PATENT DOCUMENT

Publication Number: US-9487879-B2
Application Number: US-201514694971-A
Country: US
Kind Code: B2

Title: Anodized films with branched pore structures

Abstract:
The embodiments described herein relate to anodizing and anodized films. The methods described can be used to form opaque and white anodized films on a substrate. In some embodiments, the methods involve forming anodized films having branched pore structures. The branched pore structure provides a light scattering medium for incident visible light, imparting an opaque and white appearance to the anodized film. In some embodiments, the methods involve infusing metal complex ions within pores of an anodized. Once within the pores, the metal complex ions undergo a chemical change forming metal oxide particles. The metal oxide particles provide a light scattering medium for incident visible light, imparting an opaque and white appearance to the anodized film. In some embodiments, aspects of the methods for creating irregular or branched pores and methods for infusing metal complex ions within pores are combined.

Claims:
What is claimed is: 
     
       1. A protective film on a metal part, the protective film comprising:
 a barrier layer having an exterior surface corresponding to an exterior surface of the metal part, the barrier layer having branched structures positioned only within the barrier layer and having substantially no anodic pores, wherein the branched structures are arranged in a branching pattern that diffusely reflects visible wavelengths of light incident on the exterior surface and imparts a white appearance to the barrier layer; and 
 a porous anodic layer positioned adjacent the metal part and providing structural support for the barrier layer. 
 
     
     
       2. The protective film of  claim 1 , wherein the porous anodic layer comprises pores arranged in parallel with top ends adjacent to the branched structures and bottom ends adjacent to an underlying metal surface of the metal part. 
     
     
       3. The protective film of  claim 1 , wherein the barrier layer has indented portions on the exterior surface of the barrier layer. 
     
     
       4. The protective film of  claim 1 , wherein the branched structures are formed through an entire thickness of the barrier layer. 
     
     
       5. The protective film of  claim 1 , wherein a thickness of the porous anodic layer is greater than a thickness of the barrier layer. 
     
     
       6. The protective film of  claim 1 , wherein the porous anodic layer includes anodic pores having terminal ends adjacent the metal part, wherein at least some of the terminal ends have bulbous shapes. 
     
     
       7. The protective film of  claim 6 , wherein the bulbous-shaped terminal ends provide a second light scattering medium that contributes a white appearing aspect to the protective film. 
     
     
       8. The protective film of  claim 1 , wherein the porous anodic layer includes anodic pores having irregularly shaped pore walls that contributes a white appearing aspect to the protective film. 
     
     
       9. The protective film of  claim 1 , wherein the barrier layer has an average thickness of about 1 micrometer. 
     
     
       10. An enclosure for an electronic device, the enclosure comprising:
 a protective film positioned on a surface of a metal substrate, the protective film comprising:
 a porous anodic layer adjacent the surface of the metal substrate; and 
 a barrier layer positioned on the porous anodic layer, the barrier layer having branched structures positioned only within the barrier layer, wherein the branched structures are arranged in a branching pattern that diffusely reflects visible wavelengths of light incident on the protective film, thereby imparting a white appearance to the protective film. 
 
 
     
     
       11. The enclosure of  claim 10 , wherein the barrier layer has substantially no anodic pores. 
     
     
       12. The enclosure of  claim 10 , wherein anodic pores of the porous anodic layer are substantially parallel with respect to each other and are substantially perpendicular with respect to an external surface of an external surface of the protective film. 
     
     
       13. The enclosure of  claim 10 , wherein a thickness of the porous anodic layer is greater than a thickness of the barrier layer. 
     
     
       14. The enclosure of  claim 10 , wherein some of the branched structures have an elongated shape. 
     
     
       15. The enclosure of  claim 10 , wherein the porous anodic layer includes anodic pores having terminal ends adjacent the metal substrate, wherein at least some of the terminal ends have bulbous shapes. 
     
     
       16. The enclosure of  claim 15 , wherein diameters of the bulbous-shaped terminal ends are greater than diameters of remaining portions of the anodic pores. 
     
     
       17. The enclosure of  claim 10 , wherein the porous anodic layer includes anodic pores, an average length of the branched structures less than an average length of the anodic pores. 
     
     
       18. A metal oxide film covering a surface of a substrate, the metal oxide film comprising:
 a porous anodic layer adjacent the surface of the substrate, the porous anodic layer having anodic pores with metal oxide particles positioned therein; and 
 a barrier layer adjacent the porous anodic layer, the barrier layer having branched structures positioned only within the barrier layer and having substantially no anodic pores, the branched structures arranged in a branching pattern that diffusely reflects visible wavelengths of light incident on the metal oxide film and imparts a white appearance to the barrier layer. 
 
