Method for simultaneously and stably dispersing spherical nanoparticles in oil medium by using layered nanosheets and application thereof

Abstract

Provided are a method for simultaneously and stably dispersing spherical nanoparticles in an oil medium by using layered nanosheets and an application thereof. The method comprises: (1) mixing the layered nanosheets and oil-soluble alkylamines to obtain a first mixture containing intercalated/exfoliated nano sheets; (2) mixing spherical nanoparticles and the oil medium to obtain a second mixture; and (3) mixing the first mixture, the second mixture and the oil medium to obtain a third mixture.

Claims

1. A method for simultaneously and stably dispersing spherical nanoparticles in an oil medium by using layered nanosheets, comprising: mixing the layered nanosheets and oil-soluble alkylamines to obtain a first mixture where the layered nanosheets are intercalated/exfoliated with the oil-soluble alkylamines; mixing the spherical nanoparticles and the oil medium to obtain a second mixture; and mixing the first mixture, the second mixture and the oil medium to obtain a third mixture where the spherical nanoparticles and the layered nanosheets are stably dispersed; wherein the layered nanosheets are at least one selected from clays, layered double hydroxides, layered disulfide metal salts and layered tungsten acid metal salts.

2. The method according to claim 1, wherein the layered nanosheets and the oil-soluble alkylamines are mixed by means of heat treatment, ultrasonic treatment or mechanical agitation.

3. The method according to claim 1, wherein the layered nanosheets are of a particle size of 10 to 4000 nm.

4. The method according to claim 1, wherein the oil-soluble alkylamines are primary amines, secondary amines, tertiary amines or cyclic amines.

5. The method according to claim 1, wherein the oil-soluble alkylamines are Guerbet primary amines, aliphatic amines or poly-aliphatic amines.

6. The method according to claim 5, wherein the Guerbet primary amines have a structure as shown in formula 1: ##STR00009## wherein R.sub.1 is C.sub.1-20 linear or branched hydrocarbyl.

7. The method according to claim 5, wherein the aliphatic amines have a structure as shown in formula 2: ##STR00010## wherein R.sub.2 is C.sub.4-20 linear or branched hydrocarbyl; R.sub.3 and R.sub.4 each are independently H, CH.sub.3, or CH.sub.2CH.sub.3, preferably H or CH.sub.3.

8. The method according to claim 7, wherein the aliphatic amines comprise unsaturated aliphatic primary amines containing CC.

9. The method according to claim 8, wherein the aliphatic amines are at least one selected from a group consisting of the following primary amines: oleic amine, petroselinic amine, erucic amine, linoleic amine, linolenic amine, ricinoleic amine, 10-undecylenic amine, calendic amine, vernolic amine, santalbic amine, 5-eicosenoic amine, -eleostearic amine, punicic amine, Hoffman degradation amine of oleic acid amide, Hoffman degradation amine of petroselinic acid amide, Hoffman degradation amine of erucic acid amide, Hoffman degradation amine of linoleic amide, Hoffman degradation amine of linolenic acid amide, Hoffman degradation amine of ricinoleic acid amide, Hoffman degradation amine of 10-undecylenic acid amide, Hoffman degradation amine of calendic acid amide, Hoffman degradation amine of vernolic acid amide, Hoffman degradation amine of santalbic acid amine, Hoffman degradation amine of 5-eicosenoic acid amide, Hoffman degradation amine of -eleostearic acid amide, and Hoffman degradation amine of punicic acid amide.

10. The method according to claim 5, wherein the poly-aliphatic amines are homopolymers or copolymers of the unsaturated aliphatic primary amines containing CC.

11. The method according to claim 1, wherein the spherical nanoparticles are at least one selected from a group consisting of metal oxide nanoparticles, metal nanoparticles and surface-oxidized metal nanoparticles.

12. The method according to claim 11, wherein the metal oxide nanoparticles are at least one selected from a group consisting of zinc oxide nanoparticles, aluminum oxide nanoparticles, copper oxide nanoparticles, nickel oxide nanoparticles, cobalt oxide nanoparticles, Fe.sub.2O.sub.3 nanoparticles, Fe.sub.3O.sub.4 nanoparticles, magnesium oxide nanoparticles, titanium oxide nanoparticles, zirconia nanoparticles, tungsten oxide nanoparticles, molybdenum oxide nanoparticles and tin oxide nanoparticles.

13. The method according to claim 11, wherein the metal nanoparticles are at least one selected from a group consisting of copper nanoparticles, iron nanoparticles, magnesium nanoparticles, aluminum nanoparticles, titanium nanoparticles, zirconium nanoparticles and tin nanoparticles.

14. The method according to claim 1, wherein the spherical nanoparticles have a particle size of 5 to 1000 nm.

15. The method according to claim 1, wherein in the third mixture, a molar ratio of the layered nanosheets to the oil-soluble alkylamines is 1:1 to 1:40; and a volume ratio of the layered nanosheets to the spherical nanoparticles is 1:0.001 to 1:10.

16. The method according to claim 15, wherein in the third mixture, the molar ratio of the layered nanosheets to the oil-soluble alkylamines is 1:1 to 1:25; and the volume ratio of the layered nanosheets to the spherical nanoparticles is 1:0.01 to 1:5.

17. An oil blend containing both layered nanosheets and spherical nanoparticles prepared by the method according to claim 1.

