CN112342604A

CN112342604A - Metal product and preparation method thereof, and metal composite and preparation method thereof

Info

Publication number: CN112342604A
Application number: CN202011025932.3A
Authority: CN
Inventors: 周浩; 胡玉梅; 王政权; 杨清豪; 韩家伟
Original assignee: Shenzhen Yuzhan Precision Technology Co ltd
Current assignee: Shenzhen Yuzhan Precision Technology Co ltd
Priority date: 2020-09-25
Filing date: 2020-09-25
Publication date: 2021-02-09

Abstract

A metal product comprises a metal matrix, a first hole, a second hole and a third hole, wherein the first hole is arranged on the surface of the metal matrix; the second hole is arranged on the surface of the first hole; the third hole is provided on at least one of a surface of the metal base, a surface of the first hole, and a surface of the second hole. According to the metal base body, the micron-scale first hole, the submicron-scale to micron-scale second hole and the nanometer-scale third hole are formed in the metal base body, so that the bonding strength of a metal product and a material body is enhanced. The application also provides a preparation method of the metal product, a metal composite body and a preparation method of the metal composite body.

Description

Metal product and preparation method thereof, and metal composite and preparation method thereof

Technical Field

The application relates to the field of metal materials, in particular to a metal product and a preparation method thereof, and a metal composite and a preparation method thereof.

Background

Because of the requirements of industrial products on the physical and chemical properties of materials such as strength, appearance, density and the like, the requirements cannot be met only by using metal at present, and the metal composite body is a new choice of materials for industrial products by retaining the characteristics of metal materials and introducing the characteristics of other materials. However, in actual production, the metal composite body involves compounding of two or more materials, and insufficient bonding strength between these materials occurs, resulting in poor air-tightness and water-tightness properties.

Disclosure of Invention

In view of the above, it is desirable to provide a metal product capable of being effectively combined with other materials, a method for preparing the same, a metal composite including the metal product, and a method for preparing the same.

A metal product comprises a metal matrix, a first hole, a second hole and a third hole, wherein the first hole is arranged on the surface of the metal matrix; the second hole is arranged on the surface of the first hole; the third hole is provided on at least one of a surface of the metal base, a surface of the first hole, and a surface of the second hole.

Further, the second hole and the inner wall forming the second hole are in an irregular sponge-like structure together.

Further, the opening directions of the plurality of second holes are different.

Further, the opening directions of the plurality of second holes are anisotropic.

Further, the shape of the plurality of second holes is anisotropic.

Further, the opening directions of the plurality of third holes are different.

Further, the opening directions of the plurality of third holes are anisotropic.

Further, the surface material of the third hole comprises an oxide.

Further, the first hole has a hole diameter R₁，R₁In the range of 100 μm R₁≤150μm。

Further, the aperture of the second hole is R₂，R₂In the range of 0.1 μm or less R₂≤5μm。

Further, the third hole has a hole diameter R₃，R₃R is within the range of 30nm or less₃≤70nm。

A metal composite comprises a metal product and a material body, wherein the material body is formed on the metal product; the material body comprises a combination part, and the combination part is arranged in the first hole, the second hole and the third hole so as to combine the material body with the metal product.

Further, the material of the material body is selected from at least one of plastic, metal, ceramic, glass and oxide.

Further, the joint part is of a sea urchin-like structure.

Furthermore, the joint part is of a sea cucumber-like structure.

Further, the combination part is of a durian-like structure.

Further, the joint comprises a body and a branch structure which is diverged outwards from the body.

Further, the plurality of branch structures are anisotropic in shape.

Further, the divergence directions of the plurality of branch structures are anisotropic.

