CN112920876A

CN112920876A - SiO based on core-shell structure2Titanium alloy rolling lubricating liquid of @ Graphene quantum dots and preparation method thereof

Info

Publication number: CN112920876A
Application number: CN202110131149.3A
Authority: CN
Inventors: 王伟; 朱羽; 张志波; 张卫强; 吴航兵; 张浩泽; 黄海广; 王萌
Original assignee: Kunming Iron & Steel Holding Co ltd; Xian University of Architecture and Technology; Yunnan Titanium Industry Co Ltd
Current assignee: Kunming Iron & Steel Holding Co ltd; Xian University of Architecture and Technology; Yunnan Titanium Industry Co Ltd
Priority date: 2021-01-30
Filing date: 2021-01-30
Publication date: 2021-06-08
Anticipated expiration: 2041-01-30
Also published as: CN112920876B

Abstract

The invention discloses a SiO based on a core-shell structure₂The titanium alloy rolling lubricating liquid comprises the following components in parts by weight: 1.5-2.5 parts of base oil and 1.5-2.5 parts of SiO₂@ Graphene quantum dot powder, 90-96 parts of deionized water, 0.3-0.7 part of surfactant, 0.8-1.2 parts of dispersant, 0.8-1.2 parts of sulfur-containing additive and 0.5-1.4 parts of antioxidantA curing agent and 0.5-1.4 parts of an auxiliary agent. The preparation method of the titanium alloy rolling lubrication is to apply SiO₂Mixing and stirring the @ Graphene quantum dot powder, base oil and deionized water, carrying out ultrasonic treatment, adding a dispersing agent, a sulfur-containing additive, an antioxidant and an auxiliary agent, and adjusting the pH value to be alkalescent. The invention prepares SiO by a hydrothermal method₂The @ graphene core-shell structure particle takes graphene as a core and takes nano silicon dioxide as a coating shell, and has the characteristics of high temperature resistance, low friction coefficient and good extreme pressure resistance. The rolling lubricating liquid prepared by the invention has the characteristics of excellent performance, lasting efficiency and the like, and can be suitable for the field of titanium alloy ultrathin sheet cold rolling processing.

Description

SiO based on core-shell structure2Titanium alloy rolling lubricating liquid of @ Graphene quantum dots and preparation method thereof

Technical Field

The invention belongs to the technical field of machining lubrication, and particularly relates to SiO based on a core-shell structure₂A titanium alloy rolling lubricating fluid of @ Graphene quantum dots and a preparation method thereof.

Background

When the titanium alloy is deformed by rolling, a large amount of friction heat is easily generated between a roller and a rolled piece, so that the surface of the rolled piece is abraded, and if the lubrication is insufficient, the surface quality of the rolled piece is greatly damaged, and the product quality is reduced.

Graphene as a novel two-dimensional nanomaterial with sp carbon atoms²The hybridized single-layer stacked honeycomb-shaped two-dimensional atomic crystal has a chemical form similar to the surface of a carbon nano tube. The graphene lubricant has the advantages of small shearing force among graphene sheet layers, lower friction coefficient than flake graphite, excellent heat conduction performance and friction resistance, higher melting point, capability of playing a certain lubricating role and the like, has wide application potential in rolling lubrication, however, the common graphene lubricant on the market generally has the defects of higher high-temperature friction coefficient, poorer extreme pressure resistance, more stable chemical property and difficulty in dispersion in a plurality of solvents.

At present, researches prove that the nano particles show excellent tribological properties under the lubrication conditions of high temperature, high load, and the like. The nano silicon dioxide is a common nano material, has good high-temperature performance and high diffusivity, can be used as an additive to be added into grease to improve the extreme pressure wear resistance of a product, and SiO in a lubricating liquid₂Should not be added in excess of SiO₂When the amount exceeds the optimum value, the abrasion resistance is lowered.

Therefore, in order to exert the synergistic effect of silicon dioxide and graphene, the rolling lubricating fluid of the core-shell structure material taking the graphene quantum dots as the core and the nano silicon dioxide as the film-coated shell is developed, so that the tribological performance of the composite particles is more important to be comprehensively improved.

