CN111041478A

CN111041478A - Metal product, composite body and preparation method thereof

Info

Publication number: CN111041478A
Application number: CN201911323821.8A
Authority: CN
Inventors: 杨清豪; 胡玉梅; 韩家伟
Original assignee: Shenzhen Yuzhan Precision Technology Co ltd
Current assignee: Shenzhen Yuzhan Precision Technology Co ltd
Priority date: 2019-12-20
Filing date: 2019-12-20
Publication date: 2020-04-21

Abstract

The present application provides a metal article comprising: a metal substrate; and the film layer is arranged on the surface of the metal matrix, the surface of the film layer is provided with holes, and the opening diameter of each hole is smaller than the diameter of the bottom of each hole. The present application also proposes a composite body comprising: a material body and a metal product; the body of material is disposed in a bore of a metal article. The application also provides a preparation method of the metal product, which comprises the following steps: placing a metal matrix in an electrolyte; and applying voltage to the metal base to form a metal product, wherein the metal product comprises the metal base and a film layer arranged on the surface of the metal base, the surface of the film layer is provided with holes, and the opening diameter of each hole is smaller than the diameter of the bottom of each hole. The application also provides a preparation method of the complex, which comprises the following steps: applying a substance comprising a body of material to a surface of a metal article; shaping the mass comprising the body of material to form the composite body. The combination between the metal product and the material body in the composite body is firm and more environment-friendly.

Description

Metal product, composite body and preparation method thereof

Technical Field

The present application relates to a metal article, a composite body and a method of making the same.

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, since a metal composite body involves compounding two or more materials, there arise problems that the bonding strength between these materials is insufficient, the production method is difficult, and the like.

Disclosure of Invention

In view of the above, it is desirable to provide a metal product, a composite and a method for making the same to solve the above problems.

A first aspect of the present application provides a metal article comprising:

a metal substrate; and

the film layer is arranged on the surface of the metal base body, the surface of the film layer is provided with holes, and the opening diameter of each hole is smaller than the diameter of the bottom of each hole.

Further, the hole comprises a first hole and a second hole which are communicated, the first hole is positioned between the second hole and the metal product, and the diameter of the first hole is larger than that of the second hole.

Further, the diameter d1 of the first pores ranges from 15nm to 300nm, and the diameter d2 of the second pores ranges from 10nm to 250 nm.

Further, the cell wall thickness between the first cells is W1, the cell wall thickness between the second cells is W2, and W1 is greater than W2.

Further, the range of W1 is 12nm-300nm, and the range of W2 is 10nm-100 nm.

Further, the depth of the first hole is T1, the depth of the second hole is T2, T1 is greater than T2, the range of T1 is 50nm-4000nm, and the range of T2 is 10nm-1000 nm.

A second aspect of the present application provides a composite body comprising:

a body of material; and

the metal product is the metal product; wherein the body of material is disposed in a bore of the metal product.

A third aspect of the present application provides a method of making a metal article, comprising:

placing a metal matrix in an electrolyte;

applying a voltage to the metal substrate to form the metal product, wherein the metal product comprises the metal substrate and a film layer arranged on the surface of the metal substrate, the surface of the film layer is provided with holes, and the opening diameter of each hole is smaller than the diameter of the bottom of each hole.

Further, the method of applying a voltage to the metal matrix includes:

applying a first voltage to the metal substrate to form a first film layer on the surface of the metal substrate, wherein the surface of the first film layer comprises a first hole;

and applying a second voltage to the metal substrate to form a second film layer on the surface of the first film layer, wherein the second film layer comprises a second hole, the second hole is communicated with the first hole, the diameter of the first hole is larger than that of the second hole, and the first voltage is larger than the second voltage.

In a fourth aspect, the present application provides a method for preparing a composite body, including:

applying a substance comprising a body of material to a surface of a metal article, said metal article being prepared by the above-described method of preparation;

shaping the mass comprising the body of material to form the composite body, the composite body comprising the metallic article and the body of material disposed in the pores of the metallic article.

The composite body of the present application makes the material body less likely to be detached from the metal product by disposing the material body in the hole having the opening diameter smaller than the hole bottom diameter of the metal product. The preparation method of the complex applies voltage to a metal matrix placed in electrolyte to enable the surface of the metal matrix to form a film layer, and the surface of the film layer is provided with holes with opening diameters smaller than the diameter of the bottom of the holes; then forming the material body into the hole; the opening diameter of the hole is smaller than the diameter of the bottom of the hole, so that the combination of the material body and the film layer is firmer; compared with the prior art, the combination between the metal product and the material body in the composite body is stable and more environment-friendly.

