WO2016155078A1

WO2016155078A1 - Amorphous carbon composite coating, and manufacturing method and application thereof

Info

Publication number: WO2016155078A1
Application number: PCT/CN2015/078100
Authority: WO
Inventors: 贺凤飞; 王秀丽; 李玲玲; 白文琦; 金攻; 涂江平
Original assignee: 中奥汇成科技股份有限公司
Priority date: 2015-04-03
Filing date: 2015-04-30
Publication date: 2016-10-06
Also published as: CN105441872B; CN105441872A

Abstract

An amorphous carbon composite coating is composed of a pure carbon ultra-thin bottom layer and an amorphous carbon top layer sequentially deposited on a UHMWPE matrix modified by a high-energy argon ion. The manufacturing method thereof adopts a closed field unbalanced magnetron sputtering method. The amorphous carbon composite coating improves a binding force of an amorphous carbon and the matrix, thus being applicable in biomedicine, for example for an artificial joint cup surface.

Description

Amorphous carbon composite coating and preparation method and application thereof

Technical field

The invention belongs to the field of wear-resistant coatings, and particularly relates to an amorphous carbon composite coating which is surface-modified by ultra-high molecular weight polyethylene and provided with an amorphous carbon top layer, and a preparation method and application thereof.

Background technique

Artificial joint replacement is currently the most effective method for treating diseases in the bone and joint areas, and it has caused many patients with severe bone and joint diseases to recover. However, the loosening of the artificial joint is its fatal shortcoming. According to long-term clinical observation and experimental research, the main reason for the loosening of the artificial joint is that the wear of the prosthesis interface leads to the generation of metal, ceramic and polymer debris, and the interface between the joint head and the jaw is made. The matching between the two is worse, the aseptic loosening occurs and eventually the artificial joint fails, and the debris usually causes biological reactions in the human body, such as inflammation or rejection, and the granuloma is damaged after the debris is swallowed by macrophages. It causes osteolysis and bone resorption, and even abnormal cell differentiation, carcinogenesis, necrosis, etc. The existence of these technical problems has led to the limited service life of artificial joints, which not only affects the quality of life of patients, but also causes an increase in the cost of treatment.

Reducing the wear of artificial joints is the key to solving the problem of loosening of artificial joint prosthesis. The most commonly used artificial joint friction pair is the artificial joint cup made of ultra high molecular weight polyethylene (UHMWPE) and the joint made of metal or ceramic. The friction pair formed by the ball head, how to improve the wear resistance of the soft UHMWPE material cup and reduce the generation of polymer debris is an urgent problem to be solved.

Summary of the invention

It is an object of the present invention to provide an amorphous carbon composite coating technical solution to provide a composite coating with high wear resistance and better adhesion between coatings.

The embodiments of the present invention are implemented by the following technical solutions:

An amorphous carbon composite coating consisting of a pure carbon ultrathin underlayer and an amorphous carbon top layer deposited sequentially on the surface of a UHMWPE substrate, the pure carbon ultrathin underlayer being formed of modified pure carbon, the amorphous carbon top layer being composed of Amorphous carbon is formed; the amorphous carbon includes two forms of sp ² amorphous carbon and sp ³ amorphous carbon; and the atomic percentage of the sp ³ amorphous carbon in the amorphous carbon top layer is 24 to 28% .

Further, in the top layer of the amorphous carbon, the ratio of the sp ² amorphous carbon to the sp ³ amorphous carbon in each cross section perpendicular to the thickness direction of the amorphous carbon top layer is the same.

Further, the surface of the UHMWPE substrate is a modified UHMWPE.

Further, the modified UHMWPE is UHMWPE after argon plasma modification treatment under a bias voltage of -500V.

Further, the pure carbon ultrathin underlayer has a thickness of 2 nm to 5 nm.

Further, the amorphous carbon top layer has a thickness of 700 nm to 900 nm.