18. The method according to claim 3, wherein the layered nanosheets are of a particle size of 10 to 3000 nm.

19. The method according to claim 14, wherein the spherical nanoparticles have a particle size of 50 to 800 nm.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a flow chart showing a method for simultaneously and stably dispersing spherical nanoparticles in an oil medium by using layered nanosheets according to an embodiment of the present disclosure;

(2) FIG. 2 is a schematic view showing mechanism of mixing layered nanosheets and oil-soluble alkylamines according to an embodiment of the present disclosure;

(3) FIG. 3 is a schematic view showing mechanism of mixing layered nanosheets, spherical nanoparticles and oil-soluble alkylamines according to an embodiment of the present disclosure;

(4) FIG. 4 is a picture showing different samples of lubricating oil containing base oil added with different additives after 24 hours according to an embodiment of the present disclosure. The samples are respectively shown from left to right: (a) spherical Cu nanoparticles without ligands had been dispersed in the base oil of the lubricating oil; (b) layered -ZrP unmodified by intercalating/exfoliating with oil-soluble alkylamines had been dispersed in the base oil of the lubricating oil; (c) the spherical Cu nanoparticles without ligands and the layered -ZrP unmodified by intercalating/exfoliating with oil-soluble alkylamines had been simultaneously dispersed in the base oil of the lubricating oil; (d) the base oil of the lubricating oil as a blank control group; (e) layered -ZrP modified by intercalating/exfoliating with oleic acid amines and the spherical Cu nanoparticles without ligands had been simultaneously dispersed in the base oil of the lubricating oil;

(5) FIG. 5 is XRD patterns of -ZrP fine powders synthesized by a reflux method at different phosphoric acid concentrations according to an embodiment of the present disclosure;

(6) FIG. 6 is a comparison of XRD patterns between -ZrP fine powders and -ZrP fine powders according to an embodiment of the present disclosure;

(7) FIG. 7 is an electron microscopy image showing -ZrP fine powders synthesized by a reflux method at a phosphoric acid concentration of 3 mol/L according to an embodiment of the present disclosure;

(8) FIG. 8 is a schematic diagram showing mechanism of reciprocating friction test according to an embodiment of the present disclosure;

(9) FIG. 9 is a diagram showing a test result of average friction coefficient <> of the lubricating oil containing different mass fractions of ZrP according to an embodiment of the present disclosure;

(10) FIG. 10 is a diagram showing a test result of maximum friction coefficient (.sub.max) of the lubricating oil containing different mass fractions of ZrP according to an embodiment of the present disclosure;

(11) FIG. 11 is a diagram showing a test result of friction coefficient of lubricating oil when a mass fraction of ZrP is zero according to an embodiment of the present disclosure;

(12) FIG. 12 is a diagram showing a time-friction coefficient curve of lubricating oil when a mass fraction of ZrP is 4.210.sup.4 according to an embodiment of the present disclosure;

(13) FIG. 13 is a diagram showing a time-friction coefficient curve of lubricating oil when a mass fraction of ZrP is 8.410.sup.4 according to an embodiment of the present disclosure;

(14) FIG. 14 is a diagram showing a time-friction coefficient curve of lubricating oil when a mass fraction of ZrP is 12.610.sup.4 according to an embodiment of the present disclosure;

(15) FIG. 15 is a diagram showing a time-friction coefficient curve of lubricating oil when a mass fraction of ZrP is 16.810.sup.4 according to an embodiment of the present disclosure;

(16) FIG. 16 is a diagram showing a time-friction coefficient curve of lubricating oil when a mass fraction of ZrP is 2110.sup.4 according to an embodiment of the present disclosure;

(17) FIG. 17 is a diagram showing a time-friction coefficient curve of lubricating oil when a mass fraction of ZrP is 25.210.sup.4 according to an embodiment of the present disclosure;

(18) FIG. 18 is a diagram showing a time-friction coefficient curve of lubricating oil when a mass fraction of ZrP is zero according to an embodiment of the present disclosure, in which a test ball used in such a step is a test ball obtained after the friction test when a mass fraction of -ZrP is 25.210.sup.4.

DETAILED DESCRIPTION

(19) Reference will be made in detail to embodiments of the present disclosure. The embodiments described herein with reference to drawings are explanatory, illustrative, and used to generally understand the present disclosure. The embodiments shall not be construed to limit the present disclosure. If the specific technology or conditions are not specified in the examples, a step will be performed in accordance with the techniques or conditions described in the literature in the art or the product instructions. If the manufacturers of reagents or instruments are not specified, the reagents or instruments may be commercially available. In a first aspect of the present disclosure, there is provided a method for simultaneously and stably dispersing spherical nanoparticles in an oil medium by using layered nanosheets. According to some embodiments of the present disclosure, with reference to FIG. 1, the method includes a step of (1) mixing the layered nanosheets and oil-soluble alkylamines to obtain a first mixture. The mechanism of mixing layered nanosheets and oil-soluble alkylamines is shown in FIG. 2.

(20) According to an embodiment of the present disclosure, the layered nanosheets and the oil-soluble alkylamines are mixed by means of heat treatment, ultrasonic treatment or mechanical agitation, such that the layered nanosheets and the oil-soluble alkylamines are mixed uniformly in a quick and effective manner.

