CN107011967B - Self-nanocrystallized composite preparation for metal friction and wear surface - Google Patents
Self-nanocrystallized composite preparation for metal friction and wear surface Download PDFInfo
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- CN107011967B CN107011967B CN201710256103.8A CN201710256103A CN107011967B CN 107011967 B CN107011967 B CN 107011967B CN 201710256103 A CN201710256103 A CN 201710256103A CN 107011967 B CN107011967 B CN 107011967B
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- 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
- C10M125/26—Compounds containing silicon or boron, e.g. silica, sand
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- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/10—Compounds containing silicon
- C10M2201/102—Silicates
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- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/14—Inorganic compounds or elements as ingredients in lubricant compositions inorganic compounds surface treated with organic compounds
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- 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
Abstract
The invention provides a self-nanocrystallized composite preparation for a metal friction wear surface, which comprises a liquid-phase component and a solid-phase component; the liquid phase component is dissolved in the lubricating oil base oil to form a solvent; the solid phase component is dissolved in a solvent as a solute to prepare a composite preparation; wherein the liquid phase component comprises metal ion doped hydroxyl silicate nanotubes; the solid phase component is used for generating a protective layer on the metal friction and wear surface. The invention solves the defects that the existing composite preparation for self-nanocrystallizing the metal friction wear surface from the metal friction wear surface can not be fully dispersed in lubricating oil and needs the lubricating oil to be cracked and carbonized to participate in the reaction, so that the self-nanocrystallizing efficiency is high and the forming speed of the surface nanocrystalline reinforced protective layer is high.
Description
Technical Field
The invention relates to a self-nanocrystallized composite preparation for a metal friction wear surface, belonging to the field of metal material treatment.
Background
Three major failure modes of machine parts, wear, fatigue and corrosion, all start from the surface, and the surface strengthening treatment of materials is very important.
The metal surface nano-treatment is a new surface strengthening treatment technology developed in recent years, and the self-nano treatment technology is more widely concerned. Compared with the traditional surface strengthening technologies such as thermal spraying, brush plating, laser cladding, Physical Vapor Deposition (PVD), Chemical Vapor Deposition (CVD), three-beam (laser beam, ion beam and electron beam) surface modification and the like, the surface self-nanocrystallization treatment can form a nanostructure layer without an obvious interface with a substrate on the surface of the material, so that the material is wear-resistant and corrosion-resistant, and the surface performance is greatly improved.
Previous research has focused on the realization of surface self-nanocrystallization by surface machining processes such as mechanical grinding, ultrasonic peening, high energy peening, and ultrasonic particle bombardment.
The various surface machining treatments need to generate strong plastic deformation of the material under the repeated action of an external load, and the coarse-grained structure of the surface is gradually thinned to the nanometer level. The surface self-nanocrystallization treatment belongs to an off-line technology, and needs high-energy special equipment, so that the operation time is long and the cost is high.
The relative movement of the friction partners under load is also a mechanical working of the surface, but is not sufficient under normal conditions to produce the strong plastic deformation required for the self-nanocrystallization of the surface. Mechanical alloying and high-temperature internal oxidation are two effective ways for strengthening surface nanocrystals developed in recent years, and can be used for self-nanocrystallization of the surface of metal friction wear. Under general conditions, the thermodynamic conditions of the friction interface can neither realize surface mechanical alloying nor complete high-temperature internal oxidation reaction. The existing technology for realizing self-nanocrystallization of a friction surface by simply utilizing solid-phase components has an action mechanism of mechanical alloying, and comprises three steps of surface oxidation mechanical polishing, lubricating oil cracking carbonization and mechanical alloying. There are the following problems: 1. the solid phase components cannot be dispersed and suspended in the lubricating oil sufficiently; 2. lubricating oil cracking carbonization is required to participate in the reaction; 3. it also fails to explain how the reaction layer of the non-friction contact zone (e.g. the non-contact zone of the cylinder liner surface corresponding to the skirt of the engine piston) is formed without the existence of mechanical alloying conditions; finally, the self-nanocrystallization efficiency is low, and the forming speed of the surface nanocrystalline reinforced protective layer is slow.