Disclosure of Invention

The first purpose of the invention is to provide SiO₂The quantum dots with the @ Graphene core-shell structure and the preparation method thereof; it is a second object of the present invention to provide SiO₂The application of the @ Graphene core-shell structure quantum dot; the third purpose of the invention is to provide SiO based on a core-shell structure₂A titanium alloy rolling lubricating fluid of @ Graphene quantum dots and a preparation method thereof.

The first object of the present invention is to do soRealized is SiO₂The quantum dot with the core-shell structure is characterized in that the core body of the quantum dot with the core-shell structure is Graphene, and the shell is made of nano silicon dioxide.

The SiO₂The preparation method of the @ Graphene core-shell structure quantum dot comprises the following steps:

1) mixing graphene oxide and polymethyl pyrrolidone, performing ball milling for 35-45h, centrifuging the product obtained by ball milling for 20-40min at 3000rpm 2000-;

2) dissolving ethyl orthosilicate in ethanol, stirring for 2-4h, adding the graphene oxide quantum dot aqueous solution, stirring for 8-12h to obtain a reaction solution, heating in a crucible and evaporating to obtain a crude product, washing the crude product with deionized water and ethanol for 5-8 times, and drying to obtain the SiO with the core-shell structure₂@ Graphene quantum dot powder.

The second object of the invention is achieved in that the SiO of the core-shell structure₂The application of the @ Graphene quantum dots is the application of the @ Graphene quantum dots as a base oil additive in preparation of rolling lubricating fluid.

The third purpose of the invention is realized by the SiO based on the core-shell structure₂The titanium alloy rolling lubricating liquid of the @ Graphene quantum dots comprises the following components in parts by weight: 1.5-2.5 parts of base oil, 1.5-2.5 parts of base oil additive, 90-96 parts of deionized water, 0.3-0.7 part of surfactant, 0.8-1.2 parts of dispersant, 0.8-1.2 parts of sulfur-containing additive, 0.5-1.4 parts of antioxidant and 0.5-1.4 parts of auxiliary agent; wherein the base oil additive is the SiO₂@ Graphene quantum dot powder.

SiO based on core-shell structure₂The preparation method of the titanium alloy rolling lubricating liquid of the @ Graphene quantum dot comprises the step of mixing the SiO₂Mixing and stirring the @ Graphene quantum dot powder, base oil and deionized water, carrying out ultrasonic treatment, adding a dispersing agent, a sulfur-containing additive, an antioxidant and an auxiliary agent, and adjusting the pH value to 7-9 to obtain SiO based on a core-shell structure₂The @ Graphene quantum dot titanium alloy rolling lubricating liquid.

The invention has the beneficial effects that:

1) the invention adopts a hydrothermal method to prepare SiO based on a core-shell structure for the first time₂The @ Graphene quantum dot takes Graphene as a core and takes nano silicon dioxide as a film-coated shell, and has the characteristics of low high-temperature friction coefficient and good extreme pressure resistance.

2) Aiming at the problems of higher high-temperature friction coefficient, poorer extreme pressure resistance and difficult dispersion in a plurality of solvents in the lubricating liquid in the prior art, the invention provides SiO based on a core-shell structure₂The invention discloses a titanium alloy rolling lubricating fluid of @ Graphene quantum dots and a preparation method thereof₂The @ Graphene quantum dot powder replaces the traditional SiO₂Or the graphene oxide powder is used as a base oil additive, ultrasonic dispersion is carried out by adopting ice water bath ultrasonic and cell crusher ultrasonic, and a chemical method is adopted for modification, so that uniform and stable rolling lubricating liquid is obtained. Through test detection, compared with the lubricating liquid in the prior art, the rolling lubricating liquid prepared by the invention has more excellent performance and lasting lubricating performance, has excellent performance in the field of cold rolling of titanium alloy ultrathin plates, and is worthy of further application and popularization.

Drawings

FIG. 1 is a SiO solid core-shell structure prepared in example 12₂A @ Graphene quantum dot schematic;

fig. 2 is a TEM image of graphene oxide quantum dots prepared in example 12;

FIG. 3 is a graph showing a comparison of average friction coefficients of example 12, comparative example 1 and comparative example 2 after a friction test.

FIG. 4 is a graph comparing the wear rates of example 12, comparative example 1 and comparative example 2 after the friction test.