     
     
       19. The metal oxide film of  claim 18 , wherein the metal oxide particles diffusely reflect visible light that reach the metal oxide particles imparting a white appearance to the porous anodic layer. 
     
     
       20. The metal oxide film of  claim 18 , wherein the metal oxide particles comprise titanium oxide particles.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application is a continuation of U.S. application Ser. No. 14/040,518, filed Sep. 27, 2013, entitled “METHODS FOR FORMING WHITE ANODIZED FILMS BY FORMING BRANCHED PORE STRUCTURES”, the content of which is incorporated herein by reference in its entirety for all purposes. 
    
    
     FIELD 
     The described embodiments relate to anodized films and methods for forming anodized films. More specifically, methods for providing anodized films having opaque and white appearances are described. 
     BACKGROUND 
     Anodizing is an electrochemical process that thickens and toughens a naturally occurring protective oxide on a metal surface. An anodizing process involves converting part of a metal surface to an anodic film. Thus, an anodic film becomes an integral part of the metal surface. Due to its hardness, an anodic film can provide corrosion resistance and surface hardness for an underlying metal. In addition, an anodic film can enhance a cosmetic appearance of a metal surface. Anodic films have a porous microstructure that can be infused with dyes. The dyes can add a particular color as observed from a top surface of the anodic film. Organic dyes, for example, can be infused within the pores of an anodic film to add any of a variety of colors to the anodic film. The colors can be chosen by tuning the dyeing process. For example, the type and amount of dye can be controlled to provide a particular color and darkness to the anodic film. 
     Conventional methods for coloring anodic films, however, have not been able to achieve an anodic film having a crisp and saturated looking white color. Rather, conventional techniques result in films that appear to be off-white, muted grey, milky white, or slightly transparent white. In some applications, these near-white anodic films can appear drab and cosmetically unappealing in appearance. 
     SUMMARY 
     This paper describes various embodiments that relate to anodic or anodized films and methods for forming anodic films on a substrate. Embodiments describe methods for producing protective anodic films that are visually opaque and white in color. 
     According to one embodiment, a method for forming a protective film on a metal part is described. The method involves converting a first portion of the metal part to a barrier layer. The barrier layer has a top surface corresponding to a top surface of the metal part and has substantially no pores. The method also involves forming a number of branched structures within at least a top portion of the barrier layer. The branched structures are arranged in a branching pattern within the barrier layer. The branched structures provide a light scattering medium that diffusely reflects nearly all visible wavelengths of light incident on the top surface and imparting a white appearance to the barrier layer. The method also involves converting a second portion of the metal part, below the barrier layer, to a porous anodic layer. The porous anodic layer provides structural support for the barrier layer. 
     According to another embodiment, a metal part is described. A metal part includes a protective film disposed over an underlying metal surface of the metal part. The protective film includes a barrier layer having a top surface corresponding to a top surface of the metal part. The barrier layer has a number of branched structures disposed therein. The branched structures are arranged in a branching pattern within the barrier layer with each branched structure having an elongated shape. The branched structures provide a light scattering medium that diffusely reflects nearly all visible wavelengths of light incident on the top surface and imparting a white appearance to the barrier layer. The metal part also includes a porous anodic layer disposed below the barrier layer and having a number of pores. The porous anodic layer provides structural support for the barrier layer. Each of the pores is substantially perpendicular with respect to the top surface and substantially parallel with respect to each of the other pores. 
     According to an additional embodiment, a metal substrate is described. The metal substrate includes an anodic film integrally formed over an underlying metal surface. The anodic film includes a barrier layer having a top surface corresponding to a top surface of the metal substrate. The barrier layer includes an assembly of irregularly oriented branched structures within an oxide matrix. The assembly of branched structures diffusely reflects nearly all visible wavelengths of light incident on the top surface and imparts a white appearance to the barrier layer. The anodic film also includes a structural anodic layer disposed between the barrier layer and the underlying metal surface. The structural anodic layer has a thickness sufficient for providing structural support for the barrier layer. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       The described embodiments may be better understood by reference to the following description and the accompanying drawings. Additionally, advantages of the described embodiments may be better understood by reference to the following description and accompanying drawings. 
         FIGS. 1A and 1B  illustrate perspective and cross section views, respectively, of a portion of an anodized film formed using traditional anodizing techniques. 
         FIGS. 2A-2E  illustrate cross section views of a metal substrate undergoing an anodizing process for providing an anodized film with branched pores. 
         FIG. 3  illustrates a flowchart indicating an anodizing process for providing an anodized film with branched pores. 
         FIGS. 4A-4E  illustrate cross section views of a metal substrate undergoing an anodizing process for providing an anodized film with infused metal oxide particles. 
         FIG. 5  illustrates a flowchart describing an anodizing process for providing an anodized film with infused metal complexes. 
         FIGS. 6A and 6B  illustrate a cross section view of a metal substrate undergoing an anodizing process for providing an anodized film with branched pore structure having infused metal oxide particles. 
         FIG. 7  illustrates a flowchart indicating an anodizing process for providing an anodized film with branched pores and with infused metal complexes. 
     
