CN116769382B - Modified nano Fe 3 O 4 Epoxy resin composite material and preparation method thereof - Google Patents
Modified nano Fe 3 O 4 Epoxy resin composite material and preparation method thereof Download PDFInfo
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- CN116769382B CN116769382B CN202310918144.4A CN202310918144A CN116769382B CN 116769382 B CN116769382 B CN 116769382B CN 202310918144 A CN202310918144 A CN 202310918144A CN 116769382 B CN116769382 B CN 116769382B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 134
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 134
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 claims abstract description 60
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 42
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims description 6
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- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- 238000000576 coating method Methods 0.000 abstract description 52
- 239000011248 coating agent Substances 0.000 abstract description 47
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 28
- 238000012360 testing method Methods 0.000 description 28
- 238000010521 absorption reaction Methods 0.000 description 19
- 239000011780 sodium chloride Substances 0.000 description 14
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- 239000002184 metal Substances 0.000 description 4
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- 229910000975 Carbon steel Inorganic materials 0.000 description 3
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- 244000137852 Petrea volubilis Species 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
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- 238000002604 ultrasonography Methods 0.000 description 2
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 229910017299 Mo—O Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000007545 Vickers hardness test Methods 0.000 description 1
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- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 239000003792 electrolyte Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
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Classifications
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- 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)
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
-
- 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
Abstract
The invention discloses a modified nano Fe 3 O 4 An epoxy resin composite material and a preparation method thereof, and ferroferric oxide nano particles modified by a silane coupling agent are prepared; preparation of Fe by silane coupling agent modified ferroferric oxide nano-particles 3 O 4 ‑MoS 2 A nanohybrid; addition of Fe to epoxy resin 3 O 4 ‑MoS 2 The nanometer hybrid is used for obtaining the modified epoxy resin composite material. Modification of Fe by use of silane coupling agent 3 O 4 ‑MoS 2 The nanometer hybrid is filled with pure epoxy resin, and the dispersion stability and compatibility of the inorganic nanometer hybrid and the organic epoxy resin can be further improved by optimizing the dispersion process, so that the mechanical property, the wear resistance and the corrosion resistance of the epoxy resin-based composite coating are improved.
Description
Technical Field
The invention relates to the field of oil well metal pipe anti-corrosion coating, in particular to a modified nano Fe 3 O 4 -epoxy resin composite and method of making the same.
Background
Carbon steel has been widely used as a structural material in various fields such as petrochemical industry, machinery, transportation and the like. The development of industrial modernization brings higher requirements on the surface performance of equipment parts, particularly under the actual service conditions of high speed, high temperature, corrosive medium and the like, the surface of carbon steel is easy to generate corrosion, abrasion, high temperature oxidation and other damage phenomena, and the whole failure of the components can be caused when the damage is serious, thus causing serious influence on the economic society and life of people. To improve the performance of carbon steel materials, various surface protection techniques and coating systems have been developed in an attempt to prevent or delay material failure.
As a thermosetting polymer with high adhesive force, excellent wear resistance, excellent mechanical property, good electrical insulation, good chemical and electrochemical stability and the like, the epoxy resin (EP) is widely applied to the fields of petrochemical industry, building coating, electronic materials and the like. However, the epoxy resin is easy to evaporate to form a large number of micropores in the curing process, so that electrolyte is easy to permeate into the interior to contact the surface of the steel matrix, and the protective effect of the pure epoxy resin coating on the metal matrix is reduced; secondly, the cured pure epoxy resin has a higher cross-linking structure, which can cause the deterioration of mechanical properties, such as poor impact resistance and higher brittleness; these factors greatly limit the further expansion of their application range and increasingly cannot meet the increasingly growing industrial requirements. Therefore, the epoxy resin needs to be chemically or physically modified to improve its mechanical, abrasion-resistant and corrosion-resistant properties.
Research has shown that adding nanocomposite material in certain content to epoxy resin can improve anticorrosive performance, mechanical performance, etc. obviously. Among them, a method of modifying a pure epoxy resin coating by adding a single inorganic nanoparticle has been widely studied and applied, including Fe 3 O 4 And the like, which can be dispersed in a polymer carrier to fill surface cavities, reduce surface micropores, microcracks and other defects, and enhance the integrity of the coating by adhesion of the coating to the metal surface.
However, inorganic nanoparticles have excellent physicochemical properties, but have a problem of poor compatibility with organic coatings, affecting various properties of the inorganic nanoparticle-epoxy resin composite material.
Disclosure of Invention
It is an object of the present invention to provide a modified nano Fe 3 O 4 Preparation method of epoxy resin composite material, and Fe is modified by silane coupling agent 3 O 4 -MoS 2 Nanometer hybridizationThe pure epoxy resin is filled with the material, so that the dispersion stability and compatibility of the inorganic nanometer hybrid and the organic epoxy resin are improved, and the mechanical, wear-resistant and corrosion-resistant properties of the epoxy resin matrix composite coating are improved.
Another object of the present invention is to provide a modified nano Fe 3 O 4 The epoxy resin composite material further improves the compatibility and other performances of the epoxy resin-based composite coating by optimizing the dispersion process.