FIG. 5 is a comparison of surface effects of titanium alloy sheets rolled by different rolling liquids, wherein A is a blank, B is a control, C, D parts of comparative example 1 and comparative example 2, respectively, and E is example 12.

Detailed Description

The present invention is further illustrated by the following examples, which are not intended to be limiting in any way, and any modifications or alterations based on the teachings of the present invention are intended to fall within the scope of the present invention.

The invention relates to SiO₂The quantum dot with the core-shell structure is characterized in that the core body of the quantum dot with the core-shell structure is Graphene, and the shell is made of nano silicon dioxide.

The SiO of the invention₂The preparation method of the @ Graphene core-shell structure quantum dot comprises the following steps:

In the step 1, the mass ratio of the graphene oxide to the polymethyl pyrrolidone is 10:1-5: 1.

In the step 2, the concentration of the graphene oxide quantum dot aqueous solution is 0.4-0.6%; the volume ratio of the ethyl orthosilicate to the ethanol to the graphene oxide quantum dot aqueous solution is 9-10:9-10: 1-1.05.

In the step 2, the reaction solution is heated in a crucible at the temperature of 140-160 ℃ for 8-10 hours, and the crude product is dried at the temperature of 55-70 ℃ for 10-14 hours.

The graphene oxide is prepared by the following method: mixing 0.1-1.5g of graphite powder with 3-5ml of phosphoric acid and 30-50ml of concentrated sulfuric acid, placing the mixture in an ice water bath, stirring for 15-30min, adding 2-3g of potassium permanganate, continuously stirring for 15-30min, raising the temperature of a system to 65-75 ℃, continuously stirring for 15-25h, stopping heating, adding 20-30ml of 30% hydrogen peroxide solution, washing the product with 5% hydrochloric acid (HCl) solution and excessive water until the pH value is 6.5-7.5, and finally centrifuging the product to obtain Graphene Oxide (GO).

The SiO with the core-shell structure₂The application of the @ Graphene quantum dots is the application of the @ Graphene quantum dots as a base oil additive in preparation of rolling lubricating fluid.

The invention relates to SiO based on a core-shell structure₂The titanium alloy rolling lubricating liquid of the @ Graphene quantum dots comprises the following components in parts by weight: 1.5-2.5 parts of base oil, 1.5-2.5 parts of base oil additive, 90-96 parts of deionized water, 0.3-0.7 part of surfactant, 0.8-1.2 parts of dispersant, 0.8-1.2 parts of sulfur-containing additive, 0.5-1.4 parts of antioxidant and 0.5-1.4 parts of auxiliary agent; wherein the base oil additive is the SiO₂@ Graphene quantum dot powder.

The base oil is one or more of triethanolamine, glycerol, neopentyl alcohol, coconut oil and castor oil; the surfactant is one or more of sodium dodecyl sulfate, Span-80, oleic acid and sorbitol; the dispersing agent is polyvinylpyrrolidone; the sulfur-containing additive is sulfurized olefin; the antioxidant is an amine antioxidant, and the auxiliary agent is a phenol antioxidant with molecular weight more than 400.

The amine antioxidant is one or the combination of more of N-phenyl-alpha naphthylamine, diphenylamine, naphthylamine or p-phenylenediamine.

The phenolic antioxidant with the molecular weight of more than 400 is styrenated phenol or bis (3, 5-di-tert-butyl-4-hydroxyphenyl) thioether or a composition thereof.

The SiO based on the core-shell structure₂The preparation method of the titanium alloy rolling lubricating liquid of the @ Graphene quantum dot comprises the step of mixing the SiO₂Mixing and stirring the @ Graphene quantum dot powder, base oil and deionized water, carrying out ultrasonic treatment, adding a dispersing agent, a sulfur-containing additive, an antioxidant and an auxiliary agent, and adjusting the pH value to 7-9 to obtain SiO based on a core-shell structure₂The @ Graphene quantum dot titanium alloy rolling lubricating liquid.

The present invention is further illustrated by the following examples.

