CN114875361A - A kind of high-adhesion metal coating and preparation process thereof - Google Patents

Abstract

The invention discloses a high-adhesion metal coating and a preparation process thereof, wherein the preparation process comprises the following steps: a substrate; a primer layer deposited on the substrate; a metal layer deposited on the primer layer; a transition layer deposited on the metal layer, comprising a first transition layer and a second transition layer, deposited using the FCVA method, the first transition layer and the second transition layer each comprising a nitride or carbide of a base element; the functional alternating layer is deposited on the transition layer by adopting an FCVA method and comprises a nitride or carbide of a basic element, and the surface of the second transition layer is attached with the functional alternating layer which is alternately arranged; a functional superhard layer, deposited on the functional alternating layer, is deposited by the FCVA process and comprises a nitride or carbide of one of the essential elements. The coating has the advantages of improving the hardness of the surface of the substrate, along with good uniformity of the film layer, stronger mechanical wear resistance and environmental resistance.

Description

A kind of high-adhesion metal coating and preparation process thereof

technical field

The invention relates to the technical field of composite coatings, in particular to a high-adhesion metal coating and a preparation process thereof.

Background technique

The metal material is affected by the external material environment or the friction between metal parts occurs chemical or mechanical friction, so that the metal surface is oxidized or corroded, which will significantly reduce the hardness, plasticity, toughness and other mechanical properties of the substrate, and damage the metal parts. Geometry, increased wear of parts, deterioration of physical properties such as electrical and chemical, and new surface treatment processes are urgently needed to improve the service life of metal parts and save resources.

Tetrahedral amorphous carbon is an amorphous, aperiodic, transition-state carbon crystal structure with various forms. Usually, DLC and hydrogen-free DLC films are divided according to the hydrogen content and sp3 bond content in the coating structure. Tetrahedral hydrogen-free amorphous carbon The typical characteristics of carbon are that the hydrogen content is very small (5% mol, usually ≤ 2% mol) or does not contain hydrogen, and the sp3 bond content is as high as 85% or more. The preparation method of hydrogen-free DLC mainly adopts filtered cathodic arc deposition coating process, multi-arc One or more of ion plating process or chemical vapor deposition coating process.

At present, there are many surface treatment technologies for metal materials, such as PIP, chrome plating, DLC and other surface treatment technologies for various metal parts. The more prominent problem is that the surface adhesion of the coating is not high. The shedding is serious, and this problem is significant in the table processing industry. Therefore, based on the above reasons, a new surface treatment metal coating and its preparation process are proposed to improve the strong adhesion on the surface of metal parts. The raw material of the hydrogen-free DLC film proposed in this patent is a high-purity graphite target material that contains almost no hydrogen, contains less than 2% mol of hydrogen (almost no hydrogen), and contains more than 90% of sp3 bonds. Choose to use magnetic confinement filtration focusing pure ion vacuum coating technology to develop hydrogen-free DLC coating, make a hard film with high adhesion, meet market demand, reduce use cost, and improve the level of surface treatment industry.

SUMMARY OF THE INVENTION

In view of the above-mentioned deficiencies of the prior art, the technical problem to be solved by this patent application is how to provide a high adhesion and film hardness that enhances the adhesion and film hardness of the substrate, improves the mechanical wear resistance and corrosion resistance of the substrate, prolongs the service life, and reduces the cost. Focus on metal coating and its preparation process.

