CN110317659B - Organic carbon nanosphere lubricating oil additive and preparation method and application thereof - Google Patents
Organic carbon nanosphere lubricating oil additive and preparation method and application thereof Download PDFInfo
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- CN110317659B CN110317659B CN201910654625.2A CN201910654625A CN110317659B CN 110317659 B CN110317659 B CN 110317659B CN 201910654625 A CN201910654625 A CN 201910654625A CN 110317659 B CN110317659 B CN 110317659B
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 134
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 239000000654 additive Substances 0.000 title claims abstract description 110
- 230000000996 additive effect Effects 0.000 title claims abstract description 98
- 239000002077 nanosphere Substances 0.000 title claims abstract description 93
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 39
- 239000007833 carbon precursor Substances 0.000 claims abstract description 36
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 34
- 238000003763 carbonization Methods 0.000 claims abstract description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims abstract description 5
- 229920000547 conjugated polymer Polymers 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- -1 small molecule compound Chemical class 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 26
- 239000011807 nanoball Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 16
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 claims description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 10
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 239000003879 lubricant additive Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 10
- 239000002199 base oil Substances 0.000 abstract description 9
- 238000010000 carbonizing Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 27
- 238000003756 stirring Methods 0.000 description 16
- 239000012265 solid product Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 9
- 239000002105 nanoparticle Substances 0.000 description 9
- 238000000227 grinding Methods 0.000 description 8
- 230000001050 lubricating effect Effects 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000009347 mechanical transmission Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- KAEAMHPPLLJBKF-UHFFFAOYSA-N iron(3+) sulfide Chemical compound [S-2].[S-2].[S-2].[Fe+3].[Fe+3] KAEAMHPPLLJBKF-UHFFFAOYSA-N 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/02—Carbon; Graphite
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/20—Compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/22—Compounds containing sulfur, selenium or tellurium
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/24—Compounds containing phosphorus, arsenic or antimony
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Lubricants (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides an organic carbon nanosphere lubricating oil additive and a preparation method and application thereof, and the preparation method comprises the following steps: s1, dissolving the reaction monomer in a reaction solvent, fully mixing, and reacting at 0-90 ℃ for 3-12 h to obtain an organic carbon precursor of the polymer; wherein the reactive monomer is a small molecule compound capable of polymerizing into a hypercrosslinked pi-bond conjugated polymer; s2, placing the organic carbon precursor and the doping source obtained in the step S1 in a tube furnace for doping carbonization to obtain organic carbon nanospheres containing the doping source; wherein the doping source is one or more of an N source, an S source and a P source. The dispersion stability of the carbon nanosphere additive in the base oil can be obviously improved by a method of synthesizing an organic carbon source and simply carbonizing and doping N, S, P element, and the wear resistance under high load is improved by N, S, P doping.
Description
Technical Field
The invention relates to the technical field of preparation of lubricating oil additives, in particular to an N, S, P element doped organic carbon nanosphere lubricating oil additive and a preparation method and application thereof.
Background
In recent years, friction and wear are still the main causes of fatigue fracture and mechanical energy consumption of transmission equipment, and traditional lubricating grease can not meet the harsh transmission working conditions more and more. Improving the lubricity and wear resistance of mechanical systems is critical to the development of industrialization. Today, optimizing mechanical friction conditions in addition to synthetic lubricating oils depends to a large extent on the properties of the lubricating oil additives. Carbon materials have good lubricating and self-lubricating properties from ancient times, and carbon nanomaterials like fullerene, carbon nanotubes, graphene, diamond and the like have also been widely used as additives of base oil to improve the lubricating condition. The traditional inorganic carbon materials have serious agglomeration and precipitation phenomena in basic lubricating oil, and in a high-load system, the carbon nano additives are easy to creep and cannot effectively form a lubricating film to protect mechanical transmission equipment. Therefore, it is important to develop a lubricant additive that possesses both good dispersancy and excellent wear resistance.
At present, the surface of the carbon nano material is chemically modified or a surfactant is used to form a protective layer or a long chain group on the surface of the nano particle so as to reduce the surface energy of the nano particle, thereby improving the dispersion stability of the carbon nano material in the lubricating oil. However, the method has the disadvantages of complex process, low stability of the modified nanoparticles and high cost. The physical modes of ball milling, ultrasonic treatment, stirring and the like are also strategies for improving the dispersibility of the nano additive in the lubricating oil, but the nano additive only can effectively act for a short time and cannot fundamentally solve the problem of poor dispersion stability of the nano particles in the lubricating oil.
Disclosure of Invention
In order to solve the problems that the carbon nano-material has insufficient anti-loading performance and is difficult to stably disperse in lubricating oil for a long time, the invention aims to provide a preparation method of an organic carbon nano-sphere lubricating oil additive, which mainly obtains the organic carbon nano-sphere lubricating oil additive containing doped elements by synthesizing an organic carbon source and a simple method of carbonizing and doping N, S, P elements, can obviously improve the dispersion stability of the carbon nano-sphere additive in base oil, and improves the wear resistance under high load by doping N, S, P; the method is simple to operate, low in cost and strong in universality.
