CN115198232A - A kind of high toughness erosion resistant coating and preparation method thereof - Google Patents

Abstract

The invention belongs to the technical field of material surface coatings, and discloses a high-toughness anti-erosion coating which is a Ni-Cr-N ternary coating, wherein the atomic percent of Ni element is 2-80%, the atomic percent of Cr element is 10-80%, and the atomic percent of N element is 1-50%. The preparation method of the high-toughness erosion-resistant coating selects the NiCr alloy target with proper element proportion and corresponding deposition process parameters, adopts the multi-arc ion plating technology to evaporate the metal Cr target and the NiCr alloy target, and combines the metal Cr target and the metal Cr alloy target with Ar and N in a vacuum chamber ₂ N in the mixed gas ₂ The gas reacts to form a Ni-Cr-N ternary coating with proper proportion of Ni and Cr elements, namely a high-toughness anti-erosion coating on the surface of the substrate. The ratio of Ni to Cr and the number of NiCr and Cr targets in the NiCr alloy target as the target material are adjusted to ensure that the NiCr alloy target is formed by the alloy materialThe Ni and Cr content in the coating is easy to control, and the method has simple operation, stable process and easy implementation.

Description

A kind of high toughness erosion resistant coating and preparation method thereof

technical field

The invention belongs to the technical field of material surface coatings, in particular to a high-toughness anti-erosion coating and a preparation method thereof.

Background technique

Erosive wear refers to the wear caused by the impact of high-speed particles on materials in a specific angle range. The dimensions of the parts change under erosion, and the efficiency is reduced or failed. Typical parts such as engine blades and pump blades. In order to reduce the damage to the parts caused by erosion and prolong the life of the parts, people apply the vapor-deposited hard coating on the surface of the parts to improve its erosion resistance performance. When the parts are eroded by particles, the erosion angle range is often wide. In order to effectively improve the micro-cutting damage of the parts when they are eroded by low attack angles, and at the same time resist the germination and expansion of cracks when they are eroded by high attack angles, erosion-resistant materials are required. With high hardness and good toughness. Although the new multilayer ceramic coating reported in the study has high hardness, this hard coating will reduce the fatigue life of the part, while the metal/ceramic multilayer composite coating often cannot balance the erosion resistance of high attack angle and low attack angle. .

In view of the above problems, the use of nitride-strengthened metal phase composite coatings in the present application can greatly improve the hardness of the coating, while improving the erosion resistance of the metal matrix, while retaining the advantages of high metal toughness and fatigue resistance, so nitrogen is used. As a new type of coating with both erosion resistance and fatigue resistance, metal-based coatings have good application prospects. At present, the literature on CrN hard phase-enhanced Ni-based metal anti-erosion coatings has not been reported, and there is no such thing on the market. Similar Material Design.

SUMMARY OF THE INVENTION

The purpose of the present invention is to address the above problems, and the present invention provides a high-toughness anti-erosion coating and a preparation method thereof to solve the problems raised in the background art.

In order to achieve the above-mentioned purpose, the present invention provides the following technical solutions: a high-toughness anti-erosion coating, the high-toughness anti-erosion coating is a Ni-Cr-N ternary coating, and the atomic percentage of the Ni element is 2 ~80%, the atomic percentage of Cr element is 10-80%, and the atomic percentage of N element is 1-50%.

As a preferred technical solution of the present invention, the hardness of the high-toughness erosion-resistant coating is 5-12GPa; the bonding force of the film base measured by the scratch method is greater than 80N; the particle size is 200μm silica sand is eroded at 45° The coating was eroded at a speed of 130 m/s, and the erosion rate of the coating was 0.32-0.66 mg/g.

The application also proposes a method for preparing a high-toughness anti-erosion coating, and the specific operation steps are as follows:

1) The metal Cr target and the NiCr alloy target are placed on the target seat in the vacuum chamber of the multi-arc ion plating equipment, and the base is placed on the sample stage;

2) evacuating the vacuum chamber of the multi-arc ion plating equipment, then feeding argon into the vacuum chamber and performing glow sputtering cleaning on the surface of the substrate;

3) Pour argon gas into the vacuum chamber of the multi-arc ion plating equipment to ignite the Cr target arc, and first deposit a layer of Cr metal layer on the surface of the substrate as a bottom layer;

4) A mixed gas of argon and nitrogen is introduced into the vacuum chamber of the multi-arc ion plating equipment to ignite the NiCr target arc, and the Ni-Cr-N high-toughness erosion-resistant coating is obtained by deposition.