In order to solve the above-mentioned technical problems, the present invention adopts the following technical solutions:

A high adhesion metal coating comprising:

base;

A primer layer, which is deposited on the substrate, uses PVD to deposit Ni, Cr, Ti, W, Si or their mixtures or their nitrides or their carbides to form one or several layers of high-bonding films;

Metal layer, which is deposited on the base layer, using PVD to deposit Ni, Cr, Ti, W, Si or their mixtures or their nitrides or their carbides to form one or several metal connection layers;

a transition layer, deposited on the metal layer, comprising a first transition layer and a second transition layer, deposited using the FCVA method, the first transition layer and the second transition layer each comprising an essential element nitride or carbide;

A functional alternating layer, which is deposited on the transition layer, is deposited by the FCVA method, and comprises a basic element nitride or carbide, and the alternately arranged functional alternating layers are attached on the surface of the second transition layer;

The functional superhard layer, which is deposited on the functional alternating layer, is deposited using the FCVA method, which contains a basic element nitride or carbide.

Wherein, the substrate is stainless steel, high-speed steel, alloy steel, titanium alloy or aluminum alloy.

Wherein, the first transition layer, the second transition layer, the functional alternate layer and the functional superhard layer are all hydrogen-free DLC coatings, the hydrogen content in the hydrogen-free DLC coating is less than 2%, and the sp ³ bond content is greater than 90%.

Wherein, the total thickness of the metal coating is 1-5um, and the hardness is 2500-4000Hv.

A preparation process of a high-adhesion metal coating, comprising the following steps:

S1: Select the base: stainless steel, high-speed steel, alloy steel, titanium alloy or aluminum alloy as the base part, and use the clamping fixture to clamp the base part in the vacuumed chamber for coating, and the coating tool is three-level rotation;

S2: deposit a primer layer on the substrate, and use PVD method to deposit Ni, Cr, Ti, W, Si or its mixture or its nitride or its carbide to form one or several layers of high bonding force under the action of a specific bias membrane;

S3: deposit a metal layer on the base layer, and use PVD to deposit Ni, Cr, Ti, W, Si or their mixtures or their nitrides or their carbides under a specific bias voltage to form one or several metal connection layers;

S4: depositing a first transition layer and a second transition layer on the metal layer, using the FCVA method to deposit a first transition layer under a specific first bias, comprising a first transition layer of a basic element nitride or carbide; using depositing a second transition layer under a second bias voltage by FCVA method, comprising a second transition layer of a basic element nitride or carbide;

S5: depositing a functional alternating layer on the second transition layer, using the FCVA method to deposit a functional alternating layer under a third bias voltage, and attaching several alternating functional alternating layers on the surface of the second transition layer, containing a basic element nitride or Functionally alternating layers of carbides;

S6: depositing a functional superhard layer on the functionally alternating layer, using the CVA method to deposit a functional superhard layer under a fourth bias, including a functional superhard layer of a basic element nitride or carbide.

In conclusion, the high-adhesion metal coating and its preparation process, using a new ion etching process and heating between 130°-150°C, have the best cleaning effect on the surface of the substrate, so as to enhance the bonding between the primer layer and the substrate material. Adhesion, which can significantly improve the bonding force of the film layer. The invention provides a high-adhesion metal coating and a preparation process thereof. The magnetic confinement filtration focusing pure ion coating technology is used to coat a hydrogen-free DLC film in a high vacuum state with a rigid functional film with alternating multi-layer functions. It not only improves the hardness of the surface of the substrate, but also has good uniformity of the film layer, and has strong mechanical wear resistance and environmental resistance.

Description of drawings

FIG. 1 is a schematic diagram of a high-adhesion metal coating according to the present invention.

Detailed ways

The present invention will be further described in detail below in conjunction with the accompanying drawings. In the description of the present invention, it should be understood that the orientation or positional relationship indicated by the orientation words such as "upper, lower" and "top, bottom" is usually based on the orientation or positional relationship shown in the accompanying drawings, only for the purpose of For the convenience of describing the present invention and simplifying the description, in the absence of the contrary, these directional words do not indicate or imply that the device or element referred to must have a particular orientation or be constructed and operated in a particular orientation, and therefore should not be construed as a reference to the present invention. Limitation of the protection scope of the invention; the orientation words "inside and outside" refer to the inside and outside relative to the contour of each component itself.