    
    
     DETAILED DESCRIPTION 
     The following disclosure describes various embodiments of anodic films and methods for forming anodic films. Certain details are set forth in the following description and Figures to provide a thorough understanding of various embodiments of the present technology. Moreover, various features, structures, and/or characteristics of the present technology can be combined in other suitable structures and environments. In other instances, well-known structures, materials, operations, and/or systems are not shown or described in detail in the following disclosure to avoid unnecessarily obscuring the description of the various embodiments of the technology. Those of ordinary skill in the art will recognize, however, that the present technology can be practiced without one or more of the details set forth herein, or with other structures, methods, components, and so forth. 
     This application discusses anodic films that are white in appearance and methods for forming such anodic films. In general, white is the color of objects that diffusely reflect nearly all visible wavelengths of light. Methods described herein provide internal surfaces within the anodic film that can diffusely reflect substantially all wavelengths of visible light passing through an external surface of the anodic film, thereby imparting a white appearance to the anodic film. The anodic film can act as a protective layer in that it can provide corrosion resistance and surface hardness for the underlying substrate. The white anodic film is well suited for providing a protective and attractive surface to visible portions of a consumer product. For example, methods described herein can be used for providing protective and cosmetically appealing exterior portions of metal enclosures and casings for electronic devices. 
     One technique for forming white anodic films involves an optical approach where the porous microstructures of the films are modified to provide a light scattering medium. This technique involves forming branched or irregularly arranged pores within an anodic film. The system of branched pores can scatter or diffuse incident visible light coming from a top surface of the substrate, giving the anodic film white appearance as viewed from the top surface of the substrate. 
     Another technique involves a chemical approach where metal complexes are infused within the pores of an anodic film. The metal complexes, which are ionic forms of metal oxides, are provided in an electrolytic solution. When a voltage is applied to the electrolytic solution, the metal complexes can be drawn into pores of the anodic film. Once in the pores, the metal complexes can undergo chemical reactions to form metal oxides. In some embodiments, the metal oxides are white in color, thereby imparting a white appearance to the anodic film, which is observable from a top surface of the substrate. 
     As used herein, the terms anodic film, anodized film, anodic layer, anodized layer, oxide film, and oxide layer are used interchangeably and refer to any appropriate oxide film. The anodic films are formed on metal surfaces of a metal substrate. The metal substrate can include any of a number of suitable metals. In some embodiments, the metal substrate includes pure aluminum or aluminum alloy. In some embodiments, suitable aluminum alloys include 1000, 2000, 5000, 6000, and 7000 series aluminum alloys. 
       FIGS. 1A and 1B  illustrate perspective and cross section views, respectively, of a portion of an anodized film formed using traditional anodizing techniques.  FIGS. 1A and 1B  show part  100  having anodic film  102  disposed over metal substrate  104 . In general, anodic films are grown on a metal substrate by converting a top portion of the metal substrate to an oxide. Thus, an anodic film becomes an integral part of the metal surface. As shown, anodic film  102  has a number of pores  106 , which are elongated openings that are formed substantially perpendicularly in relation to a surface of substrate  104 . Pores  106  are uniformly formed throughout anodic film  102  and are parallel with respect to each other and perpendicular with respect to top surface  108  and metal substrate  104 . Each of pores  106  have an open end at top surface  108  of anodic film  102  and a closed end proximate to metal substrate  104 . Anodic film  102  generally has a translucent characteristic. That is, a substantial portion of visible light incident top surface  108  can penetrate anodic film  102  and reflect off of metal substrate  104 . As a result, a metal part having anodic film  102  would generally have a slightly muted metallic look to it. 
     Forming Branched Pore Structures 
     One method for providing a white anodic film on a substrate involves forming a branched pore structure within the anodic film.  FIGS. 2A-2E  illustrate cross section views of a surface of a metal part  200  undergoing an anodizing process for providing an anodic film with branched pores. At  FIG. 2A , a top portion of substrate  202  is converted to barrier layer  206 . As such, the top surface of barrier layer  206  corresponds to top surface  204  of part  200 . Barrier layer  206  is generally a thin, relatively dense, barrier oxide of uniform thickness that is non-porous layer in that there are substantially no pores, such as pores  106  of part  100 . In some embodiments, forming barrier layer  206  can involve anodizing part  200  in an electrolytic bath containing a neutral to weakly alkaline solution. In one embodiment, a weakly alkaline bath that includes monoethanolamine and sulfuric acid is used. In some embodiments, barrier layer  206  has indented portions  208  at a top surface  204 . Indented portions  208  are generally broad and shallow in shape compared to pores of typical porous anodic films. Barrier layer  206  is typically grown to a thickness of less than about 1 micron. 
     At  FIG. 2B , branched structures  210  are formed within barrier layer  206 . In some embodiments, indented portions  208  can facilitate the formation of branched structures  210 . Branched structures  210  can be formed within barrier layer  206  by exposing part  200  to an electrolytic process using a weakly acid bath, similar to an anodizing process. In some embodiments, a constant voltage is applied during the formation of branched structures  210 . Table 1 provides electrolytic process condition ranges appropriate for forming branched structures  210  within barrier layer  206 . 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 1 
               