A method for preparing an amorphous carbon composite coating, comprising the steps of:

1) placing the UHMWPE substrate on a rotating table, pre-vacuating the cavity of the rotating table, introducing argon gas, performing pre-sputtering, and removing impurities and oxides on the surface of the target;

2) wherein the first carbon target current is maintained at 0.25-0.5A, the second carbon target maintains a small current throughout the whole; controlling the flow rate of the argon gas, maintaining a bias value, the UHMWPE substrate relatively staying at the first carbon target Opposite to the deposition of the modified pure carbon ultra-thin underlayer while performing argon plasma modification on the UHMWPE substrate, the deposition time is 20-35 min;

3) increasing the current of the first carbon target and maintaining it at 2 to 2.5 A, increasing the flow rate of the argon gas and maintaining the set value, and decreasing the bias value, the deposition time is 99 min to 110 min, and the amorphous carbon is completed. The deposition of the amorphous carbon top layer formed.

Further, in step 2), the flow rate of the argon gas is controlled between 20 and 35 sccm; and the bias value is maintained at -500 V.

Further, in step 3), the argon flow rate is controlled between 40 and 45 sccm; and the bias value is decreased from -500 V to -300 V.

Further, in the step 1), the first carbon target and the second carbon target are symmetrically disposed centering on the rotary table.

Further, in step 1), the distance between the UHMWPE substrate and the first carbon target is 5-15 cm.

Further, in step 1), the cavity is pre-vacuumed to 10 ^-4 to 10 ^-3 Pa, and argon gas is introduced, and the flow rate of the argon gas is controlled between 25 and 35 sccm, at -450 to -550 V. The bias voltage and the first carbon target current of 0.2 to 0.5 A are pre-sputtered for 20 to 30 minutes.

Further, the first carbon target and the second carbon target are both graphite targets.

The amorphous carbon composite coating according to any one of the above, wherein the amorphous carbon composite coating is applied to an artificial joint 臼 Cup.

The beneficial effects of the embodiments of the present invention are:

The amorphous carbon composite coating layer of the embodiment of the invention is composed of a pure carbon ultra-thin bottom layer and an amorphous carbon top layer which are sequentially deposited on a high energy argon ion modified UHMWPE substrate, high energy argon ion modification and pure carbon ultrathin bottom layer. The design can improve the bonding force of the amorphous carbon composite coating of the present invention to the substrate. Compared with the surface hardness of the untreated UHMWPE matrix of 80-100 MPa, the hardness of the amorphous carbon composite coating can reach 1-1.5 GPa (1 GPa = 1000 MPa), and the improvement is obvious. The amorphous carbon composite coating of the embodiment of the present invention exhibits excellent antifriction and wear resistance and biocompatibility in a simulated human body environment. The amorphous carbon composite coating of the embodiment of the invention has the advantages of high hardness, good bonding force, low friction coefficient and excellent wear resistance, and can be used in the field of biomedicine, such as artificial joint surface, thereby greatly improving the service life of the material. ,with broadly application foreground.

The preparation method of the amorphous carbon composite coating according to the embodiment of the invention adopts the closed field unbalanced magnetron sputtering method, the amorphous carbon composite coating is well combined with the substrate, and is convenient for continuous industrial production, and is easy to popularize and utilize.

In order to further improve the bonding force of the amorphous carbon composite coating layer in the embodiment of the present invention, preferably, the ultra-thin underlayer of pure carbon is simultaneously plated in the process of performing high-bias argon ion surface modification on the UHMWPE substrate, and the underlying layer is The top layer of the crystal carbon has different process parameters and deposition stages. While modifying the UHMWPE matrix, the polymer chain radicals of the matrix modification layer can be bonded to the carbon atoms from the target, which is more favorable for the interface bonding force. improve.

DRAWINGS

1 is a schematic structural view of an apparatus for realizing a method for preparing an amorphous carbon composite coating according to an embodiment of the present invention;

2 is a schematic structural view of an amorphous carbon composite coating according to an embodiment of the present invention;

3 is a cross-sectional SEM and a simple annotation of a silicon wafer base amorphous carbon composite coating prepared in Example 1;

4 is a crater test result of a UHMWPE matrix amorphous carbon composite coating modified by a high energy argon ion and a pure carbon ultrathin primer layer;

Figure 5 shows the crater test results of UHMWPE matrix amorphous carbon composite coating modified without high energy argon ion and pure carbon ultrathin underlayer.