Disclosure of Invention
Technical problem to be solved
The invention aims to provide a composite preparation for self-nanocrystallization of a metal friction wear surface, which solves the defects that the existing composite preparation for self-nanocrystallization of the metal friction wear surface cannot be fully dispersed in lubricating oil, and the lubricating oil needs to be cracked and carbonized to participate in reaction, so that the self-nanocrystallization efficiency is low, and the forming speed of a surface nanocrystalline reinforced protective layer is slow.
(II) technical scheme
In order to solve the technical problems, the invention provides a composite preparation with a self-nanocrystallized metal friction wear surface, which comprises a liquid-phase component and a solid-phase component; the liquid phase component is dissolved in the lubricating oil base oil to form a solvent; the solid phase component is dissolved in a solvent as a solute to prepare a composite preparation; wherein the liquid phase component comprises metal ion doped hydroxyl silicate nanotubes; the solid phase component is used for generating a protective layer on the metal friction and wear surface.
Optionally, the solid-phase component contains layered hydroxy silicate natural mineral powder particles.
Optionally, the layered hydroxyl silicate natural mineral powder is a layered silicate mineral formed by hexagonal layer network composite ions; the phyllosilicate mineral composed of hexagonal layer network composite ions is one or more of pyrophyllite, talc, mica, kaolinite, serpentine, chlorite, sepiolite and montmorillonite.
Optionally, the liquid phase component is added into the lubricating oil base oil at a concentration of 50 x 10-6-1000×10-6。
Optionally, the solid phase component is added to the solvent at a concentration of 10 × 10-6-500×10-6。
Optionally, the solid phase component further comprises a surface modifier and a redox agent; the solid phase component comprises the following components in parts by weight:
30-99 parts of layered hydroxyl silicate natural mineral powder
1-30 parts of surface modifier
0.05-5 parts of redox agent.
Optionally, the solid phase component comprises the following components in parts by weight:
60-99 parts of layered hydroxyl silicate natural mineral powder
2-30 parts of surface modifier
0.05-3 parts of redox agent.
Optionally, the solid phase component comprises the following components in parts by weight:
80-99 parts of layered hydroxyl silicate natural mineral powder
5-10 parts of surface modifier
0.05-3 parts of redox agent.
Optionally, the surface modifier is one or more of a cationic surfactant and a coupling agent.
Optionally, the cationic surfactant is one or more of a combination of a higher amine salt and a cationic modified amide.
Optionally, the coupling agent is one or a combination of more of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent.
Optionally, the redox catalyst is one or more of simple substances, oxides and chlorides of elements in groups VIIB and VIII corresponding to 3 long periods (4, 5, 6) in the periodic table.
Optionally, the metal ions in the metal ion-doped hydroxy silicate nanotube are ions of metal elements in groups VIB and VIII corresponding to 3 long periods (4, 5, 6) in the periodic table of elements.
Optionally, the lubricating base oil adopts one or more mixtures with the trade marks of 150SN, 200SN, 250SN, 350SN and 500 SN.
Optionally, the method for manufacturing the metal ion-doped hydroxy silicate nanotube includes the following steps:
1) metal chloride, magnesium nitrate, sodium silicate and sodium hydroxide are mixed according to mass concentration: 1 (20-40) (10-30) (200-);
2) dissolving metal chloride and magnesium nitrate into water, and then adding sodium silicate; continuously stirring for 10-30 minutes, adding sodium hydroxide, and continuously stirring for 10-30 minutes to obtain an intermediate solution;
3) sealing the intermediate solution and placing the intermediate solution in a reaction kettle to react for 20 to 50 hours at the temperature of 200 ℃ and 400 ℃;
4) and after the reaction is finished, centrifugally collecting precipitates, and centrifugally washing the precipitates by using solvents in sequence to obtain the metal ion doped hydroxyl silicate nanotube.