A method of making a metal article comprising: putting the metal matrix into first electrolyte as an anode, putting the first cathode body into the first electrolyte as a cathode, applying voltage to the metal matrix and the first cathode body, and electrolyzing the metal matrix to form a first hole and a second hole on the metal matrix; and placing the metal substrate having the first hole and the second hole in a second electrolyte as an anode, placing a second cathode body in the second electrolyte as a cathode, and applying a voltage to the metal substrate and the second cathode body to perform anodic oxidation to form a third hole in at least one of the surface of the metal substrate, the surface of the first hole, and the surface of the second hole; wherein the first electrolyte contains persulfate.

Further, the persulfate is selected from at least one of potassium persulfate, sodium persulfate, and ammonium persulfate.

Furthermore, the concentration of the persulfate in the electrolyte is C, and the range of C is more than or equal to 10g/L and less than or equal to 200 g/L.

A method of making a metal composite comprising: preparing a metal product; applying a substance comprising a body of material to a surface of a metal article; and shaping the mass comprising the body of material to form the metal composite.

According to the preparation method of the metal product and the preparation method of the metal composite body, the first hole and the second hole are formed by adopting the first electrolyte with persulfate, wherein the first electrolyte does not contain acidic substances such as nitrogen, phosphorus and the like, so that the first hole can be formed on the surface of the metal substrate, and the second hole can be formed under the action of persulfate; and forming third holes in the second electrolyte by anodic oxidation to form the metal product, wherein the first electrolyte and the second electrolyte adopted in the preparation method are free from halogen-containing substances such as chlorine and fluorine, and further corrosion of the metal base material by the residual electrolyte is prevented. After the material bodies are filled into the first hole, the second hole and the third hole, the binding force between the material bodies and the metal product can be greatly increased, and meanwhile, due to the fact that the triple composite structure has a complex hole structure, the difficulty of external gas and liquid passing through the triple composite structure is increased, and therefore the air tightness and the liquid tightness of the metal composite body are improved.

Drawings

Fig. 1 is a schematic structural view of a metal product according to some embodiments of the present disclosure and an enlarged schematic structural view of a region I.

Fig. 2 is a picture of a metal article according to some embodiments of the present application taken using an optical microscope.

Fig. 3 is a picture of a metal article according to some embodiments of the present application taken using an electron microscope.

Fig. 4 is a picture of a metal article according to some embodiments of the present application taken using an electron microscope.

Fig. 5 is a picture of a metal article according to some embodiments of the present application taken using an electron microscope.

Fig. 6 is a picture of a metal article according to some embodiments of the present application taken using an electron microscope.

FIG. 7 is a schematic structural view of a metal composite body according to some embodiments of the present application.

Fig. 8 is a photograph taken using an electron microscope of a bonding portion of a material body exposed after a metal product is removed from a metal composite body according to some embodiments of the present application.

Fig. 9 is a photograph taken using an electron microscope of a bonding portion of a material body exposed after a metal product is removed from a metal composite body according to some embodiments of the present application.

Fig. 10 is a photograph taken using an electron microscope of a bonding portion of a material body exposed after a metal product is removed from a metal composite body according to some embodiments of the present application.

Fig. 11 is a photograph taken using an electron microscope of a bonding portion of a material body exposed after a metal product is removed from a metal composite according to some embodiments of the present application.

Fig. 12 is a photograph taken using an electron microscope of a bonding portion of a material body exposed after a metal product is removed from a metal composite body according to some embodiments of the present application.

Fig. 13 is a photograph taken using an electron microscope of a bonding portion of a material body exposed after removing a metal product from a metal composite according to some embodiments of the present application.

Fig. 14 is a photograph taken using an electron microscope of a bonding portion of a material body exposed after removing a metal product from a metal composite body according to some embodiments of the present application.

Fig. 15 is a photograph taken using an electron microscope of a bonding portion of a material body exposed after removing a metal product from a metal composite body according to some embodiments of the present application.

Fig. 16 is a flow chart of a method of making a metal article according to some embodiments of the present application.

FIG. 17 is a schematic structural view of a metal matrix according to some embodiments of the present application.

Fig. 18 is a schematic structural view of the metal base shown in fig. 17 having a first hole and a second hole formed in the surface thereof.