In order to achieve the above object, the technical solution of the present invention is as follows.
The invention provides an organic carbon nanosphere lubricating oil additive, which comprises organic carbon nanospheres and doping elements doped on the organic carbon nanospheres through carbonization, wherein the doping elements are one or more of N, S, P elements, and the mass percent of the doping elements in the additive is 12.1-31.0 wt%.
Further, the additive is organic carbon nanospheres containing doping elements, and the particle size of the additive is 110 nm-121 nm.
The invention also provides a preparation method of the organic carbon nanosphere lubricating oil additive, which comprises the following steps:
s1, dissolving the reaction monomer in a reaction solvent, fully mixing, and reacting at 0-90 ℃ for 3-12 h to obtain an organic carbon precursor of the polymer;
wherein the reactive monomer is a small molecule compound capable of polymerizing into a hypercrosslinked pi-bonded conjugated polymer;
s2, placing the organic carbon precursor and the doping source obtained in the step S1 in a tube furnace for doping carbonization to obtain organic carbon nanospheres containing the doping source;
wherein the doping source is one or more of an N source, an S source and a P source.
Here, the mass ratio is a mass ratio of the organic carbon precursor to the doping source (such as thiourea or ammonium hypophosphite) and is set by experiment, and the N, S, P content of the final product is detected by XPS (X-ray photoelectron spectroscopy); that is, the corresponding N, S, P content in the final product was determined by XPS.
Further, the reaction monomer is one or more of aniline, pyrrole, thiophene, thiazole and styrene.
Furthermore, the reaction solvent is a mixed solution of deionized water and acetonitrile; wherein the volume ratio of the deionized water to the acetonitrile is 1-3: 1.
Further, in the step S1, the reaction stirring speed is 0-1200 rpm; and step S1, washing and drying, wherein the washing mode comprises filtering, suction filtration or centrifugation, the drying temperature is 40-100 ℃, and the drying time is 2-12 h.
Further, in the step S2, the N source is one or more of ammonium hypophosphite, ammonium salt, ammonia water, ammonia gas, and nitrogen gas; the S source is one or more of sulfur tablets, thiourea and hydrogen sulfide gas; the P source is one or more of ammonium hypophosphite, white phosphorus and red phosphorus.
Further, in the step S2, the temperature of doping carbonization is 300-500 ℃, the heating rate of doping carbonization is 2-10 ℃, and the heat preservation time of doping carbonization is 3-5 h.
Further, in step S2, the doping sources include a gas doping source and a non-gas doping source, and the ratio of the organic carbon precursor to the gas doping source and the non-gas doping source is 1 g: 200-600 ml/min: 0 to 25 g.
When the doping source is a solid doping source, before doping carbonization, the organic carbon precursor and the solid doping source are mixed by grinding, or the organic carbon precursor and the solid doping source are respectively carbonized at different positions of the tube furnace.
In addition, the invention also provides the application of the organic carbon nanosphere lubricating oil additive in lubricating oil.
Furthermore, the lubricating oil is one of 500SN, PAO, PEG and A51, and the additive amount of the organic carbon nanosphere lubricating oil additive in the lubricating oil is 0.2-5 wt%.
Wherein, the dispersion stability of the organic carbon nanospheres with the addition amount of 0.2 to 5 weight percent in the lubricating oil is basically the same.
The organic carbon nanosphere lubricating oil additive is fully mixed with the lubricating oil through stirring and ultrasonic treatment, wherein the stirring time is 30-50min, and the ultrasonic treatment time is 30-50 min.
Compared with the prior art, the invention has the beneficial effects that:
1. the carbon nanosphere prepared by the invention is an organic carbon nanosphere between a polymer precursor and an inorganic carbon material, reserves an organic phase in a part of the precursor, and can be well dispersed in various base oils on the premise of not carrying out any physical and chemical modification on the carbon nanosphere.
2. The structure of the carbon nanospheres prepared by the invention is hypercrosslinked, the morphology of the nanospheres is still maintained and not damaged after carbonization at different temperatures, and different phase compositions can be obtained: amorphous phase, Sp2Phase and Sp3And the additive can be used for a lubricating oil additive to well achieve an excellent anti-wear and anti-wear effect. Compared with the prior art that graphite and diamond are generally used for preparing two-dimensional and three-dimensional mixed carbon, the preparation method provided by the invention has the advantages of better preparation method and more excellent effect.
3. The invention further improves the bearing capacity of the basic lubricating oil by doping N, S, P and other elements into the organic carbon nanospheres, so that the organic carbon nanospheres can form an effective, lasting and stable lubricating oil film under a high-load condition, reduce the friction coefficient and protect mechanical transmission equipment.