As a preferred technical solution of the present invention, the total amount of Ni and Cr in the NiCr alloy target in the step 1) is not less than 98%, the content of Cr is 20% to 80%, and the content of Ni is 80% ~20%. Since Ni does not form nitrides, the Ni-dominated metal in the coating has high toughness and fatigue resistance. The compound formed by Cr element and nitrogen in the coating has the characteristics of high hardness and nano-scale dispersion, which not only improves the overall hardness and strength of the coating, but also retains the high toughness of the Ni-based coating. Both have excellent erosion resistance.

As a preferred technical solution of the present invention, the substrate in the step 1) is a metal substrate, and the metal is titanium alloy, zirconium alloy, steel or superalloy.

As a preferred technical solution of the present invention, vacuum is evacuated in the step 2) until the air pressure in the vacuum chamber is lower than 6×10 ^-3 Pa.

As a preferred technical solution of the present invention, in the step 2), argon gas is introduced into the vacuum chamber to make the vacuum chamber pressure at 1.0-2.0Pa, and then a bias voltage of -200--900V is applied on the substrate to generate gas. Glow discharge, and sputter cleaning of the substrate surface by ionized argon ions for not less than 5 min.

As a preferred technical solution of the present invention, in the step 3), argon gas is introduced into the vacuum chamber before the deposition starts, the pressure of the vacuum chamber is controlled at 0.2-1.6Pa, and the substrate is biased with -40V--200V to ignite the metal The Cr target arc is used to deposit a layer of Cr metal on the surface of the substrate.

As a preferred technical solution of the present invention, in the step 4), the Ni-Cr-N film is prepared by multi-arc ion plating, and the process parameters are: feeding a mixed gas of argon and nitrogen, and controlling argon and nitrogen. The flow rates are respectively 10-200 sccm and 10-1200 sccm, the working air pressure is 0.3-4.0 Pa, and the bias voltage range of the substrate is -40V--200V.

As a preferred technical solution of the present invention, in the step 4), the Ni-Cr-N film is prepared by multi-arc ion plating, and the number of deposition targets is 4 NiCr alloy targets and 4 metal Cr targets. According to the process It is necessary to select the number and combination of open targets, the target current range is 50-150A, and the duration is 20-600min.

Compared with the prior art, the beneficial effects of the present invention are as follows:

The preparation method of the high-toughness erosion-resistant coating provided by the present invention selects a NiCr alloy target with appropriate element ratio and corresponding deposition process parameters, adopts the multi-arc ion plating technology to evaporate the metal Cr target and the NiCr alloy target, and is combined with the vacuum chamber. The N ₂ gas in the mixed gas of Ar and N ₂ reacts to form a Ni-Cr-N ternary coating with a proper ratio of Ni and Cr elements on the surface of the substrate, that is, a high-toughness erosion-resistant coating. By adjusting the ratio of Ni and Cr in the target NiCr alloy target and the number of NiCr and Cr targets, the content of Ni and Cr in the coating is easy to control, and the method is simple to operate, stable in process, and easy to implement;

In the high toughness erosion resistant coating (Ni-Cr-N ternary coating) provided by the present invention, the atomic percentages of Ni, Cr and N elements are respectively 2-80%, 10-80% and 1-50%. The coating overcomes the problem of insufficient toughness of the existing hard erosion resistant coatings, and has the characteristics of high hardness and high toughness, making it suitable for compressor blades, mud pumps and other parts that are subject to erosion. prospect.

Description of drawings

Fig. 1 is the XRD figure of the high toughness anti-erosion coating that the present invention makes;

Fig. 2 is the surface morphology of the high toughness erosion resistant coating prepared by the present invention.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Example 1

1) Place 4 metal Cr targets and 4 NiCr alloy targets on the target base in the vacuum chamber of the multi-arc ion plating equipment, and the ratio of Ni:Cr in the NiCr alloy targets is 80:20;

2) Select titanium alloy as the base material, grind and polish it, clean and dry it, and place it on the sample stage in the vacuum chamber;

3) Evacuate the vacuum chamber of the multi-arc ion plating equipment until the pressure of the vacuum chamber is lower than 6×10 ^-3 Pa, pass argon gas, control the pressure to 1.0Pa, and apply -900V bias on the substrate to make the gas glow. Photodischarge, sputter cleaning the substrate surface for 20min;

