CN109627761B - Self-lubricating sterilization composite material with sliding plate-like structure and preparation method thereof - Google Patents
Self-lubricating sterilization composite material with sliding plate-like structure and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a sliding plate structure-imitated self-lubricating sterilization composite material, belonging to the technical field of sterilization composite materials, which is characterized in that cations of nano-bactericide raw materials and polymers are sting together through sting reaction, and further, the polymer molecules of zirconium phosphate inorganic materials and the cations of the sting nano-bactericide raw materials are horizontally assembled and compounded through hydrothermal reaction to form a layered structure, so that a multi-layer structure composite material is obtained, then reducing the cations in the polymer of the cations of the raw materials of the hibernating nano bactericide through reduction reaction, the spherical nano sterilizing material is synthesized in situ between the zirconium phosphate layers, the distance between the zirconium phosphate layers is enlarged, the bonding strength is further reduced, the sliding plate-like self-lubricating sterilizing composite material taking the zirconium phosphate layer sheets as plates and the spherical nano sterilizing material as pulleys is formed, and the functions of sterilization and lubrication are achieved.
Description
Technical Field
The invention relates to the technical field of sterilization composite materials, in particular to a sliding plate structure-imitated self-lubricating sterilization composite material and a preparation method thereof.
Background
In the process of development, utilization and protection of the ocean, biofouling is always an unavoidable huge problem. Statistics show that the material damage and failure related to microbial attachment accounts for 70-80% of the total loss of the sea-related material.
The bactericide can effectively control the activity of bacteria, and is beneficial to reducing the life activity and the adhesion effect with the surface. Nanomaterial (such as Ag and TiO)2ZnO) is one of the excellent bactericides. The nano sterilizing material has some problems in the using process: on one hand, the nano material is easily and rapidly oxidized and corroded when being contacted with oxidation or corrosion factors in the environment, so that the bactericidal activity is lost or the stability is uncontrollable; on the other hand, the use of the nano-materials is all requiredThe nano material is evenly dispersed in the carrier or the base material, and the nano material is easy to lose once the carrier or the base material is damaged by external force. The Liu covers a super-hydrophobic molecular layer on the surface of the nano functional coating, so that the interface shielding effect is enhanced, and the purpose of slow release is achieved. YIn prepares the Ag @ AgI nano antifouling agent with the shell-core structure, the method similar to the microcapsule coating technology improves Ag with lower internal stability by utilizing AgI material with high external layer stability, and the stability and the antifouling long-acting property are obviously improved. Although the method solves the technical problems that the nano material is in contact with oxidation or corrosion factors in the environment and is extremely easy to be rapidly oxidized and corroded to a certain degree, the interface is a complex and changeable microscopic process, the mechanical damage effects of sea waves, sand and stones, foreign matter friction and the like bring great tests to the surface of engineering facilities and protective materials, when the surface of the engineering facilities is mechanically damaged, the nano material can be lost, and the enhancement of wear resistance or lubricity is one of important conditions for reducing mechanical damage. The bactericides prepared by the method have no lubricating function.
Disclosure of Invention
In view of the above, the invention aims to provide a sliding plate structure-imitated self-lubricating sterilization composite material and a preparation method thereof.
The invention provides a preparation method of a sliding plate structure-imitated self-lubricating bactericidal composite material, which comprises the following steps of:
1) mixing the nano bactericide raw material, a polymer and water to carry out a jellyfish reaction to obtain a mixed solution; the nano bactericide raw material comprises silver nitrate, copper chloride, copper sulfate or copper nitrate; the polymer comprises polyethyleneimine, poly (allylamine hydrochloride), polydiallyldimethylammonium chloride or aliphatic polyamine polyurethane;
2) mixing the mixed solution obtained in the step 1), zirconium oxychloride, phosphoric acid and water for hydrothermal reaction to obtain a multilayer structure composite material;
3) mixing the multilayer structure composite material obtained in the step 2), a reducing agent and water for reduction reaction to obtain the sliding plate structure-imitated self-lubricating bactericidal composite material.
Preferably, the mass ratio of the nano bactericide raw material to the polymer in the step 1) is 1: 10 to 25.
Preferably, the temperature of the jellyfish reaction in the step 1) is 15-30 ℃, and the time of the jellyfish reaction is 5-10 min.
Preferably, the mass ratio of the polymer, the zirconium oxychloride and the phosphoric acid in the mixed solution in the step 2) is 1: (2.7-3.2): (4.7-5.1).
Preferably, the temperature of the hydrothermal reaction in the step 2) is 100-210 ℃, and the time of the hydrothermal reaction is 24-36 h.
Preferably, the reducing agent in step 3) is sodium borohydride, ascorbic acid, hydrazine hydrate or sodium citrate.
Preferably, the mass ratio of the multilayer structure composite material to the reducing agent in the step 3) is 1: 100 to 500.
Preferably, the temperature of the reduction reaction in the step 3) is 10-30 ℃, and the time of the reduction reaction is 2-4 min.