Drawings

Fig. 1 is a schematic structural view of a part of a longitudinal section of a composite provided in an embodiment of the present application.

Fig. 2 is a partial structural schematic view of a longitudinal section of a metal product provided by an embodiment of the present application.

Fig. 3 is a partial structural schematic view of a longitudinal section of a metal article provided by another embodiment of the present application.

FIG. 4 is a flow chart of a method of making a composite according to an embodiment of the present application.

Fig. 5 is a flowchart of a specific method of applying voltage to the metal substrate in fig. 4.

Description of the main elements

Composite body	100
		Material body	10
Metal product	20
		Metal matrix	21
Film layer	22
		Hole(s)	221
First hole	222
		Second hole	223
First film layer	224
		Second film layer	225

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

Detailed Description

The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope 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.

Some embodiments of the present application will be described in detail below with reference to the accompanying drawings. The embodiments described below and the features of the embodiments can be combined with each other without conflict.

Referring to fig. 1 and 2 together, the present application provides a composite body 100 including a body 10 and a metallic article 20.

The material body 10 includes, but is not limited to, plastic and resin. The material body 10 is made of at least one material selected from polymers (such as plastics, rubber and fibers), metals or inorganic non-metallic materials (such as ceramics and glass).

The metal product 20 includes a metal substrate 21 and a film layer 22. The film layer 22 is arranged on the surface of the metal base 21, the surface of the film layer 22 is provided with a hole 221, and the opening diameter of the hole 221 is smaller than the diameter of the bottom of the hole. The body 10 is disposed in the hole 221 of the metal product 20.

In this embodiment, the metal substrate 21 is made of aluminum alloy, and the film 22 is an oxide film of aluminum alloy. It is understood that in other embodiments, the metal substrate 21 may be made of stainless steel, magnesium aluminum alloy, or the like.

In some embodiments, each of the holes 221 includes a first hole 222 and a second hole 223 communicating with each other, the first hole 222 is located between the second hole 223 and the metal base 21, and the diameter of the first hole 222 is larger than the diameter of the second hole 223; the walls of the first hole 222 are connected to the walls of the second hole 223.

In some embodiments, the diameter d1 of the first hole 222 ranges from 15nm to 300 nm.

The diameter d2 of the second hole 223 is in the range of 10nm-250 nm.

The ratio of d1 to d2 ranges from 1.2 to 3.

When the ratio of d1 to d2 is greater than 1.2, the material body 10 will form an anchor effect with the film layer 22 after being formed in the hole 221, and will not easily fall off.

When the ratio of d1 to d2 is greater than 3, the effective surface area of the material body 10 formed in the hole 221 is reduced, and the material body 10 is easily separated from the film 22 compared to the ratio of d1 to d2 in the range of 1.2-3.

Wherein the upper range of the diameter d1 of the first hole 222 is selected from 15nm, 50nm, 100nm, 150nm, 200nm, 250nm, 300 nm;

the lower range of the diameter d1 of the first hole 222 is selected from 35nm, 75nm, 125nm, 175nm, 210nm, 260nm, 280 nm.

The upper range of the diameter d2 of the second pores 223 is selected from 10nm, 50nm, 100nm, 150nm, 200nm, 250 nm;

the lower range of the diameter d2 of the second hole 223 is selected from 35nm, 75nm, 125nm, 175nm, 210nm, 240 nm.

It should be noted that the upper limit and the lower limit of the above content range are subject to the practical meaning that the content range is not affected, that is, the lower limit is not more than the upper limit.

In some embodiments, the first hole 222 has a hole wall thickness W1.

The second hole 223 has a hole wall thickness W2.

W1 is greater than W2.

W1 ranged from 12nm to 300 nm.

W2 ranged from 10nm to 100 nm.

Specifically, the ratio of W1 to W2 is greater than 1.2.

When W1 is too high, the high wall thickness results in a significant increase in the corrosion resistance of the film layer 22.

When W2 is too low, the film 22 is prone to fracture, and when W2 is too high, the bonding surface area between the material body 10 and the film 22 is reduced, resulting in a problem of bonding stability.

Wherein the upper limit range of the pore wall thickness W1 of the first pores 222 is selected from 12nm, 50nm, 100nm, 150nm, 200nm, 250nm, 300 nm;

the lower limit of the pore wall thickness W1 of the first pores 222 is selected from the range of 35nm, 75nm, 125nm, 175nm, 210nm, 260nm, and 280 nm.

The upper limit range of the pore wall thickness W2 of the second pores 223 is selected from 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, and 100 nm;

the lower limit range of the pore wall thickness W2 of the second pores 223 is selected from the group consisting of 11nm, 21nm, 31nm, 41nm, 51nm, 61nm, 71nm, 81nm, 91nm, and 99 nm.

