CN113801569B - Regulation and control lubricating coating, preparation method and application - Google Patents
Regulation and control lubricating coating, preparation method and application Download PDFInfo
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- CN113801569B CN113801569B CN202111094397.1A CN202111094397A CN113801569B CN 113801569 B CN113801569 B CN 113801569B CN 202111094397 A CN202111094397 A CN 202111094397A CN 113801569 B CN113801569 B CN 113801569B
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- 230000033228 biological regulation Effects 0.000 title abstract description 5
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000758 substrate Substances 0.000 claims abstract description 43
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 37
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/02—Polyamines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2203/00—Other substrates
- B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/015—Dispersions of solid lubricants
- C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention belongs to the technical field of functional materials and preparation thereof, and provides a regulation and control lubricating coating, which is a core-shell structure microgel nano particle formed by taking a ferroferric oxide nano particle as a core and a thermo-sensitive polymer cross-linked network as a shell, wherein the microgel nano particle is uniformly sprayed on the surface of a silicon chip substrate precoated by polyethyleneimine in a manner of inclining 30-60 degrees to form the lubricating coating; the preparation method comprises the following steps: s1, preparing ferroferric oxide nano particles; s2, synthesizing microgel nanospheres; s3, preparing a modified silicon wafer substrate; s4, uniformly coating the microgel particles on a modified silicon wafer substrate; and S5, obtaining a hydrated lubricating coating which can respond to near infrared light stimulation and is used for preparing a friction force switching layer for realizing quick switching between low friction and high friction. The regulated and controlled lubricating coating has excellent near infrared light response performance, and the surface friction of the microgel coating can be regulated by controlling the hydration layer in hydration lubrication.
Description
Technical Field
The invention belongs to the technical field of functional materials and manufacturing thereof, and particularly relates to a lubricating coating for regulation and control, a preparation method and application thereof.
Background
The intelligent response material, especially the intelligent interface material based on the stimulus response polymer film, can generate rapid and reversible conformation and chemical change when the environment generates tiny change. Among them, hydrogel is a typical representative of intelligent response materials, and the soft material plays an important role in various fields such as tissue engineering, flexible electronics, bionic lubrication and the like. Hydrogels are known to be composed of a crosslinked three-dimensional network of high water content that allows for the storage of large amounts of fluid in the interstitial spaces of the network. Hydrogels respond to external stimuli in different ways more easily than other rigid polymeric materials. Among them, thermosensitive hydrogels based on poly (N-isopropylacrylamide) (PNIPAM) have a critical solution temperature (LCST) of about 32 ℃ in aqueous solution, and have become one of the most important stimuli-responsive hydrogels. The unique phase transition near LCST gives hydrogels with smart properties that have been used for controlled drug release, temperature sensors, selective catalysis, and interfacial friction control. Smart hydrogels have shown great potential in the field of tribology and have attracted considerable attention over the past few decades.
As a special hydrogel, the microgel is a micro/nano hydrogel which has stable colloid size and can be uniformly dispersed in a proper solvent. The microgels of a very small size can rapidly respond to various environmental changes such as temperature, pH, or light, compared to bulk hydrogels. In addition, the microgel is easy to synthesize and the size is easy to control. By controlling the composition and structure of the microgel particles, the function and properties of the coating can be easily changed since the microgel is a soft elastic polymer which increases the contact area with the surface of the substrate. Therefore, a dense microgel film can be formed by simple and rapid deposition methods such as dip coating, spin coating, physical adsorption and the like. In recent years, microgel is prepared into various intelligent coatings, and the advantages of the microgel are fully exerted. To our knowledge, few examples of photothermal microgels have been used as lubricating coatings to date, particularly those with tunable surface friction.
Polyethyleneimine (PEI) is a surface modification material that has strong adhesion to the substrate surface through hydrogen bonding or van der waals forces. Due to electrostatic repulsion between chains, PEI can only form a monomolecular layer on the surface, and the thickness of PEI cannot be increased along with the prolonging of adsorption time. In order to fix the microgel tightly on the substrate, a spray deposition technique is used, with PEI as the anchoring polymer, to adhere the microgel to the substrate using simple and effective electrostatic interactions.