Description of the reference signs:

1 plasma modified layer, 2 pure carbon ultrathin underlayer, 3 amorphous carbon top layer, 4 amorphous carbon composite layer, 5 matrix, 6 first graphite target, 7 first titanium target, 8 second graphite target, 9 Titanium target 9, 10 sample stage, 11 sample holder.

detailed description

As shown in FIG. 1 , a schematic structural view of an apparatus for implementing a method for preparing an amorphous carbon composite coating according to an embodiment of the present invention includes a rotary table and four targets disposed around the rotary table, and the rotary table includes a sample. The stage 10 and the sample holder 11 mounted on the sample stage 10 are arranged horizontally in the rotary table. Two of the four targets are graphite targets (one type of carbon target), two of which are titanium targets; two graphite targets The first graphite target 6 and the second graphite target 8, respectively, the two titanium targets are the first titanium target 7 and the second titanium target 9, respectively; the first graphite target 6 and the second graphite target 8 are symmetric about the rotating table It is provided that the first titanium target 7 and the second titanium target 9 are symmetrically disposed centering on the rotary table, and an angle formed between the adjacent two targets of the four targets and the rotary table is 90°, and the sample holder 11 is used for The substrate is placed and the targets of the four targets are oriented towards the substrate.

As shown in FIG. 2, it is a schematic view of an amorphous carbon composite coating 4 according to an embodiment of the present invention, which is deposited on the substrate 5 in sequence, and has a modified pure carbon super on the very thin plasma-modified layer 1 at the top of the substrate. The thin underlayer 2 is composed of an amorphous carbon top layer 3 formed of amorphous carbon. The modified pure carbon ultrathin underlayer 2 has a thickness of 2 nm to 5 nm, and the amorphous carbon top layer 3 formed of amorphous carbon has a thickness of 700 nm to 900 nm. Among them, the modified pure carbon refers to the deposition of pure carbon while performing plasma argon modification on the surface of the substrate, and at this time, the pure carbon and the matrix are bonded to the polymer during the modification process, that is, the pure carbon passes through the matrix. Modification.

The surface of the substrate is a modified UHMWPE matrix. For example, the modified UHMWPE matrix is a UHMWPE matrix after argon plasma modification at a bias of -500V.

The cross section of the amorphous carbon top layer 3 perpendicular to the thickness direction of the amorphous carbon top layer 3 (the upper portion refers to the cross section in either direction) has the same composition, and is composed of amorphous carbon, and the amorphous carbon includes sp ² amorphous. Both carbon and sp ³ amorphous carbon; the atomic percentage of the sp ³ amorphous carbon in the top layer is 24 to 28%.

The amorphous carbon composite coating 4 described above can be applied to an artificial joint cup. In other embodiments of the present invention, the amorphous carbon composite coating 4 can also be applied to other places where it is needed to form different products.

Example 1

The amorphous carbon composite coating was prepared by closed field unbalanced magnetron sputtering. The preparation steps were as follows:

1) Using medical ultra-high molecular weight polyethylene (UHMWPE) as a substrate, the substrate is placed on the sample holder 11 on the sample stage 10, the first graphite target 6 is a working target, the first titanium target 7, and the second graphite target 8 The second titanium target 9 is a non-working target, but maintains a small current state of 0.25 A, prevents the target from being contaminated during the coating process, adjusts the distance between the first graphite target and the substrate, adjusts the pitch to 10 cm, and the sample stage 10 The revolution remains closed, and the self-rotation rate of the sample holder 11 is 15 rpm;

The chamber was pre-vacuated to 4.0×10 ⁻³ Pa, then pure argon gas was introduced, the argon flow rate was controlled at 25 sccm, and pre-sputtering was performed for 30 min at a bias of −500 V and a first graphite target current of 0.2 A;