FIG. 19 is a flow chart of a method of making a metal composite body according to some embodiments of the present application.

Description of the main elements

Metal product	100
		Metal matrix	10
First hole	20
		Second hole	30
Third hole	40
		Metal composite body	200
Material body	210
		Joining part	215
Body	152
		Branch structure	154
Region(s)	I

The following detailed description will further illustrate the present application in conjunction with the above-described figures.

Detailed Description

In order that the above objects, features and advantages of the present application can be more clearly understood, a detailed description of the present application will be given below with reference to the accompanying drawings and detailed description. In addition, the embodiments and features of the embodiments of the present application may be combined with each other without conflict. In the following description, numerous specific details are set forth to provide a thorough understanding of the present application, and the described embodiments are merely a subset of the embodiments of the present application, rather than all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive work based on the embodiments in the present application are within the scope of protection of the present application.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and/or" includes all and any combination of one or more of the associated listed items.

In various embodiments of the present application, for convenience in description and not limitation, the term "coupled" as used in the specification and claims of the present application is not limited to physical or mechanical connections, either direct or indirect. "upper", "lower", "above", "below", "left", "right", and the like are used merely to indicate relative positional relationships, and when the absolute position of the object being described is changed, the relative positional relationships are changed accordingly.

Referring to fig. 1, some embodiments of the present application provide a metal product 100 including a metal substrate 10, a first hole 20, a second hole 30, and a third hole 40. The first hole 20 is disposed on the surface of the metal base 10; the second hole 30 is provided on a surface of the first hole 20, and the third hole 40 is provided on at least one of a surface of the metal base 10, a surface of the first hole 20, and a surface of the second hole 30.

The material of the metal base 10 may be at least one selected from aluminum and aluminum alloys.

In some embodiments, the first hole 20 opens on one of the surfaces of the metal base 10. It is understood that in other embodiments, the first hole 20 may be opened on a plurality of surfaces of the metal base 10.

Referring to fig. 2 and 3, the first hole 20 has a hole diameter R₁Aperture R of₁In the range of 100 μm R₁Less than or equal to 150 μm, i.e. the first holes 20 are holes of the order of microns. In some embodiments of the present application, the aperture R₁The lower limit of the range is selected from 102 μm, 108 μm, 115 μm, 120 μm, 126 μm, 129 μm, 137 μm, 148 μm; aperture R₁The upper limit of the range is selected from the group consisting of 103 μm, 109 μm, 118 μm, 123 μm, 128 μm, 139 μm, 141 μm, 149 μm; wherein the aperture R₁The lower limit and the upper limit of (b) are chosen reasonably, i.e. the lower limit is required to be less than or equal to the upper limit.

Referring to fig. 4 and 5, the surface of the inner wall of the first hole 20 is recessed inward to form a plurality of second holes 30 (see the area I in fig. 1), the second holes 30 are irregular in shape, and in some embodiments, the second holes 30 may also be substantially elongated slits and extend in a direction away from the inner wall of the first hole 20, that is, the second holes 30 may be substantially elongated slits and extend in a direction away from the surface of the metal substrate 10 on which the first holes 20 are disposed.

Further, the inner wall of the first hole 20 has an uneven structure.

Referring to fig. 5 again, the second hole 30 and the inner wall forming the second hole 30 form a sponge-like structure together, that is, the plurality of second holes 30 and the inner wall forming the second holes 30 form a sponge-like structure together, the second hole 30 may be semi-open, and the opening directions of the second holes 30 are different and may face various directions, so that the drawing strength of the metal product 100 and the subsequent material body 210 formed in the second hole 30 can be increased, and the bonding strength of the metal product 100 and the material body 210 can be effectively enhanced.