Example 1

1) 0.5g of graphite powder was mixed with 3ml of phosphoric acid (H)₃PO₄) And 30ml of concentrated sulfuric acid (H)₂SO₄) And (4) mixing. The mixture was cooled to 0 ℃ in an ice bath and stirred for 15 min. Subsequently, 2g of potassium permanganate (KMnO)₄) Slowly poured into the above solution and stirred at 0 deg.C for 15 min. Thereafter, the temperature of the system was raised to 65 ℃ and stirring was continued for 15 hours. Then 20ml of 30% hydrogen peroxide (H) will be contained₂O₂) Hydrogen peroxide (g) was added to the mixture and washed with 5% hydrochloric acid (HCl) solution and excess water until the filtrate PH was 6.5. And finally, centrifuging the product to obtain Graphene Oxide (GO).

2) Adding graphene oxide and polymethyl pyrrolidone (NMP) into a hard steel ball milling tank according to the mass ratio of 10:1, taking out after ball milling for 35h, centrifuging the product at 2000rpm for 20 min, extracting supernatant, centrifuging the supernatant at 10000rpm for 20 min to obtain a precipitate, and repeatedly washing with deionized water for 3 times to obtain a 0.5% graphene oxide quantum dot aqueous solution, wherein as shown in figure 2, most of graphene oxide can be seen to be smaller than 5nm in size and uniformly dispersed in the aqueous solution.

(3) Dissolving the same volume of Tetraethoxysilane (TEOS) in ethanol, stirring at room temperature for 2 hours, then adding 1/10 graphene oxide quantum dot aqueous solution with the concentration of 0.4% of the volume of tetraethoxysilane, and continuously stirring at constant temperature for 8 hours. Then, the mixed solution was placed in a crucible and heated at 140 ℃ for 8 hours. When the crucible was cooled to room temperature, the product was taken out and washed 5 times with deionized water and ethanol to remove impurities. Finally, drying the sample at 55 ℃ for 10h to obtain SiO with a core-shell structure₂The structure of the @ Graphene powder is schematically shown in figure 1.

Example 2

1) 0.8g of graphite powder was mixed with 4ml of phosphoric acid (H)₃PO₄) And 40ml of concentrated sulfuric acid (H)₂SO₄) And (4) mixing. The mixture was cooled to 0 ℃ in an ice bath and stirred for 25 min. Subsequently, 2.5g of potassium permanganate (KMnO)₄) Slowly poured into the above solution and stirred at 0 deg.C for 25 min. Thereafter, the temperature of the system was raised to 70 ℃ and stirring was continued for 20 hours. Then 25ml of 30% hydrogen peroxide (H) will be contained₂O₂) Hydrogen peroxide (g) was added to the mixture and washed with 5% hydrochloric acid (HCl) solution and excess water until the filtrate was almost neutral. Finally, the product was centrifuged and Graphene Oxide (GO) was obtained.

2) Adding graphene oxide and polymethyl pyrrolidone (NMP) into a hard steel ball milling tank according to the mass ratio of 7:1, taking out after ball milling for 40h, centrifuging the product at 3000rpm for 30min, extracting supernatant, centrifuging the supernatant at 11000rpm for 30min to obtain a precipitate, and repeatedly washing with deionized water for 4 times to obtain a 0.5% graphene oxide quantum dot aqueous solution.

(3) Dissolving the same volume of Tetraethoxysilane (TEOS) in ethanol, stirring at room temperature for 3 hours, then adding 1/10 graphene oxide quantum dot aqueous solution with the concentration of 0.5 percent of the volume of tetraethoxysilane, and continuously stirring at constant temperature for 10 hours. Then, the mixed solution was placed in a crucible and heated at 150 ℃ for 9 hours. When the crucible was cooled to room temperature, the product was taken out and washed 6 times with deionized water and ethanol to remove impurities. Finally, drying the sample at 0 ℃ for 12h to obtain SiO with the core-shell structure₂The structure of the @ Graphene powder is schematically shown in figure 1.

Example 3

1) 1.5g of graphite powder was mixed with 5ml of phosphoric acid (H)₃PO₄) And 50ml of concentrated sulfuric acid (H)₂SO₄) And (4) mixing. The mixture was cooled to 0 ℃ in an ice bath and stirred for 30 min. Subsequently, 3g of potassium permanganate (KMnO)₄) Slowly poured into the above solution and stirred at 0 deg.C for 30 min. Thereafter, the temperature of the system was raised to 75 ℃ and stirring was continued for 25 hours. Then 30ml of 30% hydrogen peroxide (H) will be contained₂O₂) Hydrogen peroxide (g) was added to the mixture and washed with 5% hydrochloric acid (HCl) solution and excess water until the filtrate was almost neutral. Finally, the product was centrifuged and Graphene Oxide (GO) was obtained.

