CN111035805B - Workpiece with graphene-titanium dioxide composite antibacterial coating and preparation method thereof - Google Patents

Workpiece with graphene-titanium dioxide composite antibacterial coating and preparation method thereof Download PDF

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CN111035805B
CN111035805B CN201911289192.1A CN201911289192A CN111035805B CN 111035805 B CN111035805 B CN 111035805B CN 201911289192 A CN201911289192 A CN 201911289192A CN 111035805 B CN111035805 B CN 111035805B
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graphene
powder
titanium dioxide
workpiece
composite
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CN111035805A (en
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王国成
杨明刚
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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Priority to PCT/CN2020/129488 priority patent/WO2021115048A1/en
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    • A—HUMAN NECESSITIES
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    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08—Materials for coatings
    • A61L31/082—Inorganic materials
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08—Materials for coatings
    • A61L31/082—Inorganic materials
    • A61L31/088—Other specific inorganic materials not covered by A61L31/084 or A61L31/086
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/16—Biologically active materials, e.g. therapeutic substances
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
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    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
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    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
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Abstract

The invention provides a workpiece with a graphene-titanium dioxide composite antibacterial coating, which comprises a workpiece substrate and the graphene-titanium dioxide composite antibacterial coating arranged on the surface of the workpiece substrate, wherein in the composite antibacterial coating, graphene is doped in the titanium dioxide coating. The composite antibacterial coating is firmly combined with the workpiece substrate, and has good biocompatibility while endowing the workpiece substrate with antibacterial performance. The invention also provides a preparation method of the workpiece with the graphene-titanium dioxide composite antibacterial coating. Wherein the composite antibacterial coating is prepared by adopting a plasma spraying technology.

Description

Workpiece with graphene-titanium dioxide composite antibacterial coating and preparation method thereof
Technical Field
The invention relates to the technical field of preparation of antibacterial coatings, in particular to a workpiece with a graphene-titanium dioxide composite antibacterial coating and a preparation method thereof.
Background
Medical implants, surgical instruments and the like need to meet various requirements of clinical use due to direct contact with human tissues, and have good biocompatibility, antibacterial property and the like in addition to good mechanical properties. TiO 22Has been widely used for surface modification of implants and the like due to advantages such as good chemical stability, biocompatibility and strong bonding with implants and the like, but TiO2It has no antibacterial property. In order to prevent the problems of bacterial infection and the like of the implant in application, the implant needs to be endowed with certain antibacterial performance and good biocompatibility, so that the long-term stability of the implant can be ensured.
The current research shows that antibacterial elements (silver, copper, gallium and the like), antibacterial polypeptide, quaternary ammonium salt and the like are added in the surface coating of the implant to endow the implant with antibacterial performance, but the antibacterial additives have potential toxicity to cells or tissues and easily generate bacterial drug resistance multi-drug property. Graphene has good antibacterial performance and biocompatibility and is used for antibacterial research of implants, but in the prior art, the graphene is mainly used for resisting bacteria in a free state, has potential nano toxicity and limits the application of the graphene in the antibacterial field.
Therefore, it is necessary to provide a workpiece having good antibacterial property, biocompatibility and low toxicity so as to satisfy clinical requirements of medical implants and the like.
Disclosure of Invention
In view of the above, the invention provides a workpiece with a graphene-titanium dioxide composite antibacterial coating, and the graphene-titanium dioxide composite antibacterial coating is arranged on a workpiece substrate, so that the existence of the composite coating endows the surface of the workpiece substrate with antibacterial performance, and meanwhile, the biocompatibility of the workpiece substrate is not obviously damaged.
In a first aspect, the invention provides a workpiece with a graphene-titanium dioxide composite antibacterial coating, which comprises a workpiece substrate and the graphene-titanium dioxide composite antibacterial coating arranged on the surface of the workpiece substrate; in the composite antibacterial coating, graphene is doped in the titanium dioxide coating.
According to the invention, the graphene-titanium dioxide composite antibacterial coating is arranged on the surface of the workpiece substrate, wherein the graphene does not exist in a free state but is doped in the titanium dioxide coating, the formed composite coating has a compact structure and strong binding force with a substrate, and the composite coating can inhibit the growth of bacteria, shows good antibacterial property, is beneficial to the adhesion of functional cells (such as osteoblasts) and has good biocompatibility.
