A kind of spherule composite type carbon-based micro-nano material lubricating oil additive and preparation method

Abstract

The application discloses a kind of ball piece composite type carbon-based micro-nano material lubricating oil additive and preparation method, the preparation method includes the following steps: a certain amount of magnetic metal oxide is added to glucose aqueous solution, and carbon microspheres containing magnetic metal oxide are obtained after hydrothermal reaction;The carbon microspheres and graphene oxide are dispersed into water according to a set mass ratio, and solid particles are obtained after reaction and separation;The solid particles are calcined to obtain ball piece composite type carbon-based micro-nano material lubricating oil additive.The carbon-based micro-nano material prepared in the application contains magnetic metal oxide in the interior of carbon microspheres, which can continuously improve the friction-reducing performance of carbon-based micro-nano material by changing the crystal structure of carbon microspheres during the friction process as a catalyst, and the friction coefficient can be significantly reduced by one order of magnitude in multiple time periods during the friction process;Easy to recycle and reuse through magnetic separation, energy saving, environmental protection, high economic value, easy to realize industrialization.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of lubricating oil, and particularly relates to a ball-plate composite carbon-based micro-nano material lubricating oil additive and a preparation method thereof. BACKGROUND

[0002] Lubricating oil plays an important role in controlling the friction and wear of mechanical parts and prolonging the service life of equipment. The additive in the lubricating oil is the key to determining its anti-wear and friction-reducing performance. In recent years, with the increasing emphasis on environmental protection, energy saving and emission reduction in the world, the use of organic compounds containing sulfur, phosphorus and chlorine as traditional anti-wear and friction-reducing additives is gradually restricted. In addition, the rapid development of high-speed heavy-load mechanical equipment and low-viscosity lubricating oil puts forward higher requirements for the tribological performance of the additive. Micro-nano particles have been widely concerned in the field of mechanical tribology due to their excellent mechanical properties, good compatibility and low environmental toxicity. Carbon-based nanomaterials containing graphene have good anti-wear and friction-reducing performance in lubricating oil, and show good application prospects as new lubricating oil additives. For example, Chinese Patent (Publication No. CN108559575A) discloses that nanometer lanthanum oxide is compounded with graphene to prepare a graphene-based nanometer lanthanum oxide composite as a lubricating oil anti-wear additive. Chinese Patent (Publication No. CN110373246A) uniformly mixes montmorillonite with functional graphene oxide and modified nanometer titanium nitride to prepare a montmorillonite-titanium nitride-functional graphene composite material lubricating oil additive. Chinese Patent (Publication No. CN110305712A) ages a prepared graphene-containing gel under hydrothermal conditions to obtain a silicate supported with graphene, and uniformly disperses and mixes the silicate supported with graphene with molybdenum disulfide and tungsten disulfide to obtain a layered silicate supported with graphene as a lubricating oil additive.

[0003] From the existing technical means, carbon-based micro-nano materials containing graphene as lubricating oil additives mainly form a friction reaction film at the friction interface to effectively block the direct contact of metal micro-protrusions, thereby achieving good anti-wear performance. However, due to the influence of factors such as shear stress between the sliding interface, non-uniformity of the friction interface and wrinkling effect of graphene, the friction-reducing performance of carbon-based micro-nano materials containing graphene at the friction interface is not outstanding. In addition, graphene is expensive, resulting in high preparation cost of the corresponding carbon-based micro-nano materials containing graphene, which seriously restricts the wide application of the carbon-based micro-nano materials containing graphene in the lubricating oil additive industry. Therefore, developing a carbon-based micro-nano material containing graphene with excellent friction-reducing performance at the friction interface and high economic value as a lubricating oil additive is the key to realizing the wide application of carbon-based micro-nano materials in the lubricating oil and corresponding additive industry. SUMMARY

[0004] In view of the above problems, the application discloses a preparation method of a ball sheet composite carbon-based micro-nano material lubricating oil additive, which comprises the following steps:

[0005] A certain amount of magnetic metal oxide is added to the glucose aqueous solution, and carbon microspheres containing the magnetic metal oxide are obtained after hydrothermal reaction;

[0006] The carbon microspheres and graphene oxide are dispersed into water according to a certain mass ratio, and solid particles are obtained after reaction and separation;

[0007] The solid particles are calcined to obtain the ball sheet composite carbon-based micro-nano material lubricating oil additive.