(21) According to an embodiment of the present disclosure, the layered nanosheets are at least one selected from -zirconium phosphate, -zirconium phosphate, -zirconium phosphate, layered metal phosphates, clays, layered double hydroxides (LDHs), layered disulfide metal salts and layered tungsten acid metal salts. As such, the spherical nanoparticles may interact with the layered nanosheets modified by intercalating efficiently in subsequent steps, so that the layered nanosheets and the spherical nanoparticles can be simultaneously and stably dispersed in the oil medium efficiently, thus obtaining an oil blend exhibiting good stability.

(22) Specifically, -zirconium phosphate (-ZrP, Zr(HPO.sub.4).sub.2.6H.sub.2O) differs from -ZrP merely in term of an interval distance between layers in their chemical structures. In specific, as compared with -ZrP having the interval distance between layers of 7.6 , -ZrP has a wider interval distance between layers of 10.3 to 10.4 . Such a subtle difference comes from the different numbers of H.sub.2O contained in -ZrP (6 H.sub.2O) and -ZrP (1 H.sub.2O). Accordingly, it becomes easier for the intercalating reaction with the increasing interval distance between layers as to -ZrP. After dehydration, -ZrP transforms to -ZrP. The latter enables the intercalated materials to be kept their original physicochemical properties if used as an original host. As such, -ZrP is an ideal host material for the intercalating reaction. Further, comparing with -ZrP and -ZrP, -zirconium phosphate (-ZrP, ZrPO.sub.4(H.sub.2PO.sub.4).2H.sub.2O) has totally different layered crystal structures. -ZrP is a more ideal host material for the intercalating reaction due to its interval distance between layers (12.2 ) wider than either -ZrP or -ZrP. Therefore, -ZrP and -ZrP can be effectively modified by intercalating/exfoliating with oil-soluble alkylamines, so that the spherical nanoparticles can be effectively stabilized in the oil medium, and thus both layered nanosheets and spherical nanoparticles can be simultaneously and stably dispersed in the oil medium.

(23) According to an embodiment of the present disclosure, the layered nanosheets are of a particle size of 10 to 4000 nm, facilitating simultaneous and stable dispersion of the layered nanosheets and the spherical nanoparticles in the oil medium, thereby obtaining an oil blend exhibiting a good stability, and thus avoiding phase separation and sedimentation for a long period.

(24) According to an embodiment of the present disclosure, the layered nanosheets are of a particle size of 10 to 3000 nm, facilitating simultaneous and stable dispersion of the spherical nanoparticles in the oil medium by such layered nanosheets, thereby obtaining an oil blend exhibiting good stability, and thus avoiding phase separation and sedimentation for a long period.

(25) According to embodiments of the present disclosure, types of the oil-soluble alkylamines are not limited specifically. According to some embodiments of the present disclosure, the oil-soluble alkylamines are primary amines, secondary amines, tertiary amines or cyclic amines, so that efficiency of the intercalating reaction between oil-soluble alkylamines and the layered nanosheets is improved effectively, thereby facilitating the simultaneous and stable dispersion of the spherical nanoparticles in the oil medium by so-prepared layered nanosheets.

(26) According to an embodiment of the present disclosure, the oil-soluble alkylamines are Guerbet primary amines, aliphatic amines or poly-aliphatic amines, so that the layered nanosheets and the spherical nanoparticles are well dispersed in the oil medium, thereby avoiding liquid phase separation and nanoparticle sedimentation.

(27) According to an embodiment of the present disclosure, the Guerbet primary amines have a structure as shown in formula 1:

(28) ##STR00005##

(29) wherein R.sub.1 is C.sub.1-20 linear or branched hydrocarbyl.

(30) According to an embodiment of the present disclosure, the aliphatic amines have a structure as shown in formula 2:

(31) ##STR00006##

(32) wherein R.sub.2 is C.sub.4-20 linear or branched hydrocarbyl; R.sub.3 and R.sub.4 each are independently H, CH.sub.3, or CH.sub.2CH.sub.3, preferably H or CH.sub.3.

(33) According to an embodiment of the present disclosure, the aliphatic amines comprise unsaturated aliphatic primary amines containing CC.

(34) According to an embodiment of the present disclosure, the aliphatic amines are at least one selected from a group consisting of the following primary amines: oleic amine, petroselinic amine, erucic amine, linoleic amine, linolenic amine, ricinoleic amine, 10-undecylenic amine, calendic amine, vernolic amine, santalbic amine, 5-eicosenoic amine, -eleostearic amine, punicic amine, Hoffman degradation amine of oleic acid amide, Hoffman degradation amine of petroselinic acid amide, Hoffman degradation amine of erucic acid amide, Hoffman degradation amine of linoleic amide, Hoffman degradation amine of linolenic acid amide, Hoffman degradation amine of ricinoleic acid amide, Hoffman degradation amine of 10-undecylenic acid amide, Hoffman degradation amine of calendic acid amide, Hoffman degradation amine of vernolic acid amide, Hoffman degradation amine of santalbic acid amine, Hoffman degradation amine of 5-eicosenoic acid amide, Hoffman degradation amine of -eleostearic acid amide, and Hoffman degradation amine of punicic acid amide. Structures of above primary amines are shown as follows from up to down. As such, the nanoparticles stabilized by the layered nanosheets are well dispersed in the oil medium, resulting in an oil blend exhibiting good stability.