The invention also provides the self-lubricating bactericidal composite material with the simulated sliding plate structure, which is prepared by the preparation method, wherein the self-lubricating bactericidal composite material with the simulated sliding plate structure is of a multilayer structure, the multilayer structure is obtained by sequentially laminating a zirconium phosphate layer and a bactericide lubricating layer, and the bactericide lubricating layer comprises a polymer and a spherical nano bactericidal material; the spherical nano sterilizing material comprises nano silver or nano copper; the polymer comprises polyethyleneimine, poly (allylamine hydrochloride), polydiallyldimethylammonium chloride, or aliphatic polyamine polyurethane.
The beneficial technical effects are as follows: the invention provides a preparation method of a sliding plate structure-imitated self-lubricating bactericidal composite material, which comprises the following steps of: mixing the nano bactericide raw material, a polymer and water to carry out a jellyfish reaction to obtain a mixed solution; the nano bactericide raw material comprises silver nitrate, copper chloride, copper sulfate or copper nitrate; the polymer comprises polyethyleneimine, poly (allylamine hydrochloride), polydiallyldimethylammonium chloride or aliphatic polyamine polyurethane; mixing the obtained mixed solution, zirconium oxychloride, phosphoric acid and water to perform hydrothermal reaction to obtain a multilayer structure composite material; and mixing the obtained multilayer structure composite material, a reducing agent and water for reduction reaction to obtain the sliding plate structure-imitated self-lubricating bactericidal composite material. According to the invention, cations of nano bactericide raw materials and a polymer are sting together through a sting reaction, further, a hydrothermal reaction is adopted to realize horizontal assembly and compounding of a zirconium phosphate inorganic material and the polymer molecules of the cations of the nano bactericide raw materials to form a layered structure, a multi-layer structure composite material is obtained, then, the cations in the polymer of the cations of the nano bactericide raw materials are reduced through a reduction reaction, the zirconium phosphate layers are used as a reactor to control the particle size, a spherical nano bactericide material is synthesized in situ between the layers, the spacing between the zirconium phosphate layers is enlarged, and hydrogen bonds between the layers are destroyed to further reduce the bonding strength, so that the sliding plate structure-imitated self-lubricating bactericide composite material which takes the zirconium phosphate layers as plates and the spherical nano bactericide material as pulleys is formed, and the sliding plate structure-imitated self-lubricating bactericide composite material has the functions of. Experimental data of an embodiment shows that the self-lubricating bactericidal composite material with the simulated sliding plate structure, which is prepared by the invention, has better lubricity and can obviously enhance the wear resistance of the surface of the material; meanwhile, the bactericidal performance is excellent, and the long-acting performance of the bactericidal performance is obviously enhanced under the protection action of zirconium phosphate layers.
Description of the drawings:
FIG. 1 is a scanning electron microscope picture of the self-lubricating bactericidal composite material with the simulated sliding plate structure obtained in example 1; (a) the image is a local high-power scanning electron microscope image of the edge of the composite material, and (b) the image is a low-power scanning electron microscope image of the appearance of the composite material;
FIG. 2 is a surface wear pattern of a friction pair using the self-lubricating bactericidal composite material with the simulated sliding plate structure obtained in example 1 as a lubricant;
FIG. 3 is a surface wear pattern of a friction pair with a common spherical bactericide (nano-silver bactericide) as a lubricant;
FIG. 4 is a friction coefficient curve chart of the self-lubricating bactericidal composite material with the simulated sliding plate structure obtained in example 1 as a lubricant;
FIG. 5 is a scanning electron microscope picture of the self-lubricating bactericidal composite material with the simulated sliding plate structure obtained in example 2;
FIG. 6 is a scanning electron microscope picture of the self-lubricating bactericidal composite material with the simulated sliding plate structure obtained in example 3;
FIG. 7 is a scanning electron microscope picture of the composite material obtained in comparative example 1;
FIG. 8 is a scanning electron microscope picture of the composite material obtained in comparative example 2;
FIG. 9 is a scanning electron microscope picture of the composite material obtained in comparative example 3;
FIG. 10 is a scanning electron microscope picture of the composite material obtained in comparative example 4;
FIG. 11 is a schematic diagram of a preparation method of the self-lubricating bactericidal composite material with the simulated sliding plate structure.
Detailed Description
The invention provides a preparation method of a sliding plate structure-imitated self-lubricating bactericidal composite material, which comprises the following steps of:
1) mixing the nano bactericide raw material, a polymer and water to carry out a jellyfish reaction to obtain a mixed solution; the nano bactericide raw material comprises silver nitrate, copper chloride, copper sulfate or copper nitrate; the polymer comprises polyethyleneimine, poly (allylamine hydrochloride), polydiallyldimethylammonium chloride or aliphatic polyamine polyurethane;
2) mixing the mixed solution obtained in the step 1), zirconium oxychloride, phosphoric acid and water for hydrothermal reaction to obtain a multilayer structure composite material;
3) mixing the multilayer structure composite material obtained in the step 2), a reducing agent and water for reduction reaction to obtain the sliding plate structure-imitated self-lubricating bactericidal composite material.