Optionally, the method for manufacturing the metal ion-doped hydroxy silicate nanotube further comprises the following modification steps:
1) dispersing metal ion doped hydroxyl silicate nanotube in organic solvent, and heating to 45-85 deg.c;
2) adding the coupling agent according to the concentration ratio of the metal ion doped hydroxyl silicate nanotube to the coupling agent of 1 (0.03-1), and continuously stirring for 1-2 hours to obtain liquid to be treated;
3) centrifugally separating the liquid to be treated, and then cleaning the liquid by using an organic solvent to obtain the oil-soluble metal ion doped hydroxyl silicate nanotube.
Optionally, the hydroxyl silicate nanotube in the modification step 1) is magnesium silicate hydroxide (Mg)6[Si4O10][OH]8) Nanotube, nickel (Ni) hydroxy silicate3Si2O5(OH)4) Nanotubes orNickel magnesium hydroxy silicate ((Ni, Mg)3Si2O5(OH)4) A nanotube.
Optionally, the organic solvent in the modification step 2) is one of monohydric alcohol, ethanol or propanol.
Optionally, the coupling agent in the modification step 2) is one or more of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent.
(III) advantageous effects
The invention provides a self-nanocrystallized composite preparation for a metal friction wear surface, which has the following advantages:
1) the invention introduces a liquid-solid composite phase component into a friction pair system, and a special internal oxidation process different from high-temperature internal oxidation is generated under the action of mechanochemistry. The action mechanism is firstly the internal oxidation of the friction surface of the metal and secondly the thinning and strengthening of the structural deformation under the action of friction and shearing. Because the liquid phase component is introduced, the concentration of the required solid phase component is greatly reduced, and the lubricating oil is only used as a carrier of the preparation and does not participate in any reaction. The internal oxidation is essentially a thermal oxidation reaction of the alloy phase in the metal surface layer, and the reaction layer in the non-friction contact area is the thermal oxidation reaction layer. In addition, the rate of the internal oxidation reaction by the liquid-solid composite phase is higher than that of the mechanical alloying process. Therefore, the self-nanocrystallization efficiency is higher, and the formation speed of the surface nanocrystalline reinforced protective layer is higher.
2) The layered hydroxyl silicate natural mineral powder is modified by adopting a cationic surfactant and a coupling agent, so that solid phase components in the preparation are fully dispersed and suspended in the lubricating oil.
Drawings
FIG. 1 is an optical microscopic image of a self-nanocrystallized layer formed by oxidation in the surface of a cast iron substrate according to the present invention;
FIG. 2 is a Transmission Electron Microscope (TEM) image of nanocrystals in a self-nanocrystalline layer on the surface of a cast iron substrate according to the present invention;
FIG. 3 is a graph of the energy spectrum analysis of the nanocrystals in the surface self-nanocrystal layer of a cast iron substrate according to the present invention;
FIG. 4 is a transmission electron micrograph of an oxidized self-nanocrystallized layer in the surface of a cast iron substrate according to the present invention;
FIG. 5 is Fe of the present invention3+Transmission Electron Microscope (TEM) images of doped magnesium silicate hydroxide nanotubes;
FIG. 6 is Fe of the present invention3+Doped magnesium silicate hydroxide nanotubes X-ray photoelectron spectroscopy (XPS) plot.
1. A cast iron matrix; 2. internal oxygen self-nanocrystalline layers.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The invention provides a self-nanocrystallized composite preparation for a metal friction wear surface, which comprises a liquid-phase component and a solid-phase component; the liquid phase component is dissolved in the lubricating oil base oil to form a solvent; the solid phase component is dissolved in a solvent as a solute to prepare a composite preparation;
Wherein the liquid phase component comprises metal ion doped hydroxyl silicate nanotubes; the solid phase component is used for generating a protective layer on the metal friction and wear surface.