(35) ##STR00007## ##STR00008##

(36) According to an embodiment of the present disclosure, the poly-aliphatic amines are homopolymers or copolymers of the unsaturated aliphatic primary amines described above, so as to improve the nanoparticles stabilized by the layered nanosheets to be well dispersed in the oil medium, resulting in an oil blend exhibiting good stability.

(37) According to embodiments of the present disclosure, the method includes a step of (2) mixing the spherical nanoparticles and the oil medium to obtain a second mixture.

(38) According to an embodiment of the present disclosure, the spherical nanoparticles and the oil medium are mixed by means of heat treatment, ultrasonic treatment or mechanical agitation, such that the spherical nanoparticles and the oil medium are mixed uniformly in an effective manner.

(39) According to an embodiment of the present disclosure, the spherical nanoparticles are at least one selected from a group consisting of metal oxide nanoparticles, metal nanoparticles and surface-oxidized metal nanoparticles, such that the spherical nanoparticles interact with the layered nanosheets modified by intercalating effectively, thereby avoiding sedimentation when dispersing the nanoparticles in the oil medium.

(40) According to an embodiment of the present disclosure, the oxide nanoparticles are at least one selected from silicon dioxide nanoparticles.

(41) According to an embodiment of the present disclosure, the metal oxide nanoparticles are at least one selected from a group consisting of zinc oxide nanoparticles, aluminum oxide nanoparticles, copper oxide nanoparticles, nickel oxide nanoparticles, cobalt oxide nanoparticles, Fe.sub.2O.sub.3 nanoparticles, Fe.sub.3O.sub.4 nanoparticles, magnesium oxide nanoparticles, titanium oxide nanoparticles, zirconia nanoparticles, tungsten oxide nanoparticles, molybdenum oxide nanoparticles and tin oxide nanoparticles, such that the spherical nanoparticles interact with the layered nanosheets modified by intercalating efficiently, thereby avoiding sedimentation when dispersing the nanoparticles in the oil medium.

(42) According to an embodiment of the present disclosure, the metal nanoparticles are at least one selected from a group consisting of copper nanoparticles, iron nanoparticles, magnesium nanoparticles, aluminum nanoparticles, titanium nanoparticles, zirconium nanoparticles and tin nanoparticles, such that the spherical nanoparticles interact with the layered nanosheets modified by intercalating efficiently, thereby avoiding sedimentation when dispersing the nanoparticles in the oil medium, and thus improving stability of the resulting oil blend.

(43) According to an embodiment of the present disclosure, the spherical nanoparticles have a particle size of 5 to 1000 nm, for example 50 to 800 nm. The spherical nanoparticles having such a particle size may interact with the layered nanosheets modified by intercalating efficiently, thereby avoiding sedimentation when dispersing the nanoparticles in the oil medium, and thus improving the dispersion of both layered nanosheets and spherical nanoparticles in the oil medium. In addition, an oil blend obtained therefrom exhibits good stability, avoiding phase separation and sedimentation for a long period of time.

(44) According to embodiments of the present disclosure, the method includes a step of (3) mixing the first mixture, the second mixture and the oil medium to obtain a third mixture, i.e., the oil blend. In the third mixture, a schematic view showing mechanism of stabilizing the spherical nanoparticles with the nanosheets modified by intercalating/exfoliating with oil-soluble alkylamines is shown in FIG. 3.

(45) According to an embodiment of the present disclosure, the first mixture, the second mixture and the oil medium are mixed by means of heat treatment, ultrasonic treatment or mechanical agitation, such that the first mixture, the second mixture and the oil medium are mixed uniformly in an effective manner, resulting in an oil blend exhibiting good dispersion and therein good stability.

(46) According to embodiments of the present disclosure, the oil medium is not limited specifically, and may be any known oil medium. According to a specific embodiment of the present disclosure, the oil medium is base oil of the lubricating oil, such that the third mixture obtained may be used as lubricating oil exhibiting good friction property, appropriate viscosity and high abrasive resistance due to the layered nanosheets and the spherical nanoparticles contained therein.

(47) According to an embodiment of the present disclosure, in the third mixture, a molar ratio of the layered nanosheets to the oil-soluble alkylamines is 1:1 to 1:40, for example 1:1 to 1:25; a volume ratio of the layered nanosheets to the spherical nanoparticles is 1:0.001 to 1:10, for example 1:0.01 to 1:5, such that the spherical nanoparticles interact with the layered nanosheets modified by intercalating effectively, thereby avoiding sedimentation when dispersing the nanoparticles in the oil medium, and thus improving the stability of the oil blend.

(48) The inventors have found that the method according to embodiments of the present disclosure stabilizes spherical nanoparticles with layered nanosheets, such that both the layered nanosheets and the spherical nanoparticles can be simultaneously and stably dispersed in the oil medium, resulting in a solution or microemulsion exhibiting good stability without sedimentation or phase separation. Such a method is easy and convenient to be operated.

(49) Further, the inventors have found that the method according to embodiments of the present disclosure can effectively disperse both layered nanosheets and spherical nanoparticles in the base oil of the lubricating oil uniformly in an effective manner, so that both the layered nanosheets and the spherical nanoparticles may be used as additives together to improve the anti-friction and the abrasive resistance properties effectively.