Mixing a nano bactericide raw material, a polymer and water to carry out jellyfish reaction to obtain a mixed solution; the nano bactericide raw material comprises silver nitrate, copper chloride, copper sulfate or copper nitrate; the polymer comprises polyethyleneimine, poly (allylamine hydrochloride), polydiallyldimethylammonium chloride, or aliphatic polyamine polyurethane.
In the present invention, the mass ratio of the nano-fungicide raw material to the polymer is preferably 1: 10-25, more preferably 1: 12-20, most preferably 1: 14 to 18.
In the invention, the jellyfish reaction temperature is preferably 15-30 ℃, and more preferably 25 ℃; the time of the hibernating reaction is preferably 5-10 min, and more preferably 7 min.
In the present invention, the method for mixing the nano bactericide raw material, the polymer and the water preferably comprises the steps of:
mixing a nano bactericide raw material with water to obtain a nano bactericide raw material aqueous solution; mixing a polymer with water to obtain a polymer aqueous solution, dropwise adding a nano bactericide raw material aqueous solution into the polymer aqueous solution, and stirring to obtain a mixed solution.
In the invention, the mass concentration of the nano bactericide raw material in the nano bactericide raw material aqueous solution is preferably 0.03-0.08 g/mL, and more preferably 0.05 g/mL; the mass concentration of the polymer in the polymer water solution is preferably 0.15-0.20 g/mL, and more preferably 0.17 g/mL; the dripping speed is preferably 2-10 mL/min, and more preferably 5 mL/min; the stirring speed is preferably 80-160 r/min, and more preferably 100 r/min; the stirring time is preferably 5-10 min.
The invention discloses a method for jellyfishing a polymer molecule by cations in a nano bactericide raw material through jellyfishing reaction.
After the mixed solution is obtained, the obtained mixed solution, zirconium oxychloride, phosphoric acid and water are mixed for hydrothermal reaction to obtain the multilayer structure composite material.
In the present invention, the mass ratio of the polymer, zirconium oxychloride, and phosphoric acid in the mixed solution is preferably 1: (2.7-3.2): (4.7-5.1), more preferably 1: 3: 5.
in the invention, the temperature of the hydrothermal reaction is preferably 100-210 ℃, more preferably 150-200 ℃, and most preferably 200 ℃; the time of the hydrothermal reaction is preferably 24-36 h, and more preferably 28-32 h.
In the present invention, the method of mixing the mixed solution, zirconium oxychloride, phosphoric acid and water preferably includes the steps of:
mixing zirconium oxychloride with water to obtain a zirconium oxychloride solution; mixing phosphoric acid and water to obtain a phosphoric acid solution; and then mixing the mixed solution, a zirconium oxychloride solution and a phosphoric acid solution and stirring.
In the invention, the zirconium oxychloride is preferably zirconium oxychloride octahydrate, and the mass concentration of the zirconium oxychloride in the zirconium oxychloride solution is preferably 0.15-0.25 g/mL, and more preferably 0.20 g/mL; the mass concentration of phosphoric acid in the phosphoric acid solution is preferably 0.10-0.20 g/mL, and more preferably 0.15 g/mL. The stirring speed is not particularly limited in the invention, and the stirring speed known by the technicians in the field can be selected; the stirring time is preferably 3-5 min.
The invention realizes the horizontal assembly and composition of the zirconium phosphate inorganic material and the polymer molecules of the cations of the raw materials of the hibernating nano bactericide by a hydrothermal reaction to form a laminated structure, thereby obtaining the multilayer structure composite material.
In the present invention, after the hydrothermal reaction, the method further preferably includes sequentially performing first water washing, second water washing, alcohol washing and drying on the obtained hydrothermal reaction solution to obtain the multilayer structure composite material.
In the present invention, the first washing is preferably performed by mixing the obtained hydrothermal reaction solution with water, stirring the mixture, and performing solid-liquid separation on the obtained mixed solution to obtain a first washed solid product. In the present invention, the mass ratio of the hydrothermal reaction solution to water is not particularly limited, and may be any mass ratio known to those skilled in the art. The stirring speed is not particularly limited in the invention, and the stirring speed known by the technicians in the field can be selected; in the invention, the stirring time is preferably 1-3 min. The method of solid-liquid separation in the present invention is not particularly limited, and a method of solid-liquid separation known to those skilled in the art may be selected, and centrifugal separation is preferable in the present invention. In the invention, the rotation speed of the centrifugal separation is preferably 4000-6000 r/min, and more preferably 5000 r/min; the time for centrifugal separation is preferably 5-10 min.
In the invention, the second washing is preferably performed by mixing the first washed solid product with water, stirring, performing solid-liquid separation on the obtained mixed solution, and repeating the steps for 2-4 times to obtain a second washed solid product. The mass ratio of the second water-washed solid product to water in the present invention is not particularly limited, and may be any mass ratio known to those skilled in the art. The stirring speed is not particularly limited in the invention, and the stirring speed known by the technicians in the field can be selected; in the invention, the stirring time is preferably 1-3 min. The method of solid-liquid separation in the present invention is not particularly limited, and a method of solid-liquid separation known to those skilled in the art may be selected, and centrifugal separation is preferable in the present invention. In the invention, the rotation speed of the centrifugal separation is preferably 4000-6000 r/min, and more preferably 5000 r/min; the time for centrifugal separation is preferably 5-10 min.
