 , AA6023, AA6024, AA6025, AA6026, AA6027, AA6028, AA6031, AA6032, AA6033, AA6040, AA6041, AA6042, AA6043, AA6151, AA6351, AA605651A, AA6451, AA60, AA60 AA1603, AA60, AA60 AA1603 , AA6360, AA6460, AA6460B, AA6560, AA6660, AA6061, AA6061A, AA6261, AA6361, AA6162, AA6262, AA6262A, AA6063, AA6063A, AA6463, AA6463A, AA60 AA6064 AA60 AA60 AA6763, A6968, , AA6081, AA6181, AA6181A, AA6082, AA6082A, AA6182, AA6091, or AA6092.

By way of non-limiting example, 7xxx series aluminum alloys for use as metal substrates are AA7011, AA7019, AA7020, AA7021, AA7039, AA7072, AA7075, AA7085, AA7108, AA7108A, AA7015, AA7017, AA7018, AA7019A, AA7025, AA7028 , AA7030, AA7031, AA7033, AA7035, AA7035A, AA7046, AA7046A, AA7003, AA7004, AA7005, AA7009, AA7010, AA7011, AA7012, AA7014, AA7016, AA7116, AA7029 AA712, AA70 , AA7034, AA7036, AA7136, AA7037, AA7040, AA7140, AA7041, AA7049, AA7049A, AA7149, AA7204, AA7249, AA7349, AA7449, AA7050, AA7050A, AA7056, AA 7055, AA7056, AA 7055, AA7250, AA 70 70 , AA7068, AA7168, AA7175, AA7475, AA7076, AA7178, AA7278, AA7278A, AA7081, AA7181, AA7185, AA7090, AA7093, AA7095, or AA7099.

By way of non-limiting example, 8xxx series aluminum alloys for use as metal substrates include AA8005, AA8006, AA8007, AA8008, AA8010, AA8011, AA8011A, AA8111, AA8211, AA8112, AA8014, AA8015, AA8016, AA8017, AA8018, AA1 , AA8021A, AA8021B, AA8022, AA8023, AA8024, AA8025, AA8026, AA8030, AA8130, AA8040, AA8050, AA8150, AA8076, AA8076A, AA8176, AA8077, AA8177, AA8079, 809.

While aluminum alloy articles are described throughout this specification, the methods and articles apply to all metal substrates. In some embodiments, the metal substrate is aluminum, aluminum alloy, magnesium, magnesium-based material, titanium, titanium-based material, copper, copper-based material, steel, steel-based material, bronze, bronze-based material, brass, brass-based material a material, composition, sheet used in the composition, or other suitable metal or combination of materials. Articles may include monolithic as well as non-monolithic materials, such as roll bond materials, clad materials, composite materials, or various other materials. In some embodiments, the metal substrate is a metal coil, metal strip, metal plate, metal sheet, metal sheet, metal billet, metal ingot, or other metal article.

Alloys may be formed by direct cold casting (including direct cold co-casting) or semi-continuous casting, continuous casting (including using twin belt casters, twin roll casters, block casters or other continuous casters), electromagnetic casting, hot top casting, or other It can be manufactured through a casting method.

The metal substrate may be made from an alloy of any heat treatment. In some embodiments, the metal substrate is an alloy subjected to F heat treatment, T4 heat treatment, or T6 heat treatment. As discussed below, the heat treatment of a metal substrate can be altered by the thermal strain described herein. In one embodiment of the method, for example, the metal substrate is provided with an F heat treatment, a pretreatment film is formed on the surface of the metal substrate, and the pretreatment metal substrate does not damage the pretreatment film and the final corrosion resistant substrate is T6 It is heated to heat treatment.

Pretreatment

The method of the present invention provides a pretreated metal substrate by forming a pretreatment film on the metal substrate. The pretreatment film in the present invention improves properties such as adhesion and/or corrosion resistance of a metal substrate on which the pretreatment film is formed on its surface.

A method of forming the pretreatment film on the surface of the metal substrate is not particularly limited, and any suitable method known in the art may be used. In some embodiments, preparing the pretreatment film may include applying a pretreatment composition (eg, an inorganic pretreatment composition) to the surface of the metal substrate. In some cases, the metallic substrate may be sprayed with a pretreatment composition (eg, an inorganic pretreatment composition) onto the surface of the metallic substrate. In some cases, the metal substrate may be immersed in a pretreatment composition (eg, an inorganic pretreatment composition). The pretreatment composition (eg, inorganic pretreatment composition) may be specially formulated to produce a pretreatment film on the surface of a metal substrate. For example, the pretreatment composition may include chromium, molybdenum, titanium, zirconium, manganese, or combinations thereof.

In some embodiments, preparing the pretreatment film may include anodizing the surface of the metal substrate. Anodizing may include, for example, contacting the surface of the metal substrate with an electrolyte solution and applying an electric current (eg, alternating current (AC) power and/or direct current (DC) power) to the metal substrate. In some cases, anodizing the metal substrate produces a pretreated metal substrate having a thin pretreatment film that may include an oxide layer. A suitable method for anodization is described in US Patent Application Publication No. 2020/0082972, which is incorporated herein by reference.

In some embodiments, preparing the pretreatment film may include an exothermic process. For example, the pretreatment film may be prepared by flame pyrolysis deposition. Flame pyrolytic deposition may include burning (eg, combustion) a metal article to form a deposit on the surface of the metal substrate. The composition of the deposit depends on the gas mixture and/or the metal compound, which can be specially formulated for flame pyrolysis deposition. In some cases, the deposits, which may include oxides, form the pretreatment film.

