HEDP modified MXene / glycerol nanofluid self-cleaning preservative as well as preparation method and application thereof

Abstract

The invention discloses an HEDP-modified MXene / glycerol nanofluid self-cleaning preservative as well as a preparation method and application thereof, relates to the technical field of anticorrosive materials, and aims to solve the problem of lack of an HEDP-modified MXene-based anticorrosive material in the prior art. The preparation method is technically characterized by comprising the following steps: step 1, adding Ti3AlC2 and NH4F into deionized water, and carrying out hydrothermal reaction to prepare MXene; step 2, dispersing an organic silane coupling agent and polyether amine in an organic solvent, and preparing an organic phase through condensation reaction; step 3, dispersing MXene in deionized water to prepare a water phase, adding the organic phase into the water phase, uniformly mixing, removing the organic solvent and the free small molecule compound, and drying to obtain the MXene nanofluid with a core-shell structure; and uniformly mixing the MXene nano-fluid with glycerol, HEDP (Hydroxyethyl Dichloro Phosphate) and deionized water, so as to obtain the HEDP modified MXene / glycerol nano-fluid self-cleaning preservative. The MXene nanofluid with the core-shell structure and the self-cleaning preservative have good application prospects in preparation of preservatives.

Description

Technical Field

[0001] This invention relates to the field of anti-corrosion materials technology, and more specifically, to a HEDP-modified MXene / glycerol nanofluid self-cleaning anti-corrosion agent, its preparation method, and its application. Background Technology

[0002] Outdoor knife switch drive bearings are directly exposed to the air and are greatly affected by environmental factors such as sunlight, rain, and temperature fluctuations. Due to infrequent operation, corrosion and jamming of the transmission mechanism are common, reducing the bearing's lifespan. Cleaning agents effectively remove corrosion products and dirt from metal surfaces and are currently the most widely used and economical method. Cleaning agents are generally divided into solid and liquid cleaners. Liquid cleaners have poor load-bearing capacity and wear resistance, while solid cleaners have poor flow and diffusion properties. Therefore, there is a need to research a semi-solid cleaning and corrosion-preventing agent with good flowability and wear resistance, which can combine the advantages of both liquid and solid cleaners to effectively reduce metal surface corrosion and friction and wear during mechanical movement.

[0003] MXene nanosheets are two-dimensional layered nanomaterials composed of transition metal carbides, nitrides, or carbonitrides. MXene exhibits weak interlayer interactions and is prone to interlayer sliding under pressure. While MXene possesses a large specific surface area, reducing the coefficient of friction and wear, it tends to aggregate in cleaning agents, making it difficult to maintain long-term dispersion and suspension stability. HEDP is an organophosphate scale and corrosion inhibitor that can form stable complexes with various metal ions such as iron, copper, and zinc, dissolving oxides on metal surfaces and achieving surface cleaning. The phosphonic acid group (-PO3H2) of HEDP can chemically react with the hydroxyl (-OH) or oxygen (-O) groups on the MXene surface to form stable chemical bonds. However, research on HEDP-modified MXene is limited, and a HEDP-modified MXene / glycerol nanofluid self-cleaning corrosion inhibitor has not yet been developed. Summary of the Invention

[0004] The technical problem to be solved by this invention is:

[0005] The existing technology lacks anti-corrosion materials based on HEDP-modified MXene.

[0006] The technical solution adopted by the present invention to solve the above-mentioned technical problems is as follows:

[0007] This invention provides a method for preparing a HEDP-modified MXene / glycerol nanofluid self-cleaning preservative, comprising the following steps:

[0008] Step 1: Add Ti3AlC2 and NH4F to deionized water and carry out a hydrothermal reaction to prepare MXene;

[0009] Step 2: Disperse the organosilane coupling agent and polyetheramine in an organic solvent and prepare the organic phase through a condensation reaction;

[0010] Step 3: Disperse MXene in deionized water to prepare an aqueous phase, add an organic phase to the aqueous phase and mix evenly to remove organic solvents and free small molecule compounds, and dry to obtain a core-shell structured MXene nanofluid; mix the MXene nanofluid with glycerol, HEDP and deionized water evenly to obtain a HEDP-modified MXene / glycerol nanofluid self-cleaning preservative.

[0011] Furthermore, the hydrothermal reaction conditions in step 1 are to react at (130-150) °C for 10-12 h.

[0012] Furthermore, in step 2, the organosilane coupling agent is selected from KH560, and the polyetheramine is selected from M2070.