Optionally, the composite antibacterial coating is prepared by a plasma spraying method. Further optionally, the composite antimicrobial coating has a thickness of 50-120 μm.
Optionally, the surface of the composite antimicrobial coating has a micro/nano structure. That is, the surface of the composite antibacterial coating layer has a microstructure containing nano-crystalline grains therein. Wherein the size of the nano crystal grains is 5nm-100 nm. The micro/nano structures are detected by Scanning Electron Microscopy (SEM).
Wherein the roughness of the composite antibacterial coating is in a micron level. The "roughness" is the surface roughness of the coating measured by a surface roughness meter (such as TR200 surface roughness meter of the beijing era company). Preferably, the roughness of the composite antibacterial coating is 1-10 μm. When the roughness of the composite antibacterial coating is in a micron level, the adhesion of cells is more facilitated.
In the present invention, the graphene includes single-layer graphene or multi-layer graphene. Optionally, the thickness of the graphene is 1-60 atomic layer thick. Wherein the multilayer graphene is preferably 2 to 10 layers.
Optionally, the grains of titanium dioxide are attached to the sheets of graphene and interspersed between the sheets of graphene. Optionally, the sheets of graphene are located on the surfaces of the titanium dioxide grains and in the interstices between the titanium dioxide grains. Therefore, in the composite antibacterial coating, the binding force between the graphene and the titanium dioxide layer is strong, and the graphene is not easy to fall off and become free.
In an embodiment of the present invention, the material of the workpiece substrate is a metal or a metal alloy. Among them, the metals include titanium, gold, platinum, niobium (Nb), tantalum (Ta); examples of the metal alloy include titanium-based alloys (e.g., TC4), cobalt-based alloys (e.g., cobalt-chromium alloys), Ni-Ti alloys, nickel-based alloys, and stainless steel. When the workpiece is used in the biomedical field, the material of the workpiece substrate is preferably a biocompatible metal or metal alloy, and more preferably titanium or a titanium-based alloy.
In other embodiments of the invention, the workpiece substrate may also be cemented carbide, silicon, glass, polymer, or the like. Wherein, the hard alloy can be tungsten carbide-based hard alloy, titanium carbonitride-based hard alloy, chromium carbide-based hard alloy and the like.
According to the workpiece with the graphene-titanium dioxide composite antibacterial coating, which is provided by the first aspect of the invention, the graphene-titanium dioxide composite antibacterial coating is arranged on the workpiece substrate, so that the composite coating has strong binding force with the workpiece substrate, and the workpiece substrate is endowed with antibacterial performance on the surface and has good biocompatibility.
In a second aspect, the invention provides a preparation method of a workpiece with a graphene-titanium dioxide composite antibacterial coating, which comprises the following steps:
providing a workpiece substrate, and carrying out sand blasting pretreatment on the workpiece substrate;
mixing graphene and titanium dioxide to obtain composite powder, sequentially performing ball milling, drying and screening on the composite powder, and taking the screened composite powder as spraying powder, or adding a polyvinyl alcohol aqueous solution into the screened composite powder for granulation, and then drying and screening the mixture to be taken as spraying powder;
and spraying the spraying powder on the workpiece substrate subjected to sand blasting pretreatment by adopting a plasma spraying method to obtain the workpiece with the graphene-titanium dioxide composite antibacterial coating.
Optionally, before the sandblasting pretreatment, further comprising: and cleaning the workpiece substrate by sequentially adopting ethanol and water.
Preferably, after the sandblasting pretreatment, ultrasonic cleaning is also required to wash off the attachments attached to the surface of the workpiece substrate. The ultrasonic cleaning may be performed by sequentially using acetone and ethanol.
Optionally, the mass fraction of the graphene in the composite powder is 1-30%. Preferably 1 to 10%. More preferably 1 to 5%.
The ball milling method comprises the following steps of (1) performing ball milling on zirconium oxide balls as ball milling media, wherein the ball milling media adopted in the ball milling process are zirconium oxide balls, and the mass ratio of the composite powder to the ball milling media is 1: (1-1.5); the rotation speed during ball milling is 350-.
In one embodiment of the invention, the zirconia milling beads include three milling beads having diameters of 5mm, 3mm and 1 mm. Further, the mass ratio of the three kinds of grinding beads with the diameters of 5mm, 3mm and 1mm is 1:2: 4. This makes it possible to grind the composite powder very uniformly.
In the present invention, the drying is carried out at 40 to 80 ℃.