4. The N, S, P element-doped organic carbon nanospheres prepared by the method can be used as lubricating oil additives and can react with the surface of metal iron of a transmission component under an extreme friction condition to form corresponding low-melting-point compounds such as iron carbonate, iron oxide, iron sulfate, iron sulfide, iron phosphate or iron phosphide, friction gullies can be filled under a high-speed high-load condition, the friction contact area is increased, and good lubricating performance is obtained.
Drawings
FIG. 1 is a scanning electron micrograph of products prepared in examples 1 to 4 of the present invention.
Fig. 2 is a picture of dispersion stability of examples 1, 4, 7, and 10 applied in the present invention.
FIG. 3 is a graph showing extreme pressure tests of examples 1, 4, 7 and 10 and comparative example 1 applied in the present invention.
FIG. 4 is a graph showing a dead load test in examples 1, 4, 7 and 10 and comparative example 1 applied in the present invention.
FIG. 5 is a bar graph of the plaque volume loss after the constant load test of the application examples 1, 4, 7, 10 and comparative example 1 in the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without any inventive step, shall fall within the scope of the present invention.
Example 1
An organic carbon nanosphere lubricating oil additive comprises an organic carbon nanosphere and doping elements doped on the organic carbon nanosphere through carbonization, wherein the doping elements are N elements, and the mass percentage of the doping elements in the additive is 18.9%.
The preparation method comprises the following steps:
s1, preparation of an organic carbon precursor:
taking 0.49mol of aniline and 0.38mol of pyrrole as reaction monomers, adding 60ml of mixed solution consisting of deionized water and acetonitrile once, and uniformly stirring, wherein the volume ratio of the deionized water to the acetonitrile in the mixed solution is 2: 1;
after stirring uniformly, the solution is colorless and transparent, then the solution is reacted for 10 hours at the temperature of 90 ℃ and the stirring speed of 1000rpm, after the reaction is finished, a solid product is separated out, and after the separated solid product is filtered and washed, the solid product is dried for 10 hours at the temperature of 80 ℃ to obtain a polymerized precursor used as an organic carbon source;
s2, preparation of an additive:
200mg of organic carbon precursor is taken and placed at the central position of a tubular furnace, and N is introduced2The flow rate is 80ml/min, the temperature in the tube furnace is raised from room temperature to 500 ℃, the temperature is preserved for 3h, the temperature raising rate is 5 ℃/min, and the product containingOrganic carbon nanosphere additive (CN) of doping source; wherein the particle size of the organic carbon nanosphere additive (CN) is 110 nm.
Example 2
An organic carbon nanosphere lubricating oil additive comprises an organic carbon nanosphere and doping elements doped on the organic carbon nanosphere through carbonization, wherein the doping element is N, S element, and the mass percentage of the doping element in the additive is 26.2%.
The preparation method comprises the following steps:
s1, preparation of an organic carbon precursor: the preparation method is completely the same as that of the embodiment 1;
s2, preparation of an additive:
200mg of organic carbon precursor is taken and placed at the central position of a tube furnace, 3g of thiourea is placed at the position of an air inlet of the tube furnace at the temperature of 180-200 ℃, and N is introduced2Heating the temperature in the tube furnace from room temperature to 500 ℃ at the flow rate of 80ml/min, and then preserving the heat for 3h at the heating rate of 5 ℃/min to obtain the organic carbon nanosphere additive (S @ CN) containing the doping source; wherein the particle size of the organic carbon nanosphere additive (S @ CN) is 115 nm.
Example 3
An organic carbon nanosphere lubricating oil additive comprises an organic carbon nanosphere and doping elements doped on the organic carbon nanosphere through carbonization, wherein the doping element is N, P element, and the mass percentage of the doping element in the additive is 23.3%.
The preparation method comprises the following steps:
s1, preparation of an organic carbon precursor: the preparation method is completely the same as that of the embodiment 1;
s2, preparation of an additive:
200mg of organic carbon precursor is taken and placed at the central position of a tube furnace, 3g of ammonium hypophosphite is placed at the air inlet position of the tube furnace at the temperature of 180-200 ℃, and N is introduced2Heating the temperature in the tubular furnace from room temperature to 500 ℃ at the flow rate of 80ml/min, and then preserving the heat for 3h at the heating rate of 5 ℃/min to obtain the organic carbon nanosphere additive (P @ CN) containing the doping source; wherein, the organic carbon nanosphere additive (P @ C)N) had a particle size of 121 nm.
Example 4
An organic carbon nanosphere lubricating oil additive comprises an organic carbon nanosphere and doping elements doped on the organic carbon nanosphere by carbonization, wherein the doping elements are N, S, P elements, and the mass percentage of the doping elements in the additive is 24.0%.