[0008] Further, the specific steps of adding a certain amount of magnetic metal oxide to the glucose aqueous solution and obtaining carbon microspheres containing the magnetic metal oxide after hydrothermal reaction are as follows:

[0009] A glucose aqueous solution with a concentration of 0.1-2.5 mol / L is taken, a certain amount of magnetic metal oxide is added, and the mixed solution is transferred into a hydrothermal reaction kettle after being fully stirred, and then the hydrothermal reaction is carried out at 150-200 DEG C for a certain time, and the carbon microspheres containing the magnetic metal oxide are obtained through magnetic separation.

[0010] Further, the magnetic metal oxide is one or a combination of several of ferric oxide, zinc ferrite, cobalt ferrite, nickel ferrite, cobalt-iron-nickel oxide and zinc-iron-nickel oxide.

[0011] The magnetic metal oxide is spherical and has a diameter of 20-50 nm.

[0012] Further, the concentration of the magnetic metal oxide is 0.1-3 g / L.

[0013] Further, the hydrothermal reaction is carried out for 3-6 h.

[0014] Further, the specific steps of dispersing the carbon microspheres and graphene oxide into water according to a certain mass ratio, and obtaining solid particles after reaction and separation are as follows:

[0015] The carbon microspheres and graphene oxide are dispersed into water according to a mass ratio of 0.1-10:1, and then stirred and reacted at 50-80 DEG C for a certain time, and then the solid particles are obtained after reaction and separation.

[0016] Further, the stirring time is 5-12 h.

[0017] Further, the specific steps of calcining the solid particles to obtain the ball sheet composite carbon-based micro-nano material lubricating oil additive are as follows:

[0018] The solid-phase microparticles are placed in a tube furnace, a protective atmosphere is introduced, and the solid-phase microparticles are calcined at 300-1000 DEG C for 1-5 hours to obtain the spherical sheet composite carbon-based micro-nano material lubricating oil additive.

[0019] The application further discloses a spherical sheet composite carbon-based micro-nano material lubricating oil additive, which comprises 0.1-10 parts of carbon microspheres and 1 part of graphene oxide in terms of weight fraction.

[0020] The magnetic metal oxide contained in the carbon microspheres accounts for 22-32% of the total weight of the carbon microspheres.

[0021] Further, the structure of the spherical sheet composite carbon-based micro-nano material lubricating oil additive is that the carbon microspheres containing the magnetic metal oxide are loaded on the graphene oxide nanosheets.

[0022] The flake diameter of the graphene oxide nanosheet is 0.5-5 mu m, and the thickness is 0.8-1.2 nm.

[0023] The diameter of the carbon microspheres is 50-150 nm, and the shell thickness is 5-30 nm.

[0024] Compared with the prior art, the embodiment of the application has at least the following advantages:

[0025] 1) In the spherical sheet composite carbon-based micro-nano material prepared by the application, the interior of the carbon microspheres contains the magnetic metal oxide, which can continuously improve the friction-reducing performance of the carbon-based micro-nano material by changing the crystal structure of the carbon microspheres during the friction process, and the friction coefficient can be significantly reduced by one order of magnitude (about 90%) in multiple time periods during the friction process.

[0026] 2) The spherical sheet composite carbon-based micro-nano material lubricating oil additive prepared by the application can be easily recycled by magnetic separation, and has the advantages of energy saving, environmental protection, high economic value and easy industrialization.

[0027] Other features and advantages of the application will be set forth in the following description of the application, and in part will become apparent to those skilled in the art upon examination of the following or can be learned from practice of the application. The objects and other advantages of the application can be realized and attained by the structure particularly pointed out in the written description and claims hereof. BRIEF DESCRIPTION OF DRAWINGS

[0028] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or the prior art description. Obviously, the drawings in the following description are some embodiments of the application, and for those skilled in the art, other drawings can also be obtained from these drawings without creative labor.

[0029] Figure 1A friction coefficient process curve of the ball-plate composite carbon-based micro-nano material lubricating oil additive according to the embodiment of the application is shown.

[0030] Figure 2 A Raman spectrum of the ball-plate composite carbon-based micro-nano material before and after friction according to the embodiment of the application is shown.

[0031] Figure 3 A morphology diagram of the ball-plate composite carbon-based micro-nano material lubricating oil additive according to the embodiment of the application is shown. DETAILED DESCRIPTION

[0032] To make the objectives, technical solutions and advantages of the embodiments of the application clearer, the technical solutions in the embodiments of the application will be described clearly and completely below with reference to the drawings in the embodiments of the application. Obviously, the described embodiments are some but not all of the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the application.