Wherein the solid phase component contains layered hydroxyl silicate natural mineral powder particles.
The action principle of the self-nanocrystallization component for realizing the metal friction and wear surface provided by the invention is as follows: (1) ultra-precision surface grinding: solid composition particles of the composition and Silica (SiO) produced by their decomposition by friction extrusion cleavage2) And aluminum oxide (Al)2O3) Nanoscale (10)-7-10-9m) superfine grinding the metal friction and wear surface under the action of friction and shearing to generate fresh active surface.
(2) Active material surface adsorption: the surface active bond of the hydroxyl silicate nanotube in the liquid phase component has good adsorbability on the surface of fresh metal, and the metal ion doping makes the nanotube have ferromagnetism, and the nanotube can be directionally arranged and enriched on the surface of the metal under the action of a surface magnetic field generated by friction.
(3) Strong diffusion of active oxygen into the metal: the hydroxyl silicate nanotube in the liquid phase component and the layered hydroxyl silicate natural mineral powder particle in the solid phase component both contain various active chemical bonds, wherein silicon-oxygen bonds, Si-O-Si and O-Si-O are easy to break to generate free oxygen with extremely high activity when cleavage and damage are carried out 2-And O, strongly diffusing into the metal. The strong diffusion effect occurs firstly by rubbing the synthetic nanotubes enriched on the surface and then by the free oxygen generated by the natural ore fines. In addition, the dehydroxylation produces active free water H2O will also diffuse into the metal;
(4) special internal oxidation different from high temperature internal oxidation: free oxygen O diffusing from the surface to the interior2-O and active H2O oxidizes the alloy components of the metal, and for ferrous metals, mainly the alloy component cementite Fe3C is oxidized, and the reaction process is as follows:
[C]Fe+O＝CO；
[C]Fe+2O＝CO2；
[C]Fe+H2O＝CO+H2；
[C]Fe+2H2O＝CO2+2H2
3[Fe]c+4O＝Fe3O4；
3[Fe]c+4H2O＝Fe3O4+4H2
fe formed by internal oxidation3O4Depositing the nano crystal grains on the substrate to form a self-nanocrystallized layer; the generated gas escapes to the surface and forms nanopores from within the nanocrystallized layer. The optical microscopic image of the self-nanocrystallized layer formed by oxidation in the surface of the cast iron substrate is shown in FIG. 1 ((a) is bright field and (b) is dark field-should be removed). FIG. 2 is a Transmission Electron Microscope (TEM) image of nanocrystals in a self-nanocrystalline layer on the surface of a cast iron substrate, (a) is a bright field; (b) is a dark field. FIG. 3 is a graph of the spectrum analysis of the nanocrystalline grains in the surface of the cast iron matrix from the nanocrystalline layer, the elements of the nanocrystalline grains being mainly composed of Fe and O. Transmission electron microscopic derivatization from nanocrystalline layers The analysis by sputtering (see FIG. 4) shows that the nanoparticles distributed on the matrix are Fe3O4. Selected area diffractogram (FIG. 4(b)) shows that Fe3O4Nanoparticles and Fe3The C matrix has a certain phase relation:
[012]Fe3C//[001]Fe3O4
(210)Fe3C//(020)Fe3O4
(011)Fe3C//(200)Fe3O4
(5) the surface self-nanocrystallization structure: the self-nano-crystalline layer formed by oxidation in the cast iron matrix is Fe dispersed on the matrix3O4The nano crystal system consists of a large number of through nano-diameter micropores, and is metallurgically bonded with a substrate without clear physical interface layering.