In the invention, the alcohol washing is to mix the second washed solid product with ethanol and then stir, and perform solid-liquid separation on the obtained mixed liquid to obtain an alcohol washed solid product. The mass ratio of the second water-washed solid product to ethanol is not particularly limited in the present invention, and may be any mass ratio known to those skilled in the art. The stirring speed is not particularly limited in the invention, and the stirring speed known by the technicians in the field can be selected; the stirring time is preferably 1-3 min. The solid-liquid separation method of the present invention is not particularly limited, and a solid-liquid separation method known to those skilled in the art may be used. In the invention, centrifugal separation is preferred, and the rotating speed of the centrifugal separation is preferably 4000-6000 r/min, and more preferably 5000 r/min; the time for centrifugal separation is preferably 5-10 min.
In the invention, the drying is to dry the alcohol-washed solid product to obtain the multilayer structure composite material. In the invention, the drying is preferably vacuum drying, and the temperature of the vacuum drying is preferably 50-70 ℃, and more preferably 60-65 ℃; the vacuum drying time is preferably 12-24 hours, and more preferably 15-20 hours.
After the multilayer structure composite material is obtained, the obtained multilayer structure composite material, a reducing agent and water are mixed for reduction reaction, and the self-lubricating bactericidal composite material with the simulated sliding plate structure is obtained.
In the present invention, the reducing agent is preferably sodium borohydride, ascorbic acid, hydrazine hydrate or sodium citrate.
In the present invention, the mass ratio of the multilayer structure composite material to the reducing agent is preferably 1: 100-500, more preferably 1: 200 to 300.
In the invention, the temperature of the reduction reaction is preferably 10-30 ℃, more preferably 25 ℃, and the time of the reduction reaction is preferably 2-4 min, more preferably 3 min.
The invention reduces the positive ions in the polymer of the positive ions of the raw material of the jellyfish nano bactericide by reduction reaction, controls the particle size by taking zirconium phosphate layers as a reactor, synthesizes the spherical nano bactericide material in situ between the layers, expands the space between the zirconium phosphate layers and destroys hydrogen bonds between the layers at the same time to further reduce the bonding strength, forms the self-lubricating bactericide composite material with the simulated sliding plate structure, which takes zirconium phosphate layers as plates and the spherical nano bactericide material as pulleys, and has the functions of sterilization and lubrication.
In the invention, after the reduction reaction, the method preferably further comprises the steps of sequentially carrying out first washing, second washing, alcohol washing and drying on the obtained reduction reaction liquid to obtain the multilayer structure composite material.
In the present invention, the first washing is preferably performed by mixing the obtained reduction reaction solution with water, stirring the mixture, and performing solid-liquid separation on the obtained mixed solution to obtain a first washing solid product. In the present invention, the mass ratio of the reduction reaction solution to water is not particularly limited, and a mass ratio known to those skilled in the art may be selected. The stirring speed is not particularly limited in the invention, and the stirring speed known by the technicians in the field can be selected; in the invention, the stirring time is preferably 1-3 min. The solid-liquid separation method of the present invention is not particularly limited, and a solid-liquid separation method known to those skilled in the art may be used. In the invention, centrifugal separation is preferred, and the rotating speed of the centrifugal separation is preferably 4000-6000 r/min, and more preferably 5000 r/min; the time for centrifugal separation is preferably 5-10 min.
In the invention, the second washing is preferably performed by mixing the first washed solid product with water, stirring, performing solid-liquid separation on the obtained mixed solution, and repeating the steps for 2-4 times to obtain a second washed solid product. The mass ratio of the second water-washed solid product to water in the present invention is not particularly limited, and may be any mass ratio known to those skilled in the art. The stirring speed is not particularly limited in the invention, and the stirring speed known by the technicians in the field can be selected; in the invention, the stirring time is preferably 1-3 min. The solid-liquid separation method is not particularly limited, and a solid-liquid separation method well known by the technical personnel in the field can be selected, centrifugal separation is preferred in the invention, and the rotating speed of the centrifugal separation is preferably 4000-6000 r/min, and more preferably 5000 r/min; the time for centrifugal separation is preferably 5-10 min.
In the invention, the alcohol washing is to mix the second washed solid product with ethanol and then stir, and perform solid-liquid separation on the obtained mixed liquid to obtain an alcohol washed solid product. The mass ratio of the second water-washed solid product to ethanol is not particularly limited in the present invention, and may be any mass ratio known to those skilled in the art. The stirring speed is not particularly limited in the invention, and the stirring speed known by the technicians in the field can be selected; the stirring time is preferably 1-3 min. The method of solid-liquid separation in the present invention is not particularly limited, and a method of solid-liquid separation known to those skilled in the art may be selected, and centrifugal separation is preferable in the present invention. In the invention, the rotation speed of the centrifugal separation is preferably 4000-6000 r/min, and more preferably 5000 r/min; the time for centrifugal separation is preferably 5-10 min.