Further, the plurality of second holes 30 may be communicated with each other from the inside of the metal base 10, and it is understood that when the material body 210 is formed in the second holes 30 communicated with each other, a part of the material body 210 may be embedded in the metal base 10, and the material body 210 is fastened to the inner wall of the second holes 30 formed in communication with each other, so that the bonding strength between the metal product 100 and the material body 210 may be further enhanced by the self-acting force of the material body 210 and the metal base 10, and the material body 210 may be prevented from falling off.

In some embodiments, the opening direction of the second plurality of holes 30 is anisotropic. The plurality of second holes 30 exhibit different opening directions along the inner wall of the first hole 20.

In some embodiments, the shape of the second plurality of holes 30 is anisotropic. The shape of the plurality of second holes 30 exhibits anisotropy in space.

Referring to fig. 5 again, the diameter of the second hole 30 is R₂Aperture R of₂In the range of 0.1 μm or less R₂Less than 5 μm, i.e., the second wells 30 are about submicron to micron sized wells. The submicron level here is 10²On the order of nm to 1 μm. In some embodiments of the present application, the aperture R₂The lower limit of the range is selected from 0.2 μm, 0.8 μm, 1.3 μm, 1.6 μm, 2.6 μm, 3.2 μm, 3.8 μm, 4.5 μm; aperture R₂The upper limit of the range is selected from 0.5 μm, 1.8 μm, 2.2 μm, 2.7 μm, 3.5 μm, 3.9 μm, 4.3 μm, 4.8 μm; wherein the aperture R₂The lower limit and the upper limit of (b) are chosen reasonably, i.e. the lower limit is required to be less than or equal to the upper limit.

The third hole 40 may be located on a surface of the metal base 10, the third hole 40 may be located on a surface of the first hole 20, and the third hole 40 may be located on a surface of the second hole 30 (see fig. 5 and 6).

Referring to fig. 6 again, in some embodiments, the third holes 40 are located on the surfaces of the second holes 30, and the opening directions of the third holes 40 located on the surfaces of the second holes 30 are different and may face various directions because the opening directions of the second holes 30 are different and the hole walls of the second holes 30 are irregular. In some embodiments, the third hole 40 may be further located at least one of a surface of the metal base 10 and a surface of the first hole 20 not covered by the second hole 30, and the location of the third hole 40 is different, resulting in a different opening direction thereof. The third hole 40 may be disposed to increase a contact area of the metal matrix 10 and the material body 210 to a greater extent, thereby further enhancing a bonding strength of the metal product 100 and the material body 210. It is understood that the arrangement of the first holes 20 and the second holes 30 can also increase the contact area between the metal matrix 10 and the material body 210.

In some embodiments, the opening direction of the third holes 40 is anisotropic. The plurality of third holes 40 each have a state in which the opening direction is different in different directions because of different positions.

Referring again to FIG. 6, the third hole 40 has an aperture R₃Aperture R of₃In the range of 30nm or less R₃Less than or equal to 70nm, i.e. the third holes 40 are holes of about nanometer order. In some embodiments of the present application, the aperture R₃The lower limit of the range is selected from 32nm, 36nm, 41nm, 46nm, 52nm, 56nm and 68 nm; aperture R₃The upper limit of the range is selected from 35nm, 39nm, 43nm, 49nm, 53nm, 57nm, 69 nm; wherein the aperture R₃The lower limit and the upper limit of (b) are chosen reasonably, i.e. the lower limit is required to be less than or equal to the upper limit.

The surface of the third hole 40 contains an oxide, and since the oxide is formed by oxidizing the material of the metal base 10, the kind of the oxide is related to the material of the metal base 10. In some embodiments, the oxide may be alumina.

Referring to fig. 7, the present application also provides a metal composite 200, where the metal composite 200 includes the metal product 100 and a material body 210. The body 210 is formed on the surface of the metal product 100.

Specifically, the material body 210 includes a bonding portion 215, and at least a portion of the bonding portion 215 is filled into an inner cavity of at least one of the first hole 20, the second hole 30, and the third hole 40, so as to compound the material body 210 with the metal product 100.