The composition or structure of the pretreatment film on the pretreated metal substrate is not particularly limited, and any pretreatment film known in the art may be prepared or used. Pretreatment films known in the art can be classified into organic pretreatment films, inorganic pretreatment films and combination pretreatment films. The organic pretreatment film includes an organic compound such as an organic polymer (ie, a carbon-containing compound). The inorganic pretreatment film includes an inorganic compound (ie, a non-carbon containing compound) such as a metal ion analogue and a metal coordination complex. The combination pretreatment film comprises an organic compound and an inorganic compound or an organic-inorganic compound comprising both organic and inorganic moieties.

In some embodiments, the pretreatment film produced by the methods disclosed herein is an organic pretreatment film. However, it is preferred if the pretreatment film is an inorganic pretreatment film or a combination pretreatment film. As described herein, thermal deformation (discussed below) of a metal substrate pretreated with an inorganic and/or combination pretreatment film surprisingly improves the properties (eg, adhesion, corrosion resistance) of the metal substrate. Conversely, the inventors have found that thermal deformation of a metal substrate pretreated with an organic pretreatment film may not improve the properties of the metal substrate (eg, it does not improve properties to the same extent). In some cases, thermal deformation of a metal substrate with an organic pretreatment film may also degrade the properties of the substrate. It is theorized that organic compounds present in conventional organic pretreatment films (eg, organic polymers) may undergo undesirable chemical reactions (eg, combustion) when subjected to the thermal strains described herein. Thus, in some embodiments of the method, the pretreatment film is not an organic pretreatment film (ie, a pretreatment film comprising only organic compounds).

In some cases, preparing a pretreatment film on the surface of a metal substrate includes creating an oxide layer on the surface. In other words, the pretreatment film may include an oxide layer. The pretreatment film may include, for example, an inorganic oxide layer. The oxide layer includes one or more oxides, such as metal oxides.

The composition of the oxide layer is not particularly limited and any suitable oxide layer known in the art may be used. For example, the oxide layer may include aluminum oxide (eg, Al ₂ O, AlO, and/or Al ₂ O ₃ ), silicon oxide (eg, SiO ₂ and/or SiO), titanium oxide (eg, , Ti ₂ O, TiO, Ti ₂ O ₃ , and/or TiO ₂ ), chromium oxide (eg CrO, Cr ₂ O ₃ , CrO ₂ and/or CrO ₅ ), manganese oxide (eg MnO, Mn ₃ O) ₄ , Mn ₂ O ₃ , MnO ₂ , MnO ₃ and/or Mn ₂ O ₇ ), nickel oxide (eg NiO and/or Ni ₂ O ₃ ), yttrium oxide (eg Y ₂ O3 ), zirconium oxide (eg, ZrO ₂ ), molybdenum oxide (eg, MoO ₂ and/or MoO ₃ ), or combinations thereof.

In some embodiments, the pretreatment film comprises an oxide layer of aluminum oxide. In some embodiments, the pretreatment film comprises an oxide layer of silicon oxide. In some embodiments, the pretreatment film comprises a combination of oxides. For example, the pretreatment film may include an oxide layer of titanium oxide and zirconium oxide.

Generally, the pretreatment film includes a thin layer on a portion (eg, at least a portion) of the surface of the metal substrate. In some cases, a pretreatment film may be formed on one surface of the metal substrate. In some cases, the pretreatment film may be formed on one or more surfaces of the metal substrate, for example two surfaces. In some cases, a pretreatment film is formed on all surfaces of the metal substrate.

The thickness of the pretreatment film may vary. As mentioned above, the pretreatment film is generally a thin layer. The thickness of the pretreatment film may range from 1 nm to 1000 nm. In some cases, the thickness of the pretreatment film is less than about 1000 nm, such as less than about 900 nm, less than about 800 nm, less than about 700 nm, less than about 600 nm, less than about 500 nm, less than about 400 nm, less than about 300 nm, about 200 nm. less than nm, or less than about 100 nm. For example, the thickness of the pretreatment film is from about 5 nm to about 1000 nm, from about 10 nm to about 900 nm, from about 20 nm to about 800 nm, or from about 30 nm to about 700 nm. In some embodiments, the thickness of the pretreatment film is about 1 nm, about 5 nm, about 10 nm, about 15 nm, about 20 nm, about 25 nm, about 30 nm, about 35 nm, about 40 nm, about 45 nm, about 50 nm, about 55 nm, about 60 nm, about 65 nm, about 70 nm, about 75 nm, about 80 nm, about 85 nm, about 90 nm, about 95 nm, about 100 nm, about 150 nm, about 200 nm, about 250 nm, about 300 nm, about 400 nm, about 500 nm, about 600, about 700 nm, about 750 nm, about 800 nm, about 850 nm, about 900 nm, about 950 nm, or about 1000 nm or the like can be anything in between.

In some cases, the pretreatment film on the pretreated metal substrate may consist of multiple layers. In particular, certain methods of making the pretreatment film may form distinct layers within the pretreatment film. For example, anodizing a metal substrate can include a barrier layer (composed of, for example, aluminum oxide, such as non-porous aluminum oxide) and a filamentary layer (eg, aluminum oxide, such as porous aluminum oxide). constituted) can be prepared. The properties of each layer can be controlled by the method of forming the pretreatment film (eg, anodization parameters or conditions).