Wherein, the layered hydroxyl silicate natural mineral powder is a layered silicate mineral formed by hexagonal layer network composite ions; the phyllosilicate mineral composed of hexagonal layer network composite ions is pyrophyllite (Al)2[Si4O10](OH)2) Talc (Mg)3[Si4O10](OH)2) Mica (KMg)3[AlSi3O10](OH)2) Kaolinite (Al)4[Si4O10](OH)8) Serpentine (Mg)6[Si4O10](OH)8) Chlorite ((Mg, Fe)2+,Fe3+)[AlSi2O16](OH)8) Sepiolite (Mg)8Si12O30(OH)4(OH2)4·8H2O), montmorillonite (Al)2(Si4O10)(OH)2) One or more of the above.
The layered hydroxyl silicate natural mineral powder is a layered silicate mineral with a crystal structure formed by six silicon-oxygen tetrahedrons which form hexagons and extend infinitely in a plane to form hexagonal layer network composite ions.
Wherein the concentration of the liquid phase component added into the lubricating oil base oil is 50 in the specification 10-6-1000×10-6。
Wherein the concentration of the solid phase component added to the solvent is 10 x 10-6-500×10-6。
Wherein, the solid phase component also comprises a surface modifier and a redox agent; the solid phase component comprises the following components in parts by weight:
30-99 parts of layered hydroxyl silicate natural mineral powder
1-30 parts of surface modifier
0.05-5 parts of redox agent.
The solid phase component comprises the following components in parts by weight:
60-99 parts of layered hydroxyl silicate natural mineral powder
2-30 parts of surface modifier
0.05-3 parts of redox agent.
The solid phase component comprises the following components in parts by weight:
80-99 parts of layered hydroxyl silicate natural mineral powder
5-10 parts of surface modifier
0.05-3 parts of redox agent.
The solid phase component (layered hydroxyl silicate natural mineral powder) of the invention is synthesized and prepared by the following steps: 1) grinding the layered hydroxyl silicate natural mineral powder and a surface modifier into submicron-order oil-soluble composite powder;
2) adding a redox agent, and continuously grinding to form uniform oil-soluble composition powder G, thus obtaining a solid phase component of the liquid-solid composite phase component of the invention as a solute for later use.
3) The composition powder G was used as a solute at 10X 10 -6-500×10-6The concentration is added into a solvent containing a liquid phase component, and the liquid-solid composite phase preparation capable of realizing self-nanocrystallization of the friction and wear surface of the metal is obtained.
Wherein, the surface modifier is one or more of cationic surfactant and coupling agent.
Wherein the cationic surfactant is one or more of higher amine salt and cation modified amide. The higher amine salt is primary amine, secondary amine, tertiary amine and quaternary amine.
Wherein the coupling agent is one or the combination of more of silane coupling agent, titanate coupling agent and aluminate coupling agent.
Wherein, the redox agent is one or more of simple substances, oxides and chlorides of elements in VIIB and VIII groups corresponding to 3 long periods (4, 5 and 6) in the periodic table. The group VIIB and VIII elements in the present invention include manganese Mn, technetium Tc, rhenium Re, iron Fe, cobalt Co, nickel Ni, ruthenium Ru, rhodium Rh, palladium Pd, osmium Os, iridium Ir, platinum Pt, etc.
Wherein, the metal ions in the metal ion doped hydroxyl silicate nanotube are ions of VIB group and VIII group metal elements corresponding to 3 long periods (4, 5, 6) in the periodic table of elements, such as Cr3+、Fe3+、Ni2+、Co+And the like.
Wherein, the lubricating oil base oil adopts one or more mixtures with the trade marks of 150SN, 200SN, 250SN, 350SN and 500 SN. Other lubricating base oils may also be employed as desired.