[0013] Furthermore, the organic solvent mentioned in step 2 is selected from methanol.

[0014] Furthermore, in step 2, the volume ratio of KH560, M2070 and methanol in the organic phase is (9-11):(8-11):(80-100).

[0015] Furthermore, the condensation reaction in step 2 takes 24-26 hours.

[0016] Furthermore, in step 3, the mass ratio of MXene nanofluid to HEDP is (0.2-0.3):(2.5-10).

[0017] The present invention provides the above-described core-shell structured MXene nanofluid.

[0018] This invention provides a self-cleaning preservative prepared by the above method.

[0019] This invention provides the application of the core-shell structured MXene nanofluid, or the self-cleaning preservative, in the preparation of preservatives.

[0020] Compared with the prior art, the beneficial effects of the present invention are:

[0021] The HEDP-modified MXene / glycerol nanofluid self-cleaning preservative of this invention is based on an MXene nanofluid with MXene as the core, silane coupling agent KH560 as the neck layer, and polyetheramine M2070 as the crown layer. Its excellent flowability prevents the aggregation of nanoparticles and improves the dispersion stability of nanoparticles in the liquid phase. In this preservative, the HEDP-modified MXene reacts with oxides on the metal surface to generate soluble metal salts, thus achieving cleaning of the metal surface. Attached Figure Description

[0022] Figure 1 The infrared spectrum of MXene-KH560-M2070 in this embodiment of the invention;

[0023] Figure 2 The thermogravimetric curve of MXene-KH560-M2070 in this embodiment of the invention;

[0024] Figure 3 This is a comparison image of the cleaning effect of the rusted Q235 steel sheet before and after in an embodiment of the present invention;

[0025] Figure 4 This is a graph showing the friction coefficient in an embodiment of the present invention;

[0026] Figure 5 This is a diagram showing the wear scar diameter in an embodiment of the present invention;

[0027] Figure 6 The impedance spectrum of Q235 steel in 3.5% NaCl solution is shown in the embodiment of the present invention. Detailed Implementation

[0028] To enable those skilled in the art to better understand the present invention, exemplary embodiments or examples of the present invention will be described below in conjunction with the accompanying drawings. Obviously, the described embodiments or examples are merely some, not all, of the embodiments or examples of the present invention. All other embodiments or examples obtained by those skilled in the art based on the embodiments or examples of the present invention without inventive effort should fall within the scope of protection of the present invention.

[0029] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0030] In a typical embodiment, the present invention provides a method for preparing a HEDP-modified MXene / glycerol nanofluid self-cleaning preservative, comprising the following steps:

[0031] Step 1: Add Ti3AlC2 and NH4F to deionized water and carry out a hydrothermal reaction to prepare MXene;

[0032] Step 2: An organic phase is prepared by dispersing an organosilane coupling agent and a polyetheramine in an organic solvent and then reacting them through a condensation reaction.

[0033] Step 3: Disperse MXene in deionized water to prepare an aqueous phase, add an organic phase to the aqueous phase and mix evenly to remove organic solvents and free small molecule compounds, and dry to obtain a core-shell structured MXene nanofluid; mix the MXene nanofluid with glycerol, HEDP and deionized water evenly to obtain a HEDP-modified MXene / glycerol nanofluid self-cleaning preservative.

[0034] This invention employs covalent bonding to form a KH560-M2070 shell, with MXene as the core, to prepare a core-shell structured MXene nanofluid (MXene-KH560-M2070). The prepared MXene nanofluid is mixed with an HEDP solution, combining the advantages of both solid and liquid lubricants to improve the dispersion stability of MXene as a lubricating additive in glycerol, achieving a dual function of self-cleaning and corrosion prevention.

[0035] Preferably, in a typical embodiment, the hydrothermal reaction in step 1 is carried out at 130-150°C for 10-12 h. This temperature range promotes the rapid and orderly hydrolysis and condensation reactions of the precursor. The 10-12 h reaction time ensures a sufficient and thorough reaction, which is beneficial for forming nanoparticles with uniform size and regular morphology.

[0036] Preferably, in a typical embodiment, the organosilane coupling agent in step 2 is selected from KH560, and the polyetheramine is selected from M2070. In this invention, KH560 is used as a "bridge," connecting the inorganic nanoparticles at one end and the flexible long chain of M2070 at the other end through covalent bonds, thus constructing a strong and dense organic polymer layer on the surface of the nanoparticles, thereby achieving stable dispersion of the nanoparticles in the base oil, playing a key role.