The material of the material body 210 is selected from at least one of plastic, metal, ceramic, glass, and oxide.

Referring to fig. 8 to 15, after the metal product 100 in the metal composite 200 is removed, the material body 210 combined with the metal product 100 is left.

In some embodiments, as can be seen from the photographs obtained by testing, the bonding portion 215 of the material body 210 in the metal product 100 has a sea urchin-like structure, i.e., the bonding portion 215 emits from the center to different directions around the periphery. The circumferentially diverging configuration of the junction 215 resembles the barbed configuration of a sea urchin shell, with the circumferentially diverging configuration of the junction 215 being formed by the material 210 being set in the second aperture 30, and with the circumferentially diverging configuration of the junction 215 having a slight bulge formed by the material 210 being set in the third aperture 40. It should be noted that the sea urchin-like structure described in the present application does not mean that the joint 215 is the same structure as that of the real sea urchin, and for example, the structure diverging in different directions around the sea urchin does not necessarily have a regular linear structure as the thorn of the sea urchin shell, but has an irregular columnar structure.

In some embodiments, it can be seen from the photographs obtained by testing that the joint 215 of the material body 210 in the metal product 100 has a sea cucumber-like structure, i.e., the joint 215 comprises an ellipsoid-like structure similar to the body of a sea cucumber, the surface of the ellipsoid-like structure has a plurality of spikes with protrusions similar to the body surface of the sea cucumber, and the surface of the spikes has small spikes with fine protrusions similar to the spikes on the body surface of the sea cucumber. This structure is formed by the metal product 100 having a triple pore structure, so that a complex structure of the bonding part 215 can be realized to facilitate the bonding force between the material body 210 and the metal product 100. It should be noted that, in the present application, the sea cucumber-like structure does not mean that the joint 215 is the same as a real sea cucumber, for example, the sea cucumber is generally in a long cylindrical shape, and the joint 215 is in an ellipsoid-like structure.

In some embodiments, it can be seen from the photographs obtained by testing that the joint 215 of the body 210 in the metal product 100 is of a durian-like structure, i.e., the joint 215 comprises an ellipsoid-like structure resembling the durian shell, the surface of the ellipsoid-like structure having a plurality of "thorn-like" structures resembling the thorns on the durian shell, and each "thorn-like" structure having a plurality of "small thorn-like" structures thereon. It should be noted that the durian-like structure described in the present application does not mean that the joint 215 is the same as the real durian, for example, the multiple "small-thorn" structures on the "thorn" structure do not exist on the thorn of the real durian shell.

Referring to fig. 8 to 15, in some embodiments, as can be seen from the test results, the joint 215 of the material body 210 in the metal product 100 includes a body 152 and a branch structure 154 (i.e., including a plurality of branches) diverging outward from the body 152, and the shape of the branch structure 154 is anisotropic. Wherein, when the body 210 is combined with the metallic article 100, the body 152 is located in the first bore 20, the outwardly diverging branch structures 154 are located in the second bore 30, and the uneven surface of the branch structures 154 is formed by the body 210 being shaped in the third bore 40.

Further, the branch structures 154 may be connected to each other, that is, the branches of different branch structures 154 are connected to each other, and it is understood that the branch structures 154 connected to each other may be formed by shaping the material bodies 210 in the second holes 30 communicated with each other.

In some embodiments, the shape of the junction 215 of the body 210 with the metallic article 100 may include both a sea urchin-like structure, and may include a body 152 and branch structures 154 that diverge outwardly from the body 152.

In the metal product 100 of the present application, the triple composite structure including the first hole 20 of a micron size, the second hole 30 of a submicron size to a micron size, and the third hole 40 of a nanometer size is formed on the metal substrate 10, and after the material bodies 210 of the metal product 100 are combined, the triple composite structure is filled in the combining portions 215 of the material bodies 210, so that the combining force between the material bodies 210 and the metal product 100 can be greatly increased, and meanwhile, the triple composite structure has a complicated hole structure, so that the difficulty of external gas and liquid passing through the triple composite structure is increased, and the airtightness and liquid tightness of the metal composite 200 are improved.