The heat treatment of the substrate is generally not affected (eg, not altered) by forming the pretreatment film. That is, the pre-treated metal substrate is generally present with the same heat treatment as the metal substrate before the pre-treatment. In some embodiments, the pretreated metal substrate is an alloy of F heat treatment, T4 heat treatment, or T6 heat treatment. As noted below, the heat treatment of a metal substrate can be altered by the thermal strain described herein. In one embodiment, for example, the pretreated metal substrate is one subjected to an F heat treatment, and thermal deformation of the pretreated metal substrate forms a substrate of the T6 heat treatment.

thermal deformation

A method according to the present invention comprises heating a pretreated metal substrate to provide a corrosion resistant substrate. As described above, the conventional method of pretreating a metal substrate avoids exposing the metal substrate to high temperatures (eg, temperatures higher than 400° C.) after the pretreatment film is formed. Those skilled in the art believed that exposure to high temperatures degraded or otherwise reduced the effectiveness of the pretreatment film. On the other hand, in the method according to the present invention, heating the pretreated metal substrate further improves the pretreatment film.

Thermal deformation in the present invention generally includes heating the pretreated metal substrate at a first temperature, which is higher than that of conventional methods. In some embodiments, the first temperature is between 300 °C and 550 °C, such as between 300 °C and 540 °C, between 300 °C and 530 °C, between 300 °C and 520 °C, between 300 °C and 510 °C, between 300 °C and 500 °C, between 325 °C and 550 °C. °C, 325 °C to 540 °C, 325 °C to 530 °C, 325 °C to 520 °C, 325 °C to 510 °C, 325 °C to 500 °C, 350 °C to 550 °C, 350 °C to 540 °C, 350 °C to 530 °C, 350 °C to 520 °C, 350 °C to 510 °C, 350 °C to 500 °C, 375 °C to 550 °C, 375 °C to 540 °C, 375 °C to 530 °C, 375 °C to 520 °C, 375 °C to 510 °C, 375 °C to 500 °C, 400 °C to 550 °C, 400 °C to 540 °C, 400 °C to 530 °C, 400 °C to 520 °C, 400 °C to 510 °C, 400 °C to 500 °C, 425 °C to 550 °C, 425 °C to 540 °C °C, 425 °C to 530 °C, 425 °C to 520 °C, 425 °C to 510 °C, 425 °C to 500 °C, 450 °C to 550 °C, 450 °C to 540 °C, 450 °C to 530 °C, 450 °C to 520 °C, 450°C to 510°C, or 450°C to 500°C.

In terms of the upper limit, the first temperature can be less than 550°C, such as less than 540°C, less than 530°C, less than 520°C, less than 510°C, or less than 500°C. In terms of the lower limit, the first temperature can be greater than 300°C, such as greater than 325°C, greater than 350°C, greater than 375°C, greater than 400°C, greater than 425°C, or greater than 450°C.

In some cases, the first temperature is about 375 °C, about 385 °C, about 395 °C, about 400 °C, about 405 °C, about 410 °C, about 415 °C, about 420 °C, about 425 °C, about 430 °C, about 435 ℃, about 440℃, about 445℃, about 450℃, about 455℃, about 460℃, about 465℃, about 466℃, about 467℃, about 468℃, about 469℃, about 470℃, about 471℃ Approx. 472 °C, Approx. 473 °C, Approx. 474 °C, Approx. 475 °C, Approx. 476 °C, Approx. 477 °C, Approx. 478 °C, Approx. 479 °C, Approx. 480 °C, Approx. 481 °C, Approx. 482 °C, Approx. ℃, about 485℃, about 486℃, about 487℃, about 488℃, about 489℃, about 490℃, about 491℃, about 492℃, about 493℃, about 494℃, about 495℃, about 496℃ about 497 °C, about 498 °C, about 499 °C, about 500 °C, about 510 °C, about 520 °C, about 525 °C, about 530 °C, about 540 °C, or about 550 °C, or any temperature in between.

Thermal deformation of the present invention may include prolonged exposure to a high temperature, eg, a first temperature. Prolonged exposure to high temperatures may improve the pretreatment film, for example by (further) drying and/or densifying the pretreatment film. Accordingly, in some embodiments, the pretreated metal substrate may be heated at the first temperature for a period of time.

In some embodiments, the pretreated metal substrate is applied for 10 seconds to 30 minutes, such as 10 seconds to 25 minutes, 10 seconds to 20 minutes, 10 seconds to 15 minutes, 10 seconds to 10 minutes, 15 seconds to 30 minutes, 15 seconds to 25 minutes, 15 seconds to 20 minutes, 15 seconds to 15 minutes, 15 seconds to 10 minutes, 30 seconds to 30 minutes, 30 seconds to 25 minutes, 30 seconds to 20 minutes, 30 seconds to 15 minutes, 30 seconds to 10 minutes, 60 seconds to 30 minutes, 60 seconds to 25 minutes, 60 seconds to 20 minutes, 60 seconds to 15 minutes, 60 seconds to 10 minutes, 75 seconds to 30 minutes, 75 seconds to 25 minutes, 75 seconds to 20 minutes , 75 seconds to 15 minutes, 75 seconds to 10 minutes, 90 seconds to 30 minutes, 90 seconds to 25 minutes, 90 seconds to 20 minutes, 90 seconds to 15 minutes, or 90 seconds to 10 minutes. .