Wherein, in one embodiment of the invention, the particle size range of the sieved composite powder is 60-120 μm. The composite powder with the particle size range has proper granularity and proper fluidity, and can be directly used as spraying powder.
Optionally, in another embodiment of the present invention, in the granulating process, the mass of the polyvinyl alcohol is 5 to 15% of the mass of the sieved composite powder. The addition of the aqueous solution of the polyvinyl alcohol can improve the fluidity of the spraying powder, and is convenient for subsequent plasma spraying.
Wherein the particle size range of the spraying powder is 60-170 mu m. Optionally 80-150 μm, or 60-120 μm.
In the invention, the process parameters of the plasma spraying method comprise: the powder feeding speed of the spraying powder is 20-45g/min, and the spraying distance is 80-120 mm; the power of the power supply is 30-50W, the voltage is 45-55V, argon is used as main gas, and hydrogen is used as auxiliary gas; wherein the argon flow is 30-50L/min, and the hydrogen flow is 2-16L/min.
Further, in the plasma spraying process, the rotating speed of the rotating platform of the plasma spraying chamber is 350-.
Wherein the thickness of the formed composite antibacterial coating is 50-120 μm.
According to the preparation method of the workpiece with the graphene-titanium dioxide composite antibacterial coating, the laminar graphene material is doped in the titanium dioxide coating by adopting a plasma spraying method to form the composite coating of the two, and graphene is not easy to dissociate; the composite coating has strong binding force with a workpiece matrix, is not easy to fall off from the matrix, and can endow the workpiece matrix with good antibacterial property, biocompatibility and low toxicity. The preparation method is simple and easy to operate, and is suitable for industrial production.
Advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of embodiments of the invention.
Drawings
FIG. 1 is a scanning electron micrograph of a coating on a workpiece prepared according to example 1, example 2, and comparative example 1 of the present invention.
FIG. 2 is a graph of the surface roughness values of the coatings on the workpieces prepared in examples 1, 2 and 1 of the present invention.
Fig. 3 is a raman spectrum characterization chart of the coating on the workpiece prepared in example 1, example 2 and comparative example 1 of the present invention.
FIG. 4 is a graph showing the results of the activity of bacteria on the coatings prepared in example 1 of the present invention and comparative example 1.
FIG. 5 shows the results of live and dead staining of bacteria on the coatings prepared in example 1 of the present invention and comparative example 1.
Fig. 6 is a graph showing the results of osteoblast activity on the coatings prepared in example 1 of the present invention and comparative example 1.
FIG. 7 shows the results of evaluation of intracellular ROS content of bacteria.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it should be noted that those skilled in the art can make various modifications and improvements without departing from the principle of the embodiments of the present invention, and such modifications and improvements are considered to be within the scope of the embodiments of the present invention.
The following examples are intended to illustrate the invention in more detail.
Example 1
A preparation method of a workpiece with a graphene-titanium dioxide composite antibacterial coating comprises the following steps:
(1) pretreatment of the surface of a workpiece substrate:
the TC4 titanium alloy sheet with the size of phi 15mm multiplied by 1mm is taken as a substrate, is sequentially cleaned by absolute ethyl alcohol and water, and is subjected to sand blasting treatment by 46-mesh brown corundum after being dried. And then ultrasonically cleaning the matrix after sand blasting in acetone and alcohol for 15 minutes respectively to wash off attachments attached to the surface of the workpiece matrix.
(2) Preparing powder for spraying:
according to Graphene (GNS) with TiO2The raw materials are weighed according to the mass ratio of 3:97 to obtain grapheneWeighing 50g of composite powder with the weight percentage of 3 percent, placing the composite powder into a ball milling tank, and mixing the powder with the powder and the powder according to the material-ball ratio of 1: 1.5 weighing 75g of zirconia ball milling beads, wherein the ratio of large, medium and small ball milling beads (the diameters are respectively 5mm, 3mm and 1mm) is 1:2:4, the mass of the large, medium and small ball grinding beads put in each 50g of the composite powder is 10.8g, 21.4g and 42.9g respectively.