2) Adding graphene oxide and polymethyl pyrrolidone (NMP) into a hard steel ball milling tank according to the mass ratio of 5:1, taking out after ball milling for 45 hours, centrifuging the product at 3000rpm for 40 minutes, extracting supernatant, centrifuging the supernatant at 12000rpm for 40 minutes to obtain a precipitate, and repeatedly washing with deionized water for 5 times to obtain a 0.5% graphene oxide quantum dot aqueous solution.

(3) Dissolving the same volume of Tetraethoxysilane (TEOS) in ethanol, stirring at room temperature for 3 hours, then adding 1/10 graphene oxide quantum dot aqueous solution with the concentration of 0.5 percent of the volume of tetraethoxysilane, and continuously stirring at constant temperature for 12 hours. Then, the mixed solution was placed in a crucible and heated at 160 ℃ for 10 hours. When the crucible was cooled to room temperature, the product was taken out and washed 8 times 6 times with deionized water and ethanol to remove impurities. Finally, drying the sample at 70 ℃ for 14h to obtain SiO with a core-shell structure₂The structure of the @ Graphene powder is schematically shown in figure 1.

Example 4

SiO based on core-shell structure₂The titanium alloy rolling lubricating liquid of the @ Graphene quantum dot comprises 0.4 part of triethanolamine, 0.4 part of glycerol, 0.3 part of neopentyl alcohol, 0.4 part of coconut oil, 0.5 part of castor oil, 93 parts of deionized water and 2 parts of SiO with a core-shell structure₂The material comprises the following components of @ Graphene quantum dot powder, 0.5 part of sodium dodecyl sulfate, 1 part of sulfurized olefin, 1.2 parts of diphenylamine, 1 part of styrenated phenol and 1 part of polyvinylpyrrolidone.

Example 5

SiO based on core-shell structure₂The titanium alloy rolling lubricating liquid of the @ Graphene quantum dot comprises 0.3 part of triethanolamine, 0.3 part of glycerol, 0.3 part of neopentyl alcohol, 0.3 part of coconut oil, 0.4 part of castor oil, 90 parts of deionized water and 1.5 parts of SiO with a core-shell structure₂@ Graphene quantum dot powder, 0.3 part of sodium dodecyl sulfate, 0.8 part of sulfurized olefin, 1 part of naphthylamine, 1 part of bis (3, 5-di-tert-butyl-4-hydroxyphenyl) sulfide and 0.8 part of polyvinylpyrrolidone.

Example 6

SiO based on core-shell structure₂The titanium alloy rolling lubricating liquid of the @ Graphene quantum dot comprises 0.5 part of triethanolamine, 0.5 part of glycerol, 0.5 part of neopentyl alcohol, 0.6 part of coconut oil, 0.4 part of castor oil, 96 parts of deionized water and 2.5 parts of SiO with a core-shell structure₂@ Graphene quantum dot powder, 0.7 part of sodium dodecyl sulfate, 1.2 parts of sulfurized olefin, 0.8 part of naphthylamine and 0.5 part ofStyrenated phenol and 1.2 parts polyvinylpyrrolidone.

Example 7

SiO based on core-shell structure₂The titanium alloy rolling lubricating liquid of the @ Graphene quantum dot comprises 1.5 parts of triethanolamine oil and 1.6 parts of SiO₂The following raw materials include @ Graphene quantum dot powder, 91 parts of deionized water, 0.3 part of Span-80, 0.8 part of sulfurized olefin, 0.5 part of N-phenyl-alpha naphthylamine, 0.5 part of bis (3, 5-di-tert-butyl-4-hydroxyphenyl) thioether and 1 part of polyvinylpyrrolidone.