2) Using a first carbon target current of 0.25A and a bias voltage of -500V, the UHMWPE substrate is subjected to high energy argon ion modification while depositing and modifying pure carbon to form a pure carbon ultrathin underlayer, and the argon flow rate is controlled at 25 sccm. Working pressure is 0.2Pa, deposition time is 20min, forming pure carbon ultra-thin bottom layer 2;

3) The first graphite target current is increased from 0.25A to 2.5A, the other three inactive target currents are maintained at 0.25A, the argon flow rate is increased from 25sccm to 45sccm, and the bias voltage is reduced from -500V to -300V, deposition time. 99min, forming an amorphous carbon top layer 3;

A scanning electron micrograph of a cross section of the amorphous carbon composite coating prepared in the first embodiment is shown in FIG. 3. The amorphous carbon composite coating prepared in the first embodiment is sequentially deposited on a UHMWPE substrate by high energy argon ion modification. The treated matrix modified layer 1, the pure carbon ultrathin underlayer 2 and the amorphous carbon top layer 3 are composed, the pure carbon ultrathin underlayer 2 has a thickness of 3.4 nm, and the amorphous carbon top layer 3 has a thickness of about 710 nm.

The thickness of the pure carbon ultrathin underlayer is measured by an ellipsometer using only the comparative test samples of steps 1) and 2). The thickness of the amorphous carbon top layer is measured by a step meter.

By Raman spectroscopy, the surface of the sample surface of the sample subjected to the friction and wear test and the non-abrasive area of the test surface of the amorphous carbon top layer maintain the integrity, that is, have good friction and wear resistance. The cross-sectional analysis of the amorphous carbon top layer by energy dispersive X-ray spectroscopy (EDX) shows that the cross-section components perpendicular to the thickness direction of the amorphous carbon top layer 3 are the same, and are composed of carbon elements and do not contain titanium elements.

X-ray photoelectron spectroscopy analysis (XPS) shows that the amorphous carbon in the top layer 3 of the amorphous carbon has two forms of sp ² and sp ³ , and the non-form of the sp ³ form of the amorphous carbon top layer 3 The crystalline carbon atom percentage content is about 24%.

Example 2

The amorphous carbon composite coating prepared by the closed field unbalanced magnetron sputtering method is a device for realizing the preparation method of the amorphous carbon composite coating of the present invention in a specific embodiment, and the preparation steps are as follows:

2) using a first graphite target current of 0.5A and a bias voltage of -500V to deposit pure carbon at the same time as high energy argon ion modification of the UHMWPE substrate to form a pure carbon ultrathin underlayer, the argon flow rate is controlled at 30 sccm, and the working pressure is 0.25Pa, deposition time is 20min, forming a pure carbon ultra-thin bottom layer 2;

3) The first graphite target current increases from 0.5A to 2.5A, the other three inactive target currents are maintained at 0.25A, the argon flow rate is increased from 30sccm to 45sccm, and the bias voltage is reduced from -500V to -300V, deposition time. 99min, forming an amorphous carbon top layer 3;

The scanning electron micrograph of the cross section of the amorphous carbon composite coating prepared in this Example 2 is shown in the figure (similar to FIG. 3), and the amorphous carbon composite coating prepared in the first embodiment is deposited on the UHMWPE substrate in this order. The high energy argon ion modified substrate modified layer 1, the pure carbon ultrathin underlayer 2 and the amorphous carbon top layer 3 are composed. The pure carbon ultrathin underlayer 2 has a thickness of 4.6 nm, and the amorphous carbon top layer 3 has a thickness of about 732 nm.

By Raman spectroscopy, the surface of the sample surface of the sample subjected to the friction and wear test and the non-abrasive area of the test surface of the amorphous carbon top layer maintain the integrity, that is, have good friction and wear resistance. The cross-sectional analysis of the amorphous carbon top layer by energy dispersive X-ray spectroscopy (EDX) shows that the cross-section components perpendicular to the thickness direction of the amorphous carbon top layer 3 are the same, and are composed of carbon elements and do not contain titanium elements. X-ray photoelectron spectroscopy (XPS) shows that the amorphous carbon in the top layer 3 of amorphous carbon has two forms of sp ² and sp ³ , and the content of amorphous carbon in the form of sp ³ in the top layer 3 of amorphous carbon is about 25 %.