In the invention, the drying is to dry the alcohol-washed solid product, so as to obtain the sliding plate structure-imitated self-lubricating bactericidal composite material. In the invention, the drying is preferably vacuum drying, and the temperature of the vacuum drying is preferably 50-70 ℃, and more preferably 60-65 ℃; the vacuum drying time is preferably 12-24 hours, and more preferably 15-20 hours.
In the present invention, a schematic diagram of the above-described production method is shown in FIG. 11.
The invention also provides the self-lubricating bactericidal composite material with the simulated sliding plate structure, which is prepared by the preparation method, wherein the self-lubricating bactericidal composite material with the simulated sliding plate structure is of a multilayer structure, the multilayer structure is obtained by sequentially laminating a zirconium phosphate layer and a bactericide lubricating layer, and the bactericide lubricating layer comprises a polymer and a spherical nano bactericidal material; the spherical nano sterilizing material comprises nano silver or nano copper; the polymer comprises polyethyleneimine, poly (allylamine hydrochloride), polydiallyldimethylammonium chloride, or aliphatic polyamine polyurethane.
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
1) Adding silver nitrate solution (0.05g/mL, 6mL) into polyethyleneimine (0.17g/mL, 25mL) solution dropwise, and slowly stirring for 7min to obtain cation-polyethyleneimine mixed solution in which the cation is hibernated.
2) Sequentially adding a zirconium oxychloride solution (0.20g/mL, 20mL), a cation-polyethyleneimine mixed solution (10mL) and phosphoric acid (0.15g/mL, 45mL) into a polytetrafluoroethylene reaction tank, fully stirring for 5min, carrying out hydrothermal reaction at 200 ℃ for 28h, after the reaction is finished, adding deionized water, sequentially washing and stirring for 1min, centrifuging (3000r/min) for 5min, collecting precipitates, repeating for 3 times, then sequentially washing and stirring for 1min by using ethanol, centrifuging (3000r/min) for 5min, collecting the precipitates, repeating for 3 times, and finally carrying out vacuum drying at 65 ℃ for 18h to obtain the multilayer structure composite material.
3) Adding NaBH into the multilayer structure composite material (10g) obtained in the step 2)4And (3) in an aqueous solution (0.0005g/mL, 100mL), controlling the reaction time for 3min, after the reaction is finished, adding deionized water, sequentially washing and stirring for 1min, centrifuging (5000r/min) for 5min, collecting precipitates, repeating for 3 times, then sequentially washing and stirring for 1min, centrifuging (5000r/min) for 5min, collecting the precipitates, repeating for 3 times, and finally performing vacuum drying at 65 ℃ for 20h to obtain the self-lubricating bactericidal composite material with the simulated sliding plate structure. The scanning electron microscope image is shown in fig. 1, wherein (a) is a local high-power scanning electron microscope image of the edge of the composite material, and (b) is a low-power scanning electron microscope image of the morphology of the composite material. FIG. 1(a) shows that the composite structure prepared in example 1 is a sliding plate-like structure, and FIG. 1(b) shows that the composite structure prepared in example 1 is entirely in the form of a laminated sheet.
The self-lubricating bactericidal composite material with the simulated sliding plate structure obtained in the example 1 and the common spherical bactericide (nano-silver bactericide) are respectively used as lubricants to carry out tribology experiments, and the results of the appearance of the wear stains on the surface of a friction pair and the data of friction and wear are shown in fig. 2, table 1, fig. 3 and table 2. The result of the friction coefficient curve graph of the self-lubricating bactericidal composite material with the simulated sliding plate structure as the lubricant is shown in figure 4.
TABLE 1 wear-leveling data of self-lubricating bactericidal composite material with simulated sliding plate structure obtained in example 1 as lubricant
| Parameter(s) | Unit of | Grain | Peak(s) |
| Surface area of abraded plaque | mm2 | 0.173 | 0.0699 |
| Wear volume | μm3 | 39661 | 2765 |
| Maximum depth to height ratio | nm | 1685 | 1019 |
| Average depth to height ratio | nm | 229 | 39.6 |
TABLE 2 general spherical biocide as lubricant scrub data
| Parameter(s) | Unit of | Grain | Peak(s) |
| Surface area of abraded plaque | mm2 | 0.394 | 0.0033 |
| Wear volume | μm3 | 627201 | 35 |
| Maximum depth to height ratio | nm | 4183 | 1654 |
| Average depth to height ratio | nm | 1593 | 107 |
As can be seen from FIGS. 2 and 3, the area within the circle of FIG. 2 is smaller than that of FIG. 3, and the surface areas of the spots in Table 1 and Table 2 are the white portions within the circle of FIGS. 2 and 3, respectively, 0.2429mm2And 0.3973mm2Wear volume 42426 μm3And 627236 μm3。
From fig. 2, table 1, and fig. 3 and table 2, it can be seen that the composite material prepared in example 1 can significantly improve the wear resistance of the surface of the friction pair. From fig. 4, it can be seen that the composite material prepared in example 1 has good lubricity.