By combining the quick response performance of the intelligent microgel and the good electrostatic interaction between the microgel and PEI, an effective near infrared light response aqueous lubricating coating is successfully prepared. In the coating, PEI serves as a bonding site to bond the microgel particles to the surface of the substrate, and the microgel particles serve as a lubricating element to regulate interfacial friction. From the viewpoint of the mechanism of hydration lubrication, the surface friction of the microgel coating layer can be regulated by controlling the appearance/disappearance of a hydration layer induced by near infrared light. The microgel coating has good water lubrication effect under the condition of no near infrared light irradiation. When the coating is irradiated by near infrared light, ferroferric oxide nanoparticles in the microgel can convert light energy into heat energy, so that the surface temperature changes. Meanwhile, the external thermosensitive microgel senses the change of temperature, and the increase of the temperature destroys the water layer around the microgel. The results show that the coating has a reduced hydrolubricity, resulting in an increased coefficient of friction.
Disclosure of Invention
The invention aims to provide a regulating and lubricating coating aiming at the traditional block-shaped hydrogel, the micro-sized microgel can quickly respond to various environmental changes such as temperature, pH value or illumination, the contact area between the microgel and the surface of a substrate is increased because the microgel is a soft elastic polymer, and a compact microgel film can be formed by simple and quick deposition methods such as dip coating, spin coating, physical adsorption and the like so as to achieve the aim of quick friction regulation.
The invention aims to provide a regulated and controlled lubricating coating, which is a core-shell structure microgel nano particle formed by taking a ferroferric oxide nano particle as an inner core and a thermosensitive polymer cross-linked network as an outer shell, wherein the microgel nano particle is uniformly sprayed on the surface of a silicon chip substrate precoated by polyethyleneimine in a manner of inclining 30-60 degrees to form the lubricating coating.
The invention also aims to provide a manufacturing method of the regulating and controlling lubricating coating, which comprises the following steps:
s1, preparing ferroferric oxide nano particles, adding 3- (trimethoxysilyl) propyl methacrylate to modify the surfaces of the ferroferric oxide nano particles, separating the ferroferric oxide nano particles by a magnet, washing the mixture, and drying the mixture at room temperature;
s2, adopting a distillation precipitation polymerization method: mixing and dispersing ferroferric oxide nanoparticles, a monomer of a temperature-sensitive polymer, a weak acid monomer, a cross-linking agent and an initiator in an acetonitrile solution, heating the mixture at a position higher than the boiling point of acetonitrile until the volume of the acetonitrile solution is reduced to half, then finishing the reaction, separating by a magnet to obtain microgel nanospheres, washing and drying at room temperature;
s3, cleaning and drying the silicon wafer substrate, then activating for 3-5 min, putting the activated silicon wafer substrate into a polyethyleneimine solution with the concentration of 1.5mg/mL for soaking for 20-30 min for pre-coating, and drying at room temperature to obtain a modified silicon wafer substrate;
s4, dispersing the microgel nanospheres obtained in the S2 by an ethanol solution to form a microgel ethanol dispersion liquid, spraying the microgel ethanol dispersion liquid onto the substrate of the modified silicon wafer obtained in the S3 in a 45-degree inclined mode until the whole surface is uniformly coated by the microgel particles, drying at room temperature, and baking at 50-70 ℃ for one night;
and S5, soaking the substrate uniformly coated with the microgel particles obtained in the step S4 in water for at least 6 hours, simultaneously replacing the water for 3 times, and cleaning until only the microgel which is electrostatically bonded to the surface of polyethyleneimine still adheres to the surface of the substrate and forms a uniform coating, thereby obtaining the hydrated lubricating coating.
Preferably, in S1, the mass ratio of the ferroferric oxide nanoparticles to the 3- (trimethoxysilyl) propyl methacrylate is 1: 3.
Preferably, in S2, the ratio of the ferroferric oxide nanoparticles: monomers of temperature-sensitive polymer: weak acid monomer: a crosslinking agent: the mass ratio of the initiator is 3-6: 38-45: 5-12: 4-8: 0.5-3.
Preferably, in S2, the monomer of the temperature-sensitive polymer is poly N-isopropylacrylamide or poly 2- (N, N-dimethylamino) methacrylate or polyvinylpyrrolidone.
Preferably, in S2, the weak acid monomer is acrylic acid or maleic anhydride.