Adding a proper amount of absolute ethyl alcohol into the composite powder, and ball-milling the mixture in a planetary ball mill for 120min at a rotating speed of 380r/min until the composite powder is uniformly mixed. Taking out the ball-milled composite powder, drying in a drying oven at 80 ℃, and grinding the dried composite powder and sieving with a 80-mesh sieve (with the granularity of 178 mu m). Then adding a proper amount of 5 percent polyvinyl alcohol (PVA) aqueous solution into the sieved composite powder for grinding and granulation, drying at 80 ℃, continuously grinding, sieving by a 80-mesh sieve, and finally preparing the powder for spraying with good fluidity. At this time, the particle size of the spray powder is in the range of 60 to 120 μm.
(3) Preparing a composite antibacterial coating:
fixing the metal cylinder with the pretreated workpiece substrate on a rotary table of a plasma spraying chamber, wiping the surface of the fixed titanium alloy sheet with absolute ethyl alcohol to remove grease, floating dust and the like on the surface, drying the titanium alloy sheet with an air gun, and then carrying out a spraying experiment.
And pouring the spraying powder into a powder feeder, feeding the powder into a plasma spraying chamber, and forming a graphene-titanium dioxide composite antibacterial coating with the thickness of 100 mu m on the surface of the substrate by a plasma spraying method. Wherein, the plasma spraying process parameters comprise: the powder feeding speed of the spraying powder is 30g/min, and the spraying distance from the spraying powder to the substrate is 100 mm; the power of a power supply is 40W, the voltage is 50V, argon is used as main gas, the flow rate of the argon is 40L/min, hydrogen is used as auxiliary gas, and the flow rate is 10L/min; the rotating speed of the rotary table is 380r/min, and the spraying time is 120 min.
After spraying is finished, the workpiece is taken down from the metal cylinder after the temperature of the spraying chamber is naturally cooled, and then the workpiece is cleaned by absolute ethyl alcohol in an ultrasonic mode, surface dust is removed, and the workpiece is dried in an oven for later use.
Example 2
A preparation method of a workpiece with a graphene-titanium dioxide composite antibacterial coating, which is different from the preparation method of the workpiece in example 1 in that: in the step (1), the mass fraction of the graphene in the composite powder is 1%.
To highlight the beneficial effects of the present invention, the following comparative example 1 was provided, which differs from example 1 in that:
in the step (2), pure TiO is weighed2And (3) directly adding 5% PVA aqueous solution into the powder, and performing corresponding granulation, drying and screening operations to obtain the spraying powder.
Effect of the experiment
Observation of coating morphology
The workpieces obtained in inventive example 1, example 2 and comparative example 1 (each denoted as 3% GNS-TiO, respectively)2、1％GNS-TiO2、TiO2) After the surface gold spraying was performed, the surface morphology of the coating formed after the spraying was observed by using a field emission scanning electron microscope (FE-SEM, ZEISS, germany, SUPRA55), and the result is shown in fig. 1.
As can be seen from FIG. 1, GNS-TiO formed in example 1-22The composite coating has a micro-nano structure, and TiO is not obviously changed after the graphene is doped2Morphology of the coating. However, with the doping of graphene, the roughness of the obtained composite coating is slightly increased (as shown in fig. 2).
Coating surface phase composition
The surface phase compositions of the coatings obtained in examples 1 to 2 and comparative example 1 were analyzed by raman spectroscopy, and the results are shown in fig. 3. As can be seen from FIG. 3, the doping of Graphene (GNS) was carried out at 1350cm-1(D)、1580cm-1(G)、2710cm-1(2D) Can obviously observe characteristic peaks of the flake graphene, which indicates that GNS is successfully doped into TiO2In the coating.
Antibacterial experiments
A. The work pieces prepared in example 1 and comparative example 1 were washed, autoclaved at 121 ℃ for 20 minutes, placed in a 24-well plate, and 1mL of each of a suspension of Escherichia coli (E.coli) and a suspension of Staphylococcus aureus (S.aureus) (each having a density of 1X 10)7CFU/mL), incubated at 37 ℃ for 24 hours, and then cultured with MTT (3- (4,5-dimethylthiazole-2) -2, 5-diphenyltetrazolium bromide salt) to detect the activity of bacteria (the optical density (OD value) is measured under the wavelength of 570nm of an enzyme-labeling instrument), and the antibacterial performance of the product is evaluated.
The results of the antibacterial experiments are shown in fig. 4. As can be seen from FIG. 4, after doping graphene in the titanium dioxide coating, GNS-TiO is formed2The composite coating shows certain antibacterial performance to E.coli and S.aureus.