The first object of the invention comprises the following steps:
preparing ferroferric oxide nano particles modified by a silane coupling agent;
preparation of Fe by silane coupling agent modified ferroferric oxide nano-particles 3 O 4 -MoS 2 A nanohybrid;
addition of Fe to epoxy resin 3 O 4 -MoS 2 The nanometer hybrid is used for obtaining the modified epoxy resin composite material.
Wherein Fe is 3 O 4 The nano particles have good mechanical property and corrosion resistance, and can improve the physical and mechanical properties and corrosion resistance of the epoxy resin to a certain extent.
MoS 2 Is a two-dimensional lamellar nano-sheet, moS 2 The nano sheet layers are connected by weak van der Waals force, and the nano sheet has the characteristics of wide interlayer spacing and low interlayer strength, so that the nano sheet has excellent lubricating property, and an effective antifriction effect can be achieved by adding the nano sheet into epoxy resin; at the same time MoS 2 The epoxy resin has stable chemical property and strong corrosion resistance, and can be used as a functional filler to be added into epoxy resin to improve the corrosion resistance.
The silane coupling agent can serve as a vehicle for linking inorganic and organic materials, mainly because it contains both organofunctional groups and siloxy groups. The silane coupling agent has two different bonding actions with the inorganic nano filler and the epoxy resin respectively. When the silane coupling agent reacts with the inorganic nanofiller, it typically reacts with hydroxyl groups (-OH) on the surface of the filler to form organosiloxane groups (-Si-O-R) linkages, where R is an organic group. When the silane coupling agent reacts with the epoxy resin, it reacts with hydroxyl functionality (-OH) in the epoxy resin to form a silicon-oxygen bond (Si-O), thereby bonding the filler to the resin. And secondly, the silane coupling agent can increase the compatibility between the silane coupling agent and the composite material, prevent mutual repulsion or separation between the silane coupling agent and the composite material, and further improve the related performance of the composite material.
Fe 3 O 4 Nanoparticles are readily attracted to each other in pure water or organic solvents to form aggregates. And MoS 2 A hydration or organic solvent molecule protective layer can be formed on the surface to prevent Fe 3 O 4 The nanoparticles are in direct contact with each other, thereby preventing aggregation and stacking thereof. Furthermore, moS 2 Interlayer gaps exist between the nano sheets, so that good dispersing space can be provided, and Fe is further prevented 3 O 4 Agglomeration between nanoparticles.
At the same time MoS 2 The surface of the nanoparticle has-OH groups which can react with the silane coupling agent and MoS coated by the silane coupling agent 2 The compatibility of the nano particles and the epoxy resin is effectively improved, and the dispersion stability is obviously improved.
Specifically, preparing ferroferric oxide nano particles modified by a silane coupling agent specifically comprises the following steps:
adding ferroferric oxide nano particles into the mixed solution, and stirring to obtain a first solution;
adding a silane coupling agent into the mixed solution, and stirring to completely hydrolyze the silane coupling agent to obtain a second solution;
mixing the first solution and the second solution into a three-neck flask, and stirring to uniformly react;
filtering and washing by using a suction filter, and drying to obtain the ferroferric oxide nano particles modified by the silane coupling agent.
Wherein, the first solution and the second solution are mixed into a three-neck flask, the digital display constant temperature oil bath pot is adjusted to 60-80 ℃, and the reflux is carried out by a condensing tube, and the mixture is stirred for 10-15 hours to lead the mixture to react uniformly;
the mixed solution comprises ethanol and deionized water;
the silane coupling agent is 3-aminopropyl triethoxysilane.
Preparation of Fe 3 O 4 -MoS 2 The nanometer hybrid specifically comprises:
dispersing molybdenum disulfide nano particles in N-N dimethylformamide, and performing ultrasonic treatment to form uniform suspension;
adding ferroferric oxide nano particles modified by a silane coupling agent into the suspension, and performing ultrasonic treatment to obtain a reaction mixture;
the reaction mixture is refluxed and stirred, filtered and washed by a suction filter, and dried to obtain Fe 3 O 4 -MoS 2 Nano hybrids.
Wherein the reaction mixture is stirred at 95-110 ℃ under reflux for 4-8h, filtered and washed using a suction filter.
Further, fe 3 O 4 -MoS 2 In the nano hybrid, the molar ratio of the ferroferric oxide nano particles to the molybdenum disulfide nano particles is 0.1-5:1. Preferably, the molar ratio of the ferroferric oxide nanoparticles to the molybdenum disulfide nanoparticles is 3:1.