In terms of the upper limit, the pretreated metal substrate may be heated at the first temperature for less than 30 minutes, such as less than 25 minutes, less than 20 minutes, less than 15 minutes, or less than 10 minutes. In the lower aspect, the pretreated metal substrate may be heated at the first temperature for at least 10 seconds, such as at least 15 seconds, at least 30 seconds, at least 60 seconds, at least 75 seconds, or at least 90 seconds.

In some cases, for example, the pretreated metal substrate is at the first temperature for about 1 minute, about 2 minutes, about 3 minutes, about 4 minutes, about 5 minutes, about 6 minutes, about 7 minutes, about 8 minutes, about 9 minutes. minutes, or about 10 minutes, or any time in between.

In some embodiments, the first temperature may be maintained for a period of time by any suitable process. In some cases, heating may be continuously and/or continuously applied to the pretreated metal substrate for a period of time.

In some embodiments, the first temperature may not be maintained for a period of time. In some cases, for example, the pretreated metal substrate may be exposed to a first temperature and no further heating may be applied during that period such that the temperature to which the pretreated metal substrate is heated during that period is slightly reduced, such as less than 25 °C, less than 20 °C, less than 15 °C, less than 10 °C, less than 5 °C, less than 3 °C, less than 2 °C or less than 1 °C.

In some embodiments, thermal transformation comprises an additional heating step. For example, the pretreated metal substrate may be heated at a second temperature (eg, before and/or after being heated at the first temperature). In some cases, heating at a second temperature according to the method of the present invention further enhances the pretreatment film, for example by drying and/or densifying the pretreatment film. As a result, the corrosion-resistant substrate may exhibit improved adhesion, bond durability, and/or corrosion resistance.

The second temperature is generally a higher temperature compared to the conventional method. The second temperature may or may not be related to the first temperature. In some embodiments, for example, the second temperature is lower than the first temperature. In some embodiments, the first temperature and the second temperature are about the same.

In some embodiments, the second temperature is between 75°C and 250°C, such as between 75°C and 240°C, between 75°C and 230°C, between 75°C and 220°C, between 75°C and 210°C, between 75°C and 200°C, between 80°C and 250 °C, 80 °C to 240 °C, 80 °C to 230 °C, 80 °C to 220 °C, 80 °C to 210 °C, 80 °C to 200 °C, 85 °C to 250 °C, 85 °C to 240 °C, 85 °C , 85 °C to 220 °C, 85 °C to 210 °C, 85 °C to 200 °C, 90 °C to 250 °C, 90 °C to 240 °C, 90 °C to 230 °C, 90 °C to 220 °C, 90 °C to 210 °C °C to 200 °C, 95 °C to 250 °C, 95 °C to 240 °C, 95 °C to 230 °C, 95 °C to 220 °C, 95 °C to 210 °C, 95 °C to 200 °C, 100 °C to 250 °C, 100 °C to 240°C, 100°C to 230°C, 100°C to 220°C, 100°C to 210°C, or 100°C to 200°C. In some embodiments, the second temperature is between 150°C and 250°C, such as between 150°C and 240°C, between 150°C and 230°C, between 150°C and 220°C, between 150°C and 210°C, between 150°C and 200°C, 155°C. to 250 °C, 155 °C to 240 °C, 155 °C to 230 °C, 155 °C to 220 °C, 155 °C to 210 °C, 155 °C to 200 °C, 160 °C to 250 °C, 160 °C to 240 °C, 160 °C to 230 °C °C, 160 °C to 220 °C, 160 °C to 210 °C, 160 °C to 200 °C, 165 °C to 250 °C, 165 °C to 240 °C, 165 °C to 230 °C, 165 °C to 220 °C, 165 °C to 210 °C, 165 °C to 200 °C, 170 °C to 250 °C, 170 °C to 240 °C, 170 °C to 230 °C, 170 °C to 220 °C, 170 °C to 210 °C, 170 °C to 200 °C, 175 °C to 250 °C, 175 °C to 240 °C, 175 °C to 230 °C, 175 °C to 220 °C, 175 °C to 210 °C, 175 °C to 200 °C, 180 °C to 250 °C, 180 °C to 240 °C, 180 °C to 230 °C, 180 °C to 220 °C °C, 180 °C to 210 °C, or 180 °C to 200 °C.

In terms of the upper limit, the second temperature can be less than 250 °C, such as less than 240 °C, less than 230 °C, less than 220 °C, less than 210 °C, or less than 200 °C. In terms of the lower limit, the second temperature can be greater than 75°C, such as greater than 80°C, greater than 85°C, greater than 90°C, greater than 95°C, or greater than 100°C.

In some cases, the second temperature is about 90 °C, about 91 °C, about 92 °C, about 93 °C, about 94 °C, about 95 °C, about 96 °C, about 97 °C, about 98 °C, about 99 °C, 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℃, Approx. 113 °C, Approx. 114 °C, Approx. 115 °C, Approx. 116 °C, Approx. 117 °C, Approx. 118 °C, Approx. 119 °C, Approx. 120 °C, Approx. 121 °C, Approx. 122 °C, Approx. 123 °C, Approx. ℃, 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 °C, about 139 °C, about 140 °C, about 141 °C, about 142 °C, about 143 °C, about 144 °C, about 145 °C, about 146 °C, about 147 °C, about 148 °C, about 149 °C, or about 150 °C, or any temperature in between.

As with the first temperature, in some cases, the pretreated metal substrate may be heated at the second temperature for an extended period of time. In some embodiments, the pretreated metal substrate is heated at the second temperature for a period longer than the time exposed to the first temperature. In some embodiments, the preheated metal substrate is heated at the second temperature for a period less than the time it is exposed to the first temperature. In some embodiments, the pretreated metal substrate is exposed to the first temperature and the second temperature for approximately the same amount of time.