B. The work pieces prepared in example 1 and comparative example 1 were washed, autoclaved at 121 ℃ for 20 minutes, placed in a 24-well plate, and 1mL of each of a suspension of Escherichia coli (E.coli) and a suspension of Staphylococcus aureus (S.aureus) (each having a density of 1X 10)7CFU/mL), cultured in an incubator at 37 ℃ for 24 hours, washed three times with PBS, live-dead-stained with a live-dead-staining kit, and then the antibacterial property of the coating was observed under a fluorescent microscope, wherein green is live bacteria and red is dead bacteria.
The results of live and dead staining of bacteria are shown in FIG. 5. from FIG. 5, it can be seen that the GNS-TiO formed after doping the titanium dioxide coating with graphene2The composite coating can inhibit the adhesion of e.coli and s.aureus to some extent.
Cell viability assay
The work pieces prepared in example 1 and comparative example 1 were washed, autoclaved at 121 ℃ for 20 minutes, placed in a 24-well plate, and 1mL of mouse preosteoblasts (MC3T3-E1) suspension (5X 10) was added4cell/mL), 5% CO at 37 deg.C2After 1 day in the incubator, CCK-8(2- (2-methoxy-4-nitrophenyl) -3- (4-nitrophenyl) -5- (2, 4-disulfophenyl) -2H-tetrazole monosodium salt) was used to measure absorbance values at 450nm and the activity of the cells on various work pieces was evaluated, and the results of cell activity are shown in FIG. 6.
As can be seen from FIG. 6, the MC3T3-E1 cells still have a cell activity greater than 90% after being cultured with the work product of example 1 for 24h, but the cell activity is higher than that of the pure TiO cell2The cellular activity on the coating was slightly reduced. This shows that the GNS-TiO of the present invention2The composite coating has good biocompatibility.
Detection of reactive oxygen species free (ROS)
The work pieces prepared in example 1 and comparative example 1 were washed, autoclaved at 121 ℃ for 20 minutes, placed in a 24-well plate, and 1mL of each of a suspension of Escherichia coli (E.coli) and a suspension of Staphylococcus aureus (S.aureus) (each having a density of 1X 10)7CFU/mL), after incubation for 3h in an incubator at 37 ℃, washed three times with PBS, and then 100 μ L of DCFH-DA dye (1: 1000 dilution), incubating for 30min at 37 ℃ in the dark, washing with PBS for three times to remove excess dye, transferring the sample into a centrifuge tube, shaking for 3min, placing 100 mu L of liquid into a 96-well plate, exciting at 488nm by a fluorescence microplate reader, and measuring the absorbance value at 525 nm. Intracellular ROS content of the bacteria is shown in FIG. 7.
As can be seen from FIG. 7, the ROS content in the bacteria was significantly increased after the titanium dioxide coating was doped with 3% GNS, indicating that GNS-TiO2The composite coating interferes with the metabolism and physiological activity of bacteria, generates ROS, further inhibits the adhesion of E.coli and S.aureus, and shows a certain antibacterial property.
Example 3
A preparation method of a workpiece with a graphene-titanium dioxide composite antibacterial coating comprises the following steps:
(1) pretreatment of the surface of a workpiece substrate:
Ni-Ti alloy sheets with the size of phi 15mm multiplied by 1mm are taken as a matrix, washed by absolute ethyl alcohol and water in sequence, dried and then subjected to sand blasting treatment by 46-mesh corundum. And then ultrasonically cleaning the matrix subjected to sand blasting in acetone and alcohol for 20 minutes respectively to wash off attachments attached to the surface of the workpiece matrix.
(2) Preparing powder for spraying:
according to Graphene (GNS) with TiO2Weighing the raw materials according to the mass ratio of 5:95 to obtain composite powder with the graphene mass fraction of 5%, weighing 50g of the composite powder, placing the composite powder in a ball milling tank, and mixing the raw materials according to the ball-to-ball ratio of 1: 1.5 weighing 75g of zirconia ball milling beads, wherein the ratio of large, medium and small ball milling beads (the diameters are respectively 5mm, 3mm and 1mm) is 1:2:4, namely the mass of the large, medium and small ball grinding beads put in each 50g of the composite powder respectively10.8g, 21.4g and 42.9 g.
