CN109112481B - Hard ceramic coating with antibacterial and corrosion-resistant properties and preparation method thereof - Google Patents

Hard ceramic coating with antibacterial and corrosion-resistant properties and preparation method thereof Download PDF

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CN109112481B
CN109112481B CN201811148672.1A CN201811148672A CN109112481B CN 109112481 B CN109112481 B CN 109112481B CN 201811148672 A CN201811148672 A CN 201811148672A CN 109112481 B CN109112481 B CN 109112481B
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coating
hard ceramic
ceramic coating
antibacterial
corrosion
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CN109112481A (en
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黄峰
李朋
葛芳芳
吴玉美
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering

Abstract

The invention discloses a hard ceramic coating with antibacterial and corrosion-resistant properties, which comprises ZrxCuyAlzN100‑x‑y‑zX is 39.1 to 45.1, y is 17.5 to 18.8, z is 4.8 to 7.2, and x, y and z are atomic ratios, wherein Cu is an amorphous structure and Cu is used as Cu+The coating is formed by compounding a ZrN crystal phase and an amorphous phase. The invention also discloses a preparation method of the hard ceramic coating, which adopts a physical vapor magnetron sputtering method to prepare the hard ceramic coating and specifically comprises the following steps: the coating obtained by cleaning the substrate, connecting a power supply and depositing the coating has high hardness, good binding force, easy release of sterilizing substances and strong corrosion resistance, and can provide effective antibacterial and corrosion-resistant protection for objects.

Description

Hard ceramic coating with antibacterial and corrosion-resistant properties and preparation method thereof
Technical Field
The invention belongs to the field of protective coatings, and particularly relates to a hard ceramic coating with antibacterial and corrosion-resistant properties and a preparation method thereof.
Background
Physical vapor deposition coating, PVD coating for short, is widely used as protective coating because of its good wear resistance, high hardness, high binding force, to improve the service life of parts, but with the improvement of people's living standard, people's requirement for the protective properties of coating is higher and higher, in daily life, the clean problem of home environment receives more and more attention from people, people not only require the coating to have excellent corrosion resistance, but also need the coating to have better antibacterial properties.
The environment such as kitchens, bathrooms and the like in human residences is the place which is most prone to bacterial breeding and corrosion due to the change of temperature, humidity and pH value, meanwhile, the kitchens and bathrooms are too small, so that household appliances and furniture are difficult to clean, and the space and the surfaces of products are coated with antibacterial and corrosion-resistant coatings or paints, so that the environment-friendly household electrical appliance is economic and environment-friendly.
However, most of the prior art is coated with antibacterial coating. The antibacterial coating has the defects of poor adhesion, low wear resistance and low surface smoothness due to the characteristics of the antibacterial coating, and the attractiveness of home decoration is influenced; some documents have also studied the deposition of an antimicrobial film on the surface of a substrate using Physical Vapor Deposition (PVD) techniques.
Chinese patent application CN102851666A discloses a surface treatment method of a composite antibacterial coating on a substrate plated with a copper layer, which has long-term antibacterial and bacteriostatic effects, and specifically comprises the following steps: firstly, cleaning and surface activating the surface of the base material which is electroplated with acid copper; then, electroplating a semi-gloss nickel layer and an antibacterial nickel layer on the base material; and finally, carrying out Physical Vapor Deposition (PVD) on the substrate to deposit a plurality of antibacterial metal film layers. The multi-layer coating is utilized, so that the surfaces of products such as bathroom accessories, door hardware, shopping carts and the like form antibacterial protection, the antibacterial performance is excellent, but the hardness and the corrosion resistance of the protective layer are poor, and the coating cannot be applied to actual life production.
Chinese patent application CN2786146Y discloses a surface antibacterial wear-resistant product, which is plated with a hard film containing silver or copper or silver-copper composite on the surface of a substrate by physical vapor deposition technology, wherein one of the targets used in the physical vapor deposition is a wear-resistant metal target titanium, chromium, aluminum or zirconium, and the other is an antibacterial target silver, copper or silver-copper composite; the surface hardness of the obtained product reaches above Hv1800, the antibacterial effect reaches the GB15979-2002 standard, the antibacterial rate is 99-99.99%, the appearance does not change for a long time, and the antibacterial capability can be maintained for a long time. Likewise, the protective layer has no corrosion resistance and has a small protection range.