It should be noted that the upper limit and the lower limit of the above range are subject to the practical meaning that the range is not affected, i.e., the lower limit is not more than the upper limit.

In some embodiments, the first hole 222 has a depth of T1, the second hole 223 has a depth of T2, and T1 is greater than T2.

T1 ranged from 50nm to 4000 nm.

T2 is in the range of 10nm-1000 nm.

Among them, when the depth of T1 is small, the hole 221 is easily incompletely filled during the setting of the material body 10.

The greater depth of T1 makes the second film layer 225 susceptible to collapse.

The smaller depth of T2 results in insufficient structural strength of the resulting anchor and failure to secure the binding force.

The greater depth of the T2 may cause the body 10 to cool and solidify in the second aperture 223 during the setting process and not pass into the first aperture 222.

Wherein the upper range of the depth T1 of the first hole 222 is selected from 50nm, 100nm, 500nm, 1000nm, 1500nm, 2000nm, 2500nm, 3000nm, 3500nm, 4000 nm;

the lower range of the depth T1 of the first hole 222 is selected from 75nm, 125nm, 300nm, 750nm, 1250nm, 1750nm, 2250nm, 32500nm, 3750nm, 3950 nm.

The upper range of the depth T2 of the second hole 223 is selected from 10nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000 nm;

the lower range of the depth T2 of the second hole 223 is selected from 11nm, 110nm, 210nm, 310nm, 410nm, 510nm, 610nm, 710nm, 810nm, 910nm, 990 nm.

Referring to fig. 4, a method for preparing a composite 100 according to an embodiment of the present disclosure includes the following steps:

s110: the metal base 21 is subjected to degreasing, alkali-biting and desmutting treatments.

Specifically, during degreasing treatment, the metal matrix 21 is placed in a degreasing agent of 40g/L-100g/L and treated at the temperature of 40 ℃ to 70 ℃ for 3min-10min to remove residual oil stains on the metal matrix 21.

During the alkali-bite treatment, the degreased metal matrix 21 is placed in a sodium hydroxide solution of 20g/L to 100g/L and treated at the temperature of 40 ℃ to 70 ℃ for 1min to 2min to remove an oxide layer naturally formed on the surface of the metal matrix 21.

During the black film stripping treatment, the metal matrix 21 after the alkali-bite treatment is placed in a 10% -40% nitric acid solution and treated at room temperature (25 ℃) for 1min-2min to remove elements which do not react on the surface of the metal matrix 21 during the alkali-bite treatment.

S120: the metal matrix 21 is placed in an electrolyte.

Specifically, the electrolyte is an acidic solution, and the acidic solution includes, but is not limited to, sulfuric acid, oxalic acid, nitric acid, phosphoric acid, carbonic acid, hydrochloric acid, sulfonic acid, and thiocarboxylic acid, which may be one or more of them. The electrolyte in this embodiment is preferably a phosphoric acid solution of 10g/L to 300 g/L. The temperature of the electrolyte is 0-60 ℃.

S130: applying a voltage to the metal base 21 to form the metal product 20, wherein the metal product 20 comprises the metal base 21 and a film layer 22 arranged on the surface of the metal base 21, the surface of the film layer 22 is provided with a hole 221, and the opening diameter of the hole 221 is smaller than the diameter of the bottom of the hole.

Specifically, referring to fig. 5, the method for applying a voltage to the metal substrate 21 includes:

s131: a first voltage is applied to the metal substrate 21 to form a first film 224 on the surface of the metal substrate 21, wherein the surface of the first film 224 includes the first hole 222.

Specifically, the first voltage V1 is 7V-150V.

The first voltage is applied for 1-50 min.

S132: applying a second voltage to the metal substrate 21 to form a second film 225 on the surface of the first film 224, wherein the second film 225 includes a second hole 223, the second hole 223 is connected to the first hole 222, the diameter of the first hole 222 is larger than that of the second hole 223, and the first voltage is larger than the second voltage.

Specifically, the second voltage V2 is 5V-100V.

The second voltage is applied for 1-50 min.

Wherein, when the ratio of the first voltage to the second voltage ranges from 1 to 1.5, W1 is less than W2, as shown in fig. 3.

When the ratio of the first voltage to the second voltage ranges from 1.5 to 6, W1 is greater than W2, as shown in fig. 1.

In the present embodiment, the second film 225 is formed on the wall of the first hole 222, wherein a cross section of a portion of the second film 225 formed on the wall of the first hole 222 is substantially dendritic.