The test of the bactericidal performance of the self-lubricating bactericidal composite material with the simulated sliding plate structure obtained in the example 1 is shown in the table 3, and the table 3 shows that the composite material prepared in the example 1 has excellent bactericidal performance, and the stability and the long-acting performance of the bactericide are obviously enhanced.
Table 3 test results of bactericidal property of self-lubricating bactericidal composite material with simulated sliding plate structure obtained in example 1
Example 2
1) Adding silver nitrate (0.05g/mL, 5mL) dropwise into polyethyleneimine (0.17g/mL, 25mL) solution, and slowly stirring for 7min to obtain cation-polyethyleneimine mixed solution in which cation has been chelated.
2) Sequentially adding a zirconium oxychloride solution (0.20g/mL, 20mL), a cation-polyethyleneimine mixed solution (9.5mL), and phosphoric acid (0.15g/mL, 45mL) into a polytetrafluoroethylene reaction tank, fully stirring for 5min, reacting for 24h at 200 ℃, after the reaction is finished, adding deionized water, sequentially washing and stirring for 1min, centrifuging (3000r/min) for 5min, collecting precipitates, repeating for 3 times, then sequentially washing and stirring for 1min with ethanol, centrifuging (3000r/min) for 5min, collecting the precipitates, repeating for 3 times, and finally vacuum drying for 18h at 60 ℃ to obtain the multilayer structure composite material.
3) Adding NaBH to the precipitate (8g) obtained in step 2)4In an aqueous solution (0.0004g/mL, 100mL),controlling the reaction time to be 2min, after the reaction is finished, adding deionized water, washing and stirring for 1min, centrifuging (5000r/min) for 5min and collecting precipitates, repeating for 3 times, then washing and stirring for 1min, centrifuging (5000r/min) for 5min and collecting precipitates, repeating for 3 times, and finally drying in vacuum at 60 ℃ for 18h to obtain the self-lubricating bactericidal composite material with the simulated sliding plate structure. An electron microscope scanning image of the composite material is shown in fig. 5, and as can be seen from fig. 5 and table 4, the composite material prepared in example 2 is lamellar, has good bactericidal property, and the stability and the long-acting property of the bactericide are enhanced.
Table 4 test results of bactericidal property of self-lubricating bactericidal composite material with simulated sliding plate structure obtained in example 2
Example 3
1) Adding silver nitrate (0.05g/mL, 6mL) dropwise into polyethyleneimine (0.17g/mL, 26mL) solution, and slowly stirring for 7min to obtain cation-polyethyleneimine mixed solution in which cation has been chelated.
2) Sequentially adding a zirconium oxychloride solution (0.20g/mL, 20mL), a cation-polyethyleneimine mixed solution (9.7mL), and phosphoric acid (0.15g/mL, 45mL) into a polytetrafluoroethylene reaction tank, fully stirring for 5min, reacting for 24h at 200 ℃, after the reaction is finished, adding deionized water, sequentially washing and stirring for 1min, centrifuging (3000r/min) for 5min, collecting precipitates, repeating for 3 times, then sequentially washing and stirring for 1min with ethanol, centrifuging (3000r/min) for 5min, collecting the precipitates, repeating for 3 times, and finally vacuum drying for 18h at 60 ℃ to obtain the multilayer structure composite material.
3) Adding NaBH to the precipitate (6g) obtained in step 2)4Controlling the reaction time to be 2min in an aqueous solution (0.0005g/mL, 60mL), adding deionized water after the reaction is finished, washing and stirring for 1min, centrifuging (5000r/min) for 5min, collecting precipitates, repeating for 3 times, and repeatingThen washing and stirring the mixture for 1min by using ethanol in sequence, centrifuging the mixture (5000r/min) for 5min, collecting precipitates, repeating the steps for 3 times, and finally drying the precipitates in vacuum at the temperature of 60 ℃ for 18h to obtain the self-lubricating bactericidal composite material with the simulated sliding plate structure. An electron microscope scanning image of the composite material is shown in fig. 6, and as can be seen from fig. 6 and table 5, the composite material prepared in example 3 is lamellar, has good bactericidal property, and the stability and the long-acting property of the bactericide are enhanced.
Table 5 test results of bactericidal property of self-lubricating bactericidal composite material with simulated sliding plate structure obtained in example 3
Comparative example 1
1) Adding silver nitrate (0.01g/mL, 6mL) dropwise into polyethyleneimine (0.17g/mL, 25mL) solution, and slowly stirring for 7min to obtain cation-polyethyleneimine mixed solution in which cation has been chelated.
2) Sequentially adding a zirconium oxychloride solution (0.20g/mL, 20mL), a cation-polyethyleneimine mixed solution (10mL) and phosphoric acid (0.15g/mL, 45mL) into a polytetrafluoroethylene reaction tank, fully stirring for 5min, reacting for 28h at 200 ℃, after the reaction is finished, adding deionized water, sequentially washing and stirring for 1min, centrifuging (3000r/min) for 5min and collecting precipitates, repeating for 3 times, then sequentially washing and stirring for 1min by using ethanol, centrifuging (3000r/min) for 5min and collecting the precipitates, repeating for 3 times, and finally vacuum-drying for 18h at 65 ℃ to obtain a powdery solid.