A high adhesion metal coating comprising:

Substrate, the substrate is stainless steel, high-speed steel, alloy steel, titanium alloy or aluminum alloy;

A primer layer, which is deposited on the substrate, using PVD to deposit Ni, Cr, Ti, W, Si or their mixtures or their nitrides or their carbides to form one or more layers of high bonding force under a first bias film; film thickness is generally 0.1-1um;

A metal layer, which is deposited on the primer layer, using PVD to deposit Ni, Cr, Ti, W, Si or mixtures thereof or their nitrides or their carbides to form one or more metal connection layers under a second bias; Thickness is generally 0.1-0.5um;

The first bias voltage and the second bias voltage of the primer layer and metal layer deposited by the PVD method are related and foundational in structure and hardness.

A transition layer deposited on the metal layer, including a first transition layer and a second transition layer, deposited using the FCVA method under a first bias voltage and a second bias voltage, respectively, the first transition layer and the second transition layer Both contain a basic element nitride or carbide; the thickness of the first transition layer is 0.2um or other, the hardness of the first transition layer coating is 1400Hv or other; the thickness of the second transition layer is 0.3um or other, the second The hardness of the transition layer coating can be 1900Hv or others.

A functional alternating layer, which is deposited on the transition layer, is deposited by the FCVA method under the third bias, and comprises a basic element nitride or carbide, and alternately arranged functional alternating layers are attached on the surface of the second transition layer; the functional alternating layer The film thickness is 0.8um or other, and the hardness of its functional alternating layer can be 2500Hv or other.

The functional superhard layer, which is deposited on the functional alternating layer, is deposited by the FCVA method under the fourth bias, and which comprises a basic element nitride or carbide. The thickness of the functional superhard layer is 1.2um or other, and the functional superhard layer can be 3200Hv or others.

The first bias, the second bias, the third bias and the fourth bias of the transition layer, the functional alternating layer and the functional superhard layer deposited by the FCVA method are related and foundational in structure and hardness, Young's Modulus and hardness remain stable or vary independently with coating sequence.

Wherein, the first transition layer, the second transition layer, the functional alternating layer and the functional superhard layer are all hydrogen-free DLC coatings, the hydrogen content in the hydrogen-free DLC coating is less than 2%, and the sp3 bond content is greater than 90% %.

The thickness of the primer layer is 0.6um or other, and the hardness of the coating with strong adhesion to the substrate is 700Hv or other.

The thickness of the metal layer is 0.3um or other, and the hardness of the metal layer is 800Hv or other.

The thickness of the first transition layer is 0.2um or other, and the hardness of the first transition layer is 1400Hv or other.

The thickness of the second transition layer is 0.3um or others, and the hardness of the second transition layer can be 1900Hv or others.

The thickness of the functional alternate layer is 0.8um or others, and the hardness of the functional alternate layer can be 2500Hv or others.

The thickness of the functional superhard layer is 1.2um or others, and the hardness of the functional superhard layer can be 3200Hv or others.

The process film thickness can reach 5um or others, and the coating hardness can also reach 3500Hv or more.

The vacuum coating equipment chamber is provided with a turret, the coating parts can be adjusted by two or three levels of rotation, and the uniformity of the coating is controllable, and the uniformity is within 5%.

Wherein, the total thickness of the metal coating is 1-5um, and the hardness is 2500-4000Hv.