[0037] Preferably, in a typical embodiment, the organic solvent in step 2 is selected from methanol.

[0038] Preferably, in a typical embodiment, the volume ratio of KH560, M2070 and methanol in the organic phase in step 2 is (9-11):(8-11):(80-100).

[0039] Preferably, in a typical embodiment, the condensation reaction in step 2 takes 24-26 hours to ensure complete grafting of the organosilane coupling agent and the polyetheramine.

[0040] Preferably, in a typical embodiment, the mass ratio of MXene nanofluid to HEDP in step 3 is (0.2-0.3):(2.5-20).

[0041] In a typical embodiment, the present invention also provides the core-shell structured MXene nanofluid, the self-cleaning preservative prepared by the method, and the self-cleaning anti-corrosion coating prepared by the self-cleaning preservative; and the application of the core-shell structured MXene nanofluid, or the self-cleaning preservative, in the preparation of preservatives also falls within the scope of protection of the present invention.

[0042] The beneficial effects of the present invention will be described below with reference to specific embodiments.

[0043] Example 1

[0044] Step 1: Add 0.2 g Ti3AlC2 and 0.3 g NH4F powder to 50 mL deionized water and stir until homogeneous to obtain a mixture; transfer the mixture to a hydrothermal reactor and react at 140 °C for 10 h; after the reaction is complete, centrifuge to remove the supernatant, collect the precipitate, and vacuum dry at 60 °C for 10 h to obtain MXene;

[0045] Step 2: Add 9 mL of organosilane coupling agent (KH560) dropwise to a mixed solution of 8 mL of polyetheramine (M2070) and 90 mL of methanol, stir for 24 h, and obtain the KH560-M2070 organic phase through covalent bonding;

[0046] Step 3: Add 0.5 g MXene to 50 mL of deionized water, disperse by ultrasonication to obtain an aqueous phase, add the prepared KH560-M2070 organic phase, mix well, dialyze for 48 h (molecular weight cutoff of 3500) to remove organic solvent and free small molecule compounds, and replace the deionized water every 4 h during dialysis. Dry the product under vacuum at 70 °C for 24 h to obtain MXene nanofluid; dissolve 0.25 g MXene nanofluid in 50 mL of glycerol, add 10 g HEDP and 100 mL of deionized water and mix well to obtain HEDP-modified MXene / glycerol nanofluid self-cleaning preservative.

[0047] Example 2

[0048] The difference between this embodiment and Example 1 is that in step 2, 9 mL of organosilane coupling agent (KH560) is added dropwise to a mixed solution of 8 mL of polyetheramine (M2070) and 80 mL of methanol, and stirred for 24 h to obtain the KH560-M2070 organic phase through covalent bonding.

[0049] Example 3

[0050] The difference between this embodiment and Example 1 is that in step 2, 11 mL of organosilane coupling agent (KH560) is added dropwise to a mixed solution of 11 mL of polyetheramine (M2070) and 100 mL of methanol, and stirred for 24 h to obtain the KH560-M2070 organic phase through covalent bonding.

[0051] Example 4

[0052] The difference between this embodiment and Example 1 is that in step 3, 0.25g of MXene nanofluid is dissolved in 50 mL of glycerol, and 2.5g of HEDP and 100 mL of deionized water are added and mixed evenly to obtain HEDP-modified MXene / glycerol nanofluid self-cleaning preservative.

[0053] Example 5

[0054] The difference between this embodiment and Example 1 is that in step 3, 0.25g of MXene nanofluid is dissolved in 50 mL of glycerol, and 5g of HEDP and 100 mL of deionized water are added and mixed evenly to obtain HEDP-modified MXene / glycerol nanofluid self-cleaning preservative.

[0055] Example 6

[0056] The difference between this embodiment and Example 1 is that in step 3, 0.25g of MXene nanofluid is dissolved in 50 mL of glycerol, and 15g of HEDP and 100 mL of deionized water are added and mixed evenly to obtain HEDP-modified MXene / glycerol nanofluid self-cleaning preservative.

[0057] Example 7

[0058] The difference between this embodiment and Embodiment 1 is that in step 3, 0.25g of MXene nanofluid is dissolved in 50 mL of glycerol, and 20g of HEDP and 100 mL of deionized water are added and mixed evenly to obtain HEDP-modified MXene / glycerol nanofluid self-cleaning preservative.