4) Before the deposition starts, pass argon gas into the vacuum chamber of the multi-arc ion plating equipment, control the air pressure to 0.2Pa, adjust the substrate bias to -40V, ignite the Cr target arc, and deposit a layer of Cr with a thickness of about 0.1 microns on the substrate surface. metal bottom layer;

5) Pour a mixture of argon and nitrogen into the vacuum chamber of the multi-arc ion plating equipment, control the flow rates of argon and nitrogen to be 10sccm and 200sccm, the vacuum chamber pressure is 0.3Pa, the bias voltage is -40V, and 4 pieces of NiCr targets are ignited And 1 piece of Cr target, the current of NiCr target and Cr target is 100A and 50A respectively, and the time is 90min. After the coating is finished, stop feeding argon and nitrogen, keep the vacuum state, until the substrate temperature is less than or equal to 60℃, and finally high toughness is obtained. Erosion resistant coating (Ni-Cr-N ternary hard coating). The atomic percentage of elements in the coating is 48.8Ni-26.8Cr-24.4N, the hardness of the coating is 8.7GPa, the bonding force of the film base is greater than 100N, and the erosion rate is 0.58mg/g.

Example 2

1) Place 4 metal Cr targets and 4 NiCr alloy targets on the target base in the vacuum chamber of the multi-arc ion plating equipment, and the ratio of Ni:Cr in the NiCr alloy targets is 80:20;

2) Select titanium alloy as the base material, grind and polish it, clean and dry it, and place it on the sample stage in the vacuum chamber;

3) Evacuate the vacuum chamber of the multi-arc ion plating equipment until the pressure of the vacuum chamber is lower than 6×10 ^-3 Pa, pass argon gas, control the air pressure to 1.5Pa, and apply -600V bias on the substrate to make the gas glow. Photodischarge, sputter cleaning the substrate surface for 15min;

4) Before the deposition starts, feed argon into the vacuum chamber of the multi-arc ion plating equipment, control the air pressure to be 0.4Pa, adjust the substrate bias to -80V, ignite the Cr target arc, and deposit a layer of Cr metal on the substrate surface to play the bottom layer;

5) Pour the mixed gas of argon and nitrogen into the vacuum chamber of the multi-arc ion plating equipment, control the flow of argon and nitrogen to be 380sccm and 10sccm, the vacuum chamber pressure is 1.0Pa, the bias voltage is -60V, and 4 pieces of NiCr targets are ignited , set the target current to 60A and the time to 120min. After the coating is over, stop feeding argon and nitrogen, keep the vacuum state until the substrate temperature is less than or equal to 60 °C, and finally obtain a high-toughness erosion-resistant coating (Ni-Cr-N ternary hard coating). The atomic percentage of elements in the coating is 79.7Ni-19.3Cr-1.0N, the hardness of the coating is 5.3GPa, the bonding force of the film base is greater than 100N, and the erosion rate is 0.66mg/g.

Example 3

1) Place 4 pieces of metal Cr targets and 4 pieces of NiCr alloy targets on the target base in the vacuum chamber of the multi-arc ion plating equipment, and the ratio of Ni:Cr in the NiCr alloy targets is 20:80;

2) Select nickel-based superalloy as the base material, grind and polish it, clean and dry it, and place it on the sample stage in the vacuum chamber;

3) Evacuate the vacuum chamber of the multi-arc ion plating equipment until the pressure of the vacuum chamber is lower than 6×10 ^-3 Pa, pass argon gas, control the pressure to 1.0Pa, and apply -800V bias on the substrate to make the gas glow. Photodischarge, sputter cleaning the substrate surface for 30min;

4) Before the deposition starts, pass argon into the vacuum chamber of the multi-arc ion plating equipment, control the air pressure to 0.8Pa, adjust the substrate bias to -100V, ignite the Cr target arc, and deposit a layer of Cr metal on the substrate surface to play the bottom layer;

5) Pour the mixed gas of argon and nitrogen into the vacuum chamber of the multi-arc ion plating equipment, control the flow rates of argon and nitrogen to be 10sccm and 1200sccm, the vacuum chamber pressure is 4.0Pa, the bias voltage is -120V, and 1 piece of NiCr target is ignited And 4 pieces of Cr target, the current of NiCr target and Cr target is 50A and 150A respectively, and the time is 240min. After the coating is finished, stop feeding argon and nitrogen, keep the vacuum state, until the substrate temperature is less than or equal to 60℃, and finally obtain high toughness. Erosion resistant coating (Ni-Cr-N ternary hard coating). The atomic percentage of elements in the coating is 2.1Ni-49.2Cr-48.7N, the hardness of the coating is 12.0GPa, the bonding force of the film base is greater than 80N, and the erosion rate is 0.32mg/g.