In some embodiments, the pre-treated metal substrate is between 1 hour and 48 hours, such as between 1 hour and 42 hours, between 1 hour and 38 hours, between 1 hour and 34 hours, between 1 hour and 30 hours, between 2 hours and 48 hours, 2 hours to 42 hours, 2 hours to 38 hours, 2 hours to 34 hours, 2 hours to 30 hours, 4 hours to 48 hours, 4 hours to 42 hours, 4 hours to 38 hours, 4 hours to 34 hours, 4 hours to 30 hours, 8 hours to 48 hours, 8 hours to 42 hours, 8 hours to 38 hours, 8 hours to 34 hours, 8 hours to 30 hours, 12 hours to 48 hours, 12 hours to 42 hours, 12 hours to 38 hours , 12 hours to 34 hours, 12 hours to 30 hours, 18 hours to 48 hours, 18 hours to 42 hours, 18 hours to 38 hours, 18 hours to 34 hours, 18 hours to 30 hours, 22 hours to 48 hours, 22 heated at the second temperature for a period of time from 42 hours to 42 hours, 22 hours to 38 hours, 22 hours to 34 hours, or 22 hours to 30 hours.

In terms of the upper limit, the pretreated metal substrate may be heated at the second temperature for less than 48 hours, such as less than 42 hours, less than 38 hours, less than 34 hours, or less than 30 hours. In terms of the lower limit, the pretreated metal substrate may be heated at the second temperature for at least 1 hour, such as at least 2 hours, at least 4 hours, at least 8 hours, at least 12 hours, at least 18 hours, or at least 22 hours.

In some cases, for example, the pretreated metal substrate is about 18 hours, about 19 hours, about 20 hours, about 21 hours, about 22 hours, about 23 hours, about 24 hours, about 25 hours, about 26 hours, about 27 hours. hours, about 28 hours, about 29 hours, about 30 hours, about 31 hours, or about 32 hours, or any time in between, at the second temperature.

Like the first temperature, in some embodiments, the second temperature may be maintained for a period of time by a suitable heating process. In some cases, for example, heating may be continuously and/or continuously applied to the pretreated metal substrate for a period of time. In some embodiments, the second temperature may not be maintained for a period of time. In some cases, for example, the pretreated metal substrate may be exposed to a second temperature, and the temperature to which the pretreated metal substrate is heated for a period of time is, for example, less than 25°C, less than 20°C, less than 15°C, 10°C. No further heating may be applied for a period of time to allow a slight decrease of less than, less than 5°C, less than 3°C, less than 2°C, or less than 1°C.

Thermal deformation according to the method of the present invention may artificially age the pretreated metal substrate. That is, the corrosion-resistant substrate produced by the method of the present invention may be an artificially aged alloy. Artificial aging may be achieved, for example, by heating the pretreated metal substrate only at a first temperature and/or by heating the pretreated metal substrate at both the first temperature and the second temperature.

By artificially aging the pretreated metal substrate, the thermal deformation in the present invention produces a corrosion-resistant substrate with a heat treatment different from the metal substrate and/or the pretreated metal substrate. In some embodiments, for example, the metal substrate is an F heat treated or a T4 heat treated, and thermal deformation produces the substrate with a T6 heat treatment. A further discussion of the heat treatment of corrosion resistance properties is given below.

corrosion-resistant substrate

The method according to the invention produces a corrosion-resistant substrate. In particular, the method produces a corrosion resistant substrate with a pretreatment film (eg, an improved pretreatment film such as a dried pretreatment film or a densified pretreatment film). The pretreatment film imparts desirable properties such as corrosion resistance and/or increased adhesion to corrosion resistant substrates. As a result of the method according to the invention, the corrosion-resistant substrate exhibits good bonding durability, adhesion and/or corrosion resistance.

In some embodiments, thermal deformation does not alter (eg, chemically change) the pretreatment film. In some cases, for example, the chemical composition of the pretreatment film is substantially unaltered by thermal deformation. In some cases, thermal deformation dries the pretreatment film (eg, absorbs and/or removes absorbed moisture). The pretreatment film of the corrosion-resistant substrate includes an oxide layer. For example, the pretreatment film of the corrosion resistant substrate may include an inorganic oxide layer. The oxide layer includes one or more oxides, such as metal oxides. In particular, the pretreatment film of the corrosion-resistant substrate may include any oxide as described above or a combination thereof.

In some cases, exposing an aluminum alloy to high temperatures strengthens the surface of certain alloying elements. For example, high temperatures typically cause surface hardening of magnesium and/or silicon, which can contribute to corrosion. Surface hardening of these and other elements is not an issue with respect to the thermal deformation of the present invention, as pretreatment films (eg, oxide layers) can act as barriers.

In some cases, the physical structure of the pretreatment film after thermal deformation remains unchanged compared to the physical structure of the pretreatment film prior to thermal deformation as described herein. In some cases, thermal deformation forms metal-oxide bridges to form a dense anhydrous oxide film. As mentioned above, the pretreatment film on the pretreated metal substrate may consist of multiple layers. This layer can remain intact even after thermal deformation. For example, a corrosion-resistant substrate comprises a pretreatment film comprising a barrier layer (e.g., composed of aluminum oxide, such as non-porous aluminum oxide) and a filamentary layer (e.g., composed of aluminum oxide, such as porous aluminum oxide) can do.