The method for manufacturing the metal ion doped hydroxyl silicate nanotube comprises the following steps:
1) metal chloride, magnesium nitrate, sodium silicate and sodium hydroxide are mixed according to mass concentration: 1 (20-40) (10-30) (200-);
2) dissolving metal chloride and magnesium nitrate into water, and then adding sodium silicate; continuously stirring for 10-30 minutes, adding sodium hydroxide, and continuously stirring for 10-30 minutes to obtain an intermediate solution;
3) sealing the intermediate solution and placing the intermediate solution in a reaction kettle to react for 20 to 50 hours at the temperature of 200 ℃ and 400 ℃;
4) and after the reaction is finished, centrifugally collecting precipitates, and centrifugally washing the precipitates by using solvents in sequence to obtain the metal ion doped hydroxyl silicate nanotube.
The manufacturing method of the metal ion doped hydroxyl silicate nanotube further comprises the following modification steps:
1) dispersing metal ion doped hydroxyl silicate nanotube in organic solvent, and heating to 45-85 deg.c;
2) adding the coupling agent according to the concentration ratio of the metal ion doped hydroxyl silicate nanotube to the coupling agent of 1 (0.03-1), and continuously stirring for 1-2 hours to obtain liquid to be treated;
3) centrifugally separating the liquid to be treated, and then cleaning the liquid by using an organic solvent to obtain the oil-soluble metal ion doped hydroxyl silicate nanotube.
Wherein the hydroxyl silicate nanotube in the modification step 1) is magnesium silicate hydroxide (Mg)6[Si4O10][OH]8) Nanotube, nickel (Ni) hydroxy silicate3Si2O5(OH)4) Nanotubes or nickel magnesium hydroxy silicate ((Ni, Mg)3Si2O5(OH)4) A nanotube.
Wherein, the organic solvent in the modification step 2) is one of monohydric alcohol, ethanol or propanol.
Wherein, the coupling agent in the modification step 2) is one or more of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent.
The following examples are intended to illustrate the present invention
Example 1:
preparing the metal ion doped hydroxyl silicate nanotube:
(1) the chemical reagents used: ferrous chloride, magnesium nitrate, sodium silicate and sodium hydroxide, wherein the mass concentration ratio is as follows: 1:20:10: 200;
(2) dissolving ferrous chloride and magnesium nitrate into water according to the mass concentration ratio in the step (1) to obtain a solution A;
(3) adding sodium silicate into the solution A according to the mass concentration ratio in the step (1) under magnetic stirring to obtain a solution B;
(4) continuously stirring the solution B10 minutes, adding sodium hydroxide according to the mass concentration ratio in the step (1), and continuously stirring for 10 minutes to obtain a solution C;
(5) sealing the solution C in a polytetrafluoroethylene hydrothermal kettle, and reacting for 20 hours at 200 ℃;
(6) After the reaction is finished, centrifugally collecting precipitate, and centrifugally washing the precipitate by using ethanol and water in sequence to remove impurity ions possibly existing to obtain Fe3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) Nanotubes, FIG. 5 is the Fe obtained3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) Nanotube Transmission Electron Microscopy (TEM) images; FIG. 6 is the result of analysis by X-ray photoelectron spectroscopy (XPS);
modification of metal ion-doped hydroxyl silicate nanotube:
(1) mixing Fe3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) Dispersing the nanotube C in a monohydric alcohol organic solvent, and heating to 45 ℃;
(2) according to Fe3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) Adding an aluminate coupling agent into the nanotube and the coupling agent at a concentration ratio of 1:0.03, and continuously stirring for 1 hour to obtain a liquid D;
(3) centrifugally separating the liquid D, and washing with organic solvent methanol to obtain white precipitate which is oil-soluble Fe3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) A nanotube.