Example 3

2) using a first graphite target current of 0.25A and a bias voltage of -500V to deposit pure carbon at the same time as high energy argon ion modification of the UHMWPE substrate to form a pure carbon ultrathin underlayer, the argon flow rate is controlled at 35 sccm, and the working gas pressure is 0.29Pa, deposition time is 20min, forming a pure carbon ultra-thin bottom layer 2;

3) The first graphite target current is increased from 0.25A to 2.5A, the other three inactive target currents are maintained at 0.25A, the argon flow rate is increased from 25sccm to 45sccm, and the bias voltage is reduced from -500V to -300V, deposition time. 110min, forming an amorphous carbon top layer 3;

The scanning electron micrograph of the cross section of the amorphous carbon composite coating prepared in this Example 3 is shown in the figure (similar to FIG. 3). The amorphous carbon composite coating prepared in the first embodiment is deposited on the UHMWPE substrate in this order. The high energy argon ion modified substrate modified layer 1, the pure carbon ultrathin underlayer 2 and the amorphous carbon top layer 3 are composed. The pure carbon ultrathin underlayer 2 has a thickness of 2.3 nm, and the amorphous carbon top layer 3 has a thickness of 875 nm.

By Raman spectroscopy, the surface of the sample surface of the sample subjected to the friction and wear test and the non-abrasive area of the test surface of the amorphous carbon top layer maintain the integrity, that is, have good friction and wear resistance. The cross-sectional analysis of the amorphous carbon top layer by energy dispersive X-ray spectroscopy (EDX) shows that the cross-section components perpendicular to the thickness direction of the amorphous carbon top layer 3 are the same, and are composed of carbon elements and do not contain titanium elements. X-ray photoelectron spectroscopy (XPS) shows that the amorphous carbon in the top layer 3 of amorphous carbon has two forms of sp ² and sp ³ , and the content of amorphous carbon in the form of sp ³ in the top layer 3 of amorphous carbon is about 27 %.

Example 4

2) using a first graphite target current of 0.5A and a bias voltage of -500V to deposit pure carbon at the same time as high energy argon ion modification of the UHMWPE substrate to form a pure carbon ultrathin underlayer 2, the argon flow rate is controlled at 35 sccm, working pressure 0.3Pa, deposition time is 20min, forming a pure carbon ultrathin underlayer 2;

3) The first graphite target current is increased from 0.25A to 2.5A, the other three inactive target currents are maintained at 0.25A, the argon flow rate is increased from 35sccm to 45sccm, and the bias voltage is reduced from -500V to -300V, deposition time. 110min, forming an amorphous carbon top layer 3;

The scanning electron micrograph of the cross section of the amorphous carbon composite coating prepared in the fourth embodiment is shown in the figure (similar to FIG. 3), and the amorphous carbon composite coating prepared in the first embodiment is deposited on the UHMWPE substrate in this order. The high energy argon ion modified substrate modified layer 1, the pure carbon ultrathin underlayer 2 and the amorphous carbon top layer 3 are composed. The pure carbon ultrathin underlayer 2 has a thickness of 3.9 nm, and the amorphous carbon top layer 3 has a thickness of 832 nm.

The amorphous carbon composite coatings prepared in Examples 1, 2, 3, and 4 of the present invention were measured by the NANO G200 nanoindenter manufactured by MTS, USA, and the measurement results are shown in Table 1. The longitudinal bonding force of the amorphous carbon composite coating and the interface of the substrate was evaluated by the crater method under a load of 1 kg. The frictional wear of amorphous carbon composite coatings prepared in Examples 1, 2, 3 and 4 of the present invention was evaluated by using Si ₃ N ₄ ceramic as a pair of grinding balls under the condition of boundary lubrication of calf serum deionized water. performance. Table 1 shows the average sliding friction coefficient of the amorphous carbon composite coating prepared in Examples 1, 2, 3, and 4, and the wear rate and hardness of the amorphous carbon composite coating before and after modification of the UHMWPE matrix. And Figure 4 shows the crater test results of UHMWPE matrix amorphous carbon composite coating modified by high energy argon ion and pure carbon ultrathin underlayer; Fig. 5 shows UHMWPE modified without high energy argon ion and pure carbon ultrathin underlayer The crater test results of the matrix amorphous carbon composite coating.