Adding a proper amount of absolute ethyl alcohol into the composite powder, and ball-milling the mixture in a planetary ball mill for 180min at a rotating speed of 400r/min until the composite powder is uniformly mixed. Taking out the ball-milled composite powder, drying the ball-milled composite powder in a drying oven at 70 ℃, and grinding the dried composite powder and sieving the powder with a 80-mesh sieve. Then adding a proper amount of 10% polyvinyl alcohol (PVA) aqueous solution into the sieved composite powder (the granularity is about 90 mu m) for grinding and granulating, drying at 70 ℃, then continuing grinding, and sieving by a 80-mesh sieve to finally prepare the spraying powder with good fluidity. At this time, the particle size of the spray powder was 120. mu.m.
(3) Preparing a composite antibacterial coating:
fixing the metal cylinder with the pretreated workpiece substrate on a rotary table of a plasma spraying chamber, wiping the surface of the fixed titanium alloy sheet with absolute ethyl alcohol to remove grease, floating dust and the like on the surface, drying the titanium alloy sheet with an air gun, and then carrying out a spraying experiment.
And pouring the spraying powder into a powder feeder, feeding the powder into a plasma spraying chamber, and forming a graphene-titanium dioxide composite antibacterial coating with the thickness of 80 microns on the surface of the substrate by a plasma spraying method. Wherein, the plasma spraying process parameters comprise: the powder feeding speed of the spraying powder is 40g/min, and the spraying distance from the spraying powder to the substrate is 120 mm; the power of the power supply is 50W, the voltage is 55V, argon is main gas, the flow of the argon is 50L/min, hydrogen is auxiliary gas, and the flow is 15L/min; the turntable was rotated at 400 rpm.
After spraying is finished, the workpiece is taken down from the metal cylinder after the temperature of the spraying chamber is naturally cooled, and then the workpiece is cleaned by absolute ethyl alcohol in an ultrasonic mode, surface dust is removed, and the workpiece is dried in an oven for later use.
The workpiece with the graphene-titanium dioxide composite antibacterial coating obtained in the embodiment 3 includes a workpiece substrate (specifically, a Ni-Ti alloy), and a graphene-titanium dioxide composite antibacterial coating (with a thickness of 80 μm) disposed on the surface of the workpiece substrate; in the composite antibacterial coating, the graphene is doped in the titanium dioxide.
Example 4
A preparation method of a workpiece with a graphene-titanium dioxide composite antibacterial coating comprises the following steps:
(1) pretreatment of the surface of a workpiece substrate:
YG8 (WC-8% Co) hard alloy milling cutter blade sold in the domestic market is used as a workpiece substrate, and is sequentially cleaned by absolute ethyl alcohol and water, and is subjected to sand blasting treatment by silicon carbide with the granularity of 300 meshes after being dried. And then ultrasonically cleaning the matrix subjected to sand blasting in acetone and alcohol for 10 minutes respectively to wash off attachments attached to the surface of the workpiece matrix.
(2) Preparing powder for spraying:
according to Graphene (GNS) with TiO2Weighing the raw materials according to the mass ratio of 8:92 to obtain composite powder with the graphene mass fraction of 8%, weighing 50g of the composite powder, placing the composite powder in a ball milling tank, and mixing the raw materials according to the ball-to-ball ratio of 1: 1.5 weighing 75g of zirconia ball milling beads, wherein the ratio of large, medium and small ball milling beads (the diameters are respectively 5mm, 3mm and 1mm) is 1:2:4, the mass of the large, medium and small ball grinding beads put in each 50g of the composite powder is 10.8g, 21.4g and 42.9g respectively.
Adding a proper amount of absolute ethyl alcohol into the composite powder, and ball-milling for 240min in a planetary ball mill at the rotating speed of 350r/min until the composite powder is uniformly mixed. And taking out the ball-milled composite powder, drying in a drying oven at 60 ℃, and grinding the dried composite powder and sieving with a 80-mesh sieve. Then adding a proper amount of 12% polyvinyl alcohol (PVA) aqueous solution into the sieved composite powder (the granularity is about 100 mu m) for grinding and granulating, drying at 60 ℃, continuously grinding, sieving by a 80-mesh sieve, and finally preparing the spraying powder with good fluidity. At this time, the particle size of the spray powder was about 130 μm.
(3) Preparing a composite antibacterial coating:
fixing the metal cylinder with the pretreated workpiece substrate on a rotary table of a plasma spraying chamber, wiping the surface of the fixed titanium alloy sheet with absolute ethyl alcohol to remove grease, floating dust and the like on the surface, drying the titanium alloy sheet with an air gun, and then carrying out a spraying experiment.