[0059] Example 8

[0060] The difference between this embodiment and Example 1 is that in step 3, 0.20 g of solvent-free MXene nanofluid is dissolved in 50 mL of glycerol and then uniformly mixed with 10 g of HEDP and 100 mL of deionized water to obtain HEDP-modified MXene / glycerol nanofluid self-cleaning preservative.

[0061] Example 9

[0062] The difference between this embodiment and Example 1 is that in step 3, 0.30 g of solvent-free MXene nanofluid is dissolved in 50 mL of glycerol and mixed evenly with 10 g of HEDP and 100 mL of deionized water to obtain HEDP-modified MXene / glycerol nanofluid self-cleaning preservative.

[0063] Infrared spectroscopy was performed on the MXene nanofluid (MXene-KH560-M2070), the KH560-M2070 organic phase, and M2070 from Example 1. The results are as follows: Figure 1 As shown, 3374 cm −1 and 3304 cm −1 The absorption peak at 843 cm⁻¹ corresponds to the asymmetric and symmetric stretching vibrations of -NH₂ in polyetheramine M₂070. However, this absorption peak disappears after the reaction of M₂070 with KH₅60, indicating that KH₅60 and M₂070 react completely and are linked by covalent bonds. −1 and 1000-1200 cm −1 The characteristic peaks at the point are related to O-Si-O and Si-O-Si bonding, indicating that in the core-shell grafting reaction, KH560 acts as a linker, enabling KH560-M2070 to be covalently bonded to the MXene surface through dehydration condensation.

[0064] Thermogravimetric analysis was performed on the MXene nanofluid (MXene-KH560-M2070) of Example 1 under a nitrogen atmosphere, as follows: Figure 2 As shown, the weight of MXene-KH560-M2070 remained unchanged below 300℃, indicating that MXene-KH560-M2070 does not undergo solvent decomposition or volatilization and possesses high thermal stability. Decomposition begins above 350℃, and the calculated mass fraction of the organic shell of MXene-KH560-M2070 is 72.9 wt%. It is noteworthy that the high content of the KH560-M2070 organic molecular chains in the shell is sufficient to act as Ti3C2T. X The flow medium of nanosheets gives them good fluidity.

[0065] The anti-corrosion effect of the MXene / glycerol nanofluid self-cleaning corrosion inhibitor in Example 1 was verified. Rusty steel sheets were immersed in the MXene / glycerol nanofluid self-cleaning corrosion inhibitor, left to stand for 200 minutes, then removed and quickly rinsed and dried with deionized water. Figure 3 As shown, the steel surface before cleaning had significant rust, appearing as yellow and brown spots and streaks, typical characteristics of rust (mainly iron oxide). After cleaning, the steel appeared cleaner, with the rust completely removed, leaving a smooth and shiny surface. The comparison clearly demonstrates that the self-lubricating cleaning and anti-corrosion material effectively removed rust from the steel surface, restoring it to a more original state.

[0066] The coefficient of friction and the wear scar diameter are quantitative indicators for evaluating the anti-wear and friction-reducing performance of lubricating oil. A friction pair on a steel ball and a friction pair on a steel disc were used to simulate the friction conditions under actual working conditions. 0.2 mL of the MXene / glycerol nanofluid self-cleaning corrosion inhibitor from Example 1 was dripped into the ball-disc contact gap. The steel ball rubbed downwards against a fixed steel disc. Friction parameters such as load, frequency, stroke, and temperature were set to 100 N, 15 Hz, 2 mm, and 25 ℃, respectively. Figure 4 As shown, the coefficient of friction fluctuates slightly at the beginning, then tends to stabilize, and finally gradually decreases. This indicates that the corrosion inhibitor needs a certain amount of time to form an effective lubricating film in the initial stage, providing continuous lubrication in the stable stage. Finally, the coefficient of friction decreases due to the consumption of the corrosion inhibitor, with an average value of 0.060. Figure 5 It can be seen that the surface around the wear scar is relatively smooth, indicating that the wear in other areas is relatively light. The wear scar diameter is 0.889 mm. The small average friction coefficient and wear scar diameter indicate that the prepared fluid-like self-cleaning corrosion inhibitor has a stable friction coefficient and good wear resistance, making it suitable for use in high-wear environments.