Preferably, in S2, the crosslinking agent is dicumyl peroxide or N, N' -methylenebisacrylamide.
Preferably, in S2, the initiator is sodium bisulfite or 2, 2-azobisisobutyronitrile.
Preferably, in S3, the ultrasonic cleaning is performed in ethanol, acetone, and ethanol solutions sequentially, and the blow-drying is performed by nitrogen blow-drying.
It is a further object of the present invention to provide the use of the above-mentioned modulated lubricious coating, which is capable of responding to near-infrared light stimuli, for the preparation of a friction-switching layer that enables fast switching between low friction and high friction.
Compared with the prior art, the invention has the beneficial effects that:
1. the photo-thermal microgel synthesized by the invention is a micro/nano hydrogel which has stable colloid size and can be uniformly dispersed in a proper solvent. Compared with bulk hydrogels, microgels of a very small size are able to respond rapidly to various environmental changes, such as temperature, pH, or light. Because the microgel is a soft elastic polymer, the contact area between the microgel and the surface of a substrate is increased, and a compact microgel film can be formed by simple and quick deposition methods such as dip coating, spin coating, physical adsorption and the like. In addition, by controlling the composition and structure of the microgel particles, the function and properties of the coating can be simply changed.
2. The lubricating coating prepared by the invention takes PEI as an anchoring polymer, and the microgel with negative charge is firmly adhered to the substrate with positive charge through electrostatic action. Hydrated lubrication can modulate surface friction of the microgel coating by controlling the appearance/disappearance of a hydrated layer, which is triggered by near infrared light. The microgel coating has good water lubrication effect under the condition of no near infrared light irradiation.
3. The friction of the microgel coating is reversibly adjusted from a low level to a high level under the help of near infrared light. In an aqueous medium, the microgel coating surface has less friction due to the hydration lubrication of the microgel on the coating surface. Under the irradiation of near infrared light, the photothermal effect of the microgel coating enables the temperature of the coating to be higher than the LCST of the microgel, in this case, the surface wettability of the coating is changed from hydrophilicity to hydrophobicity, and under the condition of high friction, the hydration lubrication is disabled, so that the friction of the lubrication coating is larger after the temperature is increased.
Drawings
FIG. 1 is an infrared spectrum of a composite microgel sphere prepared after surface modification of ferroferric oxide nanoparticles in the invention;
FIG. 2 is a graph showing the variation of the hydration dynamic diameter and particle dispersibility index of the composite microgel spheres prepared in the present invention with the temperature;
FIG. 3 is a scanning electron microscope image of a composite microgel sphere and microgel lubricating coating prepared in the present invention; wherein A is Fe3O4Nanoparticles, B is a composite microgel sphere, and C is an enlarged view of the composite microgel sphere;
FIG. 4 is a photograph of the topographical features and roughness of the composite microgel spheres and microgel lubricating coatings prepared in accordance with the present invention; wherein (1) is the surface form of an original silicon wafer, and (2) is the surface form of the modified silicon wafer; (3) the surface morphology of the microgel lubricating coating;
FIG. 5 shows the microgel lubricating coatings of examples 1 to 3 of the present invention at a wavelength of 808nm and an irradiation power of 1.15W/cm2The change curve of the temperature under the irradiation of the near infrared light along with the irradiation time;
FIG. 6 shows the average friction coefficients of pure water and the microgel lubricating coatings of examples 1 to 3 of the present invention measured at 25 ℃ and 40 ℃ respectively in a general friction and wear tester.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention, which will be limited only by the appended claims, wherein the various materials, reagents, instruments and equipment used in the following examples are commercially available or may be prepared by conventional methods. The temperature-sensitive polymer monomers used in the following examples were all N-isopropylacrylamide (NIPAM), the weak acid monomers were all Acrylic Acid (AA), the crosslinking agent was all N, N' -Methylenebisacrylamide (MBA), the initiator was all 2, 2-Azobisisobutyronitrile (AIBN), and the volume fraction of ethanol used was all 70%.
Example 1
A regulated and controlled lubricating coating is core-shell-structure microgel nanoparticles formed by taking ferroferric oxide nanoparticles as a core and a thermosensitive polymer cross-linked network as a shell, and the microgel nanoparticles are uniformly sprayed on the surface of a silicon wafer substrate precoated with polyethyleneimine in a 45-degree inclined mode to form the lubricating coating.