(50) In a second aspect of the present disclosure, there is provided an oil blend containing both layered nanosheets and spherical nanoparticles. According to embodiments of the present disclosure, the oil blend is prepared by the method described above. The inventors have surprisingly found that the oil blend containing both the layered nanosheets and the spherical nanoparticles exhibits good stability, avoiding sedimentation or phase separation for a long period of time. In addition, the oil blend containing both the layered nanosheets and the spherical nanoparticles can be effectively used in preparation of lubricating oils and lubricating greases with good anti-friction property and high abrasive resistance.

(51) In a third aspect of the present disclosure, there is provided use of the oil blend containing both the layered nanosheets and the spherical nanoparticles described above in the preparation of lubricating oils and lubricating greases. According to embodiments of the present disclosure, the lubricating oils and the lubricating greases exhibit good anti-friction property and abrasive resistance.

Example 1: Synthesis of -Zirconium Phosphate

(52) 8.0 g ZrOCl.sub.2.8H.sub.2O and 80 ml H.sub.3PO.sub.4 (a mass fraction is 85%) with concentrations of 3.0 mol/L, 6.0 mol/L, 9.0 mol/L and 12.0 mol/L were added into a three-necked flask respectively, and refluxed for 24 h at 100 C. After reaction, primary reaction products were washed three times and collected by centrifugation, thus obtaining products -ZrP (3M), -ZrP (6M), -ZrP (9M) and -ZrP (12M), respectively. Specifically, the products -ZrP (3M), -ZrP (6M), -ZrP (9M) and -ZrP (12M) are products when the concentration is 3.0 mol/L, 6.0 mol/L, 9.0 mol/L and 12 mol/L, respectively. Then, the products were dried for 24 h at 65 C. followed by grinded into -ZrP fine powders. At 25 C., the -ZrP fine powders are of a density of about 2.72 g.Math.cm.sup.3. The -ZrP fine powders were then tested by XRD and the XRD patterns of -ZrP (dehydrated -ZrP) are shown in FIGS. 5 and 6. An electron microscopy image of the -ZrP (3M) fine powders is shown in FIG. 7. It can be seen from FIG. 7, the -ZrP (3M) fine powders are of a particle size of about 100 nm.

Example 2: Synthesis of -Zirconium Phosphate

(53) 3.116 g ZrOCl.sub.2.8H.sub.2O was dissolved in 200 mL deionized water in a beaker, and then mixed with 82.19 ml H.sub.3PO.sub.4 (a mass fraction is 85%) and 117.81 ml deionized water in a round-bottom flask. Subsequently, the round-bottom flask containing H.sub.3PO.sub.4 solution was disposed in a oil bath with a constant temperature of 94 C. under agitation. After the H.sub.3PO.sub.4 solution was stabilized at the temperature of 94 C., a solution of ZrOCl.sub.2.8H.sub.2O was added into the H.sub.3PO.sub.4 solution in a dropwise manner, thus obtaining a resulting solution. The resulting solution was kept for reacting at the constant temperature of 94 C. for 48 h under agitation, followed by filtrated, thus obtaining a solid product washed by a large amount of deionized water, i.e., -ZrP. Subsequently, -ZrP was dried in a drying apparatus for 72 h at a room temperature, and dried -ZrP was grinded into fine powders. -ZrP nanosheets are of a particle size of about 400 nm. At 25 C., -ZrP fine powders are of a density of about 2.44 g.Math.cm.sup.3. The -ZrP fine powders were tested by XRD and the XRD pattern of -ZrP is shown in FIG. 6.

Example 3: Synthesis of -Zirconium Phosphate

(54) NaH.sub.2PO.sub.4.H.sub.2O (677 g, 4.91 mol) was dissolved in a mix solution containing deionized water (376 ml) and H.sub.3PO.sub.4 (182.6 g, 1.58 mol) with a mass fraction of 85%, followed by refluxing for 30 min and then adding 238 ml ZrOCl.sub.2.8H.sub.2O solution (76 g, 1 mol/L), thus obtaining colloids. The colloids were then refluxed for 72 h. Subsequently, colloids after refluxed were transferred into a hydrothermal reactor and heated to 190 C. for 120 h. After reactions, white precipitates were obtained by filtration, and washed with 4 mol/L HCl to remove sodium ions and then with 0.2 mol/L H.sub.3PO.sub.4 to remove chloride ions, thus obtaining -ZrP after washing with deionized water. Subsequently, -ZrP was dried in the drying apparatus for 72 h at a room temperature, and dried -ZrP was grinded into fine powders. of -ZrP nanosheets are of a particle size of about 150 nm. At 25 C., -ZrP fine powders are of a density of about 1.78 g.Math.cm.sup.3.

Example 4: Synthesis of 2-n-hexyl-1-n-decyl Guerbet Amine

(55) 12.122 g 2-n-hexyl-1-n-decyl Guerbet alcohol (0.05 mol) was added into a 100 ml hydrothermal reactor. Concentrated ammonia water was added into the hydrothermal reactor to satisfy a molar ratio of the Guerbet primary amine to ammonium hydroxide in the concentrated ammonia water to be 1:1.2 to 1:1.6. 10 g powders of aluminium oxide catalysts (a particle diameter is about 10 m) was added into the hydrothermal reactor. Subsequently, a hydrothermal reaction was kept for 5 h at 120-150 C. After the hydrothermal reaction and cooling, the solution inside the reactor was transferred into a 3-neck flask and refluxed for 3 h at 100 C. in oil bath, so as to remove unreacted ammonia after the hydrothermal reaction, followed by filtration with a Buchner funnel slowly to remove the catalysts, thus obtaining a liquid product. The liquid product was subsequently distillated under reduced pressure to remove moisture, thus obtaining a yellow liquid crude product. The yellow liquid crude product was kept in a refrigerator for 12 h at 0 C., followed by filtration with a Buchner funnel quickly, thus obtaining a final liquid product, i.e., 2-n-hexyl-1-n-decyl Guerbet amine At 25 C., its density is 0.84 g/ml.