[0067] The surface stains of the rusted Q235 steel were removed using clean cotton. The initial mass m0 of the steel sheet was weighed. The steel sheet was then completely immersed in the HEDP-modified MXene / glycerol nanofluid self-cleaning corrosion inhibitor (25 ℃) obtained in each embodiment. After standing for a period of time, the steel sheet was removed, quickly rinsed with deionized water, dried, and the mass m1 of the cleaned steel sheet was weighed. The rust removal rate was calculated, and the results are shown in the table. The formula for calculating the rust removal rate is shown in equation (1).

[0068]

[0069] In the formula, K is the rust removal rate (g / h); m0 is the mass of Q235 steel before rust removal (g); m1 is the mass of Q235 steel after rust removal (g); and t is the rust removal time (h).

[0070] Table 1

[0071]

[0072] According to Examples 1, 4, 5, 6, and 7 in Table 1, the rust removal rate significantly increased when the mass of the organic acid increased from 2.5g to 10g; however, the increase in rust removal rate was not significant when the mass of HEDP exceeded 10g. HEDP is a moderately strong acid; when a small amount of acid is added, the phosphonic acid groups in the solution gradually become saturated, and the dissolution reaction of iron oxides enters a complexation-precipitation dynamic equilibrium state. Therefore, considering both rust removal rate and cost, a mass of 10g of organic acid is preferred.

[0073] Electrochemical tests were conducted on Q235 steel sheets and Q235 steel sheets treated with the MXene / glycerol nanofluid self-cleaning corrosion inhibitor of Example 1 (using NaCl solution as the electrolyte to simulate the corrosion environment). Figure 6 As shown, the two samples exhibit similar results in the high-frequency region, indicating that charge transfer is the primary reaction in this region, and the impedance of the diffusion process can be ignored, resulting in minimal differences. However, in the low-frequency region, where the diffusion process is dominated by reactants and products, the capacitive curvature of the corrosion-resistant sample is significantly larger than that of the untreated sample. This demonstrates that stainless steel alone has poor corrosion resistance, while corrosion-resistant treatment effectively inhibits charge transfer during corrosion, thus improving the corrosion resistance of Q235 steel.

[0074] While the present invention has been disclosed above, its scope of protection is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and all such changes and modifications will fall within the scope of protection of the present invention.

Claims

1. A method for preparing a HEDP-modified MXene / glycerol nanofluid self-cleaning preservative, characterized in that: Includes the following steps: Step 1: Add Ti3AlC2 and NH4F to deionized water and carry out a hydrothermal reaction to prepare MXene; Step 2: Disperse the organosilane coupling agent and polyetheramine in an organic solvent and prepare the organic phase through a condensation reaction; Step 3: Disperse MXene in deionized water to prepare an aqueous phase, add an organic phase to the aqueous phase and mix evenly to remove organic solvents and free small molecule compounds, and dry to obtain a core-shell structured MXene nanofluid; mix the MXene nanofluid with glycerol, HEDP and deionized water evenly to obtain a HEDP-modified MXene / glycerol nanofluid self-cleaning preservative.

2. The method for preparing the HEDP-modified MXene / glycerol nanofluid self-cleaning preservative according to claim 1, characterized in that, The hydrothermal reaction conditions in step 1 are to react at (130-150)℃ for 10-12 h.

3. The method for preparing the HEDP-modified MXene / glycerol nanofluid self-cleaning preservative according to claim 2, characterized in that: In step 2, the organosilane coupling agent is selected from KH560, and the polyetheramine is selected from M2070.

4. The preparation method of the HEDP-modified MXene / glycerol nanofluid self-cleaning preservative according to claim 3, characterized in that: The organic solvent mentioned in step 2 is selected from methanol.

5. The preparation method of the HEDP-modified MXene / glycerol nanofluid self-cleaning preservative according to claim 4, characterized in that: In step 2, the volume ratio of KH560, M2070 and methanol in the organic phase is (9-11):(8-11):(80-100).

6. The method for preparing the HEDP-modified MXene / glycerol nanofluid self-cleaning preservative according to claim 5, characterized in that: The condensation reaction in step 2 takes 24-26 hours.

7. The method for preparing the HEDP-modified MXene / glycerol nanofluid self-cleaning preservative according to claim 6, characterized in that: In step 3, the mass ratio of MXene nanofluid to HEDP is (0.2-0.3):(2.5-10).

8. The core-shell structured MXene nanofluid according to any one of claims 1 to 6.

9. The self-cleaning preservative prepared by the method according to any one of claims 1 to 7.

10. The application of the core-shell structured MXene nanofluid of claim 8, or the self-cleaning preservative of claim 9, in the preparation of preservatives.

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