The preparation method of the regulating and controlling lubricating coating comprises the following steps:
s1 preparation of ferroferric oxide (Fe) through solvothermal reaction3O4) Nanoparticles, then modified with 3- (trimethoxysilyl) propyl Methacrylate (MPS); 1.5g of FeCl3·6H2O, 4.0g of ammonium acetate (NH)4Ac) and 0.5g trisodium citrate dihydrate in 50mL of ethylene glycol, under vigorous mechanical stirring, a homogeneous yellow solution is obtained, the stirring speed being 400 rpm; transferring the obtained solution into a polytetrafluoroethylene-lined stainless steel autoclave with the capacity of 100mL, sealing and heating at 180 ℃, reacting for 12h, and cooling the autoclave to room temperature; collecting obtained black magnetite particles by using a magnet, washing the black magnetite particles by using ethanol for multiple times, and drying the final product in vacuum at room temperature; drying Fe with mechanical stirrer3O4Nanoparticles, 0.3g of 3- (trimethoxysilyl) propyl Methacrylate (MPS), 1.5mL of ammonia (NH)3·H2O), 10mL of deionized water, 40mL of ethanol were added to a 100mL round bottom flask, stirred at 60 ℃ for 24h, the resulting product was isolated with a magnet, and washed several times with ethanol. Synthesized Fe3O4@ MPS nanoparticles were vacuum dried at room temperatureDrying;
s2, preparing the hybrid microgel by taking N, N' -Methylene Bisacrylamide (MBA) as a cross-linking agent and 2, 2-Azobisisobutyronitrile (AIBN) as an initiator by adopting an acetonitrile distillation precipitation polymerization method; 20mg of Fe3O4@ MPS nanoparticles were dispersed in 20mL acetonitrile, charged to a dry 50mL round bottom flask, heated in an oil bath with a fractionation column, a libichi condenser and a receiver, and then charged to the flask with 0.2g of N-isopropylacrylamide (NIPAM), 0.05g of Acrylic Acid (AA), 30mg of N, N' -Methylenebisacrylamide (MBA) and 5mg of AIBN; the reaction was complete by heating the mixture from ambient temperature above the boiling point of acetonitrile (90 ℃) and distilling about 10mL of acetonitrile from the flask; the obtained core/shell nanospheres were collected with the help of a magnet and washed with ethanol several times; vacuum drying the generated microgel at room temperature;
s3 ultrasonic cleaning silicon wafer in ethanol, acetone and ethanol for 20min, and treating with N2Air drying, namely activating a clean wafer by using oxygen plasma for 3min, immersing a substrate into 1.5mg/mL PEI aqueous solution for 30min, adjusting the pH to 7 by using 0.1M HCl solution, and drying the PEI precoated silicon wafer at room temperature;
s4, spraying the microgel ethanol dispersion liquid onto the PEI modified substrate in a mode of inclining at 45 degrees until the whole surface is uniformly coated by the microgel particles; the coating surface was first dried at room temperature and then left overnight in an oven at 60 ℃;
s5, soaking the dried microgel multilayer substrate in water for at least 6h, and simultaneously replacing the water for 3 times; the washing step ensures that only microgel electrostatically bound to the Polyethyleneimine (PEI) surface remains attached and forms a uniform ultra-thin coating.
Example 2
A regulated and controlled lubricating coating is core-shell-structure microgel nanoparticles formed by taking ferroferric oxide nanoparticles as a core and a thermosensitive polymer cross-linked network as a shell, and the microgel nanoparticles are uniformly sprayed on the surface of a silicon wafer substrate precoated with polyethyleneimine in a manner of inclining by 30 degrees to form the lubricating coating.