               
                   
                   
               
               
                   
                 Parameter 
                 Value range 
               
               
                   
                   
               
             
            
               
                   
                 Bath temperature 
                 16 C.-24 C. 
               
               
                   
                 Voltage (DC) 
                  5 V-30 V 
               
               
                   
                 Current Density 
                 0.2-3.0 A/dm 2   
               
               
                   
                 Duration 
                 ≦60 minutes 
               
               
                   
                   
               
            
           
         
       
     
     Since barrier layer  206  is generally non-conductive and dense, the electrolytic process forming branched structures  210  within barrier layer  206  is generally slow compared to forming pores using a typical anodizing process. The current density value during this process is generally low since the electrolytic process is slow. Instead of long parallel pores, such as pores  106  of  FIGS. 1A and 1B , branched structures  210  grow down in a branching pattern commensurate with the slow branched structure  210  formation. Branched structures  210  are generally non-parallel with respect to each other and are generally shorter in length compared to typical anodic pores. As shown, branched structures  210  are arranged in irregular and non-parallel orientations with respect to surface  204 . Thus, light entering from top surface  204  can scatter or be diffusely reflected off of the walls of branched structures  210 . To illustrate, light ray  240  can enter from top surface  204  and reflect off a portion of branched structures  210  at a first angle. Light ray  242  can enter top surface  204  and reflect off a different portion of branched structures  210  at a second angle different from the first angle. In this way, the assembly of branched structures  210  within barrier layer  206  can act as a light scattering medium for diffusing incident visible light entering from top surface  204 , giving barrier layer  206  and part  200  an opaque and white appearance. The amount of opacity of barrier layer  206  will depend upon the amount of light that is reflecting off of the walls of branched structures  210  rather than penetrating through barrier layer  206 . 
     When branched structures  210  have completed formation through the thickness of barrier layer  206 , the current density reaches what can be referred to as a recovery current value. At that point, the current density rises and the electrolytic process continues to convert metal substrate  202  to a porous anodic oxide.  FIG. 2C  shows a portion of metal substrate  202 , below barrier layer  206 , converted to porous anodic layer  212 . Pores  214  begin formation as soon as the current recovery value is attained and proceed to form and convert a portion of metal substrate  202  until a desired thickness is achieved. In some embodiments, the time in which it takes to reach the current recovery value is between about 10 to 25 minutes. In some embodiments, after the current recovery value is reached, a constant current density anodizing process is used. As porous anodic layer  212  continues to build up, the voltage can be increased to retain the constant current density. Porous anodic layer  212  is generally grown to a greater thickness than barrier layer  206  and can provide structural support to barrier layer  206 . In some embodiments, porous anodic layer  212  is grown to between about 5 microns and 30 microns in thickness. 
     Pores  214  actually continue or branch out from branched structures  210 . That is, the acidic electrolytic solution can travel through to the bottoms of branched structures  210  where pores  214  begin to form. As shown, pores  214  are formed in substantially parallel orientation with respect to each other and are substantially perpendicular with respect to top surface  204 , much like standard anodizing processes. Pores  214  have top ends that continue from branched structures  210  and bottom ends adjacent to the surface of underlying metal substrate  202 . After porous anodic layer  212  is formed, substrate  202  has protective layer  216  that includes a system of branched structures  210 , imparting an opaque and white quality to part  200 , and supporting porous anodic layer  212 . 
     In some embodiments, an opaque and white quality can also be imparted to porous anodic layer  212 .  FIG. 2D  shows part  200  after porous anodic layer  212  has been treated to have an opaque and white appearance. The opaque and white appearance can be achieved by exposing part  200  to an electrolytic process having an acidic bath with a relatively weak voltage. In some embodiments, the electrolytic bath solution contains phosphoric acid. Table 2 provides anodizing process condition ranges appropriate for forming bulbous-shaped bottom portions  218 . 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 2 
               
               
                   
                   
               
               
                   
                 Parameter 
                 Value range 
               
               
                   
                   
               
             
            
               
                   
                 Bath temperature 
                 12 C.-30 C. 
               