Example 5: Synthesis of Hoffman Degradation Amine of Oleic Acid Amide

(56) 120 ml ethanol was added into a 500 ml 3-neck flask and then 40.20 g oleic acid amide with a mass friction of 70% was also added therein. Subsequently, in a nitrogen atmosphere, the 3-neck flask was heated in water bath under quick agitation. Subsequently, 8 g sodium hydroxide was dissolved in 80 ml sodium hypochlorite solution (a content of active chlorine is 100-140 g/L) in a 150 ml constant pressure funnel, thus obtaining a mix solution. The mixed solution was added into a 3-neck flask kept at a temperature between 30 C. and 40 C. for 6 h under agitation. After reactions, a resulting solution was distillated under reduced pressure to remove ethanol, thus obtaining an oil phase primary product after liquid-separation. The oil phase primary product was further mixed with a large amount of saturated NaCl solution, so that a final product was obtained after another liquid-separation. At 25 C., its density is 0.83 g/ml.

Example 6: Mixing -ZrP and Zinc Oxide Nanoparticles

(57) Firstly, 0.2 g -ZrP (3M) obtained in Example 1 (a particle size is about 100 nm as shown in FIG. 7, a density of the fine powders is about 2.72 g.Math.cm.sup.3, and its molecular weight is 301.19 g.Math.mol.sup.1) and 4.0 g Hoffman degradation amine of oleic acid amide obtained in Example 5 (the density is 0.83 g/ml and a molecular weight is 253.46 g.Math.mol.sup.1) were mixed in a 10 ml glass vial with a molar ratio of the -ZrP nanosheets to Hoffman degradation amine of oleic acid amide of 1:23.75, followed by subjected to ultrasonic treatment, thus being dispersed uniformly. Secondly, 0.2 g zinc oxide nanoparticles (a particle size is 40-60 nm and a density of fine powders is about 5.61 g.Math.cm.sup.3) and 10 g base oil of the lubricating oil (a density is about 0.87 g/ml) were mixed and subjected to the ultrasonic treatment, thus being dispersed uniformly.

(58) Thirdly, after the ultrasonic treatment, -ZrP-amine mixture and ZnO-oil mixture were dispersed in the lubricating oil at a volume ratio of the -ZrP-amine mixture to the ZnO-oil mixture of 1:3, in which a volume ratio of the -ZrP nanosheets to the ZnO spherical nanoparticles is about 1:0.62, thus obtaining lubricating oil dispersed with -ZrPZnO-amine mixture, which is stable transparent solution or microemulsion in light blue color, keeping in static state at room temperature for at least one month.

(59) According to parameters provided by embodiments of the present disclosure, a principle of calculating the volume ratio of the layered nanosheets to the spherical nanoparticles is as follows:

(60) It is assumed that (1) the total volume of the mixture is a sum of every component when adding inorganic nanoparticles into the oil medium due to poor lipophilicity of the inorganic nanoparticles; (2) densities of the nanosheets-oil-soluble amine mixture and spherical nanoparticle-oil mixture after the ultrasonic treatment are uniform during operation.

(61) As such, a volume fraction of -ZrP in the -ZrP-amine mixture is:

(62) $\frac{\frac{0.2}{2.72}}{\frac{4.0}{0.83}+\frac{0.2}{2.72}}$

(63) and a volume fraction of ZnO in the ZnO-oil mixture is:

(64) $\frac{\frac{0.2}{5.61}}{\frac{10}{0.87}+\frac{0.2}{5.62}}$

(65) Then, in this embodiment, the volume ratio of -ZrP nanosheets to ZnO nanoparticles in the -ZrP-amine-ZnO-oil mixture is about:

(66) $\frac{\frac{0.2}{2.72}}{\frac{4.0}{0.83}+\frac{0.2}{2.72}}:3\frac{\frac{0.2}{5.61}}{\frac{10}{0.87}+\frac{0.2}{5.62}}1\text{:}0.62$

Example 7: Mixing -ZrP and Zirconium Oxide Nanoparticles

(67) Firstly, 0.2 g -ZrP obtained in Example 2 (a particle size is about 400 nm, the density of the fine powders is about 2.44 g.Math.cm.sup.3, and its molecular weight is 391.27 g.Math.mol.sup.1) and 3.0 g 2-n-hexyl-1-n-decyl Guerbet amine obtained in Example 4 (the density is 0.84 g/ml and a molecular weight is 241.46 g.Math.mol.sup.1) were mixed in a 10 ml glass vial with a molar ratio of the -ZrP nanosheets to 2-n-hexyl-1-n-decyl Guerbet amine of 1:24.33, followed by subjected to ultrasonic treatment, thus being dispersed uniformly.