The preparation method of the regulating and controlling lubricating coating comprises the following steps:
s1 preparation of Fe by solvothermal reaction3O4Nanoparticles, then modified with MPS; 1.5g of FeCl3·6H2O, 4.0g NH4Ac and 0.5g trisodium citrate dihydrate are dissolved in 50mL of ethylene glycol, and a uniform yellow solution is obtained under strong mechanical stirring at the stirring speed of 400 rpm; transferring the obtained solution into a polytetrafluoroethylene-lined stainless steel autoclave with the capacity of 100mL, sealing and heating at 180 ℃, reacting for 12h, and cooling the autoclave to room temperature; collecting obtained black magnetite particles by using a magnet, washing the black magnetite particles by using ethanol for multiple times, and drying the final product in vacuum at room temperature; drying Fe with mechanical stirrer3O4Nanoparticles, 0.3g MPS, 1.5mL NH3·H2O, 10mL of deionized water, 40mL of ethanol were added to a 100mL round-bottom flask, stirred at 60 ℃ for 24h, and the resulting product was isolated with a magnet and washed several times with ethanol. Synthesized Fe3O4@ MPS nanoparticles were vacuum dried at room temperature;
s2, preparing the hybrid microgel by using MBA as a cross-linking agent and AIBN as an initiator and adopting a method of acetonitrile distillation precipitation polymerization; 30mg of Fe3O4@ MPS nanoparticles were dispersed in 20mL acetonitrile, charged to a dry 50mL round bottom flask, heated in an oil bath with a fractionation column, a libichi condenser and receiver, then 0.2g of NIPAM, 0.025g of AA, 30mg of MBA and 5mg of AIBN were added to the flask; the reaction was complete by heating the mixture from ambient temperature above the boiling point of acetonitrile (90 ℃) and distilling about 10mL of acetonitrile from the flask. The obtained core/shell nanospheres were collected with the help of a magnet and washed with ethanol several times. Vacuum drying the generated microgel at room temperature;
s3 ultrasonic cleaning silicon wafer in ethanol, acetone and ethanol for 10min, and treating with N2Air drying, namely activating a clean wafer by using oxygen plasma for 4min, immersing a substrate into 1.5mg/mL PEI aqueous solution for 25min, adjusting the pH to 7 by using 0.1M HCl solution, and drying the PEI precoated silicon wafer at room temperature;
s4, spraying the microgel ethanol dispersion liquid onto the PEI modified substrate in a manner of inclining by 30 degrees until the whole surface is uniformly coated by the microgel particles; the coating surface was first dried at room temperature and then left overnight in an oven at 70 ℃;
s5, soaking the dried microgel multilayer substrate in water for at least 6h, and simultaneously replacing the water for 3 times; the cleaning step ensures that only microgels electrostatically bound to the PEI surface remain attached and form a uniform ultra-thin coating.
Example 3
A regulated and controlled lubricating coating is core-shell-structure microgel nanoparticles formed by taking ferroferric oxide nanoparticles as a core and a thermosensitive polymer cross-linked network as a shell, and the microgel nanoparticles are uniformly sprayed on the surface of a silicon wafer substrate precoated with polyethyleneimine in a 60-degree inclined mode to form the lubricating coating.
The preparation method of the regulating and controlling lubricating coating comprises the following steps:
s1 preparation of Fe by solvothermal reaction3O4Nanoparticles, then modified with MPS; 1.5g of FeCl3·6H2O, 4.0g NH4Ac and 0.5g trisodium citrate dihydrate were dissolved in 50mL of ethylene glycol, and a homogeneous yellow solution was obtained under vigorous mechanical stirring at a speed of 400 rpm; transferring the obtained solution into a polytetrafluoroethylene-lined stainless steel autoclave with the capacity of 100mL, sealing and heating at 180 ℃, reacting for 12h, and cooling the autoclave to room temperature; collecting obtained black magnetite particles by using a magnet, washing the black magnetite particles by using ethanol for multiple times, and drying the final product in vacuum at room temperature; drying Fe with mechanical stirrer3O4Nanoparticles, 0.3g MPS, 1.5mL NH3·H2O, 10mL of deionized water, 40mL of ethanol were added to a 100mL round-bottom flask, stirred at 60 ℃ for 24h, and the resulting product was isolated with a magnet and washed several times with ethanol. Synthesized Fe3O4@ MPS nanoparticles were vacuum dried at room temperature;