Referring to fig. 16 to 18 and fig. 1, some embodiments of the present application further provide a method for manufacturing the metal product 100, including the following steps:

step S1: referring to fig. 17 and 18, a metal substrate 10 is placed in a first electrolyte as an anode, a first cathode is placed in the first electrolyte as a cathode, a voltage is applied to the metal substrate 10 and the first cathode, and the metal substrate 10 is electrolyzed to form a first hole 20 and a second hole 30 on the metal substrate 10; wherein the first electrolyte contains persulfate.

Step S2: referring to fig. 1 again, the metal substrate 10 having the first hole 20 and the second hole 30 is placed in a second electrolyte as an anode, a second cathode is placed in the second electrolyte as a cathode, and a voltage is applied to the metal substrate 10 and the second cathode to perform anodic oxidation, so as to form a third hole 40 on at least one of the surface of the metal substrate 10, the surface of the first hole 20, and the surface of the second hole 30.

In step S1, the persulfate may be selected from at least one of potassium persulfate, sodium persulfate, and ammonium persulfate.

The concentration of the persulfate in the first electrolyte is C, and the range of the concentration C is more than or equal to 10g/L and less than or equal to 200 g/L. In some embodiments of the present application, the lower limit of the concentration C range is selected from 12g/L, 35g/L, 58g/L, 82g/L, 125g/L, 145g/L, 168g/L, 188 g/L; the upper limit of the concentration C range is selected from 22g/L, 42g/L, 68g/L, 85g/L, 128g/L, 149g/L, 172g/L and 198 g/L; wherein, the selection of the lower limit and the upper limit of the concentration C needs to be reasonable, i.e. the lower limit needs to be less than or equal to the upper limit.

Further, the first electrolyte also comprises a pH regulator, and the pH regulator is used for regulating the pH value of the first electrolyte. The pH regulator is at least one selected from sulfuric acid, oxalic acid and organic acids, wherein the organic acids do not contain nitrogen and phosphorus, such as citric acid. Namely, the pH regulator can avoid the introduction of substances containing nitrogen and phosphorus, and is beneficial to environmental protection.

The concentration of the pH regulator in the first electrolyte is C₁Concentration C of₁In the range of 10 g/L-C₁Less than or equal to 100 g/L. In some embodiments of the present application, the concentration C₁The lower limit of the range is selected from12g/L, 25g/L, 38g/L, 52g/L, 55g/L, 65g/L, 78g/L and 88 g/L; concentration C₁The upper limit of the range is selected from 22g/L, 32g/L, 48g/L, 55g/L, 68g/L, 79g/L, 82g/L, 98 g/L; wherein, the concentration C₁The lower limit and the upper limit of (b) are chosen reasonably, i.e. the lower limit is required to be less than or equal to the upper limit.

The temperature of the electrolytic treatment is T, and the range of the temperature T is more than or equal to 20 ℃ and less than or equal to 50 ℃. In some embodiments of the present application, the lower limit of the temperature T range is selected from 22 ℃, 25 ℃, 30 ℃, 33 ℃, 39 ℃, 42 ℃, 46 ℃, 48 ℃; the upper limit of the temperature T range is selected from 23 ℃, 27 ℃, 32 ℃, 35 ℃, 40 ℃, 43 ℃, 47 ℃ and 49 ℃; the lower limit and the upper limit of the temperature T are reasonably selected, i.e. the lower limit is less than or equal to the upper limit.

The time of the electrolytic treatment is t, and the range of the time t is more than or equal to 5min and less than or equal to 50 min. In some embodiments of the present application, the lower limit of the time t range is selected from 7min, 15min, 23min, 30min, 35min, 39min, 43min, 47 min; the upper limit of the time t range is selected from 8min, 16min, 24min, 31min, 37min, 41min, 45min and 48 min; the lower limit and the upper limit of the time t need to be reasonably selected, namely the lower limit needs to be less than or equal to the upper limit.