Example 4

1) Place 4 metal Cr targets and 4 NiCr alloy targets on the target base in the vacuum chamber of the multi-arc ion plating equipment, and the ratio of Ni:Cr in the NiCr alloy targets is 80:20;

2) Select zirconium alloy as the base material, grind and polish it, clean and dry it, and place it on the sample stage in the vacuum chamber;

3) Evacuate the vacuum chamber of the multi-arc ion plating equipment until the pressure of the vacuum chamber is lower than 6×10 ^-3 Pa, pass argon gas, control the pressure to 1.0Pa, and apply -900V bias on the substrate to make the gas glow. Photodischarge, sputter cleaning the substrate surface for 30min;

4) Before the deposition starts, pass argon into the vacuum chamber of the multi-arc ion plating equipment, control the air pressure to 0.6Pa, adjust the substrate bias to -120V, ignite the Cr target arc, and deposit a layer of Cr metal on the substrate surface to play the bottom layer;

5) Pour the mixed gas of argon and nitrogen into the vacuum chamber of the multi-arc ion plating equipment, control the flow of argon and nitrogen to be 40sccm and 500sccm, the vacuum chamber pressure is 1.5Pa, the bias voltage is -200V, and 4 pieces of NiCr targets are ignited And 3 pieces of Cr target, the current of NiCr target and Cr target is 150A and 120A respectively, and the time is 20min. After the coating is finished, stop feeding argon and nitrogen, keep the vacuum state, until the substrate temperature is less than or equal to 60℃, and finally obtain high toughness. Erosion resistant coating (Ni-Cr-N ternary hard coating). The atomic percentage of the elements in the coating is 38.4Ni-31.7Cr-29.9N, and the hardness of the coating is 9.0GPa, which is about 3 times that of the titanium alloy substrate. The bonding force of the film base is greater than 100N, the erosion rate is 0.46mg/g, and the erosion resistance is 2.6 times that of the titanium alloy base. For details, see Table 1 and Table 2.

Example 5

1) Place 4 metal Cr targets and 4 NiCr alloy targets on the target base in the vacuum chamber of the multi-arc ion plating equipment, and the ratio of Ni:Cr in the NiCr alloy targets is 80:20;

2) Select H13 steel as the base material, grind and polish it, clean and dry it, and place it on the sample stage in the vacuum chamber;

3) Evacuate the vacuum chamber of the multi-arc ion plating equipment until the pressure of the vacuum chamber is lower than 6×10 ^-3 Pa, pass argon gas, control the pressure to 2.0Pa, and apply -200V bias on the substrate to make the gas glow. Photodischarge, sputter cleaning the substrate surface for 30min;

4) Before the deposition starts, pass argon gas into the vacuum chamber of the multi-arc ion plating equipment, control the air pressure to 1.6Pa, adjust the substrate bias to -200V, ignite the Cr target arc, and deposit a layer of Cr metal on the substrate surface to play the bottom layer;

5) Pour the mixed gas of argon and nitrogen into the vacuum chamber of the multi-arc ion plating equipment, control the flow of argon and nitrogen to be 200sccm and 100sccm, the vacuum chamber pressure is 0.8Pa, the bias voltage is -100V, and 2 pieces of NiCr targets are ignited And 2 pieces of Cr target, the current of NiCr target and Cr target is 50A and 50A respectively, and the time is 600min. After the coating is finished, stop feeding argon and nitrogen, keep the vacuum state, until the substrate temperature is less than or equal to 60℃, and finally obtain high toughness. Erosion resistant coating (Ni-Cr-N ternary hard coating). The atomic percentage of the elements in the coating is 28.3Ni-45.6Cr-26.1N, the hardness of the coating is 8.4GPa, the bonding force of the film base is greater than 100N, and the erosion rate is 0.53mg/g.