Disclosure of Invention
The invention aims to provide a hard ceramic coating with antibacterial and corrosion-resistant properties, and the obtained coating has high hardness, good binding force, easy release of bactericidal substances and strong corrosion resistance by controlling the components and the structure of the coating, and can provide effective antibacterial and corrosion-resistant protection for objects.
The technical scheme of the invention is as follows:
a hard ceramic coating with antibacterial and corrosion-resistant properties, the hard ceramic coating comprises ZrxCuyAlzN100-x-y-z39.1 to 45.1, 17.5 to 18.8, and 4.8 to 7.2, wherein x, y, and z are atomic ratios, and Cu is an amorphous structure and Cu is used as Cu+The hard ceramic coating is formed by compounding a ZrN crystal phase and an amorphous phase.
The Cu+The form shows that Cu element exists in +1 valence in the hard ceramic coating.
The invention forms a two-phase composite Zr-Cu-Al-N coating structure with secondary ZrN grains uniformly distributed in a main amorphous phase by designing coating components and process, and Cu element is Cu in the coating+The form and the amorphous structure exist, and Cu exists in the amorphous structure, which is beneficial to Cu+The release of the active ingredients can better play a role in sterilization.
The invention also limits the atomic ratio y of the Cu element to 17.5-18.8, which is because experiments show that when the atomic ratio y of the Cu element is less than 17.5, the coating can not effectively release the Cu+Ion, and the bactericidal effect of the coating obtained at this time is not obvious.
The components and the structure of the coating have larger influence on the performance of the coating, and the hardness of ZrN crystal grains in the ZrN crystal phase is high, so that the coating has higher hardness and excellent mechanical behavior. The main element amorphous phase structure is compact, the amorphous structure has no defects such as crystal boundary and the like, the coating is compact and has no through pore defect, so that corrosive substances are difficult to corrode protected objects through the coating, and the coating has good corrosion resistance.
The size of the ZrN crystal grains in the hard ceramic coating is 6-15 nm, and the thickness of the amorphous phase of two adjacent ZrN crystal grains is 10-30 nm.
The hard ceramic coating is Cu in a bacterial solution+The release amount of ions is 0.44-0.62 mg/L, Cu+The release amount of ions in the solution is a key factor for determining the antibacterial performance of the coating, the higher the release amount is, the more obvious the sterilization is, and the Cu+The release amount of the ions is 0.44-0.62 mg/L, and the antibacterial rate of the coating to escherichia coli within 48h can reach 100%.
The thickness of the hard ceramic coating is 2-3 mu m, and the density of the coating is 5.2-6.4 g/cm3。
The surface roughness Ra of the hard ceramic coating is less than 1 nm.
The hardness value of the hard ceramic coating is 22-26 Gpa, and the binding force of the hard ceramic coating is 30-50N.
The hard ceramic coatingThe layer has a corrosion potential of-0.34V to-0.2V and a corrosion current density of 4.21 x 10 in a 3.5 wt% NaCl solution according to standard tests-9～8.61×10-8A/cm2The corrosion current density is preferably 2.63X 10-8～6.98×10-8A/cm2Compared with stainless steel, the corrosion resistance is improved by 1-2 orders of magnitude.
The hard ceramic coating has an antibacterial rate of 100% to escherichia coli within 48 h.
The invention also provides a preparation method of the hard ceramic coating with antibacterial and corrosion-resistant properties, which is prepared by a magnetron reactive sputtering method and comprises the following steps:
(1) cleaning a substrate;
(2) connecting a power supply: adding Zr58Cu30Al12The target is connected with a direct current power supply, the Cu target is connected with a radio frequency power supply, and Zr is added58Cu30Al12The target and the Cu target are arranged on a cathode;
(3) coating deposition: loading the cleaned substrate into a vacuum chamber with a vacuum degree of less than or equal to 5 × 10-5When Pa is needed, starting to introduce reactive sputtering gas and controlling sputtering pressure, and adjusting Zr58Cu30Al12And (3) applying negative bias to the substrate and heating the substrate according to the sputtering power density of the target and the Cu target, and depositing the substrate by controlling the deposition rate to obtain the hard ceramic coating.
In the step (1), the cleaning method of the substrate is chemical cleaning or combined cleaning of chemical cleaning and plasma glow etching.