Furthermore, the invention also provides a second invention object, namely the nano Fe3O4 modified epoxy resin composite material prepared by the preparation method.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention relates to nano Fe 3 O 4 Modified epoxy resin composite material and preparation method thereof, and Fe is modified by using silane coupling agent 3 O 4 -MoS 2 The nanometer hybrid is filled with pure epoxy resin, and the dispersion stability and compatibility of the inorganic nanometer hybrid and the organic epoxy resin can be further improved by optimizing the dispersion process, so that the mechanical property, the wear resistance and the corrosion resistance of the epoxy resin-based composite coating are improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiments of the invention. In the drawings:
FIG. 1a isFe 3 O 4 -MoS 2 (3:1) SEM images of nanohybrids;
FIG. 1b is a mapping image of Fe element;
FIG. 1c is a Mo element map image;
FIG. 2 is Fe 3 O 4 、Fe 3 O 4 -MoS 2 (3:1) a nanohybrid XRD pattern;
FIG. 3 is Fe 3 O 4 、Fe 3 O 4 -MoS 2 (3:1) infrared spectrogram of the nano-hybrid;
FIG. 4 shows that the composition contains 1wt.% Fe immediately after sonication 3 O 4 -MoS 2 EP (1-5) of (C) containing 1wt.% Fe 3 O 4 EP (6) of (2) containing 1wt.% MoS 2 Is a physical image of EP (7);
FIG. 5 shows that the composition contains 1wt.% Fe 15 days after sonication 3 O 4 -MoS 2 EP (1-5) of (C) containing 1wt.% Fe 3 O 4 EP (6) of (2) containing 1wt.% MoS 2 Is a physical image of EP (7);
FIG. 6 is a frictional wear test chart;
FIG. 7 is a composition containing 1wt.% Fe 3 O 4 -MoS 2 EP (3:1, 1:1, 1:3, 1:5, 1:7), containing 1wt.% Fe 3 O 4 Contains 1wt.% MoS 2 Friction coefficient images of EP and pure EP;
FIG. 8 is 1wt.% Fe 3 O 4 -MoS 2 /EP(Fe 3 O 4 ：MoS 2 The molar ratios are (a) 3:1, (b) 1:1, (c) 1:3, (d) 1:5, (e) 1:7), (f) 1wt.% Fe, respectively 3 O 4 /EP、(g)1wt.％MoS 2 Grinding mark morphology image of/EP and (h) pure EP;
FIG. 9 shows 1wt.% Fe after seven days of soaking 3 O 4 -MoS 2 EP (a-e) of (3:1, 1:1, 1:3, 1:5, 1:7), containing 1wt.% Fe 3 O 4 EP (f) of (2) containing 1wt.% MoS 2 Contact angle images of EP (g) and pure EP (h);
FIG. 10 is an AC impedance spectrum of the coating after 3 days of immersion in a 3.5wt.% sodium chloride solution;
FIG. 11 is an AC impedance spectrum of the coating after 7 days of immersion in a 3.5wt.% sodium chloride solution;
fig. 12 is a plot of the potentiodynamic polarization of the coating after 7 days of immersion in a 3.5wt.% sodium chloride solution.
Detailed Description
The present invention will be described in further detail with reference to the following examples and drawings for the purpose of making the objects, technical solutions and advantages of the present invention more apparent, but the present invention is not limited to the scope of the examples. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Example 1
Step 1: preparing ferroferric oxide nano particles modified by a silane coupling agent:
weighing nano Fe 3 O 4 0.2g of particles, adding the particles into a mixed solution of 80mL of ethanol and 20mL of deionized water, stirring and ultrasonic treatment for 60min to obtain a first solution;
transferring 2mL of 3-aminopropyl triethoxysilane into a three-neck flask, adding 80mL of ethanol and 20mL of deionized water, heating and stirring at 50 ℃ for 1h to completely hydrolyze the 3-aminopropyl triethoxysilane, and obtaining a second solution;
mixing the first solution and the second solution into a three-neck flask, adjusting the temperature of a digital display constant-temperature oil bath pot to 70 ℃, refluxing by using a condensing tube, and stirring for 12 hours to uniformly react;
after the reaction is completed, filtering and washing are carried out by using a suction filter, and drying is carried out for 5 hours at 60 ℃ to obtain the ferroferric oxide nano particles modified by the silane coupling agent.
Step 2: preparation of Fe 3 O 4 -MoS 2 Nano hybrid:
weighing nano MoS with the corresponding molar ratio of 3:1 when the ferroferric oxide nano particles modified by the silane coupling agent are 0.04g 2 Particles, nanometer MoS 2 Dispersing the particles in 100mLN-N dimethylformamide, and performing ultrasonic treatment for 0.5h to form a uniform suspension;
adding the ferroferric oxide nano particles modified by the silane coupling agent into the suspension for continuous ultrasonic treatment for 0.5h, and then refluxing and stirring the reaction mixture for 5h at 105 ℃;
taking out the solution after the reaction is finished, filtering and washing the solution by using a suction filter, and drying the solution at 60 ℃ for 5 hours to obtain Fe 3 O 4 -MoS 2 Nano hybrids.
Step 3: fe (Fe) 3 O 4 -MoS 2 Preparation of EP composite coating:
addition of Fe to epoxy resin 3 O 4 -MoS 2 Nanometer hybrid to obtain Fe 3 O 4 -MoS 2 EP composite coating.
Example 2
On the basis of the above examples, for Fe 3 O 4 -MoS 2 The nano-hybrids were analyzed and characterized.