In this embodiment, the first voltage may be gradually increased to the second voltage; multiple changes may also be made and ramped to a second voltage.

S140: the metal product 20 is subjected to a drying process.

Specifically, the drying temperature was 40 ℃. The drying time is 10min-40 min.

S150: applying a substance comprising the body of material 10 to a surface of a metal article 20.

S160: the mass comprising the body of material 10 is shaped to form a composite 100, the composite 100 comprising a metal product 20 and the body of material 10 disposed in a hole 221 of the metal product 20.

In the above steps, the material of the material body 10 may be at least one selected from a polymer (e.g., plastic, rubber, fiber), a metal or an inorganic non-metal material (e.g., ceramic, glass), etc.

Applying a substance comprising the body of material 10 to the surface of the metallic article 20. The material body 10 may be at least one selected from a polymer (e.g., plastic, rubber, fiber, etc.), a metal or an inorganic non-metal material (e.g., ceramic, glass, etc.), and so on.

The manner of setting of the mass 10 may be set according to the material and condition of the mass 10.

For example, if the material body 10 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 10 is formed from a polymer: 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 10 is made of ceramic and is in the form of powder, it may be fixed by bonding with a binder or by powder sintering.

For example, if the body 10 is made of 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 materials and the shaping method used for the material body 10 are not limited to the above examples.

Please refer to the following table, which shows the test results of the tensile test of the test block of the composite obtained by applying the single-stage low voltage, the double-stage voltage and the single-stage high voltage to the metal substrate. Wherein the two-segment voltage is the first voltage and the second voltage in this application. The single-stage low voltage is equal to the second voltage of the present application. The single-stage high voltage is equal to the first voltage of the present application.

According to the table, after the tensile force test of the test block, compared with the condition that the metal substrate is electrified with a single-section low voltage or a single-section high voltage, the metal substrate is electrified with a double-section voltage to obtain a composite body with stronger bonding force between the metal product and the plastic part.

The composite body 100 of the present application makes the material body 10 less likely to be detached from the metal product 20 by disposing the material body 10 in the hole 221 having an opening diameter smaller than a hole bottom diameter of the metal product 20. In the preparation method of the complex 100, a voltage is applied to the metal matrix 21 placed in the electrolyte, so that the surface of the metal matrix 21 forms a film layer 22, and the surface of the film layer 22 is provided with a hole 221 with an opening diameter smaller than the diameter of the bottom of the hole; the body 10 is then injection moulded into the bore 221; the opening diameter of the hole 221 is smaller than the diameter of the bottom of the hole, so that the combination of the material body 10 and the film layer 22 is more stable; the combination between the metal product 20 and the material body 10 in the composite body 100 of the present application is robust and more environmentally friendly than the prior art.

The application is suitable for combining metal machine components and plastics in mobile phones and pencils; the shapes of holes and oxide layers formed on the surface of the metal machine member are controlled by utilizing the voltage adjustment in the oxidation process of the metal machine member, so that the corrosion resistance of the product is improved, and a waterproof test can be passed. And the dendritic structure oxide film of the application forms the barb-shaped hole, and is effectively combined with the plastic, the cross section of the hole is narrow outside and wide inside, meanwhile, the wall thickness is thicker, and the acid-base corrosion resistance is better.

Although the present application has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims

1. A metal article comprising:

a metal substrate; and

2. The metal article of claim 1,

each hole comprises a first hole and a second hole which are communicated, the first hole is positioned between the second hole and the metal matrix, and the diameter of the first hole is larger than that of the second hole.

3. The metal article of claim 2,

the diameter d1 of the first pores ranges from 15nm to 300nm, and the diameter d2 of the second pores ranges from 10nm to 250 nm.

4. The metal article of claim 3,

the cell wall thickness of the first cell is W1, the cell wall thickness of the second cell is W2, and W1 is greater than W2.

5. The metal article of claim 4,

w1 is in the range of 12nm-300nm, and W2 is in the range of 10nm-100 nm.

6. The metal article of claim 2,

the first hole has a depth of T1, the second hole has a depth of T2, T1 is greater than T2; the range of T1 is 50nm-4000nm, and the range of T2 is 10nm-1000 nm.

7. A composite body, comprising:

a body of material; and

a metal article according to any one of claims 1 to 6; wherein the body of material is disposed in a bore of the metal product.

8. A method of making a metal article comprising:

placing a metal matrix in an electrolyte;

9. The production method according to claim 8, wherein,

the method for applying voltage to the metal matrix comprises the following steps:

10. A method of making a composite comprising:

applying a substance comprising a body of material to a surface of a metal article prepared by the method of any one of claims 8-9;