3) Adding the powdery solid obtained in step 2) (10g) to NaBH4Carrying out reduction reaction in an aqueous solution (0.0005g/mL, 100mL), controlling the reaction time for 3min, after the reaction is finished, adding deionized water, washing and stirring for 1min, centrifuging (5000r/min) for 5min, collecting precipitates, repeating for 3 times, then washing and stirring for 1min, centrifuging (5000r/min) for 5min, collecting precipitates, repeating for 3 times, and finally carrying out vacuum drying at 65 ℃ for 20h to obtain the composite material. The scanning electron microscope image of the antiskid plate is shown in FIG. 7, the morphology of the composite material prepared in comparative example 1 in FIG. 7 shows the antiskid plate structure of the composite material with the simulated skateboard structure prepared under the experimental conditions of comparative example 1As is not as evident from example 1; it can be seen from table 6 that the composite material prepared in comparative example 1 has low bactericidal properties. From the comparative example 1, the method can be found that the use amount of silver nitrate is changed, the cation content of the nano bactericide raw material is lower than the preferable range value, so that the interlayer cation concentration of the finally formed composite material is too low, the nano bactericide material formed after in-situ reduction is less, the size is smaller, and the bactericidal performance is lower; meanwhile, the interlayer spacing cannot be enlarged, interlayer bonding cannot be reduced, and the lubricating property is not high.
Table 6 shows the bactericidal properties of the composite obtained in comparative example 1
Comparative example 2
1) Adding silver nitrate (0.05g/mL, 6mL) dropwise into polyethyleneimine (0.17g/mL, 25mL) solution, and slowly stirring for 7min to obtain cation-polyethyleneimine mixed solution in which cation has been chelated.
2) Sequentially adding a zirconium oxychloride solution (0.20g/mL, 20mL), a cation-polyethyleneimine mixed solution (10mL) and phosphoric acid (0.15g/mL, 45mL) into a polytetrafluoroethylene reaction tank, fully stirring for 5min, reacting for 28h at 80 ℃, after the reaction is finished, adding deionized water, sequentially washing and stirring for 1min, centrifuging (3000r/min) for 5min and collecting precipitates, repeating for 3 times, then sequentially washing and stirring for 1min by using ethanol, centrifuging (3000r/min) for 5min and collecting the precipitates, repeating for 3 times, and finally vacuum-drying for 18h at 65 ℃ to obtain a powdery solid.
2) Adding NaBH to the powdery solid obtained in step 2) (10g)4And (3) controlling the reaction time to be 3min in an aqueous solution (0.0005g/mL, 100mL), after the reaction is finished, adding deionized water, washing and stirring for 1min, centrifuging (5000r/min) for 5min and collecting precipitates, repeating for 3 times, then washing and stirring for 1min, centrifuging (5000r/min) for 5min and collecting precipitates, repeating for 3 times, and finally vacuum-drying at 65 ℃ for 20h to obtain the composite material. The scanning electron microscope image is shown in FIG. 8, and it can be seen from FIG. 8 that the sliding plate structure-imitated composite material prepared under the experimental conditions of comparative example 2 is not as prepared as in example 1The antiskid plate has obvious structure. From comparative example 2, it can be found that the hydrothermal reaction temperature has a great influence on the assembly process and the material structure of the composite material, and the composite material with the simulated sliding plate structure is difficult to prepare below the preferred range.
Comparative example 3
1) Adding silver nitrate (0.05g/mL, 6mL) dropwise into polyethyleneimine (0.17g/mL, 25mL) solution, and slowly stirring for 7min to obtain cation-polyethyleneimine mixed solution in which cation has been chelated.
2) Sequentially adding a zirconium oxychloride solution (0.20g/mL, 20mL), a cation-polyethyleneimine mixed solution (10mL) and phosphoric acid (0.15g/mL, 45mL) into a polytetrafluoroethylene reaction tank, fully stirring for 5min, reacting for 28h at 200 ℃, after the reaction is finished, adding deionized water, sequentially washing and stirring for 1min, centrifuging (3000r/min) for 5min and collecting precipitates, repeating for 3 times, then sequentially washing and stirring for 1min by using ethanol, centrifuging (3000r/min) for 5min and collecting the precipitates, repeating for 3 times, and finally vacuum-drying for 18h at 65 ℃ to obtain a powdery solid.