Example 8

SiO based on core-shell structure₂The titanium alloy rolling lubricating liquid of the @ Graphene quantum dot comprises 1.5 parts of triethanolamine oil, 1 part of glycerol and 1.8 parts of SiO₂The material comprises the following components of @ Graphene quantum dot powder, 92 parts of deionized water, 0.3 part of Span-80, 1.3 parts of sulfurized olefin, 0.9 part of phenothiazine, 1.1 part of bis (3, 5-di-tert-butyl-4-hydroxyphenyl) thioether and 0.9 part of polyvinylpyrrolidone.

Example 9

SiO based on core-shell structure₂The titanium alloy rolling lubricating liquid of the @ Graphene quantum dot comprises 1 part of triethanolamine oil, 0.7 part of castor oil and 2.2 parts of SiO₂@ Graphene quantum dot powder, 94 parts of deionized water, 0.4 part of sorbitol, 1.2 parts of sulfurized olefin, 0.6 part of p-phenylenediamine, 0.3 part of styrenated phenol, 0.9 part of bis (3, 5-di-tert-butyl-4-hydroxyphenyl) sulfide and 1.1 part of polyvinylpyrrolidone.

Example 10

SiO based on core-shell structure₂The titanium alloy rolling lubricating liquid of @ Graphene quantum dots comprises 0.8 part of neopentyl alcohol, 0.9 part of coconut oil and 1.5 parts of SiO₂@ Graphene quantum dot powder, 95 parts of deionized water, 0.3 part of oleic acid, 0.9 part of sulfurized olefin, 0.8 part of naphthylamine, 0.6 part of N-phenyl-alpha naphthylamine, 0.6 part of bis (3, 5-di-tert-butyl-4-hydroxyphenyl) thioether, 0.7 part of styrenated phenol and 1.2 parts of polyvinylpyrrolidone.

Example 11

SiO based on core-shell structure₂The titanium alloy rolling lubricating liquid of the @ Graphene quantum dot comprises 1.2 parts of neopentyl alcohol, 1.3 parts of castor oil and 1.3 parts of SiO₂@Graphene quantum dot powder, 94 parts of deionized water, 0.3 part of sorbitol, 0.9 part of sulfurized olefin, 0.6 part of p-phenylenediamine, 0.5 part of N-phenyl-alpha naphthylamine, 0.7 part of bis (3, 5-di-tert-butyl-4-hydroxyphenyl) thioether, 0.7 part of styrenated phenol and 1.2 parts of polyvinylpyrrolidone.

Example 12

According to the lubricating fluid formulation of example 4, 0.4 part of triethanolamine, 0.4 part of glycerin, 0.3 part of neopentyl alcohol, 0.4 part of coconut oil, and 0.5 part of castor oil were mixed, and 93 parts of deionized water was added to obtain a base oil, and then 2 parts of SiO having a core-shell structure were added₂@ Graphene powder, stirred and sonicated. 0.5 part of sodium dodecyl sulfate is added to modify the primary emulsion so that the primary emulsion is uniformly dispersed. Finally, sequentially adding 1 part of sulphurated olefin, 1.2 parts of diphenylamine, 1 part of styrenated phenol and 1 part of polyvinylpyrrolidone, adjusting the pH to 7, and finally obtaining SiO based on the core-shell structure₂The @ Graphene quantum dot titanium alloy rolling lubricating liquid.

Example 13

According to the lubricating fluid formulation of example 5, 0.3 part of triethanolamine, 0.3 part of glycerin, 0.3 part of neopentyl alcohol, 0.3 part of coconut oil, and 0.4 part of castor oil were mixed, 90 parts of deionized water was added to obtain a base oil, and then 1.5 parts of SiO having a core-shell structure was added₂@ Graphene powder, stirred and sonicated. 0.3 part of sodium dodecyl sulfate is added to modify the primary emulsion so that the primary emulsion is uniformly dispersed. Finally, 1 part of sulphurated olefin, 1 part of naphthylamine, 1 part of bis (3, 5-di-tert-butyl-4-hydroxyphenyl) thioether and 0.8 part of polyvinylpyrrolidone are sequentially added, the pH value is adjusted to 8, and finally the SiO based on the core-shell structure is obtained₂The @ Graphene quantum dot titanium alloy rolling lubricating liquid.