A preparation process of a high-adhesion metal coating, comprising the following steps:

S1: Select the base: stainless steel, high-speed steel, alloy steel, titanium alloy or aluminum alloy as the base part, and use the clamping fixture to clamp the base part in the vacuumed chamber for coating, and the coating tool is three-level rotation;

S2: deposit a primer layer on the substrate, and use PVD method to deposit Ni, Cr, Ti, W, Si or its mixture or its nitride or its carbide to form one or several layers of high bonding force under the action of a specific bias membrane;

S3: deposit a metal layer on the base layer, and use PVD to deposit Ni, Cr, Ti, W, Si or their mixtures or their nitrides or their carbides under a specific bias voltage to form one or several metal connection layers;

S4: depositing a first transition layer and a second transition layer on the metal layer, using the FCVA method to deposit a first transition layer under a specific first bias, comprising a first transition layer of a basic element nitride or carbide; using depositing a second transition layer under a second bias voltage by FCVA method, comprising a second transition layer of a basic element nitride or carbide;

S5: depositing a functional alternating layer on the second transition layer, using the FCVA method to deposit a functional alternating layer under a third bias voltage, and attaching several alternating functional alternating layers on the surface of the second transition layer, containing a basic element nitride or Functionally alternating layers of carbides;

S6: depositing a functional superhard layer on the functionally alternating layer, using the CVA method to deposit a functional superhard layer under a fourth bias, including a functional superhard layer of a basic element nitride or carbide.

The invention provides a high-adhesion metal coating and a preparation process thereof. The base is made of hard alloy material, and ion etching is sequentially performed on the surface of the base from the inside to the outside to clean the surface of the base; The bottom layer (such as Cr, NiCr layer); the metal layer is also deposited by magnetron sputtering (such as Ti, TiC layer); the functional layer is coated by the magnetic confinement filter focusing pure ion coating technology. , which consists of the above-mentioned main process sequence of multi-layer alternating hydrogen-free-DLC film high-adhesion metal coating.

Example 1

The invention provides a high-adhesion metal coating and a preparation process thereof, wherein a specific implementation of the coating film system scheme (as shown in Figure 1) is: substrate/Cr/NiCr/Ti/TiC/hydrogen-free DLC/ Air;

The base is made of cemented carbide material, in which the thickness of the first layer of Cr is 0.3um, the thickness of the second layer of NiCr is 0.5um; the thickness of the Ti layer is 0.2um, the thickness of the TiC layer is 0.3um, and the multilayer The thickness of the alternating hydrogen-free DLC layers is 2.5um, and the total film thickness is 3.8um.

The coating process and preparation method of this example are as follows:

The high-speed steel substrate is cleaned with the best ultra-cleaning process using a fully automatic ultrasonic cleaning machine, and clamped in a high vacuum environment of a pure ion coating machine using a three-stage rotation tooling. Under the environment of furnace temperature of 100°-130° and vacuum degree of 3*10 ^-3 Pa, IBM was used to ion-etch the surface of the substrate to clean the surface of the substrate to improve the adhesion of the film.

The vacuum of the coating machine chamber is evacuated to below 3*10 ^-3 Pa, and the chamber temperature is about 100-130 ℃ in the working gas environment. First, magnetron sputtering is used for the bottom layer deposition, and the Cr target is biased under the external voltage. Under the condition of 1, sputtering the coating on the surface of the substrate will obtain a Cr film with high adhesion on the substrate. Then, under the condition of a specific external bias voltage 2, the magnetron sputtering of the NiCr layer will be carried out to further improve the Cr film. Bonding force; then use magnetron sputtering to deposit the metal layer, perform sputtering coating of the Ti layer under the condition of a specific external bias voltage 3, and deposit TiC by magnetron sputtering of the transition layer of the metal layer to improve the metal layer and the free Adhesion of the hydrogen DLC layer; finally, the hydrogen-free DLC layer is deposited by the FCV method, and the magnetic confinement filtration focusing pure ion coating technology will be used to act on the carbon in a working gas environment with a vacuum degree of 2*10 ^-3 Pa or less at room temperature On the target, a high-purity hydrogen-free-DLC film will be deposited on the surface of the transition layer under the condition of applying different bias voltages. By adjusting the coating process parameters, the multi-layer hydrogen-free-DLC film will be alternately plated under the bias voltage difference. After the deposition is completed, the film layer will become a hard functional film with high adhesion.