Wherein, the chemical cleaning comprises: putting the basal body or the workpiece into 30-60% aqueous solution of cleaning powder and saturated Na in sequence2CO3Ultrasonic cleaning is carried out on the water solution, acetone, absolute ethyl alcohol and deionized water for 10-20 min respectively, and then air drying is carried out for 1-2 h in a drying box at the temperature of 80-100 ℃, or high-purity nitrogen with the purity of 99.99% is adopted for blow drying.
The combined cleaning of the chemical cleaning and the plasma glow etching comprises the following steps: firstly, the basal body is chemically cleaned, then the basal body after chemical cleaning is placed on a sample table in a vacuum chamber, and when the vacuum is lower than 1 multiplied by 10-3And after Pa, introducing argon gas and maintaining the gas pressure at 0.5-2 Pa, then turning on a power supply and simultaneously applying negative bias to the substrate, and etching the substrate for 10-20 min by using the generated plasma.
After plasma glow etching cleaning, water molecules, gas molecules or micro dust particles attached to the surface of the substrate are completely bombed, and the growth of the coating is facilitated.
In the step (2), the power supply is connected in a radio frequency auxiliary direct current connection mode, the density and the energy of plasma can be improved, deposited atoms have enough energy diffusion, and the formed coating is compact and has less stress.
In the step (3), the reactive sputtering gas is N2And mixed gas of Ar and N2The flow ratio of Ar to Ar is 0.08-0.18, N2The flow ratio to Ar also affects the elemental composition in the final coating.
In the step (3), the heating temperature is 100-200 ℃, and the diffusion of atoms can be promoted by heating the substrate, so that the principal element amorphous coating is compact, the defects of the coating are further reduced, and the coating becomes compact.
In the step (3), Zr58Cu30Al12The sputtering power density of the target and the Cu target is 3.24-4.15W/cm2Said Zr58Cu30Al12Ratio of elements in target and double-target co-sputtering of Zr58Cu30Al12The sputtering power density of the target and the Cu target has a corresponding relation with the content of each element in the finally obtained coating, wherein the Cu target power density is a factor for determining the content of Cu, and the higher the power density is, the more the content of Cu is.
Composition of two targets, sputtering power density of two targets and N in reactive sputtering gas2The flow ratio of the metal oxide to Ar influences the components of the finally obtained coating, and the components of the coating are controlled to realize that Cu in the coating is in an amorphous structure and Cu is used+The form exists and the coating is formed by compounding two phases of ZrN crystal phase and amorphous phase.
In the step (3), the sputtering air pressure is 0.5 Pa; the deposition rate is 25-30 nm/min; the bias voltage is-8 to-10V.
Compared with the prior art, the invention has the following advantages:
(1) the invention obtains the two-phase composite Zr-Cu-Al-N ceramic coating formed by uniformly distributing the minor ZrN crystal grains in the major amorphous phase, wherein the Cu element is Cu+The coating has an amorphous structure, a principal component amorphous phase structure is compact, no penetrating gap exists, and the coating with the structure can release Cu in solution+The ions can kill bacteria and play a role in antibiosis, and the antibiosis rate to the escherichia coli within 48 hours reaches 100%.
(2) The coating obtained by the invention has a dense principal element amorphous phase structure, an amorphous structure and no crystal boundary defect, and the coating is dense and has no through-penetration pore defect, so that corrosive substances are difficult to corrode protected objects through the coating, the obtained coating shows better corrosion resistance, and the corrosion current density is 1.61 multiplied by 10 in a standard polarization test in 3.5 wt% NaCl solution-8A/cm2～7.61×10-9A/cm2Compared with the corrosion of stainless steel, the corrosion is improved by 1-2 orders of magnitude.
(3) The ZrN crystal grains in the ZrN crystal phase of the coating obtained by the method have high hardness, so that the coating has high hardness and excellent mechanical behavior, the hardness of the coating can reach 22-26 GPa, and the binding force can reach 30-50N.