The preparation method comprises the following steps:
s1, preparation of an organic carbon precursor: the preparation method is completely the same as that of the embodiment 1;
s2, preparation of an additive:
200mg of organic carbon precursor is taken, fully ground and mixed with 1.5g of thiourea and 1.5g of ammonium hypophosphite, placed at the central position of a tubular furnace, and N is introduced2Heating the temperature in the tube furnace from room temperature to 300 ℃ at the flow rate of 80ml/min, and then preserving the heat for 5h at the heating rate of 5 ℃/min to obtain an organic carbon nanosphere additive (SP @ CN) containing a doping source; wherein the particle size of the organic carbon nanosphere additive (SP @ CN) is 118 nm.
Example 5
An organic carbon nanosphere lubricating oil additive comprises an organic carbon nanosphere and doping elements doped on the organic carbon nanosphere through carbonization, wherein the doping elements are N, S elements, and the mass percentage of the doping elements in an additive is 21.6%.
The preparation method comprises the following steps:
s1, preparation of an organic carbon precursor: the preparation method is completely the same as that of the embodiment 1;
s2, preparation of an additive:
taking 200mg of organic carbon precursor, placing the organic carbon precursor at the central position of a tube furnace, placing 400mg of thiourea at the position of an air inlet of the tube furnace at 180-200 ℃, and introducing N2And (3) heating the temperature in the tube furnace from room temperature to 500 ℃ at the flow rate of 40ml/min, and then preserving the heat for 3h at the heating rate of 2 ℃/min to obtain the organic carbon nanosphere additive (S @ CN) containing the doping source.
Example 6
An organic carbon nanosphere lubricating oil additive comprises an organic carbon nanosphere and doping elements doped on the organic carbon nanosphere through carbonization, wherein the doping elements are N, S elements, and the mass percentage of the doping elements in an additive is 31.0%.
The preparation method comprises the following steps:
s1, preparation of an organic carbon precursor: the preparation method is completely the same as that of the embodiment 1;
s2, preparation of an additive:
200mg of organic carbon precursor is taken and placed at the central position of a tube furnace, 5g of thiourea is placed at the position of an air inlet of the tube furnace at the temperature of 180-200 ℃, and N is introduced2And (3) heating the temperature in the tube furnace from room temperature to 500 ℃ at the flow rate of 120ml/min, and then preserving the heat for 3h at the heating rate of 10 ℃/min to obtain the organic carbon nanosphere additive (S @ CN) containing the doping source.
Example 7
An organic carbon nanosphere lubricating oil additive comprises an organic carbon nanosphere and doping elements doped on the organic carbon nanosphere through carbonization, wherein the doping elements are N, P elements, and the mass percentage of the doping elements in the additive is 12.1%.
The preparation method comprises the following steps:
s1, preparation of an organic carbon precursor: the preparation method is completely the same as that of the embodiment 1;
s2, preparation of an additive:
taking 200mg of organic carbon precursor, placing the organic carbon precursor at the central position of a tube furnace, placing 400mg of ammonium hypophosphite at the air inlet position of the tube furnace at 180-200 ℃, and introducing N2And (3) heating the temperature in the tube furnace from room temperature to 500 ℃ at the flow rate of 40ml/min, and then preserving the heat for 3 hours at the heating rate of 2 ℃/min to obtain the organic carbon nanosphere additive (P @ CN) containing the doping source.
Example 8
An organic carbon nanosphere lubricating oil additive comprises an organic carbon nanosphere and doping elements doped on the organic carbon nanosphere through carbonization, wherein the doping element is N, P element, and the mass percentage of the doping element in the additive is 27.4%.
The preparation method comprises the following steps:
s1, preparation of an organic carbon precursor: the preparation method is completely the same as that of the embodiment 1;
s2, preparation of an additive:
200mg of organic carbon precursor is taken and placed at the central position of a tube furnace, 5g of ammonium hypophosphite is placed at the air inlet position of the tube furnace at 180-200 ℃, and N is introduced2And (3) heating the temperature in the tube furnace from room temperature to 500 ℃ at the flow rate of 120ml/min, and then preserving the heat for 3h at the heating rate of 10 ℃/min to obtain the organic carbon nanosphere additive (P @ CN) containing the doping source.
Example 9
An organic carbon nanosphere lubricating oil additive comprises an organic carbon nanosphere and doping elements doped on the organic carbon nanosphere through carbonization, wherein the doping elements are N elements, and the mass percentage of the doping elements in the additive is 18.9%.
The preparation method comprises the following steps:
s1, preparation of an organic carbon precursor:
1mol of aniline is used as a reaction monomer, 100ml of mixed solution consisting of deionized water and acetonitrile is added at one time and is stirred uniformly, wherein the volume ratio of the deionized water to the acetonitrile in the mixed solution is 1:1 (or 100ml of deionized water is directly used);
after stirring uniformly, the solution is colorless and transparent, then at 0 ℃, the solution is stirred and rotated at the speed of 600rpm for 8 hours, after the reaction is finished, a solid product is separated out, and after the separated solid product is filtered and washed, the solid product is dried at 60 ℃ for 10 hours to obtain a polymerized precursor as an organic carbon source;
s2, preparation of an additive: the preparation method is completely the same as that of the embodiment 1.