Example 14

According to the lubricating fluid formulation of example 6, 0.5 part of triethanolamine, 0.5 part of glycerin, 0.5 part of neopentyl alcohol, 0.6 part of coconut oil, and 0.4 part of castor oil were mixed, 96 parts of deionized water was added to obtain a base oil, and then 2.5 parts of SiO having a core-shell structure was added₂@ Graphene powder, stirred and sonicated. 0.7 part of sodium dodecyl sulfate is added to modify the primary emulsion so as to lead the primary emulsion to be dispersed evenlyAnd (4) homogenizing. Finally, 1.2 parts of sulphurated olefin, 1.4 parts of naphthylamine, 1.2 parts of styrenated phenol and 1.2 parts of polyvinylpyrrolidone are sequentially added, the pH is adjusted to 9, and finally the SiO based on the core-shell structure is obtained₂The @ Graphene quantum dot titanium alloy rolling lubricating liquid.

Comparative example 1

SiO (silicon dioxide)₂Rolling lubricant was prepared in the same manner as in example 12 except that the base oil additive and the other components were the same as in example 12, in which SiO was used as a reference₂The particles act as base oil additives.

Comparative example 2

SiO (silicon dioxide)₂Rolling lubricant was prepared in the same manner as in example 12 except that the base oil additive and other components were the same as in example 12, and in this comparative example, SiO was not contained₂The coated graphene oxide powder is used as a base oil additive.

Test example 1: lubricating fluid friction performance testing

The friction performance of the lubricating fluid prepared in example 12 is measured and compared with comparative examples 1 and 2 by taking example 12 as an example.

The test method comprises the following steps: the friction wear performance test of the prepared lubricating fluid was investigated using a friction wear tester to test example 1, comparative example 1 and comparative example 2 with reference to national standards.

Steel ball material used in the test: GCr15 steel, 4mm in diameter.

The test conditions are as follows: the main shaft rotating speed is 150r/min, the testing force is 5N, the testing time is 30 minutes, and the testing temperature is 20 ℃.

And (3) detection results:

as shown in FIGS. 3 and 4, SiO prepared in example 12₂The lubricant with the @ Graphene core-shell structure quantum dots has excellent and lasting lubricating performance, and utilizes SiO₂After friction test is carried out on the lubricant rolling fluid of the @ Graphene core-shell structure quantum dot, the friction coefficient is lower, the average friction coefficient is 0.31, the surface wear loss is smaller, and the wear rate is 40 multiplied by 10^-6mm³/N·m。

Friction test Using the Rolling lubricating fluid of comparative example 1The average friction coefficient after the test was 0.44, which was higher than that of example 1, the surface wear amount was also larger than that of example 12, and the wear rate was 60X 10^-6mm³/N·m。

The rolling lubricant of comparative example 2 was used in a friction test, and the average friction coefficient was 0.52, which was higher than that of example 12, the surface wear amount was also larger than that of example 12, and the wear rate was 75X 10^-6mm³/N·m。

In conclusion, the SiO prepared by the invention₂The friction coefficient and the surface wear loss of the lubricating fluid of the @ Graphene core-shell structure quantum dot are lower than those of the prior art.

Test example 2 comparison of Rolling Effect of different lubricating oils

The test method comprises the following steps: the annealed TC4 sheet was selected as the test material, with an original dimension of 100 × 30mm and a total reduction of 50%. And (3) performing multi-pass rolling by using a two-roll mill, wherein the diameter of the roll is 130mm, the length of the roll is 260 mm, and the rolling speed is 13 r/min. And comparing the surface quality of the titanium alloy ultrathin plates rolled under different lubricating liquids.

The surface quality of the rolled titanium alloy sheets obtained by using the group without the lubricant as a blank and the group of the base oil of example 12 as a control, and the groups of comparative example 12, comparative example 1, comparative example 2, and the blank and the control are shown in FIG. 5.

And (4) analyzing results: as can be seen from FIG. 5, example 12 of the present invention is based on SiO₂Compared with other groups, the titanium alloy plate rolled by the rolling lubricating liquid of the @ Graphene quantum dot has serious surface cracking and obvious cracks (figure 5A) after no-lubrication rolling; after the base liquid lubrication rolling, cracks still generated (FIG. 5B) through G0 and SiO₂The specific surface of the lubricated plate is reduced compared to the cracks, and smooth areas are generated (fig. 5C and D); when added on the basis of SiO₂In the rolling lubricating fluid of the @ Graphene quantum dot, the surface of the plate is basically free of cracks, the surface is flat and tends to be smooth (FIG. 5E), and the description shows that SiO₂The rolling lubricating fluid of the @ Graphene quantum dots has good lubricating property, and the wear resistance of the plate is improved.