(68) Secondly, 0.3 g zirconium oxide nanoparticles (a particle size is 200-400 nm and a density of fine powders is about 5.89 g.Math.cm.sup.3) and 10 g base oil of the lubricating oil (the density is about 0.87 g/ml) were mixed in a 20 ml glass vial and subjected to the ultrasonic treatment, thus being dispersed uniformly.

(69) Thirdly, after the ultrasonic treatment, -ZrP-amine mixture and ZrO.sub.2-oil mixture were dispersed in the lubricating oil at a volume ratio of the -ZrP-amine mixture to the ZrO.sub.2-oil mixture of 1:2, in which a volume ratio of the -ZrP nanosheets to the ZrO.sub.2 spherical nanoparticles is about 1:0.39 (the calculation is the same as in Example 6), thus obtaining lubricating oil dispersed with -ZrPZrO.sub.2-amine mixture, which is stable transparent solution or microemulsion in light blue color, keeping in static state at a room temperature for at least one month.

Example 8: Mixing -ZrP, Zirconium Oxide Nanoparticles and Silicon Oxide Nnanoparticles

(70) Firstly, 0.2 g -ZrP obtained in Example 3 (a particle size is about 150 nm, the density of the fine powders is about 1.78 g.Math.cm.sup.3, and its molecular weight is 319.21 g.Math.mol.sup.3) and 3.0 g 2-n-hexyl-1-n-decyl Guerbet amine obtained in Example 4 (the density is 0.84 g/ml and the molecular weight is 241.46 g.Math.mol.sup.3) were mixed in a 10 ml glass vial with a molar ratio of the -ZrP nanosheets to 2-n-hexyl-1-n-decyl Guerbet amine of 1:19.84, followed by subjected to ultrasonic treatment, thus being dispersed uniformly.

(71) Secondly, 0.4 g zirconium oxide nanoparticles (the particle size is 200-400 nm and the density of fine powders is about 5.89 g.Math.cm.sup.3) and 10 g base oil of the lubricating oil (the density is about 0.87 g/ml) were mixed in a 20 ml glass vial and subjected to the ultrasonic treatment, thus being dispersed uniformly. 0.3 g silicon oxide nanoparticles (the particle size is about 50 nm and a density of fine powders is about 2.60 g.Math.cm.sup.3) and 10 g base oil of the lubricating oil (the density is about 0.87 g/ml) were mixed in another 20 ml glass vial and subjected to the ultrasonic treatment, thus being dispersed uniformly.

(72) Thirdly, after the ultrasonic treatment, -ZrP-amine mixture, ZrO.sub.2-oil mixture and SiO.sub.2-oil mixture were dispersed in the lubricating oil at a volume ratio of the -ZrP-amine mixture to the ZrO.sub.2-oil mixture to the SiO.sub.2-oil mixture of 1:2:2, in which a volume ratio of the -ZrP nanosheets to the ZrO.sub.2 spherical nanoparticles to the SiO.sub.2 spherical nanoparticles is about 1:0.39:0.65 (the calculation is the same as in Example 6), thus obtaining lubricating oil dispersed with -ZrPZrO.sub.2SiO.sub.2-amine mixture, which is stable transparent solution or microemulsion in light blue color, keeping in static state at a room temperature for at least one month.

Example 9: Mixing -ZrP and Copper Nanoparticles

(73) Firstly, 0.4 g -ZrP (3M) obtained in Example 1 (the particle size is about 100 nm as shown in FIG. 7, the density of the fine powders is about 2.72 g.Math.cm.sup.3, and the molecular weight is 301.19 g.Math.mol.sup.1) and 8.0 g oleic acid amine (a density is 0.81 g/ml and its molecular weight is 267.49 g.Math.mol.sup.1) were mixed in a 10 ml glass vial with a molar ratio of the -ZrP nanosheets to oleic acid amine of 1:22.52, followed by subjected to ultrasonic treatment, thus being dispersed uniformly.

(74) Secondly, 0.06 g copper nanoparticles (a particle size is 80-100 nm and a density of fine powders is about 8.94 g.Math.cm.sup.3) and 16 g base oil of the lubricating oil (a density is about 0.87 g/ml) were mixed and subjected to the ultrasonic treatment, thus being dispersed uniformly.

(75) Thirdly, -ZrP-amine mixture and Cu-oil mixture were dispersed in the lubricating oil at a volume ratio of 1:1, so that six groups of mixtures with different -ZrP mass fractions of 4.210.sup.4, 8.410.sup.4, 12.610.sup.4, 16.810.sup.4, 2110.sup.4 and 25.210.sup.4, respectively, were prepared, in which a volume ratio of the -ZrP nanosheets to the Cu spherical nanoparticles is about 1:0.025 (the calculation is the same as in Example 6). The preparation method was as follows: (1) 10 drops of well-dispersed -ZrP-amine mixture pipetted by a plastic-head pipette were weighted to be 0.30 g, so that mass of -ZrP in each drop was about 0.30/(2110)=1/7000.0014 g; (2) 3, 6, 9, 12, 15 and 18 drops of -ZrP-amine mixture were added into six 10 ml glass vials by the plastic-head pipette, respectively, and then 3, 6, 9, 12, 15 and 18 drops of Cu-oil mixture were added correspondingly in this six 10 ml glass vials by the plastic-head pipette, respectively; (3) base oil of lubricating oil was added in each vial until the mass of each mixture in the vial was up to 10 g; (4) after the ultrasonic treatment, -ZrPCu-amine-oil mixture dispersed uniformly was obtained.