[0033] The application provides a preparation method of a ball-plate composite carbon-based micro-nano material lubricating oil additive, which comprises the following steps:

[0034] A certain amount of magnetic metal oxide is added to a glucose aqueous solution, and carbon microspheres containing the magnetic metal oxide are obtained after hydrothermal reaction;

[0035] The carbon microspheres and graphene oxide are dispersed into water according to a certain mass ratio, and solid microparticles are obtained after reaction and separation;

[0036] The solid microparticles are calcined to obtain the ball-plate composite carbon-based micro-nano material lubricating oil additive.

[0037] In some embodiments, the specific steps of adding a certain amount of magnetic metal oxide to a glucose aqueous solution and obtaining carbon microspheres containing the magnetic metal oxide after hydrothermal reaction are as follows:

[0038] A 0.1-2.5 mol / L glucose aqueous solution is taken, a certain amount of magnetic metal oxide is added, and the mixed solution is transferred to a hydrothermal reaction kettle after sufficient stirring. The carbon microspheres containing the magnetic metal oxide are obtained by magnetic separation after hydrothermal reaction at 150-200℃ for a certain time. Preferably, the concentration of the glucose aqueous solution is 1.6 mol / L.

[0039] In some embodiments, the magnetic metal oxide is one or a combination of several of ferric oxide, zinc ferrite, cobalt ferrite, nickel ferrite, cobalt-iron-nickel ferrite, zinc-iron-nickel ferrite. Among them, the magnetic metal oxide is spheroid-like, with a diameter of 20-50 nm. The above-mentioned metal oxide, as a transition metal oxide, has a catalytic effect of changing the molecular structure of amorphous carbon to a fullerene-like structure and a graphitized carbon structure with a lubricating effect.

[0040] In some embodiments, the concentration of the magnetic metal oxide is 0.1-3 g / L.

[0041] In some embodiments, the hydrothermal reaction time is 3-6 h.

[0042] In some embodiments, the specific steps of dispersing the carbon microspheres and graphene oxide into water according to a set mass ratio, and separating the solid particles after reaction are as follows:

[0043] The carbon microspheres and graphene oxide are dispersed into water according to a mass ratio of 0.1-10:1, and stirred at 50-80℃ for a set time. After the reaction is completed, the solid particles are separated. Too many or too few carbon microspheres added on the graphene oxide nanosheet are not conducive to the friction reduction performance of the nanocomposite. After a large number of experiments, it is found that when the mass ratio of carbon microspheres to graphene oxide is 0.1-10:1, the friction reduction performance is optimal.

[0044] In some embodiments, the stirring time is 5-12 h.

[0045] In some embodiments, the specific steps of calcining the solid particles to obtain a spherical sheet composite carbon-based micro-nano material lubricating oil additive are as follows:

[0046] The solid particles are placed in a tube furnace, a protective atmosphere is introduced, and calcination is carried out at 300-1000℃ for 1-5 h to obtain a spherical sheet composite carbon-based micro-nano material lubricating oil additive. Among them, the protective atmosphere is nitrogen.

[0047] The application also discloses a spherical sheet composite carbon-based micro-nano material lubricating oil additive, comprising:

[0048] 0.1-10 parts of carbon microspheres and 1 part of graphene oxide by weight;

[0049] Among them, the magnetic metal oxide contained in the carbon microspheres accounts for 22-32% of the total weight of the carbon microspheres.

[0050] In some embodiments, the structure of the spherical sheet composite carbon-based micro-nano material lubricating oil additive is graphene oxide nanosheet loaded with carbon microspheres containing magnetic metal oxide;

[0051] The graphene oxide nanosheet has a sheet diameter of 0.5-5 μm and a thickness of 0.8-1.2 nm.

[0052] The carbon microspheres have a diameter of 50-150 nm and a shell thickness of 5-30 nm.

[0053] Through control of the process combination of the above preparation process, the spherical sheet composite carbon-based micro-nano material lubricating oil additive with excellent friction reduction performance is finally obtained.

[0054] Example 1

[0055] Take 1.6 mol / L glucose aqueous solution, add 1.12 g of zinc ferrite, and after sufficient stirring, transfer the mixed solution to a hydrothermal reaction kettle, and after hydrothermal reaction at 175℃ for 4 h, magnetically separate to obtain carbon microspheres containing magnetic metal oxides;

[0056] Disperse the carbon microspheres and graphene oxide into water according to a mass ratio of 5.5:1, and stir and react at 65℃ for 8 h, and after the reaction is completed, separate the solid-phase microparticles;

[0057] Place the solid-phase microparticles in a tube furnace, introduce nitrogen, and calcine at 680℃ for 2 h to obtain the spherical sheet composite carbon-based micro-nano material lubricating oil additive.