And pouring the spraying powder into a powder feeder, feeding the powder into a plasma spraying chamber, and forming a graphene-titanium dioxide composite antibacterial coating with the thickness of 60 mu m on the surface of the substrate by a plasma spraying method. Wherein, the plasma spraying process parameters comprise: the powder feeding speed of the spraying powder is 20g/min, and the spraying distance from the spraying powder to the substrate is 80 mm; the power of the power supply is 30W, the voltage is 45V, argon is used as main gas, the flow rate of the argon is 30L/min, hydrogen is used as auxiliary gas, and the flow rate is 5L/min; the rotational speed of the turntable was 360 revolutions per minute.
After spraying is finished, the workpiece is taken down from the metal cylinder after the temperature of the spraying chamber is naturally cooled, and then the workpiece is cleaned by absolute ethyl alcohol in an ultrasonic mode, surface dust is removed, and the workpiece is dried in an oven for later use.
The workpiece with the graphene-titanium dioxide composite antibacterial coating obtained in this embodiment 4 includes a workpiece substrate (specifically, YG8 cemented carbide), and a graphene-titanium dioxide composite antibacterial coating (with a thickness of 60 μm) disposed on a surface of the workpiece substrate; in the composite antibacterial coating, the graphene is doped in the titanium dioxide.
The above-mentioned embodiments only express exemplary embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (8)

1. The workpiece with the graphene-titanium dioxide composite antibacterial coating is characterized by comprising a workpiece substrate and the graphene-titanium dioxide composite antibacterial coating arranged on the surface of the workpiece substrate, wherein in the composite antibacterial coating, graphene is doped in the titanium dioxide coating; the crystal grains of the titanium dioxide are attached to the sheet layers of the graphene and are inserted between the sheet layers of the graphene; the roughness of the composite antibacterial coating is 1-10 mu m; the composite antibacterial coating is prepared by adopting a plasma spraying technology, and the spraying powder adopted by the plasma spraying technology is obtained by adopting the following modes: sequentially carrying out ball milling, drying and sieving on the composite powder obtained by mixing the graphene and the titanium dioxide to obtain the spraying powder; or carrying out ball milling, drying and screening on the composite powder obtained by mixing the graphene and the titanium dioxide in sequence, then adding a polyvinyl alcohol aqueous solution for granulation, and then drying and screening to obtain the spraying powder.
2. The workpiece with the graphene-titanium dioxide composite antibacterial coating of claim 1, wherein the material of the workpiece substrate is metal, metal alloy, hard alloy or glass.
3. A preparation method of a workpiece with a graphene-titanium dioxide composite antibacterial coating is characterized by comprising the following steps:
providing a workpiece substrate, and carrying out sand blasting pretreatment on the workpiece substrate;
mixing graphene and titanium dioxide to obtain composite powder, sequentially performing ball milling, drying and screening on the composite powder, and taking the screened composite powder as spraying powder, or adding a polyvinyl alcohol aqueous solution into the screened composite powder for granulation, and then drying and screening the mixture to be taken as spraying powder;
spraying the spraying powder on the workpiece substrate subjected to sand blasting pretreatment by adopting a plasma spraying method to obtain a workpiece with a graphene-titanium dioxide composite antibacterial coating; wherein the crystal grains of the titanium dioxide are attached to the sheets of the graphene and are inserted between the sheets of the graphene; the roughness of the composite antibacterial coating is 1-10 mu m.
4. The method according to claim 3, wherein the composite powder contains 1 to 30% by mass of graphene.
5. The preparation method of claim 3, wherein the ball milling medium used in the ball milling is zirconia balls, and the mass ratio of the composite powder to the ball milling medium is 1: (1-1.5); the rotation speed during ball milling is 350-.
6. The method according to claim 3, wherein the particle size of the spray powder is in the range of 80 to 170 μm.
7. The method of claim 6, wherein the process parameters of the plasma spray process include: the powder feeding speed of the spraying powder is 20-45g/min, and the spraying distance is 80-120 mm; the power of the power supply is 30-50W, the voltage is 45-55V, argon is used as main gas, and hydrogen is used as auxiliary gas; wherein the argon flow is 30-50L/min, and the hydrogen flow is 2-16L/min.
8. The method according to claim 3, wherein the mass of the polyvinyl alcohol is 5 to 15% of the mass of the sieved composite powder.
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