Drawings
FIG. 1 is a schematic structural view of a Zr-Cu-Al-N ceramic coating according to the present invention;
FIG. 2 is XPS and Auger electron (Auger) spectra of the coatings prepared in examples 1 and 2, wherein (a-1) is Cu of the XPS spectrum of the coating prepared in example 1+(a-2) is Cu of Auger spectrum of the coating prepared in example 1+A characteristic spectrum of (a); (b-1) Cu as XPS spectrum of coating prepared in example 2+(b-2) is Cu of Auger spectrum of the coating prepared in example 2+A characteristic spectrum of (a);
FIG. 3 is an XRD spectrum of the coatings prepared in examples 1 and 2, wherein line (a) is example 1; line (b) is example 2;
FIG. 4 is a photomicrograph of a cross-section of the coating prepared in example 1, with (a) an SEM topography and (b) a TEM topography;
FIG. 5 is a photograph of the surface topography of the coatings prepared in examples 1 and 2 and comparative example 1 after polarization in a 3.5 wt% NaCl aqueous solution, wherein (a-1) is a digital photograph of the surface of the coating prepared in comparative example 1 after polarization and (a-2) is a partial SEM micrograph of the coating prepared in comparative example 1 after polarization; (b-1) is a digital photograph of the surface of the polarized film in example 1, and (b-2) is a local SEM microscopic magnification of the polarized film in example 1; (c-1) is a digital photograph of the surface of the polarized film in example 2, and (c-2) is a local SEM microscopic magnification of the polarized film in example 2;
FIG. 6 is a graph showing the E.coli resistance test of the coatings prepared in examples 1 and 2 and comparative example 1, wherein (a-1) is after 24 hours of the antibacterial test of comparative example 1, and (a-2) is after 48 hours of the antibacterial test of comparative example 1; (b-1) after 24h of the antibacterial experiment of example 1, and (b-2) after 48h of the antibacterial experiment of example 1; the (c-1) is 24h after the antibacterial experiment of the example 2, and the (c-2) is 48h after the antibacterial experiment of the example 2.
Detailed Description
The coating composition, coating density, coating crystal structure, coating cross-section and surface morphology, coating hardness, coating corrosion resistance behavior and coating antimicrobial effect in the following examples were determined as follows:
1. coating composition
EDS function measurement of FEI Quanta (TM) 250 FEG is utilized to measure the composition of the coating, and EDA is configuredXSi (Li) probe, calibrated by ZAF, selected for an area of not less than 40 mm per sample2And area, the average value of its composition is measured.
2. Coating structure
(1) Crystal structure
Using a German Bruker D8 Advance X-ray diffractometer (XRD) with Cu KαMeasuring crystal structure of the coating by controlling an X-ray tube at 40kV and 40mA in a radiation incidence mode and a theta/theta mode, and filtering out K by using a nickel filterβAnd (3) ray, setting a detection angle 2 theta to be 20-80 degrees, setting the step length to be 0.01 degrees, and measuring the crystalline phase structure in the coating.
(2) Growth structure
The cross-sectional morphology of the coating was observed using a FEI Tecnai Transmission Electron Microscope (TEM).
3. Density of coating
Depositing a coating with the thickness of 3-5 mu m on a regular substrate, calculating the volume of the coating and weighing the mass of the coating, and calculating according to a density calculation formula, wherein the density calculation formula (1) is as follows:
Figure BDA0001817405360000071
where ρ is the density, M is the mass, and V is the volume.
4. Sample surface chemistry State
The chemical state of the elements on the surface of the coating was measured using the Kratos Axis ULTRA DLD XPS system, and its Cu2p, Cu LMMa (Auger Electron) spectra were measured, using 2kV Ar for each sample+Ion etching for 5 minutes to remove the surface oxide layer.
5. Hardness of coating
Using MTS NANO G200 NANO indenter, Berkovich diamond indenter, to eliminate the influence of the substrate effect and the surface roughness, the maximum indentation depth was 1/10 of the film thickness, the load was changed with the indentation depth, and 10 matrix points were measured for each sample and averaged.
6. Corrosion resistance behavior of the coating
The coatings were tested for seawater corrosion resistance using an electrochemical workstation (modular, Solartron, USA). The test mode is a standard polarization test of a three-electrode system, the corrosion medium is 3.5 wt% of NaCl aqueous solution, the reference electrode is a saturated calomel electrode, and the test area is 1cm2The test potential range is-1.0V, and the potential scanning rate is 1mV. s-1。
7. Antibacterial rate of coating
The coating was subjected to an antibacterial test by a liquid culture method using 304 stainless steel as a control, and the species used was Escherichia coli (ATCC 25922). Firstly, obtaining a bacteria liquid with a certain concentration, putting a sample into the bacteria liquid for culturing, extracting a culture solution for dilution, dripping the culture solution into nutrient agar for culturing, and judging the antibacterial rate of the sample according to the number of bacterial colonies on the nutrient agar. The antibacterial ratio calculation formula (2) is as follows:
Figure BDA0001817405360000081
wherein N is0The number of bacteria visible in the uncoated 304 stainless steel sample, N is the number of bacteria remaining after the coating was sterilized.