(1) Scanning electron microscope testing
Observation of Fe with a scanning electron microscope (ZEISSEV 0MA 15) 3 O 4 -MoS 2 (3:1) micro-morphology of nanohybrids, prior to measurement, samples were gold plated using a sputter coater to render them conductive, fe was observed 3 O 4 -MoS 2 (3:1) microcosmic morphology of nanohybrids, FIG. 1 (a) is Fe 3 O 4 -MoS 2 (3:1) Scanning Electron Microscope (SEM) microscopic morphology of the nanohybrids, fe can be seen 3 O 4 MoS distributed in flower-like structure 2 Between them. In order to analyze the distribution region of each element in the hybrid, the element surface scanning analysis was performed using EDS, and as shown in FIG. 1 (b, c), fe element and Mo element were observed in Fe 3 O 4 -MoS 2 The distribution of the nanometer hybrids is more uniform, further illustrating the nanometer Fe 3 O 4 The balls are distributed in the layered MoS 2 Between them. Semi-quantitative results of EDS show that the contents of Fe and Mo are 85.21% and 14.79%, respectively, and Fe can be obtained by calculation 3 O 4 ：MoS 2 The molar content ratio of (2) is close to 3:1, indicating Fe 3 O 4 -MoS 2 The addition amounts of the (3:1) nanometer hybrid and the experiment are consistent.
(2) XRD testing
Nanometer Fe by adopting DX-2700B type X-ray diffractometer 3 O 4 Particles and Fe 3 O 4 -MoS 2 (3:1) the nanohybrid samples were subjected to phase composition analysis. The crystal structure is determined mainly by analyzing the diffraction pattern generated by characteristic X-rays passing through the crystal, wherein the target material is Cu-K alpha, the tube voltage is 40KV, the tube current is 30mA, the scanning range is 3-80 DEG, the scanning speed is 5 DEG/min, and the step is 0.03 deg.
For nano Fe 3 O 4 、Fe 3 O 4 -MoS 2 (3:1) nanohybrids two samples were subjected to XRD testing and the results are shown in figure 2. From Fe 3 O 4 -MoS 2 The XRD patterns of the (3:1) nanohybrids can see that the diffraction peaks at 2θ=30.2°, 35.5 °, 43.2 °, 57.1 ° and 62.7 ° respectively belong to Fe 3 O 4 Surfaces (220), (331), (400), (511) and (440), and Fe 3 O 4 Standard card pdf#88-0866 matches. Diffraction peaks at 2θ=14.4 °, 32.8 °, 39.6 ° and 58.7 ° respectively belong to MoS 2 The (002), (100), (103) and (110) faces, and MoS 2 Standard card PDF #73-1508 match. In addition, no other diffraction peaks appear, indicating Fe 3 O 4 -MoS 2 The (3:1) nanometer hybrid contains Fe 3 O 4 And MoS 2 The sample did not have a new phase. In addition to this, fe was observed 3 O 4 -MoS 2 (3:1) Fe in XRD spectra of nanohybrids 3 O 4 And the partial diffraction peak of (2) disappeared. The reason for this is Fe 3 O 4 And MoS 2 Has different lattice structures, moS when they are mixed to form nano-hybrids 2 The presence of (2) is such that Fe 3 O 4 Is generated by the lattice structure of (a)Distortion, thereby causing some characteristic peaks to disappear.
(3) Fourier transform infrared spectroscopy test
Testing MoS by IRPrestinge-21 type Fourier transform infrared spectrometer 2 Nanoparticle and Fe 3 O 4 -MoS 2 And (3) obtaining a corresponding infrared spectrogram by the nano hybrid sample (3:1). The results of the IR spectrum analysis are shown in FIG. 3, comparing untreated MoS 2 (a) And Fe modified by silane coupling agent KH550 3 O 4 -MoS 2 (3:1) FT-IR curve of nanohybrids (b) found: 460cm in curve a -1 、782cm -1 The Mo-S stretching vibration peak and the Mo-O stretching vibration absorption peak appear at the position of MoS 2 Is characterized by an absorption peak; 509cm in the b curve -1 The absorption peak at the position is caused by Fe-O vibration and is Fe 3 O 4 Characteristic absorption peak of 3441cm -1 Characteristic absorption peak of (2) corresponds to Fe 3 O 4 -OH of the nanoparticle. Comparing the a, b curves, it can be found that: fe modified by silane coupling agent 3 O 4 After connection, moS 2 At 545cm -1 Shifts the characteristic absorption peak of (2) to 583cm -1 the-OH characteristic peak disappeared and 1403cm -1 、2340cm -1 The absorption peaks, which are characteristic groups of the silane coupling agent KH550, are caused by the C-H group and the R-NH group, respectively, which indicate MoS 2 Interaction with a silane coupling agent KH550 and Fe modified by the silane coupling agent 3 O 4 Successful connection of MoS 2 。
Example 3
Based on the above examples, weighing nano MoS with the corresponding molar ratio of 3:1, 1:1, 1:3, 1:5 and 1:7 when the ferroferric oxide nano particles modified by the silane coupling agent are 0.04g 2 And (3) particles.
In this example, seven epoxy resin coating parallel test groups were arranged to perform dispersion stability test, and the composition tables are shown in table 1, and are respectively: adding 1wt.% MoS to EP 2 、1wt.％Fe 3 O 4 、1wt.％Fe 3 O 4 -MoS 2 Nanohybrids (wherein Fe 3 O 4 ：MoS 2 The molar ratios are 3:1, 1:1, 1:3, 1:5, 1:7, respectively). After adding the diluent and the defoamer and performing ultrasonic treatment for 30min, the dispersion stability of the nano particles in the epoxy resin is analyzed by comparing pictures of seven groups of samples after ultrasonic treatment and standing for 15 days after ultrasonic treatment.