Claims

1. SiO (silicon dioxide)₂The @ Graphene core-shell structure quantum dot is characterized in that a core body of the core-shell structure quantum dot is Graphene, and a shell is made of nano silicon dioxide.

2. SiO as claimed in claim 1₂The preparation method of the @ Graphene core-shell structure quantum dot is characterized by comprising the following steps:

3. SiO as claimed in claim 2₂The preparation method of the @ Graphene quantum dot core-shell structure is characterized in that in the step 1, the mass ratio of the Graphene oxide to the polymethyl pyrrolidone is 10:1-5: 1.

4. SiO as claimed in claim 2₂The preparation method of the @ Graphene quantum dot core-shell structure is characterized in that in the step 2, the concentration of the Graphene oxide quantum dot aqueous solution is 0.4-0.6%; the volume ratio of the ethyl orthosilicate to the ethanol to the graphene oxide quantum dot aqueous solution is 9-10:9-10: 1-1.05.

5. SiO as claimed in claim 2₂The preparation method of the @ Graphene quantum dot core-shell structure is characterized in that in the step 2, the reaction liquid is heated in a crucible at the temperature of 140-160 ℃ for 8-10 hours, and the crude product is dried at the temperature of 55-70 ℃ for 10-14 hours.

6. According to the rightSiO according to claim 2₂The preparation method of the @ Graphene quantum dot core-shell structure is characterized in that the Graphene oxide is prepared by the following method: mixing 0.1-1.5g of graphite powder with 3-5ml of phosphoric acid and 30-50ml of concentrated sulfuric acid, placing the mixture in an ice water bath, stirring for 15-30min, adding 2-3g of potassium permanganate, continuously stirring for 15-30min, raising the temperature of a system to 65-75 ℃, continuously stirring for 15-25h, stopping heating, adding 20-30ml of 30% hydrogen peroxide solution, washing the product with 5% hydrochloric acid (HCl) solution and excessive water until the pH value is 6.5-7.5, and finally centrifuging the product to obtain Graphene Oxide (GO).

7. SiO with core-shell structure as claimed in claim 1₂The application of the @ Graphene quantum dots as the base oil additive in the preparation of rolling lubricating fluid.

8. SiO based on core-shell structure₂The titanium alloy rolling lubricating liquid of the @ Graphene quantum dots is characterized by comprising the following components in parts by weight: 1.5-2.5 parts of base oil, 1.5-2.5 parts of base oil additive, 90-96 parts of deionized water, 0.3-0.7 part of surfactant, 0.8-1.2 parts of dispersant, 0.8-1.2 parts of sulfur-containing additive, 0.5-1.4 parts of antioxidant and 0.5-1.4 parts of auxiliary agent; wherein the base oil additive is the SiO of claim 1₂@ Graphene quantum dot powder.

9. SiO based on core-shell structure according to claim 8₂The titanium alloy rolling lubricating liquid of the @ Graphene quantum dots is characterized in that the base oil is one or more of triethanolamine, glycerol, neopentyl alcohol, coconut oil and castor oil; the surfactant is one or more of sodium dodecyl sulfate, Span-80, oleic acid and sorbitol; the dispersing agent is polyvinylpyrrolidone; the sulfur-containing additive is sulfurized olefin; the antioxidant is an amine antioxidant; the auxiliary agent is a phenol antioxidant with molecular weight more than 400.

10. SiO based on core-shell structure according to claim 8₂Method for rolling titanium alloy lubricating liquid with @ Graphene quantum dotsThe preparation method is characterized in that the SiO is mixed₂Mixing and stirring the @ Graphene quantum dot powder, base oil and deionized water, carrying out ultrasonic treatment, adding a dispersing agent, a sulfur-containing additive, an antioxidant and an auxiliary agent, and adjusting the pH value to 7-9 to obtain SiO based on a core-shell structure₂The @ Graphene quantum dot titanium alloy rolling lubricating liquid.