Wherein, in the process of applying voltage to the anode and the cathode, the metal substrate is electrified, partial surface of the metal substrate is passivated by the first electrolyte containing persulfate, the current is concentrated on the unpassivated area of the surface of the metal substrate, the equivalent resistance of the unpassivated area is smaller than that of the passivated area, and the electrolytically etched area is generated on the area with weak equivalent resistance (i.e. unpassivated area), so that the unpassivated area is electrolytically etched to form the first hole 20 and the second hole 30.

In step S2, the second electrolyte solution may include at least one of oxalic acid, sulfuric acid, and phosphoric acid. In the anodizing process, a part of the material located on the surface of the first hole 20, a part of the material located on the surface of the second hole 30, and a part of the material located on the surface of the metal base 10 react to form the third hole 40, and at the same time, the above materials are oxidized to form an oxide located on the surface of the third hole 40.

Referring to fig. 19, some embodiments of the present disclosure further provide a method for preparing a metal composite 200, including the steps of:

step S11: the metal product 100 described above is prepared.

Step S12: applying a substance comprising a body of material 210 to a surface of a metallic article 100;

step S13: the mass comprising the body of material 210 is shaped to form the metal composite 200.

In step S11, the metal product 100 is produced by the above-described production method of the metal product 100.

In step S12, the material of the material body 210 may be selected from at least one of plastic, metal, ceramic, glass, and oxide.

In step S13, the material body 210 is applied to the surface of the metal base 10, and at least a part of the metal base 10 enters the first hole 20, the second hole 30, and the third hole 40. After the body of material 210 is shaped, the body of material 210 located in the cavities of the first hole 20, the second hole 30, and the third hole 40 forms a bonding portion 215 to bond the body of material 210 to the metal product 100 to form the metal composite 200.

The setting manner of the material body 210 may be set according to the material and state of the material body 210.

For example, if the material body 210 is made of metal and is in the form of powder, the material body can be shaped by a laser fusion compounding technique.

For example, if the body 210 is made of plastic: when the form is liquid (solution), the shaping can be realized by adopting a solvent evaporation mode; when the form is powder, the powder can be treated by heating, melting, cooling and shaping; when the shape is molten, the plastic can be shaped by injection molding; when the form is gas, the shaping can be carried out by adopting the technical means of gas in-situ polymerization.

For example, if the material body 210 is made of ceramic and is in the form of powder, it may be formed by bonding with a binder or by powder sintering.

For example, if the body 210 is a glass: when the shape is powder, the shaping can be carried out by adopting a mode of heating, melting and then cooling for shaping; when the form is molten, the treatment can be carried out by adopting a cooling and shaping mode.

The above examples are merely descriptions of some embodiments, and the material and the shaping method of the material body 210 are not limited to the above examples.

Specifically, in some embodiments of the present invention, the metal product 100 is placed in a heated mold, and the molten plastic is injected into the surface of the metal product 100, and the molten plastic enters the first hole 20, the second hole 30, and the third hole 40, and is injection molded to obtain the metal composite 200.

According to the method for manufacturing the metal product 100 and the method for manufacturing the metal composite 200, the first hole 20 and the second hole 30 are formed by electrolysis of the first electrolyte solution with persulfate, wherein the first electrolyte solution does not contain acidic substances such as nitrogen and phosphorus, the first hole 20 can be formed on the surface of the metal substrate 10, and the second hole 30 can be formed under the action of persulfate; and forming a third hole 40 in the second electrolyte by anodic oxidation to form the metal product 100, wherein the first electrolyte and the second electrolyte used in the above-described production method are free from halogen-containing substances such as chlorine and fluorine, and further corrosion of the metal base material by the remaining electrolyte is prevented. After the material body 210 is filled in the first hole 20, the second hole 30 and the third hole 40, the coupling force of the material body 210 and the metal product 100 can be greatly increased, and the triple composite structure has a complicated hole structure, so that the difficulty of passing external gas and liquid through the triple composite structure is increased, thereby improving the gas tightness and the liquid tightness of the metal composite 200.