Table 1

The results of the measurement of the amorphous carbon composite coating prepared in accordance with Examples 1, 2, 3, and 4 of the present invention in Table 1 show that the characteristics and advantages of the amorphous carbon composite coating of the embodiment of the present invention are as follows:

1. The amorphous carbon composite coating of the embodiment of the invention has good bonding strength with the substrate. The surface of the UHMWPE substrate of the

embodiments

1, 2, 3 and 4 of the invention is subjected to high energy argon ion modification treatment, and an ultra-thin carbon film is designed simultaneously with high energy argon ion modification, and the ultra-thin carbon film and the top layer are not The crystal carbon has different process parameters, and can be connected downwards with the broken polymer chain radicals, and can be up to the top of the amorphous carbon. The carbon atoms are connected to enhance the bonding force. Films and UHMWPE of Example 1, Example 2, Example 3 and Example 4 evaluated by crater method under a 1 kg load with respect to a comparative test without high energy argon ion modification treatment and pure carbon ultrathin primer design The bonding condition of the substrate is better, and the film does not crack and peel off at the edge of the crater.

Second, low friction coefficient, excellent wear resistance. The amorphous carbon composite coatings prepared in Example 1, Example 2, Example 3 and Example 4 were subjected to a frictional wear test under boundary lubrication conditions of deionized aqueous solution of calf serum, and after a friction distance of 180864 mm (radius 5 mm, 192 rpm, The average kinetic friction coefficients of the 30 min, 1A frictional wear test, 5760 friction cycle processes were 0.125, 0.118, 0.129 and 0.132, respectively, and the friction coefficient fluctuated less. The wear rate of the amorphous carbon composite coating was 3.90×10 ^-13 , 3.96×10 ^-13 , 3.80×10 ^-13 and 3.73×10 ^-13 , respectively, and it has excellent wear resistance.

3. Depositing an abrasion-resistant coating on the surface of UHMWPE, and plasma-modifying the surface of the material before depositing the wear-resistant coating is a method to improve the surface wear resistance of UHMWPE. Amorphous carbon coatings are widely used in various fields such as friction and biology because of their high hardness, good wear resistance, good chemical stability and excellent biocompatibility. However, due to the difference in physical properties between the amorphous carbon coating and the UHMWPE matrix, how to improve the interfacial bonding strength between the amorphous carbon coating and the substrate is the key to the problem, and at the same time, due to the large internal stress of the amorphous carbon coating, the limitation is limited. The thickness of the amorphous carbon coating is so thick that the deposited amorphous carbon coating should not be too thick. For example, the thickness of the deposited layer may be between 700 and 900 nm.

In order to improve the interfacial bonding strength between the amorphous carbon coating and the substrate, it is a good method to modify the UHMWPE substrate before the amorphous carbon deposition. The surface of the substrate is treated with argon ions under a large bias voltage. Some changes will occur in the range of tens to hundreds of nanometers of the UHMWPE surface rather than the entire body material. These changes include the breakage of the polymer chain, the formation of free radicals, and the re-bonding of the polymer chain after breaking. Some long molecular chain structures are destroyed, the degree of cross-linking of the materials is improved, and the accompanying change is an increase in surface hardness.

In addition, the fractured surface polymer chain can be bonded to the carbon atom from the target. Since the polymer chain is composed of C and H atoms, the bonding of the polymer chain and the carbon atom is relatively easy, by passing the plasma at a high bias voltage. In the process of bulk modification, a layer of pure carbon ultra-thin primer layer is introduced at the same time. The pure carbon ultra-thin primer layer and the amorphous carbon top layer have different preparation process parameters and are deposited in different stages. The pure carbon ultra-thin primer layer is produced on the UHMWPE substrate surface. During the modification process, the UHMWPE matrix is connected downwards, upward and amorphous carbon The top layer is joined to act as a bridge to enhance the interfacial adhesion between the coating and the UHMWPE matrix.