[0058] Add the prepared spherical sheet composite carbon-based micro-nano material to the lubricating oil base oil according to a certain amount to prepare a lubricating oil containing 0.02wt% carbon-based micro-nano material. The MGV-001 diesel lubricating performance evaluation tester is used to investigate the friction reduction performance (test conditions: sliding speed of 0.10 m / s, frequency of 50 Hz, stroke of 1000 μm, and time of 30 min). Raman spectroscopy is used to characterize the carbon structure change of the prepared spherical sheet composite carbon-based micro-nano material before and after friction.

[0059] The experimental results show that, as shown in Figure 1 the spherical sheet composite carbon-based micro-nano material as a friction reduction additive can significantly reduce the friction coefficient of the lubricating oil at the friction interface, and can reduce the friction coefficient by an order of magnitude (about 90%) at multiple time periods during the friction process, such as at 450 s, the friction coefficient of the base oil is 0.24, and the friction coefficient of the lubricating oil containing the spherical sheet composite carbon-based micro-nano material is 0.025, which reflects excellent friction reduction performance. As shown in Figure 2 From the Raman spectrum, the D characteristic peak of the carbon-based micro-nano composite material after friction becomes wider, and the G characteristic peak of the graphitized carbon becomes stronger, which means that the fullerene-like structure in the carbon-based micro-nano material after friction increases significantly, which indicates that the crystal structure of the carbon microspheres will continuously improve the friction reduction performance through the transformation to the fullerene-like structure under the catalysis of the magnetic metal oxides during the friction process. As shown in Figure 3As shown, carbon microspheres loaded with magnetic metal oxides in graphene oxide nanosheets can be seen, the diameter of the magnetic metal oxides is 20-50 nm, the diameter of the carbon microspheres is 50-150 nm, and the shell thickness is 5-30 nm.

[0060] Example 2

[0061] Take 1.6 mol / L of glucose aqueous solution, add 1.12 g of zinc ferrite, and after fully stirring, transfer the mixed solution to a hydrothermal reaction kettle, hydrothermal reaction at 185℃ for 4h, and then magnetically separate to obtain carbon microspheres containing magnetic metal oxides;

[0062] Disperse the carbon microspheres and graphene oxide into water according to a mass ratio of 7:1, stir and react at 70℃ for 12h, and then separate the solid particles after the reaction is completed;

[0063] Place the solid particles in a tube furnace, introduce nitrogen, and calcine at 800℃ for 1h to obtain a spherical sheet composite carbon-based micro-nano material lubricating oil additive.

[0064] Example 3

[0065] Take 1.6 mol / L of glucose aqueous solution, add 1.12 g of zinc ferrite, and after fully stirring, transfer the mixed solution to a hydrothermal reaction kettle, hydrothermal reaction at 180℃ for 3.5h, and then magnetically separate to obtain carbon microspheres containing magnetic metal oxides;

[0066] Disperse the carbon microspheres and graphene oxide into water according to a mass ratio of 4.5:1, stir and react at 70℃ for 7h, and then separate the solid particles after the reaction is completed;

[0067] Place the solid particles in a tube furnace, introduce nitrogen, and calcine at 750℃ for 1.5h to obtain a spherical sheet composite carbon-based micro-nano material lubricating oil additive.

[0068] Example 4

[0069] Take 1.6 mol / L of glucose aqueous solution, add 1.12 g of zinc ferrite, and after fully stirring, transfer the mixed solution to a hydrothermal reaction kettle, hydrothermal reaction at 170℃ for 5h, and then magnetically separate to obtain carbon microspheres containing magnetic metal oxides;

[0070] Disperse the carbon microspheres and graphene oxide into water according to a mass ratio of 0.1:1, stir and react at 75℃ for 6h, and then separate the solid particles after the reaction is completed;

[0071] Place the solid particles in a tube furnace, introduce nitrogen, and calcine at 500℃ for 4h to obtain a spherical sheet composite carbon-based micro-nano material lubricating oil additive.

[0072] Example 5

[0073] Take 1.6mol / L glucose aqueous solution, add 1.12g of zinc ferrite, stir thoroughly, then transfer the mixed solution to a hydrothermal reaction kettle, hydrothermal reaction at 200℃ for 3h, then magnetic separation to obtain carbon microspheres containing magnetic metal oxides;

[0074] Disperse the carbon microspheres and graphene oxide into water according to a mass ratio of 10:1, stir and react at 70℃ for 8h, then separate the solid particles after the reaction is completed;

[0075] Place the solid particles in a tube furnace, pass nitrogen, calcine at 1000℃ for 5h, to obtain a spherical sheet composite carbon-based micro-nano material lubricating oil additive.