(76) The lubricating oil with different solid concentrations from low to high, which contains -ZrPCu-amine mixture dispersed therein, is stable transparent solution or microemulsion in light blue color, keeping in static state at a room temperature for at least one month. FIG. 4 is a comparison picture showing different samples of lubricating oil containing base oil well dispersed with -ZrPCu-amine mixture and other additives, for observing stabilities. The samples are as follows from left to right: (a) spherical Cu nanoparticles without ligands had been dispersed in the base oil of the lubricating oil; (b) layered -ZrP unmodified by intercalating/exfoliating with oil-soluble alkylamines had been dispersed in the base oil of the lubricating oil; (c) the spherical Cu nanoparticles without ligands and the layered -ZrP unmodified by intercalating/exfoliating with oil-soluble alkylamines had been simultaneously dispersed in the base oil of the lubricating oil; (d) the base oil of the lubricating oil as a blank control group; (e) layered -ZrP modified by intercalating/exfoliating with oleic acid amines and the spherical Cu nanoparticles without ligands had been simultaneously dispersed in the base oil of the lubricating oil. It can be seen from FIG. 4 that -ZrPCu-amine mixture is stably dispersed in the base oil of the lubricating oil.

Example 10: Reciprocating Friction Test

(77) In this example, the lubricating oil containing -ZrPCu-amine mixture dispersed therein in Example 9 was subjected to the reciprocating friction test. Specifically, the standard of the reciprocating friction test is G133 standard of American Society for Testing Materials (ASTM G133) and a schematic diagram showing mechanism of the reciprocating friction test is shown in FIG. 8. In the test, all test balls (HRc is 30, surface accuracy is G100) were made of 304 stainless steel, and were immersed in the lubricating oil, and test parameters are shown in the following table:

(78) TABLE-US-00001 Parameters model/value sampling linear model full amplitude 6.00 mm maximum line velocity 0.25 cm/s frequency 0.00 Hz standard load 7.00 N terminal condition 1.60 m effective termination Meters sampling velocity 5.0 Hz sampling period once per period test temperature 24 C. relative air humidity 60.00%

(79) FIG. 9 is a diagram showing a test result of average friction coefficient <> of the lubricating oil containing different mass fractions of ZrP and it can be seen from that, <> is gradually decreased with the mass friction of -ZrP being increased. FIG. 10 is a diagram showing a test result of maximum friction coefficient (.sub.max) of the lubricating oil containing different mass fractions of ZrP and it can be seen from that, .sub.max is decreased with the mass friction of -ZrP being increased. It can be seen from FIGS. 9 and 10, a threshold of the mass fraction of -ZrP is about 4.210.sup.4.

(80) Specifically, <> is a time average value of an instantaneous friction coefficient , and the calculation formula is as follow:

(81) $.Math..Math.=\frac{dt}{dt}$

(82) A error bar of the friction coefficient is calculated by absolute minimum variance method, and the calculation formula is as follow:

(83) $=\frac{.Math.-.Math..Math..Math.dt}{dt}$

(84) FIG. 11 is a diagram showing a test result of a friction coefficient of lubricating oil when a mass fraction of -ZrP is zero. FIG. 12 is a diagram showing a time-friction curve of lubricating oil when a mass fraction of -ZrP is 4.210.sup.4. FIG. 13 is a diagram showing a time-friction curve of lubricating oil when a mass fraction of -ZrP is 8.410.sup.4. FIG. 14 is a diagram showing a time-friction curve of lubricating oil when a mass fraction of -ZrP is 12.610.sup.4. FIG. 15 is a diagram showing a time-friction curve of lubricating oil when a mass fraction of -ZrP is 16.810.sup.4. FIG. 16 is a diagram showing a time-friction curve of lubricating oil when a mass fraction of -ZrP is 2110.sup.4. FIG. 17 is a diagram showing a time-friction curve of lubricating oil when a mass fraction of -ZrP is 25.210.sup.4. FIG. 18 is a diagram showing a time-friction curve of lubricating oil when a mass fraction of -ZrP is zero, in which a test ball used in such a step is a test ball obtained after the friction test when a mass fraction of -ZrP is 25.210.sup.4. It can be seen from the test results of FIGS. 9-18, even if layered zirconium phosphate nanosheets and spherical nanoparticles of the present disclosure are in extremely low addition amount, they may be effectively used as abrasive resistance additives for lubricating oils and greases.

(85) In the description of the present disclosure, it should be understood that terms such as first and second are used herein for purposes of description and are not intended to indicate or imply relative importance or significance. Thus, the feature defined with first and second may comprise one or more this feature. In the description of the present disclosure, unless specified otherwise, a plurality of means two or more than two.

(86) Reference throughout this specification to an embodiment, some embodiments, one embodiment, another example, an example, a specific example, or some examples, means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. Thus, the appearances of the phrases such as in some embodiments, in one embodiment, in an embodiment, in another example, in an example, in a specific example, or in some examples, in various places throughout this specification are not necessarily referring to the same embodiment or example of the present disclosure. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments or examples.

(87) Although explanatory embodiments have been shown and described, it would be appreciated by those skilled in the art that the above embodiments cannot be construed to limit the present disclosure, and changes, alternatives, and modifications can be made in the embodiments without departing from spirit, principles and scope of the present disclosure.