Example 10
An organic carbon nanosphere lubricating oil additive comprises an organic carbon nanosphere and doping elements doped on the organic carbon nanosphere through carbonization, wherein the doping elements are N elements, and the mass percentage of the doping elements in the additive is 18.9%.
The preparation method comprises the following steps:
s1, preparation of an organic carbon precursor:
taking 1mol of aniline and 1mol of thiophene as reaction monomers, adding 60ml of mixed solution consisting of deionized water and acetonitrile once, and uniformly stirring, wherein the volume ratio of the deionized water to the acetonitrile in the mixed solution is 1: 1;
after stirring uniformly, the solution is colorless and transparent, then at 25 ℃, the solution is stirred and rotated at the speed of 400rpm for 12 hours, after the reaction is finished, a solid product is separated out, and after the separated solid product is filtered and washed, the solid product is dried at 40 ℃ for 8 hours to obtain a polymerized precursor used as an organic carbon source;
s2, preparation of an additive: the preparation method is completely the same as that of the embodiment 1.
Example 11
An organic carbon nanosphere lubricating oil additive comprises an organic carbon nanosphere and doping elements doped on the organic carbon nanosphere through carbonization, wherein the doping elements are N elements, and the mass percentage of the doping elements in the additive is 18.9%.
The preparation method comprises the following steps:
s1, preparation of an organic carbon precursor:
taking 1mol of thiophene as a reaction monomer, adding 400ml of mixed solution consisting of deionized water and acetonitrile once, and uniformly stirring, wherein the volume ratio of the deionized water to the acetonitrile in the mixed solution is 3: 1;
after stirring uniformly, the solution is colorless and transparent, then at 90 ℃, the solution is reacted for 3 hours at the stirring rotation speed of 750rpm, after the reaction is finished, a solid product is separated out, and after the separated solid product is filtered and washed, the solid product is dried for 10 hours at 50 ℃ to obtain a polymerized precursor used as an organic carbon source;
s2, preparation of an additive: the preparation method is completely the same as that of the embodiment 1.
Application example 1
2mg of the organic carbon nanoball additive (CN) prepared from example 1 was added to 998mg of 500SN lubricating oil, magnetically stirred for 30min and then ultrasonically mixed for 30 min.
The fretting friction wear test is carried out by using a SRV5 fretting friction wear tester, the extreme pressure test condition is 200 ℃, the load change is that 50N load is suddenly added every 5 minutes, the amplitude is 1mm, and the frequency is 25 HZ. Compared with the base oil 500SN, after 0.2wt% of CN is added, the limit load of the lubricating oil is increased from 250N to 550N, and the average friction coefficient before occlusion is reduced from 0.171 to 0.131; the constant load test conditions are 50 ℃, 100N, the amplitude is 1mm, the frequency is 25HZ, the friction coefficient is reduced from 0.233 to 0.113, and then the constant load test conditions fail in 25min, and the volume of the grinding spots is reduced to 35 percent of the original volume.
Application example 2
30mg of the organic carbon nanoball additive (CN) prepared from example 1 was added to 970mg of 500SN lubricating oil, and was magnetically stirred for 30min and then was ultrasonically mixed for 30 min.
Application example 3
50mg of the organic carbon nanoball additive (CN) prepared from example 1 was added to 950mg of 500SN lubricating oil, magnetically stirred for 30min and then ultrasonically mixed for 30 min.
Application example 4
2mg of the organic carbon nanoball additive (S @ CN) prepared from example 2 was added to 998mg of 500SN oil, magnetically stirred for 30min and then sonicated for 30min to be well mixed.
The fretting friction wear test is carried out by using a SRV5 fretting friction wear tester, the extreme pressure test condition is 200 ℃, the load change is that 50N load is suddenly added every 5 minutes, the amplitude is 1mm, and the frequency is 25 HZ. Compared with the base oil 500SN, after 0.2wt% of S @ CN is added, the limit load of the lubricating oil is increased from 250N to 800N, and the average friction coefficient before occlusion is reduced from 0.171 to 0.129; the constant load test conditions are 50 ℃, 100N, the amplitude is 1mm, the frequency is 25HZ, the friction coefficient is reduced from 0.233 to 0.097, the stability is high, and the grinding spot volume is reduced to 23 percent of the original volume.
Application example 5
30mg of the organic carbon nanoball additive (S @ CN) prepared from example 2 was added to 970mg of 500SN lubricating oil, magnetically stirred for 30min and then ultrasonically mixed for 30 min.