In the example of the present invention, the SP ³ bond content of the hydrogen-free-DLC film layer is as high as 90% or more, and the purity of the graphite target is more than 99.999%. Combined with multiple alternating functional layers, it becomes a hard film with extremely high adhesion and wear resistance. Among them, the purity of the magnetron sputtering targets are all high-purity targets of more than 99.999%.

Now the test block of the above-mentioned hydrogen-free DLC hard film is carried out the following performance tests to detect, and the test results are as follows:

In summary, the high-adhesion hard film coating process of the present invention realizes three-level rotation on the workpiece disk in the vacuum chamber, and has good film uniformity, firm adhesion, high hardness, strong corrosion resistance, and high processing yield. , low cost, high efficiency, is a high-adhesion hard functional film worthy of promotion.

Finally, it should be noted that those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, provided that these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.

Claims (5)

1. A high adhesion metal coating, comprising:

a substrate;

the base layer is deposited on the substrate, and one or more layers of high-bonding-force films consisting of Ni, Cr, Ti, W, Si or a mixture thereof or a nitride thereof or a carbide thereof are deposited by using a PVD method;

a metal layer deposited on the primer layer, wherein one or more metal connecting layers consisting of Ni, Cr, Ti, W, Si or their mixture or their nitride or their carbide are deposited by PVD;

a transition layer deposited on the metal layer, comprising a first transition layer and a second transition layer, deposited using the FCVA method, the first transition layer and the second transition layer each comprising a nitride or carbide of a base element;

the functional alternating layer is deposited on the transition layer by adopting an FCVA method and comprises a nitride or carbide of a basic element, and the functional alternating layer is attached to the surface of the second transition layer in an alternating mode;

a functional superhard layer, deposited on the functional alternating layer, is deposited by the FCVA process and comprises a nitride or carbide of one of the essential elements.

2. The high adhesion metal coating of claim 1, wherein the substrate is stainless steel, high speed steel, alloy steel, titanium alloy, or aluminum alloy.

3. The high adhesion metal coating of claim 1, wherein the first transition layer, the second transition layer, the functional alternating layer and the functional superhard layer are all hydrogen-free DLC coatings with a hydrogen content of less than 2%, sp ³ The bond content is greater than 90%.

4. The high adhesion metal coating as claimed in claim 1, wherein the total thickness of the metal coating is 1-5 μm, and the hardness is 2500-.

5. A preparation process of a high-adhesion metal coating is characterized by comprising the following steps:

s1: selecting a substrate: stainless steel, high-speed steel, alloy steel, titanium alloy or aluminum alloy are used as substrate parts, the substrate parts are clamped in a vacuumized chamber by utilizing a clamping fixture for coating, and the coating tool is subjected to three-stage rotation;

s2: depositing a priming layer on a substrate, and depositing one or more layers of high-bonding-force films consisting of Ni, Cr, Ti, W, Si or a mixture thereof or a nitride thereof or a carbide thereof by using a PVD method under the action of a specific bias voltage;

s3: depositing a metal layer on the priming layer, and depositing a metal connecting layer consisting of one or more layers of Ni, Cr, Ti, W, Si or a mixture thereof or a nitride thereof or a carbide thereof by using PVD under a second specific bias;

s4: depositing a first transition layer and a second transition layer on the metal layer, the first transition layer comprising a nitride or carbide of a base element, being deposited using the FCVA method at a specific first bias; depositing a second transition layer at a second bias, the second transition layer comprising a nitride or carbide of a base element, using the FCVA method;

s5: depositing a functional alternating layer on the second transition layer, depositing the functional alternating layer under a third bias by using an FCVA method, and attaching several alternating functional alternating layers comprising a nitride or carbide of a basic element on the surface of the second transition layer;

s6: depositing a functional superhard layer on the functional alternating layer, and depositing the functional superhard layer under a fourth bias voltage by using a CVA method, wherein the functional superhard layer comprises a nitride or carbide of a basic element.

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