In addition, Cu of the coating in solution+The amount of released ions was measured by ICP-OES (inductively coupled plasma emission spectrometer).
Example 1
(1) Cleaning the polished 304 stainless steel substrate, and sequentially putting the substrate into 60 percent aqueous solution of cleaning powder and saturated Na2CO3Ultrasonically cleaning the water solution, acetone, absolute ethyl alcohol and deionized water for 15min respectively, and then blowing the water solution by using high-purity nitrogen with the purity of 99.99 percent; then the substrate is loaded on a sample stage in a vacuum chamber, when the vacuum degree is lower than 1 × 10-3After Pa, introducing argon gas and maintaining the gas pressure at 0.5Pa, then starting a power supply and applying negative bias to the substrate at the same time, and etching and cleaning the substrate for 15min by utilizing plasma glow generated by the argon gas;
(2) adding Zr58Cu30Al12The target is connected with a direct current power supply, the Cu target is connected with a radio frequency power supply, and the purity of the two targets is more than 99.9%;
(3) loading the cleaned substrate into a vacuum chamber with a vacuum degree of less than or equal to 5 × 10-5When Pa, introducing Ar and N2Controlling the sputtering pressure to be 0.5Pa, and adjusting Zr58Cu30Al12And (3) applying negative bias to the substrate according to the sputtering power density of the target and the Zr target, then opening the sample baffle, depositing the substrate, and controlling the deposition rate to obtain the hard ceramic coating.
Wherein, the specific parameters in the step (3) are as follows: cu target power density: 3.24W/cm2； Zr58Cu30Al12Power density of the target: 4.15W/cm2(ii) a The flow ratio of nitrogen to argon is N2Ar is 0.14; substrate biasing: -10V; addingThermal temperature: 100 ℃; the coating deposition rate was 25 nm/min.
The resulting coating was subjected to structural characterization: the coating obtained in example 1 was found to contain Zr as a component41.1Cu17.5Al4.8N36.6The two-phase composite structure of amorphous coated ZrN crystal grains is shown as figure 1 and figure 2(a), wherein the ZrN crystal grains have a size of 6-10 nm, and the amorphous phase thickness of two adjacent ZrN crystal grains is 10-20 nm.
XPS as shown in FIG. 3(a-1) and Auger spectrum as shown in FIG. 3(a-2) show that the Cu element on the surface of the coating is +1 valence. Further observing the cross-sectional morphology of the coating by using an electron microscope, wherein the coating does not have columnar crystals and obvious penetrating gaps as shown in an SEM picture of figure 4 (a); the growth structure of the coating was observed with a larger magnification TEM, and the coating was free of microporosities and holes as shown in fig. 4(b), indicating that the coating structure was dense. The coating density was measured to be 6.4g/cm3。
Performance testing of the coating: the coating is subjected to polarization test by three-electrode standard electrochemistry, and the corrosion current density of the coating is 7.61 multiplied by 10-9A/cm2Compared with stainless steel (1.74 multiplied by 10)-7A/cm2) The lower magnification is 23 times, the digital photograph after polarization etching is shown in FIG. 5(b-1), and no etching trace is observed on the surface of the coating, and further, when the observation is carried out under SEM magnification, as shown in FIG. 5(b-2), no pitting is formed on the surface of the coating, indicating that the coating is very corrosion resistant.
The antibacterial experiment of the coating is tested by using anti-Escherichia coli, and FIG. 6(b-1) shows the antibacterial effect after 24 hours of coating, the number of residual colonies is few, the antibacterial rate reaches more than 97.8 percent, and the Cu is at the moment+The released amount of (A) was 0.44 mg/L. The antibacterial effect after 48 hours is shown in FIG. 6(b-2), where no residual colonies were present, the antibacterial rate reached 100%, and Cu was present1+The released amount of (A) was 0.57 mg/L. The mechanical property of the coating is tested, the hardness of the coating is 26GPa, is improved by 4-5 times compared with that of stainless steel, and the bonding force of the coating is tested to be 50N.