As mentioned above, thermal deformation can artificially age the pretreated metal substrate. So, the corrosion-resistant substrate can be subjected to a heat treatment corresponding to an artificially aged alloy. In some embodiments, the corrosion resistant substrate may be subjected to a T5 heat treatment, a T6 heat treatment, a T61 heat treatment, a T7 heat treatment, a T8x heat treatment, or a T9 heat treatment. In some cases, a particularly corrosion resistant substrate may be subjected to a T6 heat treatment.

Use of corrosion-resistant substrate

Corrosion resistant substrates made in accordance with the present invention can be used to produce articles, including articles for use in automotive, electronic, and transportation applications, such as commercial vehicle, aircraft or rail applications, among others. The continuous coils and methods described herein provide articles with desired surface properties for a variety of applications. The articles described herein may have high strength, high deformability (elongation, stamping, shaping, formability, bendability or hot formability) and/or high corrosion resistance. Preparing the corrosion-resistant substrate as a continuous coil produces a deformable product without compromising the pretreatment.

According to one aspect of the present invention, the corrosion resistant substrate may be coated such as zinc-phosphating and electrocoating (E-coating). Corrosion resistant substrates exhibit improved coating adhesion compared to continuous coils without pretreatment film.

According to some further aspects of the present invention, the corrosion resistant substrate exhibits a high level of adhesion of a laminate or lacquer film on the surface of the continuous coil. Additionally, laminates and lacquers can be cured after application at temperatures up to about 230°C. Corrosion resistant substrates are not damaged by the high temperatures used in certain downstream processing of aluminum alloy products, providing a heat resistant pretreatment for aluminum alloy products.

Also in some aspects of the invention, the corrosion-resistant substrate exhibits excellent bond durability.

In some embodiments, corrosion-resistant substrates can be used for chassis, cross members, and internal chassis components (including but not limited to all components between two C channels of a commercial vehicle chassis) to achieve strength, such that high tensile steel Acts as a substitute for all or part of In certain aspects, the corrosion-resistant substrate can be used in automotive body parts such as bumpers, side beams, roof beams, cross beams, column reinforcements (eg A-pillars, B-pillars and C-pillars), interior panels, side panels, floors It can be used to manufacture automotive body parts products such as panels, tunnels, structural panels, reinforcement panels, interior hoods or trunk lid panels. The corrosion-resistant substrates of the present invention may also be used in aircraft or rail vehicle applications, for example to fabricate exterior and interior panels.

In some embodiments, the corrosion-resistant substrate may also be used to manufacture housings for electronic devices, including cell phones and tablet computers. For example, corrosion-resistant substrates can be used to prepare housings for the outer casings of cell phones (eg smartphones) and tablet bottom chassis. Exemplary consumer electronic products include cell phones, audio devices, video devices, cameras, laptop computers, desktop computers, tablet computers, televisions, displays, consumer electronics, video playback and recording devices, and the like. Exemplary consumer electronic product components include an outer housing (eg, a front) and an inner component for the consumer electronic product.

The corrosion resistant substrate may be used for any other desired application.

Examples

Example 1 is a method of manufacturing a corrosion-resistant substrate, the method comprising the steps of forming a pre-treatment film on the surface of the metal substrate to provide a pre-treated metal substrate, and heating the pre-treated metal substrate at a first temperature to provide a corrosion-resistant substrate includes; The first temperature is greater than 300° C., and the metal substrate and/or the pretreated metal substrate are F heat treated, T4 heat treated, or T6 heat treated.

Example 2 is the method of any preceding or subsequent example, wherein the metal substrate comprises an aluminum alloy.

Example 3 is the method of any preceding or subsequent example, wherein the metal substrate comprises a 5xxx series aluminum alloy, a 6xxx series aluminum alloy, or a 7xxx series aluminum alloy.

Example 4 is the method of any preceding or subsequent example, wherein the corrosion resistant substrate is T6 heat treated.

Example 5 is the method of any preceding or subsequent illustration, wherein the pretreatment film comprises an oxide layer.

Example 6 is the method of any preceding or subsequent illustration, wherein the oxide layer comprises aluminum oxide, silicon oxide, titanium oxide, chromium oxide, manganese oxide, nickel oxide, yttrium oxide, zirconium oxide, molybdenum oxide, or a combination thereof. do.

Example 7 is the method of any preceding or subsequent example, wherein preparing the pretreatment film comprises applying an inorganic pretreatment composition to the surface of the metal substrate.

Example 8 is the method of any preceding or subsequent example, wherein preparing the pretreatment film includes anodizing the surface of the metal substrate.

Example 9 is the method of any preceding or subsequent example, wherein preparing the pretreatment film comprises flame hydrolyzing the surface of the metal substrate.

Example 10 is the method of any preceding or subsequent illustration, wherein the first temperature is between 300°C and 550°C.

Example 11 is the method of any preceding or subsequent example, wherein the heating step includes heating the pretreatment metal substrate at a first temperature for less than 30 minutes.

Example 12 is the method of any preceding or subsequent example, wherein the heating further comprises heating the pretreated metal substrate at a second temperature.

Example 13 is the method of any preceding or subsequent example, wherein the second temperature is lower than the first temperature.

Example 14 is the method of any preceding or subsequent example, wherein the second temperature is between 75°C and 250°C.

Example 15 is the method of any preceding or subsequent example, wherein the heating step includes heating the pretreated metal substrate at the second temperature for 1 hour to 48 hours.

Example 16 is the method of any preceding or subsequent example, wherein the metal substrate is a continuous coil.