[0076] The spherical sheet composite carbon-based micro-nano material lubricating oil additive and the preparation method thereof provided in the application, the carbon microspheres contain magnetic metal oxides in the interior, which can continuously improve the friction-reducing performance of the carbon-based micro-nano material by changing the crystal structure of the carbon microspheres during the friction process, and the friction coefficient can be significantly reduced by one order of magnitude (about 90%) in multiple time periods during the friction process; the spherical sheet composite carbon-based micro-nano material lubricating oil additive is easy to recycle by magnetic separation, and has the advantages of energy saving, environmental protection, high economic value and easy industrialization.

[0077] Although the application has been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that the technical solutions recorded in the foregoing embodiments can still be modified, or some technical features can be replaced by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the application.

Claims

1. A preparation method of a spherical sheet composite type carbon-based micro-nano material lubricating oil additive, characterized by, The method comprises the following steps: The specific steps of adding a set amount of magnetic metal oxide into the glucose aqueous solution and obtaining the carbon microspheres containing the magnetic metal oxide after hydrothermal reaction are as follows: The glucose aqueous solution with a concentration of 1.6-2.5 mol / L is taken, a set amount of magnetic metal oxide is added, and the mixed solution is transferred into a hydrothermal reactor after being fully stirred, and then the carbon microspheres containing the magnetic metal oxide are obtained by magnetic separation after hydrothermal reaction at 150-185 ℃ for a set time. The specific steps of dispersing the carbon microspheres and graphene oxide into water according to a set mass ratio and then separating the solid particles after reaction are as follows: The carbon microspheres and graphene oxide are dispersed into water according to a mass ratio of 4.5-10:1, and the solid particles are obtained after reaction at 50-80 ℃ for a set time. The specific steps of calcining the solid particles to obtain the spherical sheet composite carbon-based micro-nano material lubricating oil additive are as follows: The solid particles are placed in a tube furnace, a protective atmosphere is introduced, and the spherical sheet composite carbon-based micro-nano material lubricating oil additive is obtained after calcination at 680-800 ℃ for 1-5 h. The structure of the spherical sheet composite carbon-based micro-nano material lubricating oil additive is that the carbon microspheres containing the magnetic metal oxide are loaded on the graphene oxide nanosheets. The spherical sheet composite carbon-based micro-nano material lubricating oil additive comprises 4.5-10 parts of carbon microspheres and 1 part of graphene oxide by weight. The magnetic metal oxide contained in the carbon microspheres accounts for 22-32% of the total weight of the carbon microspheres. The flake diameter of the graphene oxide nanosheet is 0.5-5 μm, and the thickness is 0.8-1.2 nm. The diameter of the carbon microspheres is 50-150 nm, and the shell thickness is 5-30 nm. The magnetic metal oxide is spherical with a diameter of 20-50 nm.

2. The preparation method of the ball sheet composite type carbon-based micro-nano material lubricating oil additive according to claim 1, characterized in that, The magnetic metal oxide is one or a combination of several of ferric oxide, zinc ferrite, cobalt ferrite, nickel ferrite, cobalt-iron-nickel oxide, and zinc-iron-nickel oxide.

3. The preparation method of the ball sheet composite type carbon-based micro-nano material lubricating oil additive according to claim 1, characterized in that, The concentration of the magnetic metal oxide is 0.1-3 g / L.

4. The preparation method of the spherical sheet composite type carbon-based micro-nano material lubricating oil additive according to claim 1, characterized in that, The hydrothermal reaction time is 3-6 h.

5. The preparation method of the spherical sheet composite type carbon-based micro-nano material lubricating oil additive according to claim 1, characterized in that, The stirring time is 5-12 h.

6. A kind of ball piece composite type carbon-based micro-nano material lubricating oil additive, by the preparation method of the ball piece composite type carbon-based micro-nano material lubricating oil additive described in claim 1 is prepared, it is characterized in that, The method comprises: The spherical sheet composite carbon-based micro-nano material lubricating oil additive comprises 4.5-10 parts of carbon microspheres and 1 part of graphene oxide by weight. The magnetic metal oxide contained in the carbon microspheres accounts for 22-32% of the total weight of the carbon microspheres. The structure of the spherical sheet composite carbon-based micro-nano material lubricating oil additive is that the carbon microspheres containing the magnetic metal oxide are loaded on the graphene oxide nanosheets. The flake diameter of the graphene oxide nanosheet is 0.5-5 μm, and the thickness is 0.8-1.2 nm. The diameter of the carbon microspheres is 50-150 nm, and the shell thickness is 5-30 nm. The magnetic metal oxide is spherical with a diameter of 20-50 nm.

Images