Example 2
Preparing a hard ceramic coating according to the method described in example 1;
whereinAnd the specific parameters in the step (3) are as follows: cu target power density: 4.15W/cm2； Zr58Cu30Al12Power density of the target: 4.15W/cm2(ii) a The flow ratio of nitrogen to argon is N2Ar is 0.18; substrate biasing: -8V; heating temperature: 200 ℃; the coating deposition rate was 25 nm/min.
The resulting coating was subjected to structural characterization: it was found that the coating obtained in example 2 had Zr as a component43.1Cu18.8Al5.2N32.9The two-phase composite structure of amorphous coated ZrN crystal grains is shown as figure 1 and figure 2(b), wherein the size of the ZrN crystal grains is 6-15 nm, and the thickness of the amorphous phase of two adjacent ZrN crystal grains is 10-25 nm.
XPS as shown in FIG. 3(b-1) and Auger spectrum as shown in FIG. 3(b-2) show that the Cu element on the surface of the coating layer has a valence of + 1. Further observing the cross-sectional appearance of the coating by using an electron microscope, the coating has no columnar crystal, obvious penetrating gaps, micropores or holes and compact structure. The coating density was measured to be 6.0g/cm3。
Performance testing of the coating: the coating is subjected to polarization test by three-electrode standard electrochemistry, and the corrosion current density of the coating is 1.61 multiplied by 10-8A/cm2Compared with stainless steel (1.74 multiplied by 10)-7A/cm2) The lower power is 10 times, and the digital photograph after polarization etching is shown in FIG. 5(c-1), and no etching trace is observed on the surface of the coating, and further, when the observation is carried out under SEM magnification, as shown in FIG. 5(c-2), no pitting is formed on the surface of the coating, indicating that the coating is very corrosion resistant.
The antibacterial experiment of the coating is tested by using anti-Escherichia coli, and FIG. 6(c-1) shows the antibacterial effect of the coating after 24 hours, almost no residual bacterial colony exists, the antibacterial rate reaches more than 99.6 percent, and the Cu content at the moment+The released amount of (A) was 0.57 mg/L. The antibacterial effect after 48 hours is shown in FIG. 6 (c-2), where no residual colonies were present, the antibacterial rate reached 100%, and Cu was present1+The released amount of (A) was 0.62 mg/L. The mechanical property of the coating is tested, the hardness of the coating is 25GPa, which is improved by 5 times compared with that of stainless steel, and the bonding force of the coating is tested to be 43N.
Example 3
Preparing a hard ceramic coating according to the method described in example 1;
wherein, the specific parameters in the step (3) are as follows: cu target power density: 3.24W/cm2； Zr58Cu30Al12Power density of the target: 3.65W/cm2(ii) a The flow ratio of nitrogen to argon is N2Ar is 0.06; substrate biasing: -10V; heating temperature: 150 ℃; the coating deposition rate was 30 nm/min.
The resulting coating was subjected to structural characterization: the coating obtained in example 1 was found to contain Zr as a component39.1Cu18.0Al4.8N38.1The two-phase composite structure of amorphous coated ZrN crystal grains is shown as figure 1, wherein the size of the ZrN crystal grains is 10-15 nm, and the thickness of the amorphous phase of two adjacent ZrN crystal grains is 10-30 nm.
XPS and Auger spectrograms show that the Cu element on the surface of the coating is +1 valence. Further observing the cross-sectional morphology of the coating by using an electron microscope, wherein the coating has no columnar crystal and no obvious penetrating gap; the growth structure of the coating is observed by using a TEM with larger magnification, and the coating has no obvious micropores and holes, which shows that the coating has a compact structure. The coating density was measured to be 5.2g/cm3。
Performance testing of the coating: the coating is subjected to polarization test by three-electrode standard electrochemistry, and the corrosion current density of the coating is 8.61 multiplied by 10-8A/cm2Compared with stainless steel (1.74 multiplied by 10)-7A/cm2) The corrosion resistance of the coating is lower than that of the example, the coating is 2 times lower, no obvious corrosion trace is left on the surface of the coating of the digital photo after polarization corrosion, and further SEM magnification observation shows that very few pitting pits are generated on the surface of the coating.
The antibacterial experiment of the coating is tested by using escherichia coli, the antibacterial effect after 24 hours is achieved, the antibacterial rate is over 100 percent, and at the moment, Cu+The released amount of (A) was 0.61 mg/L. The mechanical property of the coating is tested, the hardness of the coating is 22GPa, is improved by 3-4 times compared with that of stainless steel, and the bonding force of the coating is tested to be 30N.