3) Adding NaBH into the powdery solid (10g) obtained in the step 2)4Controlling the reaction time to be 3min in an aqueous solution (0.01g/mL, 100mL), adding deionized water after the reaction is finished, washing and stirring for 1min, centrifuging (5000r/min) for 5min and collecting precipitates, repeating for 3 times, then washing and stirring for 1min, centrifuging (5000r/min) for 5min and collecting precipitates, repeating for 3 times, and finally vacuum drying at 65 ℃ for 20h to obtain the composite material. An electron microscope scanning image of the composite material is shown in fig. 9, and it can be known from fig. 9 that the antiskid plate structure of the composite material with the simulated skateboard structure prepared under the experimental conditions of comparative example 3 is not as obvious as that of the antiskid plate prepared in example 1. It can be seen from comparative example 3 that changing the amount of sodium borohydride beyond the preferred range causes the reduction process to be too vigorous (the reduction process generates hydrogen gas) and the structural damage to be severe.
Comparative example 4
1) Adding silver nitrate (0.05g/mL, 6mL) dropwise into polyethyleneimine (0.17g/mL, 25mL) solution, and slowly stirring for 7min to obtain cation-polyethyleneimine mixed solution in which cation has been chelated.
2) Sequentially adding a zirconium oxychloride solution (0.20g/mL, 20mL), a cation-polyethyleneimine mixed solution (10mL) and phosphoric acid (0.15g/mL, 65mL) into a polytetrafluoroethylene reaction tank, fully stirring for 5min, reacting for 28h at 200 ℃, after the reaction is finished, adding deionized water, sequentially washing and stirring for 1min, centrifuging (3000r/min) for 5min and collecting precipitates, repeating for 3 times, then sequentially washing and stirring for 1min by using ethanol, centrifuging (3000r/min) for 5min and collecting the precipitates, repeating for 3 times, and finally vacuum-drying for 18h at 65 ℃ to obtain a powdery solid.
3) Adding NaBH to the powdery solid obtained in step 2) (10g)4And (3) controlling the reaction time to be 3min in an aqueous solution (0.0005g/mL, 100mL), after the reaction is finished, adding deionized water, washing and stirring for 1min, centrifuging (5000r/min) for 5min and collecting precipitates, repeating for 3 times, then washing and stirring for 1min, centrifuging (5000r/min) for 5min and collecting precipitates, repeating for 3 times, and finally vacuum-drying at 65 ℃ for 20h to obtain the composite material. An electron microscope scanning image of the composite material is shown in fig. 10, and it can be known from fig. 10 that the antiskid plate structure of the composite material with the simulated skateboard structure prepared under the experimental conditions of comparative example 4 is not as obvious as that of the antiskid plate structure obtained in example 1. From comparative example 4, it can be found that changing the amount of phosphoric acid, the amount of phosphoric acid exceeding the preferable range, causes the size of the formed sheet material to be excessively large, and therefore, the size of the synthesized zirconium phosphate has a large relationship with the amount of phosphoric acid.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. A preparation method of a sliding plate structure-imitated self-lubricating sterilization composite material comprises the following steps:
1) mixing the nano bactericide raw material, a polymer and water to carry out a jellyfish reaction to obtain a mixed solution; the nano bactericide raw material comprises silver nitrate, copper chloride, copper sulfate or copper nitrate; the polymer comprises polyethyleneimine, poly (allylamine hydrochloride), polydiallyldimethylammonium chloride or aliphatic polyamine polyurethane;
2) mixing the mixed solution obtained in the step 1), zirconium oxychloride, phosphoric acid and water for hydrothermal reaction to obtain a multilayer structure composite material;
3) mixing the multilayer structure composite material obtained in the step 2), a reducing agent and water for reduction reaction to obtain a sliding plate structure-imitated self-lubricating sterilization composite material;
the mass ratio of the nano bactericide raw material to the polymer in the step 1) is 1: 10-25;
the mass ratio of the polymer, the zirconium oxychloride and the phosphoric acid in the mixed solution in the step 2) is 1: (2.7-3.2): (4.7-5.1);
the temperature of the hydrothermal reaction in the step 2) is 100-210 ℃, and the time of the hydrothermal reaction is 24-36 h;
the mass ratio of the multilayer structure composite material to the reducing agent in the step 3) is 1: 100 to 500.
2. The preparation method according to claim 1, wherein the temperature of the jellyfish reaction in the step 1) is 15 to 30 ℃, and the time of the jellyfish reaction is 5 to 10 min.
3. The method according to claim 1, wherein the reducing agent in step 3) is sodium borohydride, ascorbic acid, hydrazine hydrate or sodium citrate.
4. The preparation method according to claim 1 or 3, wherein the temperature of the reduction reaction in the step 3) is 10 to 30 ℃ and the time of the reduction reaction is 2 to 4 min.
5. The self-lubricating bactericidal composite material with the simulated sliding plate structure prepared by the preparation method of any one of claims 1 to 4 is characterized in that the self-lubricating bactericidal composite material with the simulated sliding plate structure is of a multilayer structure, the multilayer structure is formed by sequentially laminating a zirconium phosphate layer and a bactericide lubricating layer, the bactericide lubricating layer comprises a polymer and a spherical nano bactericidal material, and the spherical nano bactericidal material comprises nano silver or nano copper; the polymer comprises polyethyleneimine, poly (allylamine hydrochloride), polydiallyldimethylammonium chloride, or aliphatic polyamine polyurethane.
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