TABLE 1
FIG. 4 is a real image of an instantaneous epoxy resin composite coating after ultrasound, FIG. 5 is an image of an epoxy resin composite coating after 15 days of standing after ultrasound, and it can be seen by comparing FIG. 4 and FIG. 5 that after 15 days of standing, 1wt.% nano Fe is added 3 O 4 The layering phenomenon of the granular epoxy resin composite coating is obvious, which shows that the dispersion stability is poor. While adding nano MoS 2 Particle formation of Fe 3 O 4 -MoS 2 After the (3:1, 1:1, 1:3, 1:5 and 1:7) nanometer hybrid, the dispersion stability of the epoxy resin composite coating is improved, and no obvious layering phenomenon occurs.
The result shows that nano MoS is added 2 Particle formation of Fe 3 O 4 -MoS 2 The nanometer hybrid is beneficial to improving Fe 3 O 4 Dispersion stability in epoxy resin coatings.
The reason for this is that magnetic Fe 3 O 4 Nanoparticles are generally hydrophilic and lipophilic, and in pure water or an organic solvent, nanoparticles are easily attracted to each other to form aggregates. And MoS 2 A hydration or organic solvent molecule protective layer can be formed on the surface to prevent Fe 3 O 4 The nanoparticles are in direct contact with each other, thereby preventing aggregation and stacking thereof. Furthermore, moS 2 Interlayer gaps exist between the nano sheets, so that good dispersing space can be provided, and Fe is further prevented 3 O 4 Agglomeration between nanoparticles.
Example 4
Based on the above examples, the silane coupling agent modified ferroferric oxide nanoparticles were weighedNano MoS with corresponding molar ratio of 3:1, 1:1, 1:3, 1:5 and 1:7 at 0.04g 2 And (3) particles.
In this example, a total of seven epoxy resin coating parallel test groups were set for testing, and the composition tables are shown in table 2, and are: pure EP, addition of 1wt.% MoS to EP 2 、1wt.％Fe 3 O 4 、1wt.％Fe 3 O 4 -MoS 2 Nanohybrids (wherein Fe 3 O 4 ：MoS 2 The molar ratios are 3:1, 1:1, 1:3, 1:5, 1:7, respectively).
TABLE 2
(1) Micro Vickers hardness test
The HVS-1000STA type micro Vickers hardness tester was used, the load was 10gf, and the holding time was set to 5s. The flat surface of the bottom surface of each sample is selected as a test surface, seven points are uniformly selected and tested, the maximum value and the minimum value are removed, the hardness test values of the other five points are averaged, and the micro Vickers hardness values of different samples are shown in Table 3.
TABLE 3 Table 3
Experimental results show that the hardness value of the pure epoxy resin sample is the lowest, and the hardness value of the epoxy resin sample can be increased after the nano filler is added. And with the addition of Fe 3 O 4 -MoS 2 Fe in nanometer hybrid 3 O 4 The content of nano particles increases, the hardness of the nano particles monotonically increases, and when Fe 3 O 4 And MoS 2 The maximum hardness is 16.190HV0.01 when the molar ratio is 3:1, and the hardness value is improved by 11.2 percent compared with the pure epoxy resin sample. Fe (Fe) 3 O 4 -MoS 2 The improvement of the micro Vickers hardness of the nanometer hybrid is beneficial to improving the wear resistance of the epoxy resin composite coating. Wherein Fe is 3 O 4 Hardness value of EP sampleThe maximum difference is due to Fe 3 O 4 The aggregation phenomenon of nano particles in the epoxy resin coating is serious, and the poor dispersibility leads to uneven hardness distribution.
(2) Friction wear test
After the corrosion oxide layer on the surface of the 20 steel sheet is premilled on a metallographic premiller, the 20 steel sheet is soaked in absolute ethyl alcohol for ultrasonic treatment for 10min, and then the 20 steel sheet is sequentially ground by using 600-800-mesh sand paper. Finally, the prepared seven groups of epoxy resin composite coatings and pure EP coating are fixedly coated on 20 steel sheets by 0.2g, and the friction and wear test pieces are obtained by curing. The test sample is vertically applied with a load, the adopted friction pair is GCr15 steel balls with good wear resistance for cyclic reciprocating friction, the test sample is fixed on a test sample table, the initial load is 20N, the friction speed is 50mm/min, the friction length is 5mm, and the friction is 20min. The frictional wear test was performed, and the test results are shown in fig. 6 and 7.
From FIGS. 6 and 7, fe 3 O 4 Nanoparticles do not exhibit good friction drag reduction effects, whereas MoS 2 Nanoparticles and Fe 3 O 4 -MoS 2 The nanometer hybrid can effectively reduce the friction coefficient, fe 3 O 4 -MoS 2 The antifriction effect of the nanometer hybrid is better. Fe (Fe) 3 O 4 -MoS 2 Fe in nanometer hybrid 3 O 4 ：MoS 2 The friction coefficient values are similar when the mole ratio of Fe is different 3 O 4 And MoS 2 The friction reducing effect is best when the molar ratio is 3:1, the friction coefficient is 0.626 at the minimum, and the friction coefficient of the friction and abrasion sample is reduced by 20.4 percent compared with the friction and abrasion sample of the pure epoxy resin.