Example 17 is a corrosion-resistant coil including an aluminum alloy continuous coil, wherein the surface of the aluminum alloy continuous coil includes an inorganic pretreatment film, and the aluminum alloy continuous coil is subjected to F heat treatment, T4 heat treatment, or T6 heat treatment.

Example 18 is the method of any preceding or subsequent example, wherein the aluminum alloy continuous coil comprises a 5xxx series aluminum alloy, a 6xxx series aluminum alloy, or a 7xxx series aluminum alloy.

Example 19 is the method of any preceding or subsequent illustration, wherein the inorganic pretreatment film comprises an oxide layer.

Example 20 is the corrosion resistant coil of the method of any preceding or subsequent example, wherein the oxide layer is aluminum oxide, silicon oxide, titanium oxide, chromium oxide, manganese oxide, nickel oxide, yttrium oxide, zirconium oxide, molybdenum oxide, or a combination thereof. includes

Example 21 is a method of manufacturing a corrosion-resistant substrate, the method comprising a table of a metal substrate

providing a pretreated metal substrate by preparing a pretreatment film on a surface thereof and heating the pretreated metal substrate at a first temperature to provide a corrosion resistant substrate; The metal substrate and/or the pre-treated metal substrate is F heat-treated, and the corrosion-resistant substrate is T5 heat treatment, T6 heat treatment, T61 heat treatment, T7 heat treatment, T8x heat treatment, and T9 heat treatment.

Example

The following examples do not constitute any limitation to the present invention, but serve to further illustrate the present invention. On the other hand, it should be clearly understood that, after reading the description of the present specification, various embodiments, modifications and equivalents thereof can be devised by those skilled in the art without departing from the spirit of the present invention.

Example 1: Bonding Durability Test

As noted above, the thermal deformation methods described herein produce corrosion-resistant substrates that exhibit excellent bonding durability. This example serves to illustrate the improvement of bond durability of corrosion-resistant substrates prepared according to the methods described herein compared to metal substrates that have not been thermally deformed and pretreated according to conventional methods.

In order to test the properties of the corrosion-resistant substrate, a plurality of samples of the corrosion-resistant substrate were prepared according to the method according to the present invention using AA7075 aluminum alloy. Each sample tested is shown in Table 1. As shown in Table 1, samples containing various pretreatment methods and various components were prepared. In addition, samples were prepared from various heat treatments as shown in Table 1. Each sample was subjected to heat deformation as follows: each sample was heated at 485° C. for 5 minutes and then at 125° C. for 24 hours. After this thermal deformation, each sample was subjected to T6 heat treatment.

As shown in Table 1, several comparative samples (Comparative Examples 1-7) were also prepared and tested. Comparative samples were prepared by preparing a pretreatment film. These samples were not subjected to thermal deformation.

Table 1

A bonding durability test was performed on the above samples and comparative examples. In this test, six lap joint/bond sets of each sample were bolted in sequence and placed vertically in a 90% relative humidity (RH) humidity cabinet. The temperature was maintained at 50°C. A force load of 2.4 kN was applied to the bond sequence. The bond durability test is a periodic exposure test for up to 60 cycles. Each cycle lasts 24 hours. In each cycle, the bonds were exposed to a humidity cabinet for 22 h, followed by immersion in 5% sodium chloride (NaCl) for 15 min and finally air-dried for 105 min. If any of the four joints break, testing for that particular set of joints is stopped and marked as a joint failure. For the present invention, completion of 45 cycles without joint failure indicates that the joint set passed the joint durability test. When 60 cycles are complete, the test is stopped.

The bonding durability test results are shown in Table 2 below. In Table 2 above, each joint is numbered from 1 to 6, and when vertically aligned, joint 1 is the top joint and joint 6 is the bottom joint. Unless otherwise specified, the number of cells indicates the number of successful cycles before interruption. An asterisk ("*") next to the number indicates that the joint was not broken but the test was interrupted. The results are summarized in Table 2 below:

Table 2

Exemplary corrosion-resistant substrates subjected to thermal deformation according to the present invention exhibited excellent bonding durability while passing the tests except for three samples (Sample 5, Sample 12, and Sample 13). In particular, two of the three samples that did not pass the durability test contained organic pretreatment films. The comparative substrates exhibited relatively poorer bond durability, and each comparative substrate failed the durability test.

Example 2: Bonding Durability Test

This embodiment further exemplifies the improvement of the bonding durability of the corrosion-resistant substrate according to the present invention compared to a metal substrate that has been pretreated and not thermally deformed according to a conventional method.

Several samples of corrosion-resistant substrates were prepared in accordance with the present invention using AA7075 aluminum alloy to test the properties of the corrosion-resistant substrates. Each sample tested is shown in Table 3. As detailed in Table 3, samples were prepared by etching the samples with acid and applying various titanium/zirconium pretreatments (Gardobond 4591 from Chemetall GmbH, Frankfurt, Germany). Each sample was prepared in an initial F heat treatment. Each sample was heat deformed to adjust the heat treatment as indicated in Table 3.