Table 1 Hardness and bonding force of the high-toughness erosion-resistant coating (Example 4) prepared by the present invention

Table 2 Comparison table of erosion rate between high toughness erosion resistant coating (Example 4) made by the present invention and titanium alloy substrate

It should be noted that, in this document, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any relationship between these entities or operations. any such actual relationship or sequence exists. Moreover, the terms "comprising", "comprising" or any other variation thereof are intended to encompass a non-exclusive inclusion such that a process, method, article or device that includes a list of elements includes not only those elements, but also includes not explicitly listed or other elements inherent to such a process, method, article or apparatus.

Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, and substitutions can be made in these embodiments without departing from the principle and spirit of the invention and modifications, the scope of the present invention is defined by the appended claims and their equivalents.

Claims (10)

1. A high toughness, erosion resistant coating characterized by: the high-toughness anti-erosion coating is a Ni-Cr-N ternary metal-nitride multiphase single-layer coating, wherein the atomic percent of Ni element is 2-80%, the atomic percent of Cr element is 10-80%, and the atomic percent of N element is 1-50%.

2. A high toughness impact resistant coating according to claim 1 wherein: the hardness of the high-toughness anti-erosion coating is 5-12 GPa; the bonding force of the film base is more than 80N measured by a scratch method; the silicon dioxide sand grains with the grain size of 200 mu m erode the coating at an erosion angle of 45 degrees and a speed of 130m/s, and the erosion rate of the coating is 0.32-0.66 mg/g.

3. A preparation method of a high-toughness anti-erosion coating is characterized by comprising the following specific operation steps:

1) Placing a metal Cr target and a metal NiCr alloy target on a target seat in a vacuum chamber of multi-arc ion plating equipment, and placing a substrate on a sample table;

2) Vacuumizing a vacuum chamber of the multi-arc ion plating equipment, introducing argon into the vacuum chamber, and performing glow sputtering cleaning on the surface of the substrate;

3) Introducing argon into a vacuum chamber of multi-arc ion plating equipment, igniting a Cr target arc, and depositing a Cr metal layer on the surface of a substrate to be used as a priming layer;

4) And introducing mixed gas of argon and nitrogen into a vacuum chamber of the multi-arc ion plating equipment, igniting NiCr target arc, and depositing to obtain the Ni-Cr-N high-toughness anti-erosion coating.

4. A method of producing a high toughness erosion resistant coating in accordance with claim 3, wherein: the total amount of Ni and Cr in the NiCr alloy target in the step 1) is not less than 98%, the content of Cr is 20-80%, and the content of Ni is 80-20%.

5. A method of producing a high toughness erosion resistant coating in accordance with claim 3, wherein: the substrate in the step 1) is a metal substrate, and the metal is titanium alloy, zirconium alloy, steel or high-temperature alloy.

6. A process for preparing a high toughness impact resistant coating as claimed in claim 3, wherein: vacuumizing in the step 2) until the air pressure of the vacuum chamber is lower than 6 x 10 ^-3 Pa。

7. A process for preparing a high toughness impact resistant coating as claimed in claim 3, wherein: introducing argon into the vacuum chamber in the step 2), enabling the air pressure of the vacuum chamber to be 1.0-2.0 Pa, then applying a bias voltage of-200 to-900V on the substrate, enabling the gas to generate glow discharge, and carrying out sputtering cleaning on the surface of the substrate for not less than 5min through ionized argon ions.

8. A method of producing a high toughness erosion resistant coating in accordance with claim 3, wherein: in the step 3), argon is introduced into the vacuum chamber before deposition is started, the air pressure of the vacuum chamber is controlled to be 0.2-1.6 Pa, the substrate is applied with a bias voltage of-40V to-200V, a metal Cr target arc is ignited, and a Cr metal priming layer is deposited on the surface of the substrate.

9. A method of producing a high toughness erosion resistant coating in accordance with claim 3, wherein: in the step 4), a multi-arc ion plating mode is adopted to prepare the Ni-Cr-N film, and the technological parameters are as follows: introducing mixed gas of argon and nitrogen, controlling the flow rates of the argon and the nitrogen to be 10-200 sccm and 10-1200 sccm respectively, controlling the working pressure to be 0.3-4.0Pa, and controlling the bias range of the substrate to be-40V to-200V.

10. A method of producing a high toughness erosion resistant coating in accordance with claim 3, wherein: in the step 4), a multi-arc ion plating mode is adopted to prepare the Ni-Cr-N film, the number of the deposited target materials is 4 NiCr alloy targets and 4 metal Cr targets, the number and the combination of the starting targets can be selected according to the process requirements, the target current range is 50-150A, and the duration is 20-600 min.

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