               
                   
                 Voltage (DC) 
                  2 V-25 V 
               
               
                   
                 Duration 
                 0.5 min-16 min 
               
               
                   
                   
               
            
           
         
       
     
     As shown, the shapes of bottom portions  218  of pores  214  have been modified to have bulbous shapes. The average width of bulbous-shaped bottom portions  218  is wider than the average width of remaining portions  220  of pores  214 . Bulbous-shaped bottom portions  218  have rounded sidewalls that extend outward with respect to remaining portions  220  of pores  214 . Light ray  244  can enter from top surface  204  and reflect off a portion of bulbous-shaped bottom portions  218  at a first angle. Light ray  246  can enter top surface  204  and reflect off a different portion of bulbous-shaped bottom portions  218  at a second angle different from the first angle. In this way, the assembly of bulbous-shaped bottom portions  218  within porous anodic layer  212  can act as a light scattering medium for diffusing incident visible light entering from top surface  204 , adding an opaque and white appearance to porous anodic layer  212  and part  200 . The amount of opacity of porous anodic layer  212  can depend upon the amount of light that is reflecting off of bulbous-shaped bottom portions  218  rather than penetrating through porous anodic layer  212 . 
     In some embodiments, additional treatments can be applied to porous anodic layer  212 .  FIG. 2E  shows part  200  after porous anodic layer  212  has undergone an additional treatment. As shown, walls  232  of pores  214  are roughened to have bumpy or irregular shapes. In some embodiments, the process for producing irregular pore walls  232  can also involve widening pores  214 . Formation of irregular pore walls  232  can be accomplished by exposing part  200  to a weakly alkaline solution. In some embodiments, the solution includes a metal salt. Table 3 provides typical solution condition ranges appropriate for roughening pore walls  232 . 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 3 
               
               
                   
                   
               
               
                   
                 Parameter 
                 Value range 
               
               
                   
                   
               
             
            
               
                   
                 Bath temperature 
                  30 C.-100 C. 
               
               
                   
                 pH 
                 1-3 
               
               
                   
                 Duration 
                 2 sec-2 min 
               
               
                   
                   
               
            
           
         
       