s2, preparing the hybrid microgel by using MBA as a cross-linking agent and AIBN as an initiator and adopting a method of acetonitrile distillation precipitation polymerization; 30mg of Fe3O4@ MPS nanoparticles dispersed in 20mL acetonitrile, Add DryIn a dry 50mL round bottom flask, heated in an oil bath with a fractionation column, Liebig condenser and receiver, then 0.22g NIPAM, 0.05g AA, 30mg MBA and 5mg AIBN are added to the flask; the reaction was complete by heating the mixture from ambient temperature above the boiling point of acetonitrile (90 ℃) and distilling about 10mL of acetonitrile from the flask; the obtained core/shell nanospheres were collected with the help of a magnet and washed with ethanol several times. Vacuum drying the generated microgel at room temperature;
s3 ultrasonic cleaning silicon wafer in ethanol, acetone, and ethanol for 5min, and treating with N2Air drying, namely activating a clean wafer by using oxygen plasma for 5min, immersing a substrate into 1.5mg/mL PEI aqueous solution for 20min, adjusting the pH to 7 by using 0.1M HCl solution, and drying the PEI precoated silicon wafer at room temperature;
s4, spraying the microgel ethanol dispersion liquid onto the PEI modified substrate in a mode of inclining by 60 degrees until the whole surface is uniformly coated by the microgel particles; the coating surface was first dried at room temperature and then left overnight in an oven at 50 ℃;
s5, soaking the dried microgel multilayer substrate in water for at least 6h, and simultaneously replacing the water for 3 times; the cleaning step ensures that only microgels electrostatically bound to the PEI surface remain attached and form a uniform ultra-thin coating.
Example 4
A regulated and controlled lubricating coating is core-shell-structure microgel nanoparticles formed by taking ferroferric oxide nanoparticles as a core and a thermosensitive polymer cross-linked network as a shell, and the microgel nanoparticles are uniformly sprayed on the surface of a silicon wafer substrate precoated with polyethyleneimine in a 45-degree inclined mode to form the lubricating coating.
The preparation method of the regulating and controlling lubricating coating comprises the following steps:
s1 preparation of Fe by solvothermal reaction3O4Nanoparticles, then modified with MPS; 1.5g of FeCl3·6H2O, 4.0g NH4Ac and 0.5g trisodium citrate dihydrate were dissolved in 50mL of ethylene glycol, and a homogeneous yellow solution was obtained under vigorous mechanical stirring at a speed of 400 rpm; the obtained solution isTransferring the mixture into a polytetrafluoroethylene-lined stainless steel autoclave with the capacity of 100mL, sealing the autoclave, heating the mixture at 180 ℃, reacting the mixture for 12 hours, and cooling the autoclave to room temperature; collecting obtained black magnetite particles by using a magnet, washing the black magnetite particles by using ethanol for multiple times, and drying the final product in vacuum at room temperature; drying Fe with mechanical stirrer3O4Nanoparticles, 0.3g MPS, 1.5mL NH3·H2O, 10mL of deionized water, 40mL of ethanol were added to a 100mL round-bottom flask, stirred at 60 ℃ for 24h, and the resulting product was isolated with a magnet and washed several times with ethanol. Synthesized Fe3O4@ MPS nanoparticles were vacuum dried at room temperature;
s2, preparing the hybrid microgel by using MBA as a cross-linking agent and AIBN as an initiator and adopting a method of acetonitrile distillation precipitation polymerization; 20mg of Fe3O4The @ MPS nanoparticles were dispersed in 20mL of acetonitrile, charged to a dry 50mL round bottom flask, heated in an oil bath, and attached to a fractionation column, a libichi condenser, and a receiver. Then 0.22g of NIPAM, 0.025g of AA, 30mg of MBA and 5mg of AIBN were added to the flask; the reaction was complete by heating the mixture from ambient temperature above the boiling point of acetonitrile (90 ℃) and distilling about 10mL of acetonitrile from the flask; the obtained core/shell nanospheres were collected with the help of a magnet and washed with ethanol several times. Vacuum drying the generated microgel at room temperature;
s3 ultrasonic cleaning silicon wafer in ethanol, acetone and ethanol for 15min, and treating with N2Air drying, namely activating a clean wafer by using oxygen plasma for 3min, immersing a substrate into 1.5mg/mL PEI aqueous solution for 30mn, adjusting the pH to 7 by using 0.1M HCl solution, and drying the PEI precoated silicon wafer at room temperature;
s4, spraying the microgel ethanol dispersion liquid onto the PEI modified substrate in a mode of inclining at 45 degrees until the whole surface is uniformly coated by the microgel particles; the coating surface was first dried at room temperature and then left overnight in an oven at 60 ℃;
s5, soaking the dried microgel multilayer substrate in water for at least 6h, and simultaneously replacing the water for 3 times; the cleaning step ensures that only microgels electrostatically bound to the PEI surface remain attached and form a uniform ultra-thin coating.