This phenomenon is due to magnetic Fe 3 O 4 The nano particles are easy to agglomerate, and the antifriction effect is poor. And MoS 2 The nano particles have a layered structure and are easy to adsorb on a contact surface to form a friction film in the sliding process, so that a good lubricating effect is achieved, and the friction coefficient is effectively reduced. Fe (Fe) 3 O 4 -MoS 2 The nano-hybrid has the best antifriction effect because of combining Fe 3 O 4 And MoS 2 Characteristics of the nanoparticles. Magnetic Fe 3 O 4 The nanometer hybrid can be adsorbed on the friction surfaces to prevent the two friction surfaces from being directly contacted; and MoS 2 Can improve Fe 3 O 4 And plays a good lubricating role.
(3) Observation of wear scar morphology
And observing the grinding marks formed after the friction and wear test of the epoxy resin composite coating by adopting an SZ4-DS type visual microscope. The length of the grinding mark is 5mm, after a picture is taken by using a stereo microscope, the width of the grinding mark is measured and recorded by adopting AdobeP holothshop 2023 software, the appearance of the grinding mark is shown in figure 8, and the width of the grinding mark is gradually increased along with the increase of the friction coefficient of the epoxy resin sample. MoS can also be seen from the wear scar topography 2 、Fe 3 O 4 -MoS 2 Nanometer hybrid and Fe 3 O 4 Compared with the prior art, the grinding mark has smaller width and better antifriction effect. Wherein Fe is 3 O 4 ：MoS 2 The best antifriction effect is achieved at a molar ratio of 3:1, and the minimum wear scar width is 546.562 μm.
Example 5
Based on the embodiment, the steel sheet adopted is Q235 corrosion hanging sheet I type, and the steel sheet is sequentially polished by 600, 800, 1000, 1200, 1500 and 2000 meshes of sand paper and then put into absolute ethyl alcohol for standby. Seven groups of epoxy resin composite coatings and pure EP coatings with the thickness of 150 mu m are coated on the surface of the Q235 corrosion hanging piece I type by using a film coater, and eight groups of electrochemical test samples are obtained by curing. Finally, the sample was immersed in a configured 3.5wt.% sodium chloride solution. Among these, the test used by the electrochemical workstation was a three-electrode system. The epoxy resin composite coating sample is a working electrode, an Ag/AgCl electrode is used as a reference electrode, and a Pt electrode is used as an auxiliary electrode. The relevant parameters of the electrochemical test are as follows: the open circuit voltage test time is 200s, the impedance range is 105 Hz-10-2 Hz, the polarization curve scanning range is-1.5V-1V, and the scanning rate is 0.001V/s.
(1) Water absorption test
The sample was put into 3.5wt.% sodium chloride solution for seven days, then the sample was taken out and dried, the weight of the sample was weighed by an analytical balance, the mass change of the sample before and after the soaking was calculated by percentage, the water absorption of the sample was analyzed to see the ability to withstand 3.5wt.% sodium chloride solution permeation, and the water absorption value of the epoxy resin sample in 3.5wt.% sodium chloride solution for seven days was observed, as shown in table 4.
TABLE 4 Table 4
| Sample of | Before soaking (g) | After soaking | Water absorption (%) |
| Fe 3 O 4 -MoS 2 (3:1)/EP | 1.3016 | 1.3072 | 0.430 |
| Fe 3 O 4 -MoS 2 (1:1)/EP | 0.7944 | 0.7979 | 0.441 |
| Fe 3 O 4 -MoS 2 (1:3)/EP | 1.4039 | 1.4104 | 0.463 |
| Fe 3 O 4 -MoS 2 (1:5)/EP | 1.4043 | 1.4114 | 0.506 |
| Fe 3 O 4 -MoS 2 (1:7)/EP | 1.4992 | 1.5069 | 0.514 |
| Fe 3 O 4 /EP | 1.4272 | 1.4344 | 0.504 |
| MoS 2 /EP | 1.6270 | 1.6348 | 0.479 |
| EP | 1.3327 | 1.3399 | 0.540 |
The water absorption of the pure epoxy samples was the greatest and the ability to prevent 3.5wt.% sodium chloride solution penetration was the worst. Whereas the water absorption of the epoxy resin sample added with the nanofiller is reduced, wherein Fe 3 O 4 -MoS 2 The water absorption of the (3:1)/EP sample is 0.430% minimum, and the water absorption is reduced by 0.11% compared with that of the pure epoxy resin. Fe (Fe) 3 O 4 -MoS 2 The improvement of the water absorption of the nanometer hybrid indicates that the size of micropores generated in the curing process of the epoxy resin composite coating is reduced, the compactness of a sample is improved, and the corrosion resistance is enhanced.