     
     Portions of irregularly shaped pore walls  232  extend outward with respect to remaining portions  220  of pores  214 , creating a surface that incoming light can scatter off of. Light ray  248  can enter from top surface  204  and reflect off irregularly shaped pore walls  232  at a first angle. Light ray  250  can enter top surface  204  and reflect off a different portion of irregularly shaped pore walls  232  at a second angle different from the first angle. In this way, the assembly of irregularly shaped pore walls  232  within porous anodic layer  212  can act as a light scattering medium for diffusing incident visible light entering from top surface  204 , thereby adding to the opaque and white appearance of porous anodic layer  212  and part  200 . 
       FIG. 3  shows flowchart  300  indicating an anodizing process for forming an anodized film with a branched pore system on a substrate, in accordance with described embodiment. Prior to the anodizing process of flowchart  300 , the surface of the substrate can be finished using, for example, a polishing or texturing process. In some embodiments, the substrate undergoes one or more pre-anodizing processes to clean the surface. At  302 , a first portion of the substrate is converted to a barrier layer. In some embodiments, the barrier layer has a top surface that has indented portions that are broad and shallow compared to anodic pores. These indented portions can facilitate the formation of branched structures. At  304 , branched structures are formed within the barrier layer. The branched structures can be formed by exposing the substrate to an acidic electrolytic bath at lower voltages or current densities compared to a typical anodizing process. The branched structures are elongated in shape and grow in a branching pattern commensurate with a reduced voltage or current density applied during the anodizing process. The branched or irregular arrangement of the branched structures can diffuse incident visible light, giving the barrier layer an opaque and white appearance. At  306 , a second portion of the substrate, below the barrier layer, is converted to a porous anodic layer. The porous anodic layer can add structural support to the barrier layer. The porous anodic layer can be formed by continuing the anodizing process for forming the branched structures until the electrical current reaches a recovery current value, then continuing the anodizing process until a target anodic layer thickness is achieved. After processes  302 ,  304  and  306 , the resultant anodic film can have an opaque and white appearance that can be sufficiently thick to provide protection for underlying substrate. 
     At  308 , the shapes of the bottoms of the pores are optionally modified to have a bulbous shape. The bulbous shape of the pore bottoms within the porous anodic layer can act as a second light scattering medium for adding an opaque and white quality to the substrate. At  310 , the pores are optionally widened and the pore walls are optionally roughened. The roughened irregularly shaped walls can increases the amount of light scattered from the porous anodic layer and add to the white color and opacity of the substrate. 
     Infusing Metal Complexes 
     Another method for providing a white anodic film on a substrate involves infusing metal complexes within the pores of an anodic film. Standard dyes that are white in color are generally not able to fit within the pores of an anodic film. For example, some white dyes contain titanium dioxide (TiO 2 ) particles. Titanium dioxide generally forms in particles that have a diameter on the scale of 2 to 3 microns. However, the pores of typical aluminum oxide films typically have diameters on the scale of 10 to 20 nanometers. Methods described herein involve infusing metal complexes into the pores of anodic films, where they undergo chemical reactions to form metal oxide particles once lodged within the pores. In this way, metal oxide particles can be formed within anodic pores that would not otherwise be able to fit within the anodic pores. 
       FIGS. 4A-4E  illustrate cross section views of a surface of a metal substrate undergoing an anodizing process for providing an anodic film using infused metal complexes. At  FIG. 4A , a portion, including top surface  404 , is converted to a porous anodic layer  412 . As such, the top surface of porous anodic layer  412  corresponds to top surface  404  of part  400 . Porous anodic layer  412  has pores  414  that are elongated in shape and that are substantially parallel with respect to each other and substantially perpendicular with respect to top surface  404 . Pores  414  have a top ends at top surface  404  and bottom ends adjacent to the surface of underlying metal  402 . Any suitable anodizing conditions for forming porous anodic layer  212  can be used. Porous anodic layer  412  is generally translucent in appearance. As such, the surface of underlying metal  402  can be partially visible through porous anodic layer  412 , giving part  400 , as viewed from top surface  404 , a muted metallic color and appearance. In some embodiments, anodic layer  412  is grown to between about 5 microns and 30 microns in thickness. 
     At  FIG. 4B , pores  414  of anodic layer  412  are optionally widened to an average diameter  430  that is wider than the average diameter of pores  414  before widening. Pores  414  can be widened to accommodate the infusion of a metal complex in a subsequent procedure. The amount of widening of pores  414  can depend on particular application requirements. In general, the wider pores  414  allow more space for metal complex to be infused therein. In one embodiment, widening of pores  414  is achieved by exposing part  400  to an electrolytic process having an acidic bath with a relatively weak voltage. In some embodiments, the solution includes a metal salt. In some cases, the widening process also roughens the walls of pores  414  and/or modified the bottom portions of pores  414 . 
     At  FIG. 4C , pores  414  are infused with metal complexes  424 , which are metal-containing compounds. In some embodiments, metal complexes  424  are metal oxide compounds in ionic form. Metal complexes  424  have an average diameter that is smaller than the average pore size of a typical aluminum oxide film, with or without a pore widening process. Therefore, metal complexes  424  can readily fit within pores  414  of anodic layer  412 . In addition, in embodiments where metal complexes  424  are in anionic from, metal complexes  424  are attracted toward the substrate  402  electrode and driven into the bottoms of pores  414  when a voltage is applied to the solution in an electrolytic process. In some embodiments, metal complexes  424  are added until pores  414  are substantially filled with metal complexes  424 , as shown in  FIG. 4C . In one embodiment, metal complexes  424  include titanium oxide anions. The titanium oxide anions can be formed by providing titanium oxysulfate (TiOSO 4 ) and oxalic acid (C 2 H 2 O 4 ) in an aqueous electrolytic solution. In solution, titanium oxysulfate forms a titanium oxide (IV) complex ([TiO(C 2 O 4 ) 2 ] 2− ). In one embodiment, the titanium oxide (IV) anions are formed by providing Ti(OH) 2 [OCH(CH 3 )COOH] 2 +C 3 H 8 O in an aqueous electrolytic solution. Table 4 provides typical electrolytic process condition ranges appropriate for infusing pores  414  with titanium oxide metal complexes. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 4 
               
               
                   
                   
               
               
                   
                 Parameter 
                 Value range 
               
               
                   
                   
               
             
            
               
                   
                 Bath temperature 
                 10 C.-80 C. 
               
               
                   
                 pH 
                 1-7 
               
               
                   
                 Duration 
                 30 sec-60 min 
               
               
                   
                 Voltage 
                 ≧2 V 
               
               
                   
                   
               
            
           
         
       
     
     At  FIG. 4D , once inside pores  414 , metal oxide complexes  424  can undergo a chemical reaction to form metal oxide compound  434 . For example, titanium oxide complex ([TiO(C 2 O 4 ) 2 ] 2− ) can undergo the following reaction within pores  414 .
 