Preparing layered hydroxyl silicate natural mineral powder:
sepiolite (Mg) made of trioctahedral layered hydroxy silicate8Si12O30(OH)4(OH2)4·8H2O) and dioctahedral phyllosilicate kaolinite (A)14(Si4O10)(OH)8) The combination of two kinds of natural mineral powder is used as base material to synthesize layered hydroxyl silicate natural mineral powder, and the preparation steps are as follows:
(1) mixing two natural mineral powder sepiolite (Mg)8Si12O30(OH)4(OH2)4·8H2O) and kaolinite (A1) 4(Si4O10)(OH)8) With cationic polyacrylamide (([ CH)2CH]nCONH2-) and HD-22 silane coupling agent in parts by weight: 15:15:0.5: 0.5, and grinding the mixture into submicron oil-soluble composite powder by a planetary high-energy ball mill;
(2) adding a redox catalyst cobalt dichloride (CoCl) into submicron oil-soluble composite powder2)0.05 part of the mixture is continuously ground to form uniform composition powder, namely solute solid-phase component G.
Preparing a self-nanocrystallized composite preparation for the surface of metal friction and wear:
1) mixing oil soluble Fe3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) Nanotubes at a concentration of 50X 10-6Adding the mixture into lubricating oil base oil to obtain a liquid phase component Y of the liquid-solid composite phase component of the invention, and using the liquid phase component Y as a solvent for later use.
2) Mixing the prepared solid phase component G at a ratio of 10 × 10-6The concentration ratio of the components is added into the liquid-phase component Y to obtain the liquid-solid composite phase preparation for realizing the self-nanocrystallization of the friction and wear surface of the metal, and the liquid-solid composite phase preparation can be directly added into lubricating oil for use. The concentration ratio of the additive to the lubricating oil is 20X 10-6。
The influence test of the engine performance is carried out on 1.6 rows of two passenger cars (one car runs 8 kilometres for the A group, and the other car runs 11 kilometres for the B group), after 3000 kilometres of composite preparation with self-nanocrystallization of the metal friction wear surface is used for running, the result is compared with that when 6000 kilometres of composite preparation with the existing lubricating oil is added for running, the result shows that:
(1) When the self-nanocrystallized composite preparation with the metal friction wear surface runs for 3000km, the cylinder pressure of the engine obviously rises, the group A averagely rises by 4.5 percent, the group B averagely rises by 4.83 percent, and the maximum cylinder pressure rise is 7.5 percent.
(2) When the self-nanocrystallized composite preparation with a metal friction wear surface runs for 3000km, the noise of the engine is obviously reduced, the average of the group A is reduced by 16.93%, the average of the group B is reduced by 16.78%, and the maximum noise reduction value is 20.7dB (noise in the vehicle).
(3) When the self-nanocrystallized composite preparation with the metal friction wear surface is added to run for 3000km, compared with the time when the self-nanocrystallized composite preparation is not added to run for 6000km, the CO of the A group vehicle is reduced by 24 percent, and the HC + NOx is reduced by 23 percent; the CO of the B group vehicle is reduced by 19 percent, and the HC + NOx is reduced by 21 percent.
Example 2
Preparing the metal ion doped hydroxyl silicate nanotube:
(1) the chemical reagents used: chromium chloride, magnesium nitrate, sodium silicate and sodium hydroxide, wherein the mass concentration ratio is as follows: 1:40:30: 450;
(2) dissolving chromite chloride and magnesium nitrate into water according to the mass concentration ratio in the step (1) to obtain a solution A;
(3) adding sodium silicate into the solution A according to the mass concentration ratio in the step (1) under magnetic stirring to obtain a solution B;
(4) continuously stirring the solution B for 30 minutes, adding sodium hydroxide according to the mass concentration ratio in the step (1), and continuously stirring for 30 minutes to obtain a solution C;
(5) Sealing the solution C in a polytetrafluoroethylene hydrothermal kettle, and reacting for 50 hours at 400 ℃;
(6) after the reaction is finished, centrifugally collecting precipitate, and centrifugally washing the precipitate by using ethanol and water in sequence to remove impurity ions possibly existing to obtain Cr3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) A nanotube;
modification of metal ion-doped hydroxyl silicate nanotube:
(1) mixing Cr3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) Dispersing the nanotube C in a monohydric alcohol organic solvent, and heating to 85 ℃;
(2) according to Cr3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) Adding an aluminate coupling agent into the nanotube and the coupling agent at a concentration ratio of 1:1, and continuously stirring for 2 hours to obtain a liquid D;
(3) centrifugally separating the liquid D, washing with organic solvent methanol to obtain white precipitate as oil soluble Cr3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) A nanotube.