Example 4
Preparing a hard ceramic coating according to the method described in example 1;
wherein, the specific parameters in the step (3) are as follows: cu target power density: 3.24W/cm2； Zr58Cu30Al12Power density of the target: 3.88W/cm2(ii) a The flow ratio of nitrogen to argon is N2Ar is 0.10; substrate biasing: -10V; heating temperature: 200 ℃; the coating deposition rate was 28 nm/min.
The resulting coating was subjected to structural characterization: it was found that the coating obtained in example 4 had Zr as a component45.1Cu18.3Al7.2N29.4The two-phase composite structure of amorphous coated ZrN crystal grains is shown as figure 1, wherein the ZrN crystal grains have the size of 5-8 nm, and the amorphous phase thickness of two adjacent ZrN crystal grains is 20-30 nm.
XPS and Auger spectrograms show that the Cu element on the surface of the coating is +1 valence. Further observing the cross-sectional morphology of the coating by using an electron microscope, wherein the coating has no columnar crystal and no obvious penetrating gap; and observing the growth structure of the coating by using a TEM with larger magnification, wherein the coating has no micropores and holes, and the coating has a compact structure. The coating density was measured to be 5.8g/cm3。
Performance testing of the coating: the coating is subjected to polarization test by three-electrode standard electrochemistry, and the corrosion current density of the coating is 3.21 multiplied by 10-8A/cm2Compared with stainless steel (1.74 multiplied by 10)-7A/cm2) The corrosion resistance of the coating is good, and the corrosion resistance of the coating is good, wherein the corrosion resistance is 6 times lower, the surface of the coating of the digital photo after polarization corrosion has no obvious corrosion trace, and further SEM magnification observation shows that no pit is generated on the surface of the coating.
The antibacterial experiment of the coating is tested by using escherichia coli, the antibacterial effect after 24 hours is achieved, the antibacterial rate is over 99.9 percent, and at the moment, Cu+The release amount of (A) is 0.59mg/L, the antibacterial effect after 36 hours, the antibacterial rate is more than 100%, and the Cu is in the time+The released amount of (A) was 0.62 mg/L. The mechanical property of the coating is tested, the hardness of the coating is 26GPa, is improved by 4-5 times compared with that of stainless steel, and the bonding force of the coating is 35N.
Example 5
Preparing a hard ceramic coating according to the method described in example 1;
wherein, the specific parameters in the step (3) are as follows: cu target power density: 3.67W/cm2； Zr58Cu1Al12Power density of the target: 3.83W/cm2(ii) a The flow ratio of nitrogen to argon is N2Ar is 0.12; substrate biasing: -10V; heating temperature: 100 ℃; the coating deposition rate was 25 nm/min.
The resulting coating was subjected to structural characterization: the coating obtained in example 5 was found to have Zr as a component43.2Cu17.9Al6.5N32.4The two-phase composite structure of amorphous coated ZrN crystal grains is shown as figure 1, wherein the size of the ZrN crystal grains is 10-15 nm, and the thickness of the amorphous phase of two adjacent ZrN crystal grains is 10-20 nm.
XPS and Auger spectrograms show that the Cu element on the surface of the coating is +1 valence. Further observing the cross-sectional morphology of the coating by using an electron microscope, wherein the coating has no columnar crystal and no obvious penetrating gap; and observing the growth structure of the coating by using a TEM with larger magnification, wherein the coating has no micropores and holes, and the coating has a compact structure. The coating density was measured to be 6.2g/cm3。
Performance testing of the coating: the coating was polarization tested by three-electrode standard electrochemistry and the corrosion current density of the coating was 4.21X 10-9A/cm2Compared with stainless steel (1.74 multiplied by 10)-7A/cm2) The corrosion resistance of the coating is good, and the corrosion resistance of the coating is good, wherein the corrosion resistance is 40 times lower, the surface of the coating of the digital photo after polarization corrosion has no obvious corrosion trace, and further SEM magnification observation shows that no pit is generated on the surface of the coating.
The antibacterial experiment of the coating is tested by using escherichia coli, the antibacterial effect after 24 hours is achieved, the antibacterial rate is over 100 percent, and at the moment, Cu+The release amount of the coating is 0.62mg/L, the mechanical property of the coating is tested, the hardness of the coating is 26GPa, the hardness is improved by 4-5 times compared with that of stainless steel, and the bonding force of the coating is 45N.