Although the present application has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the present application.

Claims

1. A metal product comprising

A metal substrate;

a first hole provided in a surface of the metal base;

a second hole provided on a surface of the first hole; and

and a third hole provided in at least one of a surface of the metal base, a surface of the first hole, and a surface of the second hole.

2. The metal article of claim 1, wherein the second pores and the inner walls forming the second pores collectively have an irregular sponge-like structure.

3. The metal product according to claim 1, wherein the opening directions of the plurality of second holes are different.

4. The metal product according to claim 1, wherein the opening direction of the plurality of second holes is anisotropic.

5. The metal article of claim 1, wherein a shape of the second plurality of pores is anisotropic.

6. The metal product according to claim 1, wherein the opening directions of the plurality of third holes are different.

7. The metal product according to claim 1, wherein the opening directions of the plurality of third holes are anisotropic.

8. The metal article of claim 1, wherein the surface material of the third hole comprises an oxide.

9. The metal article of claim 1, wherein the first pores have a pore diameter R₁Said R is₁In the range of 100 μm R₁≤150μm。

10. The metal article of claim 1, wherein the metal article is a metal articleThe diameter of the second hole is R₂Said R is₂In the range of 0.1 μm or less R₂≤5μm。

11. The metal article of claim 1, wherein the third hole has a pore size of R₃Said R is₃In the range of 30nm or less R₃≤70nm。

12. A metal composite body comprising:

a metal article; and

the material body is formed on the metal product; wherein,

the metal article is as defined in any one of claims 1 to 11;

the material body includes a bonding portion disposed in the first hole, the second hole, and the third hole to bond the material body with the metal product.

13. The metal composite of claim 12 wherein the material body is selected from at least one of a plastic, a metal, a ceramic, a glass, and an oxide.

14. The metal composite according to claim 12, wherein the bonding portion has a sea urchin-like structure.

15. The metal composite according to claim 12, wherein the bonding portion has a sea cucumber-like structure.

16. The metal composite according to claim 12, wherein the bonding portion is in a durian-like structure.

17. The metal composite according to claim 12, wherein the bonding portion comprises a body and a branch structure diverging outwardly from the body.

18. The metal composite according to claim 17, wherein the plurality of branch structures are anisotropic in shape.

19. The metal composite according to claim 17, wherein the plurality of branch structures have anisotropic divergence directions.

20. A method of making a metal article comprising:

putting a metal matrix into a first electrolyte as an anode, putting a first cathode body into the first electrolyte as a cathode, applying voltage to the metal matrix and the first cathode body, and electrolyzing the metal matrix to form a first hole and a second hole on the metal matrix; and

placing the metal base body having the first hole and the second hole in a second electrolytic solution as an anode, placing a second cathode body in the second electrolytic solution as a cathode, and applying a voltage to the metal base body and the second cathode body to perform anodic oxidation to form a third hole in at least one of the surface of the metal base body, the surface of the first hole, and the surface of the second hole;

wherein the first electrolyte contains persulfate.

21. The method of producing a metal product according to claim 20, wherein the persulfate is at least one selected from the group consisting of potassium persulfate, sodium persulfate, and ammonium persulfate.

22. The method of claim 20, wherein the persulfate salt has a concentration C in the electrolyte in the range of 10g/L C200 g/L.

23. A method of making a metal composite comprising:

preparing a metal product;

applying a substance comprising a body of material to a surface of the metal article; and

shaping a mass comprising the body of material to form a metal composite; wherein,

the step of producing a metal product employs a method of producing a metal product as claimed in any one of claims 20 to 22.