(2) Contact angle test
And (3) a DataPhysics OCA25 type full-automatic contact angle tester is adopted, a sample is soaked in a sodium chloride solution with the weight of 3.5% for seven days and then is wiped to be measured, the sample is placed on a sample table, the surface level of the sample is kept, a liquid drop image is shot, and a datum line is determined to obtain a contact angle. Finally, the image is annotated by using AdobeP photoshop2023 software.
After soaking in 3.5wt.% sodium chloride solution for seven days, the corrosive medium gradually damages the coating and the matrix, and the corrosion products are in a majority of hydrophilic substances, so that the contact angle of the coating is reduced, and the corrosion resistance is weakened along with the prolonged soaking time. As shown in fig. 9, the results indicate that the contact angle of the pure epoxy sample is the smallest and the corrosion resistance is the worst; and Fe (Fe) 3 O 4 -MoS 2 The contact angle of the EP sample is larger, and the corrosion resistance is better. The reason is that the corrosive medium can easily reach the metal matrix through the micropores generated by the pure epoxy resin sample, and the nano particles can be added to block the micropores, so that the invasion of the corrosive medium is prevented. Addition of Fe alone in epoxy resin coating 3 O 4 The nano particles are easy to agglomerate, and Fe is added 3 O 4 -MoS 2 The nanometer hybrid can improve Fe 3 O 4 Agglomeration phenomenon of (2). Thus Fe 3 O 4 -MoS 2 The preservative capacity of the EP sample is best.
(3) Impedance testing
The ac impedance spectra measured by testing the electrochemical behavior of the epoxy resin composite coating after three and seven days of immersion in 3.5wt.% sodium chloride solution in an electrochemical workstation, respectively, are shown in fig. 10 and 11. From the test results, it was found that the resistance of the epoxy resin coating is significantly increased after the addition of the nanofiller, the corrosion resistance is enhanced, wherein Fe is added 3 O 4 -MoS 2 The (3:1)/EP coating has the greatest radius of resistance to arc and the greatest corrosion resistance. Meanwhile, by comparing the impedance spectra after soaking for three days and seven days, it can be found that as the soaking time of the sample in the sodium chloride solution of 3.5wt.% increases, the radius of the impedance arc is continuously reduced, and the low-frequency impedance value is also continuously decreased. The reason is that as the soaking time increases, the coating cannot prevent water and ions from penetrating into the coating for a long time due to tiny pores on the surface of the coating, thereby increasing the conductivity of the coatingThis tends to result in a decrease in the corrosion protection of the epoxy coating.
(4) Polarization Curve test
The electrokinetic polarization method is adopted to evaluate the corrosion behavior of the epoxy resin composite coating, and Fe is respectively added in the research 3 O 4 -MoS 2 (3:1, 1:1, 1:3, 1:5, 1:7) nanohybrids, nano Fe 3 O 4 Particle, nano MoS 2 The particles have seven groups of corrosion resistance of the epoxy resin composite coating and the pure epoxy resin coating. Fig. 12 is a plot of the potentiodynamic polarization of the prepared epoxy resin composite coating after 7 days of immersion in a 3.5wt.% sodium chloride solution.
The polarization resistance Rp and the corrosion rate CR (mm/y) can be obtained by drawing anode and cathode slope lines using electrochemical analyzer software, then crossing the two lines over the corrosion potential value (Ecorr) to obtain the corrosion current density (Icorr), and then calculating by the stem-Geary equation as shown in formulas (1), (2), (3):
C R ＝22.85*I Corr (3)
wherein: icorr is the corrosion current density in: a/cm2; ba is anode Tafel slope in units: mv; bc is the cathode Tafel slope in units: mv; the weight of the formula with A being Q235 is 55.85g/mol; ρ is a density of 7.85g/cm3; n is the chemical valence of Fe and is 2; f is faraday constant (f= 96485C/mol=26.8ah).
The potentiodynamic polarization curve parameters obtained according to the above formula are shown in table 5:
TABLE 5
| Sample of | E corr /mV | I corr /Acm -2 | R p /Ω | C R /mm/y |
| Fe 3 O 4 -MoS 2 (3:1)/EP | -503.86 | 1.00266 | 896.43 | 22.911 |
| Fe 3 O 4 -MoS 2 (1:1)/EP | -628.82 | 1.00307 | 438.71 | 22.931 |
| Fe 3 O 4 -MoS 2 (1:3)/EP | -688.4 | 1.00566 | 308.21 | 22.979 |
| Fe 3 O 4 -MoS 2 (1:5)/EP | -703.35 | 1.00704 | 244.22 | 23.011 |
| Fe 3 O 4 -MoS 2 (1:7)/EP | -868.09 | 1.00801 | 145.11 | 23.033 |
| Fe 3 O 4 /EP | -769.67 | 1.00745 | 183.83 | 23.020 |
| MoS 2 /EP | -847.31 | 1.00765 | 170.33 | 23.025 |
| EP | -903.01 | 1.00833 | 124.85 | 23.041 |
From the potentiodynamic polarization measurement of the epoxy coating versus the immersion time in 3.5wt.% sodium chloride solution and the potentiodynamic polarization parameter values obtained from the polarization curve, it can be seen from table 5: the nano particles can be added to effectively improve the corrosion resistance of the epoxy resin coating, and Fe is added 3 O 4 -MoS 2 Nanometer hybrid is compared with singly adding Fe 3 O 4 Or MoS 2 The modifying effect of the nano particles is better; corrosion by corrosionThe samples with the smallest current density and the largest corrosion potential were Fe 3 O 4 -MoS 2 (3:1)/EP coating, the best corrosion resistance; corrosion current density of test specimen with MoS 2 The content is increased gradually, and the corrosion potential value is increased with MoS 2 The content increases and gradually decreases, and it can be seen that in Fe 3 O 4 -MoS 2 MoS in nanometer hybrid 2 The content of the epoxy resin coating is proper, the corrosion resistance of the epoxy resin coating can be improved, and MoS is excessively added 2 The nanoparticle dispersibility is poor and the corrosion resistance is deteriorated.