[TiO(C 2 O 4 ) 2 ] 2− +2OH − →TiO 2 .H 2 O+2C 2 O 4   2− 
 
     Thus, once inside pores  414 , the titanium oxide (IV) complex can be converted to a titanium oxide compound. Once inside pores  414 , particles  434  of the metal oxide compound generally have a size larger than metal complexes  424  and are thereby entrapped within pores  414 . In some embodiments, metal oxide particles  434  conform to a shape and size in accordance with pores  414 . In embodiments described herein, metal oxide particles  434  are generally white in color in that they substantially diffusely reflect all visible wavelengths of light. For example, light ray  444  can enter from top surface  404  and reflect off a portion of metal oxide particles  434  at a first angle. Light ray  446  can enter top surface  404  and reflect off a different portion of metal oxide particles  434  at a second angle different from the first angle. In this way, the metal oxide particles  434  within porous anodic layer  412  can act as a light scattering medium for diffusing incident visible light entering from top surface  404 , giving porous anodic layer  412  and part  400  an opaque and white appearance. The whiteness of porous anodic layer  412  can be controlled by adjusting the amount of metal complexes  424  that are infused within pores  414  and converted to metal oxide particles  434 . In general, the more metal oxide particles  434  within pores  414 , the more saturated white porous anodic layer  412  and part  400  will appear. 
     At  FIG. 4E , pores  414  are optionally sealed using a sealing process. Sealing closes pores  414  such that pores  414  can assist in retaining metal oxide particles  434 . The sealing process can swell the pore walls of porous anodic layer  412  and close the top ends of pores  414 . Any suitable sealing process can be used. In one embodiment, the sealing process includes exposing part  400  to a solution containing hot water with nickel acetate. In some embodiments, the sealing process forces some of metal oxide particles  434  to be displaced from top portions of pores  414 . As shown, in  FIG. 4D , portions of metal oxide particles  434  at top portions of pores  414  have been displaced during the sealing process. In some embodiments, metal oxide particles  434  resides within the bottom portions of pores  414 . Thus, portions of metal oxide particles  434  still remain within the pores even after the sealing process. 
       FIG. 5  shows flowchart  500  indicating an anodizing process for forming an anodized film with infused metal oxide particles, in accordance with described embodiment. Prior to the anodizing process of flowchart  500 , the surface of a substrate can be finished using, for example, a polishing or texturing process. In some embodiments, the substrate undergoes one or more pre-anodizing processes to clean the surface. At  502 , a porous anodic film is formed in the substrate. The porous anodic film has elongated pores formed in parallel orientation with respect to each other. At this point, the porous anodic film generally has a translucent appearance. At  504 , the pores are optionally widened to accommodate more metal complexes in subsequent procedure  506 . At  506 , the pores are infused with metal complexes. An electrolytic process can be used to drive the anionic metal complexes towards the substrate electrode and into the bottoms of the pores. Once within the pores, the metal complexes can undergo a chemical reaction to form metal oxide particles that impart an opaque and white appearance to the porous anodic film and the substrate. In one embodiment, the metal oxide particles include titanium oxide, which has a white appearance. At  508 , the pores of the porous anodic film are optionally sealed using a sealing process. The sealing process retains the metal oxide particles within the pores after the anodizing and whitening processes. 
     In some embodiments, the aspects of the methods of forming branched pores structures and the methods of infusing metal complexes described above can be combined.  FIG. 6A  shows part  600  with barrier layer  606  and porous anodic layer  612  formed over substrate  602 . Barrier layer  606  has branched structures  610  that are continuous with pores  614  within porous anodic layer  612 . As shown, metal complexes  628  are infused within branched structures  610  and pores  614 , similar to the metal complexes of  FIG. 4C . At  FIG. 6B , metal complexes  628  have been chemically altered to form metal oxide particles  630 , similar to the metal oxide particles of  FIG. 4D . Metal oxide particles  630  generally conform to a shape and size in accordance with branched structures  610  and pores  614 . Metal oxide particles  630  are generally white in color since they can diffusely reflect substantially all wavelengths of visible light. For example, light ray  644  can enter from top surface  604  and reflect off a portion of metal oxide particles  630  at a first angle. Light ray  646  can enter top surface  604  and reflect off a different portion of metal oxide particles  630  at a second angle different from the first angle. In this way, the metal oxide particles  630  within barrier layer  606  and porous anodic layer  612  can act as a light scattering medium for diffusing incident visible light entering from top surface  604 , giving barrier layer  606  and porous anodic layer  612  and part  400  an opaque and white appearance 
     Flowchart  700  indicates an anodizing process for forming an anodized film with branched pores and infused metal complexes, such as shown in  FIG. 6 . Prior to the anodizing process of flowchart  700 , the surface of a substrate can be finished using, for example, a polishing or texturing process. In some embodiments, the substrate undergoes one or more pre-anodizing processes to clean the surface. At  702 , branched structures and pores are formed within a protective anodic layer over a substrate. At  704 , the branched structures and pores are infused with metal complexes. Once within the pores, at  706 , the metal complexes can undergo a chemical reaction to form metal oxide particles that can diffuse incident visible light, thereby imparting an opaque and white appearance to the porous anodic film and the substrate. At  706 , the branched structures and pores of the porous anodic film are optionally sealed using a sealing process. 
     Note that after any of the processes of flowcharts  300 ,  500 , and  700  are complete, the substrates can be further treated with one or more suitable post-anodizing processes. In some embodiments, the porous anodic film is further colored using a dye or electrochemical coloring process. In some embodiments, the surface of the porous anodic film is polished using mechanical methods such as buffing or lapping. 
     In some embodiments, portions of a part can be masked prior to one or more of the whitening processes described above such that the masked portions of the part are not exposed to the whitening processes. For example, portions of the part can be masked off using a photoresist material. In this way, portions of the part can have a white anodic film and other portions can have a standard translucent anodic film. 
     The foregoing description, for purposes of explanation, used specific nomenclature to provide a thorough understanding of the described embodiments. However, it will be apparent to one skilled in the art that the specific details are not required in order to practice the described embodiments. Thus, the foregoing descriptions of specific embodiments are presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the described embodiments to the precise forms disclosed. It will be apparent to one of ordinary skill in the art that many modifications and variations are possible in view of the above teachings.