Application example 6
50mg of the organic carbon nanoball additive (S @ CN) prepared from example 2 was added to 950mg of 500SN lubricating oil, magnetically stirred for 30min and then ultrasonically mixed for 30 min.
Application example 7
2mg of the organic carbon nanoball additive (P @ CN) prepared in example 3 was added to 998mg of 500SN lubricant oil, magnetically stirred for 30min and then sonicated for 30min to be well mixed.
The fretting friction wear test is carried out by using a SRV5 fretting friction wear tester, the extreme pressure test condition is 200 ℃, the load change is that 50N load is suddenly added every 5 minutes, the amplitude is 1mm, and the frequency is 25 HZ. Compared with the base oil 500SN, after 0.2wt% of P @ CN is added, the limit load of the lubricating oil is increased from 250N to 1050N, and the average friction coefficient before occlusion is reduced from 0.171 to 0.098; the constant load test conditions are 50 ℃, 100N, the amplitude is 1mm, the frequency is 25HZ, the friction coefficient is reduced from 0.233 to 0.089, the stability is high, and the grinding spot volume is reduced to 21 percent of the original volume.
Application example 8
30mg of the organic carbon nanoball additive (P @ CN) prepared in example 3 was added to 970mg of 500SN lubricating oil, magnetically stirred for 30min and then ultrasonically mixed for 30 min.
Application example 9
50mg of the organic carbon nanoball additive (P @ CN) prepared in example 3 was added to 950mg of 500SN lubricating oil, magnetically stirred for 30min and then ultrasonically mixed for 30 min.
Application example 10
2mg of the organic carbon nanoball additive (SP @ CN) prepared from example 4 was added to 998mg of 500SN lubricant oil, magnetically stirred for 30min and then sonicated for 30min to be well mixed.
The fretting friction wear test is carried out by using a SRV5 fretting friction wear tester, the extreme pressure test condition is 200 ℃, the load change is that 50N load is suddenly added every 5 minutes, the amplitude is 1mm, and the frequency is 25 HZ. Compared with the base oil 500SN, after 0.2wt% of SP @ CN is added, the limit load of the lubricating oil is increased from 250N to 850N, and the average friction coefficient before occlusion is reduced from 0.171 to 0.122; the constant-load test conditions are 50 ℃, 100N, the amplitude is 1mm, the frequency is 25HZ, the friction coefficient is reduced from 0.233 to 0.104, the test conditions are extremely stable, and the grinding spot volume is reduced to 22 percent of the original volume.
Application example 11
30mg of the organic carbon nanoball additive (SP @ CN) prepared from example 4 was added to 970mg of 500SN lubricating oil, magnetically stirred for 30min and then ultrasonically mixed for 30 min.
Application example 12
50mg of the organic carbon nanoball additive (SP @ CN) prepared from example 4 was added to 950mg of 500SN lubricating oil, magnetically stirred for 30min and then ultrasonically mixed for 30 min.
Comparative example 1
1000mg of 500SN lubricating oil is taken, stirred magnetically for 30min and then treated with ultrasound for 30min to serve as a blank control group. The fretting wear test was performed using a SRV5 fretting wear tester, and the results are shown in table 5.
In examples 1 to 4, the carbonization temperature of the dope in example 4 was 300 ℃ which is lower than that in examples 1 to 3, because the decomposition temperatures of thiourea and ammonium hypophosphite were 180 ℃ to 200 ℃. After the thiourea, the ammonium hypophosphite and the organic carbon precursor are ground and mixed together, experimental results show that if the carbonization temperature is too high, the thiourea and the ammonium hypophosphite can be decomposed too fast, and cannot be doped or the doping amount is less.
The carbonization temperature of 500 ℃ was employed in examples 1 to 3 above because the organic carbon source and thiourea or ammonium hypophosphite were not mixed together, but they were carbonized by placing them at different temperature positions in a tube furnace; the thiourea or ammonium hypophosphite is firstly decomposed at 200 ℃ and then accompanied by inert gas N2The carbon precursor flows to the position of the organic carbon precursor with the central temperature of 500 ℃, and is doped into the organic carbon through physicochemical reaction at high temperature.
The mass ratio of the organic carbon precursor to the doping source (such as thiourea or ammonium hypophosphite) is 1: 2-25, the mass ratio is set by experiments, and the N, S, P content of the final product is detected by XPS (X-ray photoelectron spectroscopy); that is, the corresponding N, S, P content in the final product was determined by XPS.
TABLE 1 The percentages by mass of the elements in the final products obtained in examples 1-8
From the results in Table 1, it is understood that the doping element (N, S, P element) is present in the additive in an amount of 12.1 to 31.0% by mass.