In summary, in the epoxy resin, fe modified by the silane coupling agent 3 O 4 -MoS 2 Nanometer hybrid and Fe 3 O 4 Compared with the nano particles, the dispersion stability is improved;
addition of Fe to epoxy resin 3 O 4 -MoS 2 Micro Vickers hardness ratio of nano hybrid post-coating added with Fe 3 O 4 Or MoS 2 The hardness value of the nano-particles is larger, and when Fe 3 O 4 -MoS 2 Fe in nanometer hybrid 3 O 4 And MoS 2 The molar ratio is 3:1, the micro Vickers hardness is the largest, and the hardness of the epoxy resin cured block is improved by 11.2 percent compared with that of the pure epoxy resin cured block;
addition of Fe to epoxy resin coating 3 O 4 -MoS 2 Antifriction effect ratio of nano-hybrids to Fe addition 3 O 4 Or MoS 2 The antifriction effect of the nano-particles is better. Wherein when Fe 3 O 4 -MoS 2 Fe in nanometer hybrid 3 O 4 And MoS 2 The friction reducing effect is best when the molar ratio is 3:1, the friction coefficient is 0.626 at the minimum, and the friction coefficient is reduced by 20.4 percent compared with that of a pure epoxy resin curing block;
addition of Fe to epoxy resin 3 O 4 -MoS 2 Nanometer hybrid and addition of Fe 3 O 4 Or MoS 2 After nanoparticles, the contact angle of the solidified block is increased, the water absorption is reduced, the corrosion resistance is increased, and Fe 3 O 4 -MoS 2 The nano hybrid has better corrosion resistance. When Fe is 3 O 4 And MoS 2 When the molar ratio is 3:1, the contact angle is maximum, the water absorption is minimum, the alternating current impedance is increased, the corrosion potential is maximum, the corrosion rate is minimum, the corrosion resistance is best, the contact angle is increased by 19.4 degrees, the water absorption is reduced by 0.11 percent, and the corrosion rate is reduced by 0.13mm/y compared with the pure epoxy resin cured block.
The foregoing description of the embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (4)
1. Modified nano Fe 3 O 4 -a process for the preparation of an epoxy resin composite, characterized in that it comprises the following steps:
preparing ferroferric oxide nano particles modified by a silane coupling agent;
preparation of Fe by silane coupling agent modified ferroferric oxide nano-particles 3 O 4 -MoS 2 A nanohybrid;
addition of Fe to epoxy resin 3 O 4 -MoS 2 The nanometer hybrid is used for obtaining a modified epoxy resin composite material;
wherein, preparing ferroferric oxide nano particles modified by a silane coupling agent, which comprises the following steps:
adding ferroferric oxide nano particles into the mixed solution, and stirring to obtain a first solution;
adding a silane coupling agent into the mixed solution, and stirring to completely hydrolyze the silane coupling agent to obtain a second solution;
mixing the first solution and the second solution into a three-neck flask, adjusting the temperature of a digital display constant-temperature oil bath pot to 60-80 ℃, refluxing by using a condensing tube, and stirring for 10-15 hours to uniformly react;
filtering and washing by using a suction filter, and drying to obtain ferroferric oxide nano particles modified by a silane coupling agent;
preparation of Fe 3 O 4 -MoS 2 The nanometer hybrid specifically comprises:
dispersing molybdenum disulfide nano particles in N, N-dimethylformamide, and performing ultrasonic treatment to form uniform suspension;
adding ferroferric oxide nano particles modified by a silane coupling agent into the suspension, and performing ultrasonic treatment to obtain a reaction mixture;
reflux-stirring the reaction mixture at 95-110deg.C for 4-8 hr, filtering with suction filter, washing, and drying to obtain Fe 3 O 4 -MoS 2 A nanohybrid;
Fe 3 O 4 -MoS 2 in the nano hybrid, the molar ratio of the ferroferric oxide nano particles to the molybdenum disulfide nano particles is 3:1.
2. A modified nano Fe according to claim 1 3 O 4 -a method for preparing an epoxy resin composite, characterized in that the mixed solution comprises ethanol and deionized water.
3. A modified nano Fe according to claim 1 3 O 4 The preparation process of epoxy resin composite material features that the silane coupling agent is 3-amino propyl triethoxy silane.
4. A modified nano Fe prepared according to any one of the preparation methods of claims 1 to 3 3 O 4 -an epoxy resin composite.
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