To confirm the successful synthesis of the near-infrared light-responsive microgel spheres in example 1, the chemical composition thereof was analyzed. The results are shown in FIG. 1, and it can be seen from the characteristic peaks in the IR spectrum that MPS has been successfully grafted to Fe3O4The surface of the nanoparticles. In addition, the characteristic peak position of the microgel is consistent with the characteristic peak positions of functional groups of NIPAM and AA monomers, which shows that the synthesized microgel is formed by crosslinking NIPAM and acrylic acid. As shown in fig. 2, the hydrodynamic diameter of the microgel decreases from 543nm to 434nm at a temperature ranging from 25 to 45 c, and the swelling ratio is calculated to be 1.96. In addition, the Particle Dispersion Index (PDI) is kept below 0.4 during the whole heating process, which shows that the microgel has narrow particle size distribution in an aqueous medium, good monodispersity and good temperature response performance.
Transmission electron microscope is used for observing Fe3O4Morphology of nanoparticles and composite microgels. As shown in FIG. 3, wherein FIG. 3A shows Fe3O4The nano particles have uniform particle size, and the diameter is about 360 +/-10 nm; as can be seen from FIG. 3B, Fe3O4The nano particles are successfully coated by a polymer shell layer to form spherical microgel with a clear core-shell structure; as can be seen from the enlarged view of FIG. 3C, the diameter of the final microgel is about 420. + -.10 nm and the thickness of the polymer layer is about 30 nm.
The corresponding surface morphology and roughness of the composite microgel coating, as shown in FIG. 4, the surface of the original silicon wafer is very smooth, as shown in FIG. 4(1), the roughness is only 1.78nm, but the surface roughness is increased to 9.67nm after PEI modification, as shown in FIG. 4 (2); when the microgel completely covered the substrate, the roughness increased to 78.22nm, as shown in fig. 4 (3). The significant changes in surface morphology and roughness indicate that the microgel successfully adsorbs on the substrate to form a dense lubricating coating.
Test example 1
For the lubricating coatings in the embodiments 1-4 of the invention, the wavelength is 808nm, and the irradiation power is 1.15W/cm2The irradiation distance is 10cm, and the diameter of a light spot is 8 mm.
From the results in fig. 5, the temperature switch indicates that the photothermal conversion performance of the microgel coating is reversible and stable. Within 5min of near infrared laser irradiation, the coating was immersed in water and the temperature was raised from room temperature to 40.1 ℃. After the irradiation was stopped, the coating temperature was returned to ambient temperature. From the photo-thermal conversion result, the composite microgel has good photo-thermal conversion efficiency for near infrared, in other words, the composite microgel lubricating coating with excellent near infrared light response performance is successfully prepared.
Test example 2
For the change law of the friction coefficient and the time of the microgel coating in pure water and the microgel coating in the embodiments 1 to 4 of the invention at the temperature above the LCST and below the LCST on a general friction wear testing machine, the average friction coefficient measured at the temperature below the LCST of 25 ℃ and the temperature above the LCST of 40 ℃ is adopted in the test.
The upper friction pair selects Polydimethylsiloxane (PDMS) hemisphere with the diameter of 6mm, the load is constant to be 0.5N, the sliding frequency is 1Hz, and the amplitude is 5 mm. The temperature of the microgel coating is controlled by near infrared light, the temperature rises to 40 ℃ when the irradiation is continuously carried out for five minutes, and the microgel balls can collapse when the temperature reaches above LCST. Each set of experiments was performed three times to reduce the error, black representing the coefficient of friction of pure water, red representing the coefficient of friction of microgel dispersion at 25 ℃, and blue representing the coefficient of friction of microgel dispersion at 45 ℃. The average friction coefficients of pure water and the microgel coatings of examples 1 to 4 of the present invention at 25 ℃ and 40 ℃ are shown in fig. 6.