Metadata:
Filing Date: 20150423
Publication Date: 20161108
Grant Date: 20161108
Priority Date: 20130927
Inventors: TATEBE MASASHIGE
AKANA JODY R.
OSHIMA TAKAHIRO
RUSSELL-CLARKE PETER N.
SAKOGUCHI MASAYUKI
HARA KENJI
Assignee: APPLE INC
CPC Classifications: [{"code": "C25D11/246", "inventive": false, "first": false, "tree": "[]"}, {"code": "C25D11/16", "inventive": true, "first": false, "tree": "[]"}, {"code": "C25D11/12", "inventive": true, "first": true, "tree": "[]"}, {"code": "C25D11/20", "inventive": true, "first": false, "tree": "[]"}, {"code": "C25D11/12", "inventive": true, "first": false, "tree": "[]"}, {"code": "C25D11/246", "inventive": false, "first": false, "tree": "[]"}, {"code": "C25D11/22", "inventive": true, "first": false, "tree": "[]"}, {"code": "C25D11/02", "inventive": true, "first": false, "tree": "[]"}, {"code": "C25D9/06", "inventive": true, "first": true, "tree": "[]"}, {"code": "C25D11/22", "inventive": true, "first": false, "tree": "[]"}, {"code": "C25D11/045", "inventive": true, "first": false, "tree": "[]"}, {"code": "C25D11/10", "inventive": false, "first": false, "tree": "[]"}, {"code": "C25D11/243", "inventive": false, "first": false, "tree": "[]"}, {"code": "C25D11/24", "inventive": true, "first": false, "tree": "[]"}, {"code": "C25D11/18", "inventive": false, "first": false, "tree": "[]"}, {"code": "C25D11/18", "inventive": false, "first": false, "tree": "[]"}, {"code": "C25D11/24", "inventive": true, "first": false, "tree": "[]"}, {"code": "C25D11/10", "inventive": false, "first": false, "tree": "[]"}, {"code": "C25D11/12", "inventive": true, "first": false, "tree": "[]"}, {"code": "C25D9/06", "inventive": true, "first": true, "tree": "[]"}, {"code": "C25D11/16", "inventive": true, "first": false, "tree": "[]"}, {"code": "C25D11/02", "inventive": true, "first": false, "tree": "[]"}, {"code": "C25D11/243", "inventive": false, "first": false, "tree": "[]"}, {"code": "C25D11/22", "inventive": false, "first": false, "tree": "[]"}, {"code": "C25D11/045", "inventive": true, "first": false, "tree": "[]"}, {"code": "C25D11/20", "inventive": true, "first": false, "tree": "[]"}, {"code": "C25D11/246", "inventive": false, "first": false, "tree": "[]"}]
Family ID: 52739018