TABLE 2 particle size of the final products obtained in examples 1-4
| Examples | 1 | 2 | 3 | 4 |
| Final product | CN | S@CN | P@CN | SP@CN |
| Particle size | 110nm | 115nm | 121nm | 118nm |
Table 2 shows the results of particle size measurements of the final product, namely the organic carbon nanosphere lubricating oil additive obtained in examples 1-4, wherein the particle size of the polymer as the organic carbon source precursor before doping and carbonization ranges from 120nm to 160nm, and the average particle size is 137 nm. After doping and carbonization, the grain size of the product is reduced to be within the range of 110 nm-121 nm.
The organic carbon nanoball additives (CN, S @ CN, P @ CN, SP @ CN) obtained in examples 1 to 4 were added to the 500SN lubricating oil at 0.2wt%, respectively, and dispersion stability in the base oil is shown in FIGS. 1 to 2. FIG. 1 is a scanning electron micrograph of the products CN, S @ CN, P @ CN and SP @ CN. In FIG. 2, from left to right, are images of the stability of the blends after CN, S @ CN, P @ CN and SP @ CN, respectively, were used as 500SN additives. As can be seen from fig. 2, after 30 minutes of stirring and 30 minutes of ultrasonic treatment, the initial 4 mixed oils are basically not different, and after standing for 45 days, 500SN lubricating oil added with 0.2wt% CN is just layered, while the organic carbon nanospheres doped with S, P are obviously more stably present in the 500SN lubricating oil.
It can be seen that the N, S, P element doped organic carbon nanospheres prepared in the examples of the present invention have good dispersion stability in the base lubricant oil as the lubricant oil additive, wherein the stability of the organic carbon nanospheres doped with more than 2 elements (S @ CN, P @ CN and SP @ CN) is better than that of the organic carbon nanospheres doped with only N element (CN).
In order to better determine the dispersion stability of the organic carbon nanoball as the 500SN lubricating oil additive, comparative tests were performed with different addition amounts, and the results are shown in table 4.
Table 4 shows the dispersion stability of the organic carbon nanoball in 500SN lubricating oil
As can be seen from the results in Table 4, when CN was added in an amount of 0.2wt%, 3 wt% or 5wt% as a 500SN lubricating oil additive, the initial 3 types of mixed oils were almost no different after 30 minutes of stirring and 30 minutes of ultrasonic treatment, and delamination was observed immediately after standing for 45 days. And 0.2wt%, 3 wt% and 5wt% of S @ CN, P @ CN and SP @ CN are added to be used as 500SN lubricating oil additives, after 30 minutes of stirring and 30 minutes of ultrasonic treatment, the initial 3 kinds of mixed oil have no difference, after standing for 45 days, 5wt% of S @ CN, P @ CN and SP @ CN are added to start layering in the 500SN lubricating oil, and other addition amounts of S @ CN, P @ CN and SP @ CN can be stable and do not delaminate.
It is further illustrated that the organic carbon nanoball doped with P, S element is obviously more stable in 500SN lubricating oil than the organic carbon nanoball CN doped with only N. Although the dispersibility of CN is better than that of other existing non-polar carbon nanospheres, after standing for 45 days, the dispersibility of the organic carbon nanosphere doped with P, S is further enhanced than that of CN, and the phenomenon of delamination of CN is more obvious with the increase of the addition amount. The optimum addition amount of the organic carbon nanoball in the lubricating oil is 0.2wt% to 5wt% as can be obtained from the above experiments.
Fretting friction wear test:
the final products (CN, S @ CN, P @ CN, SP @ CN) prepared in examples 1 to 4 were dispersed in 500SN lubricating oil as 500SN lubricating oil additives at 0.2wt%, respectively, and then subjected to fretting wear tests using SRV5 fretting wear testing machine, the test results being shown in FIGS. 3 to 5. Wherein FIG. 3 is a graph of an extreme pressure test of CN, S @ CN, P @ CN, SP @ CN as a 500SN lubricating oil additive; FIG. 4 is a graph of deadload testing of CN, S @ CN, P @ CN, SP @ CN as a 500SN lubricating oil additive; FIG. 5 is a bar graph of the loss of plaque volume after a constant load test using CN, S @ CN, P @ CN, SP @ CN as a 500SN lubricating oil additive.
In fig. 3-4, the "peak" on the coefficient of friction curve indicates the friction seizure and can be considered as the smoothness of the friction, i.e., the stability portion of table 5. Fig. 5 is a bar graph of the amount of loss relative to a wear volume.
Table 5 shows the results of the fretting wear test in application examples 1, 4, 7 and 10 and comparative example 1
According to the results in table 5, the embodiment of the present invention can effectively improve the bearing capacity of the lubricating oil by doping N, S, P element into the organic carbon nanospheres, and the bearing capacity of the organic carbon nanosphere additive (S @ CN, P @ CN, SP @ CN) is higher than that of the organic carbon nanosphere additive (CN), so that the organic carbon nanosphere additive can form an effective, durable and stable lubricating oil film under a high load condition, reduce the friction coefficient, and protect the mechanical transmission device.