Comparative example 1
Stainless steel with the surface roughness of 1.6nm is selected as comparison to reflect the performance of the hard ceramic coating.
After standard polarization test of a three-electrode system, the corrosion current density of the stainless steel is 1.74 multiplied by 10-7A/cm2The digital photograph after the polarization etching is shown in FIG. 5(a-1), and it is found that rust is generated on the surface, and further, when it is partially magnified by SEM microscopy, as shown in FIG. 5(a-2), a site-specific etch pit appears on the stainless steel surface.
As a result of the experiment for Escherichia coli resistance of comparative example 1, as shown in FIGS. 6(a-1) and 6(a-2), it was found that stainless steel had no antibacterial effect, the numbers of colonies at 24 hours and 48 hours were not greatly different, and a large number of bacterial colonies were present in the culture dish. The hardness of the stainless steel is further tested and is only 5-6 GPa.
Furthermore, it should be understood that various changes and modifications can be made by those skilled in the art after reading the above description of the present invention, and such equivalent technical solutions also fall within the scope of the present invention as defined in the appended claims.

Claims (9)

1. A hard ceramic coating with antibacterial and corrosion-resistant properties, characterized in that the hard ceramic coating comprises ZrxCuyAlzN100-x-y-zX is 39.1 to 45.1, y is 17.5 to 18.8, z is 4.8 to 7.2, and x, y and z are atomic ratios, wherein Cu is an amorphous structure and Cu is used as Cu+The hard ceramic coating is formed by compounding a ZrN crystal phase and an amorphous phase.
2. The hard ceramic coating with antibacterial and corrosion-resistant properties according to claim 1, wherein the size of ZrN crystal grains in the hard ceramic coating is 6-15 nm, the thickness of an amorphous phase between two adjacent ZrN crystal grains is 10-30 nm, and the ZrN crystal grains are uniformly distributed in the amorphous phase.
3. The hard ceramic coating having antibacterial and corrosion resistant properties according to claim 1, wherein said hard ceramic coating is Cu in bacterial solution+The release amount of the ions is 0.44-0.62 mg/L.
4. The hard ceramic coating with antibacterial and corrosion-resistant properties according to claim 1, wherein the hard ceramic coating has a thickness of 2 to 3 μm and a density of 5.2 to 6.4g/cm3。
5. The hard ceramic coating with antibacterial and corrosion-resistant properties according to claim 1, wherein the hardness of the hard ceramic coating is 22-26 GPa, and the bonding force is 30-50N.
6. The hard ceramic coating with antibacterial and corrosion-resistant properties according to claim 1, wherein said hard ceramic coating has a corrosion potential of-0.34V to-0.2V in 3.5 wt% NaCl solution and a corrosion current density of 4.21 x 10-9～8.61×10-8A/cm2。
7. The method for preparing a hard ceramic coating having antibacterial and corrosion-resistant properties according to any one of claims 1 to 6, comprising in particular the steps of:
(1) cleaning a substrate;
(2) connecting a power supply: adding Zr58Cu30Al12The target is connected with a direct current power supply, the Cu target is connected with a radio frequency power supply, and Zr is added58Cu30Al12The target and the Cu target are arranged on a cathode;
(3) coating deposition: loading the cleaned substrate into a vacuum chamber with a vacuum degree of less than or equal to 5 × 10-5When Pa is needed, starting to introduce reactive sputtering gas and controlling sputtering pressure, and adjusting Zr58Cu30Al12And (3) applying negative bias to the substrate and heating the substrate according to the sputtering power density of the target and the Cu target, and depositing the substrate by controlling the deposition rate to obtain the hard ceramic coating.
8. The method for preparing a hard ceramic coating with antibacterial and corrosion-resistant properties according to claim 7, wherein in step (3), the reactive sputtering gas is N2Mixed gas of Ar and ArBody, N2The flow ratio of Ar to Ar is 0.06-0.18.
9. The method for preparing a hard ceramic coating with antibacterial and corrosion-resistant properties according to claim 7, wherein in step (3), Zr is added58Cu30Al12The sputtering power density of the target and the Cu target was 3.24W/cm2～4.15W/cm2(ii) a The heating temperature is 100-200 ℃.
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