Table 3

The above samples were tested for bonding durability. In this test, six lap joint/bond sets of each sample were bolted in sequence and placed vertically in a 90% relative humidity (RH) humidity cabinet. The temperature was maintained at 50°C. A force load of 2.4 kN was applied to the bond sequence. The bond durability test is a periodic exposure test for up to 60 cycles. Each cycle lasts 24 hours. In each cycle, the bonds were exposed to a humidity cabinet for 22 h, followed by immersion in 5% sodium chloride (NaCl) for 15 min and finally air-dried for 105 min. If any of the four joints fails, the test for that particular set of joints is stopped and marked as a joint failure. For the present invention, completion of 45 cycles without joint failure indicates that the joint set passed the joint durability test. The test is stopped at the completion of 60 cycles. The results of the bond durability test are shown in Table 4 below. In Table 4, each joint is numbered 1-6, with joint 1 being the top joint and joint 6 being the bottom joint when aligned vertically. Unless otherwise specified, the number in the cell represents the number of successful cycles prior to interruption. An asterisk ("*") next to the number indicates that the joint was not broken but the test was interrupted. The results are summarized in Table 4 below:

Table 4

Exemplary corrosion-resistant substrates subjected to thermal deformation according to the present invention exhibited excellent bonding durability while passing all tests except for one sample (Sample 17).

Example 3: GDOES Depth Profiling

Several samples of corrosion-resistant substrates were prepared according to the present invention using AA7075 aluminum alloy to test the properties of the corrosion-resistant substrates. Each sample tested is shown in Table 5. As detailed in Table 5, samples were prepared by etching the samples with acid and applying various titanium/zirconium pretreatments (Gardobond 4591 from Chemetall GmbH, Frankfurt, Germany). Each sample was prepared in an initial F heat treatment. Each sample was heat deformed to adjust the heat treatment as indicated in Table 5.

Table 5

Glow discharge optical emission spectroscopy (GDOES) was applied to each sample to analyze the surface and depth profiles. GDOES provides a quantitative depth distribution of elements in a thin surface film of each sample. The results of GDOES depth profiling are shown in Fig. 1, which shows that the sample surface is rich in copper and silicon. With respect to copper, samples 25 and 26 showed a profile similar to the presence of copper enrichment after 12 seconds of sputtering. Regarding silicon, sample 25 had a higher but thinner silicon concentration than sample 26, which may be due to the difference in acid etching between the two samples.

Claims (21)

A method of manufacturing a corrosion-resistant substrate, comprising:
The method comprises the steps of forming a pretreatment film on the surface of the metal substrate to provide a pretreated metal substrate; and
heating the pretreated metal substrate at a first temperature to provide a corrosion resistant substrate;
The first temperature is higher than 300 ℃,
The metal substrate and / or the pre-treated metal substrate is F heat treatment, T4 heat treatment, or T6 heat treatment, the method of manufacturing a corrosion-resistant substrate. The method of claim 1 , wherein the metal substrate comprises an aluminum alloy. The method of claim 2 , wherein the metal substrate comprises a 5xxx series aluminum alloy, a 6xxx series aluminum alloy, or a 7xxx series aluminum alloy. The method of claim 1 , wherein the corrosion-resistant substrate is T6 heat treated. The method of claim 1 , wherein the pretreatment film comprises an oxide layer. 6. The corrosion-resistant substrate of claim 5, wherein the oxide layer comprises aluminum oxide, silicon oxide, titanium oxide, chromium oxide, manganese oxide, nickel oxide, yttrium oxide, zirconium oxide, molybdenum oxide, or combinations thereof. manufacturing method. The method of claim 1 , wherein the process of forming the pretreatment film comprises applying an inorganic pretreatment composition to the surface of the metal substrate. The method of claim 1 , wherein the step of forming the pretreatment film comprises anodizing the surface of the metal substrate. The method of claim 1 , wherein the step of forming the pretreatment film comprises flame hydrolyzing the surface of the metal substrate. The method of claim 1, wherein the first temperature is 300°C to 550°C. The method of claim 1 , wherein the heating step comprises heating the pretreated metal substrate at the first temperature for less than 30 minutes. The method of claim 1 , wherein the heating step further comprises heating the pretreated metal substrate at a second temperature. The method of claim 12 , wherein the second temperature is lower than the first temperature. The method of claim 12, wherein the second temperature is 75°C to 250°C. The method of claim 12 , wherein the heating step comprises heating the pretreated metal substrate at the second temperature for 1 hour to 48 hours. The method of claim 1 , wherein the metal substrate is a continuous coil. A corrosion-resistant coil comprising an aluminum alloy continuous coil, comprising:
The aluminum alloy continuous coil comprises an inorganic pretreatment film,
The aluminum alloy continuous coil is F heat treatment, T4 heat treatment or T6 heat treatment, corrosion resistance coil. The corrosion resistant coil of claim 17 , wherein the aluminum alloy continuous coil comprises a 5xxx series aluminum alloy, a 6xxx series aluminum alloy, or a 7xxx series aluminum alloy. 18. The coil of claim 17, wherein the inorganic pretreatment film comprises an oxide layer. The corrosion resistant coil of claim 19 , wherein the oxide layer comprises aluminum oxide, silicon oxide, titanium oxide, chromium oxide, manganese oxide, nickel oxide, yttrium oxide, zirconium oxide, molybdenum oxide, or combinations thereof. A method of manufacturing a corrosion-resistant substrate, the method comprising:
providing a pretreated metal substrate by forming a pretreatment film on the surface of the metal substrate; and
heating the pretreated metal substrate at a first temperature to provide a corrosion-resistant substrate;
The metal substrate and / or the pre-treated metal substrate is F heat-treated,
The corrosion-resistant substrate is T5 heat treatment, T6 heat treatment, T61 heat treatment, T7 heat treatment, T8x heat treatment, or T9 heat treatment, the method of manufacturing a corrosion resistant substrate.

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