The formation of the lubricating oil film is mainly a weak electromagnetic field generated in the friction process, and the lubricating oil film has the function of adsorbing strong-polarity nano particles, so that the nano particles move to the metal surface and are precipitated on the friction surface, a layer of deposited film consisting of nitride, sulfide and phosphide is formed, the contact area of a friction pair is increased, and the adhesive wear is reduced or avoided.
The wear surface appearance of a sample is observed through an NPFLEX three-dimensional surface profiler, the cross section area of the grinding spot is calculated according to the grinding spot profile of the surface, the wear volume loss is obtained according to the grinding spot length, and the ratio of the wear volume loss to the stroke is used as the wear rate to evaluate the wear resistance of the sample.
As can be seen from the results in Table 5, the stability of the organic carbon nanoball additives (S @ CN, P @ CN, SP @ CN) is higher than that of the organic carbon nanoball additive (CN), and it can be found from the reduction of the wear-resistant spot volume that the organic carbon nanoball with N, S, P element added has more excellent anti-wear and anti-wear effects as 500SN lubricating oil additive, wherein the anti-wear performance of the organic carbon nanoball additives (S @ CN, P @ CN, SP @ CN) is the best.
The N, S, P element-doped organic carbon nanospheres as lubricating oil additives can react with the metal iron surface of a transmission component under extreme friction conditions to form corresponding low-melting-point compounds such as iron carbonate, iron oxide, iron sulfate, iron sulfide, iron phosphate or iron phosphide, and the like, and can fill friction gullies under high-speed and high-load conditions, increase the friction contact area and obtain good lubricating performance. The nano particles form a permeable layer and a diffusion layer with good friction performance on the surface of a friction pair through diffusion and permeation under the action of friction, and meanwhile, the nano particles are subjected to the action of shearing force to perform chemical reaction to produce a chemical reaction film with abrasion resistance, namely, the nano particles react on the surface of metal iron to form corresponding low-melting-point compounds such as iron carbonate, iron oxide, ferric sulfate, ferric sulfide, ferric phosphate or iron phosphide and the like, so that friction gully is filled, the friction contact area is increased, and the lubricating performance is improved.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The preparation method of the organic carbon nanosphere lubricating oil additive is characterized in that the organic carbon nanosphere lubricating oil additive comprises organic carbon nanospheres and doping elements doped on the organic carbon nanospheres through carbonization, wherein the doping elements are N, S, P element or more, and the mass percentage of the doping elements in the additive is 12.1% -31.0%;
the preparation method of the organic carbon nanosphere lubricating oil additive comprises the following steps of:
s1, dissolving the reaction monomer in the reaction solvent, fully mixing, and placing at 0-90 DEG CoReacting for 3-12 h under C to obtain an organic carbon precursor of the polymer;
wherein the reactive monomer is a small molecule compound capable of polymerizing into a hypercrosslinked pi-bond conjugated polymer; the reaction monomer is one or more of aniline, pyrrole, thiophene, thiazole and styrene;
s2, placing the organic carbon precursor and the doping source obtained in the step S1 in a tube furnace for doping carbonization, wherein the temperature of the doping carbonization is 300-500 DEGoC, obtaining a mixture containingOrganic carbon nanospheres of heterosources;
wherein the doping source is one or more of an N source, an S source and a P source;
in step S2, the heating rate of the doping carbonization is 2-10oC/min, and the heat preservation time of doping carbonization is 3-5 h.
2. The method according to claim 1, wherein in step S1, the reaction solvent is a mixture of deionized water and acetonitrile; wherein the volume ratio of the deionized water to the acetonitrile is 1-3: 1.
3. The method according to claim 1, wherein in step S2, the N source is one or more of ammonium hypophosphite, ammonium salt, ammonia water, ammonia gas, and nitrogen gas; the S source is one or more of sulfur tablets, thiourea and hydrogen sulfide gas; the P source is one or more of ammonium hypophosphite, white phosphorus and red phosphorus.
4. The method of claim 3, wherein in step S2, the doping sources include a gas doping source and a non-gas doping source, and the ratio of the dosage of the organic carbon precursor to the dosage of the gas doping source and the non-gas doping source is 1 g: 200-600 ml/min: 0 to 25 g.
5. The organic carbon nanosphere lubricating oil additive prepared by the preparation method of claim 1, wherein the particle size of the organic carbon nanosphere lubricating oil additive is 110 nm-121 nm.
6. The organic carbon nanoball lubricant oil additive of claim 5 is used in lubricant oil.
7. The use of claim 6, wherein the lubricant is one of 500SN, PAO, PEG, A51, and the organic carbon nanosphere lubricant additive is added in the lubricant in an amount of 0.2wt% to 5 wt%.
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| CN110317659A (en) | 2019-10-11 |
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