While the embodiments of the present invention have been shown and described, it will be understood by those skilled in the art The scope of the invention is defined by the appended claims and their equivalents.

Claims

An amorphous carbon composite coating comprising: a pure carbon ultrathin underlayer and an amorphous carbon top layer sequentially deposited on a surface of a UHMWPE substrate, the pure carbon ultrathin underlayer being formed of modified pure carbon, the non- The top layer of the crystalline carbon is formed of amorphous carbon; the amorphous carbon includes two forms of sp 2 amorphous carbon and sp 3 amorphous carbon; and the atomic percentage of the sp 3 amorphous carbon in the amorphous carbon top layer is 24 to 28%.
The amorphous carbon composite coating according to claim 1, wherein said sp 2 amorphous carbon and sp of each cross section perpendicular to a thickness direction of said amorphous carbon top layer in said amorphous carbon top layer 3 The ratio of amorphous carbon is the same.
The amorphous carbon composite coating according to claim 1, wherein the surface of the UHMWPE substrate is a modified UHMWPE.
The amorphous carbon composite coating according to claim 3, wherein the modified UHMWPE is UHMWPE after argon plasma modification treatment under a bias of -500V.
The amorphous carbon composite coating according to claim 1, wherein the pure carbon ultrathin underlayer has a thickness of from 2 nm to 5 nm.
The amorphous carbon composite coating according to claim 1, wherein the amorphous carbon top layer has a thickness of from 700 nm to 900 nm.
A method for preparing an amorphous carbon composite coating, comprising the steps of:

1) placing the UHMWPE substrate on a rotating table, pre-vacuating the cavity of the rotating table, introducing argon gas, performing pre-sputtering, and removing impurities and oxides on the surface of the target;

2) wherein the first carbon target current is maintained at 0.25-0.5A, the second carbon target maintains a small current throughout the whole; controlling the flow rate of the argon gas, maintaining a bias value, the UHMWPE substrate relatively staying at the first carbon target Opposite to the deposition of the modified pure carbon ultra-thin underlayer while performing argon plasma modification on the UHMWPE substrate, the deposition time is 20-35 min;

3) increasing the current of the first carbon target and maintaining it at 2 to 2.5 A, increasing the flow rate of the argon gas and maintaining the set value, and decreasing the bias value, the deposition time is 99 min to 110 min, and the amorphous carbon is completed. The deposition of the amorphous carbon top layer formed.
The method for preparing an amorphous carbon composite coating according to claim 7, wherein in the step 2), the flow rate of the argon gas is controlled between 20 and 35 sccm; and the bias value is maintained at -500 V. .
The method for preparing an amorphous carbon composite coating according to claim 7, wherein In step 3), the argon flow rate is controlled between 40 and 45 sccm; and the bias value is reduced from -500 V to -300 V.
The method for preparing an amorphous carbon composite coating according to claim 7, wherein in the step 1), the first carbon target and the second carbon target are symmetrically arranged centering on the rotary table .
The method for preparing an amorphous carbon composite coating according to claim 7, wherein in the step 1), the distance between the UHMWPE substrate and the first carbon target is 5-15 cm.
The method for preparing an amorphous carbon composite coating according to claim 7, wherein in the step 1), the cavity is pre-vacuumed to 10 -4 to 10 -3 Pa, and argon gas is introduced. The argon gas flow rate is controlled between 25 and 35 sccm, and is pre-sputtered for 20 to 30 minutes under a bias of -450 to 550 V and a first carbon target current of 0.2 to 0.5 A.
The method for producing an amorphous carbon composite coating according to claim 7 or 10, wherein the first carbon target and the second carbon target are both graphite targets.
The amorphous carbon composite coating according to any one of claims 1 to 13, characterized in that the amorphous carbon composite coating is applied to an artificial joint cup.