From the results of the law of change of the average friction coefficient in fig. 6, the microgel coating had an average friction coefficient at 40 ℃ higher than that at 25 ℃, but at any temperature, the friction coefficient was lower than that of pure water. This result demonstrates that temperature is successful for friction control, being able to switch rapidly between a low friction state and a high friction state. Meanwhile, the microgel lubricating coating can generate a hydration lubricating effect under water.
It should be noted that, when the present invention relates to a numerical range, it should be understood that two endpoints of each numerical range and any value between the two endpoints can be selected, and since the steps and methods adopted are the same as those in the embodiment, in order to prevent redundancy, the present invention describes a preferred embodiment. While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (5)
1. A regulated and controlled lubricating coating is characterized in that ferroferric oxide nanoparticles are used as an inner core, a temperature-sensitive polymer cross-linked network is used as an outer shell to form microgel nanoparticles with a core-shell structure, and the microgel nanoparticles are uniformly sprayed on the surface of a silicon wafer substrate precoated with polyethyleneimine in an inclined manner of 30-60 degrees to form a lubricating coating;
the preparation method of the regulating and controlling lubricating coating is characterized by comprising the following steps:
s1, preparing ferroferric oxide nano particles, adding 3- (trimethoxysilyl) propyl methacrylate to modify the surfaces of the ferroferric oxide nano particles, separating the ferroferric oxide nano particles by a magnet, washing and drying the ferroferric oxide nano particles at room temperature;
s2, adopting a distillation precipitation polymerization method: mixing and dispersing ferroferric oxide nanoparticles, a monomer of a temperature-sensitive polymer, a weak acid monomer, a cross-linking agent and an initiator in an acetonitrile solution, heating the mixture at a temperature higher than the boiling point of acetonitrile until the volume of the acetonitrile solution is reduced to half, then finishing the reaction, separating by a magnet to obtain microgel nanospheres, washing and drying at room temperature;
s3, cleaning and drying the silicon wafer substrate, activating for 3-5 min, putting the activated silicon wafer substrate into a polyethyleneimine solution with the concentration of 1.5mg/mL for soaking for 20-30 min for pre-coating, and drying at room temperature to obtain a modified silicon wafer substrate;
s4, dispersing the microgel nanospheres obtained in the S2 by an ethanol solution to form a microgel ethanol dispersion liquid, spraying the microgel ethanol dispersion liquid onto the substrate of the modified silicon wafer obtained in the S3 in a 45-degree inclined mode until the whole surface is uniformly coated by the microgel particles, drying at room temperature, and baking at 50-70 ℃ for one night;
s5, soaking the substrate uniformly coated with the microgel particles obtained in the step S4 in water for at least 6h, simultaneously replacing the water for 3 times, cleaning until only the microgel which is electrostatically bonded to the surface of polyethyleneimine still adheres to the surface of the substrate, and forming a uniform coating to obtain a hydrated lubricating coating;
the lubricating coating can respond to near-infrared light stimulation and is used for preparing a friction force switching layer for realizing quick switching between low friction and high friction;
the monomer of the temperature-sensitive polymer is poly-N-isopropylacrylamide, poly-2- (N, N-dimethylamino) methacrylate or polyvinylpyrrolidone;
the weak acid monomer is acrylic acid or maleic anhydride;
the cross-linking agent is dicumyl peroxide or N, N' -methylene bisacrylamide.
2. The preparation method of the regulating and lubricating coating according to claim 1, wherein in S1, the mass ratio of the ferroferric oxide nanoparticles to the 3- (trimethoxysilyl) propyl methacrylate is 1: 3.
3. The method for preparing a conditioning lubricating coating according to claim 1, wherein in S2, the ratio of the ferroferric oxide nanoparticles: monomers of temperature-sensitive polymer: weak acid monomer: a crosslinking agent: the mass ratio of the initiator is 3-6: 38-45: 5-12: 4-8: 0.5-3.
4. The method of claim 1, wherein in S2, the initiator is sodium bisulfite or 2, 2-azobisisobutyronitrile.
5. The preparation method of the control lubricating coating according to claim 1, wherein in S3, the cleaning mode is ultrasonic cleaning in ethanol, acetone and ethanol solution in sequence, and the blow-drying mode is nitrogen blow-drying.
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