Preparing layered hydroxyl silicate natural mineral powder:
sepiolite (Mg) made of trioctahedral layered hydroxy silicate8Si12O30(OH)4(OH2)4·8H2O) and dioctahedral phyllosilicate kaolinite (A)14(Si4O10)(OH)8) The combination of two kinds of natural mineral powder is used as base material to synthesize layered hydroxyl silicate natural mineral powder, and the preparation steps are as follows:
(1) mixing two natural mineral powder sepiolite (Mg)8Si12O30(OH)4(OH2)4·8H2O) and kaolinite (A1)4(Si4O10)(OH)8) With cationic polyacrylamide (([ CH)2CH]nCONH2-) and HD-22 silane coupling agent were added in parts by weight 49.5:49.5: 15: 15, grinding the mixture into submicron oil-soluble composite powder by a planetary high-energy ball mill;
(2) Adding an oxidation reducing agent cobalt dichloride (CoCl) into submicron oil-soluble composite powder2) And 5 parts of the mixture is continuously ground to form uniform composition powder, namely solute solid-phase component G.
Preparing a self-nanocrystallized composite preparation for the surface of metal friction and wear:
1) mixing oil soluble Cr3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) Nanotubes at a concentration of 50X 10-6-500×10-6Adding the mixture into lubricating oil base oil to obtain a liquid phase component Y of the liquid-solid composite phase component of the invention, and using the liquid phase component Y as a solvent for later use.
2) Mixing the prepared solid phase component G at 100 × 10-6The concentration ratio of the components is added into the liquid-phase component Y to obtain the liquid-solid composite phase preparation for realizing the self-nanocrystallization of the friction and wear surface of the metal, and the liquid-solid composite phase preparation can be directly added into lubricating oil for use. The concentration ratio of the additive to the lubricating oil is 20X 10-6-200×10-6。
The influence test of the engine performance is carried out on 1.6 rows of two passenger cars (one car runs 8 kilometres for the A group, and the other car runs 11 kilometres for the B group), after 3000 kilometres of composite preparation with self-nanocrystallization of the metal friction wear surface is used for running, the result is compared with that when 6000 kilometres of composite preparation with the existing lubricating oil is added for running, the result shows that:
(1) when the self-nanocrystallized composite preparation with the metal friction wear surface runs for 3000km, the cylinder pressure of the engine obviously rises, the group A averagely rises by 5.5 percent, the group B averagely rises by 5.6 percent, and the maximum cylinder pressure rise is 8.9 percent.
(2) When the self-nanocrystallized composite preparation with a metal friction wear surface runs for 3000km, the noise of the engine is obviously reduced, the average of the group A is reduced by 19.73 percent, the average of the group B is reduced by 18.58 percent, and the maximum noise reduction value is 21.5dB (noise in a vehicle).
(3) When the self-nanocrystallized composite preparation with the metal friction wear surface runs for 3000km, compared with 6000km without the metal friction wear surface, the CO of the A group vehicle is reduced by 25 percent, and the HC + NOx is reduced by 26 percent; the CO of the B group vehicle is reduced by 21 percent, and the HC + NOx is reduced by 23 percent.
Example 3
Preparing the metal ion doped hydroxyl silicate nanotube:
(1) the chemical reagents used: nickel chloride, magnesium nitrate, sodium silicate and sodium hydroxide, wherein the mass concentration ratio is as follows: 1:30:20: 325;
(2) dissolving nickel chloride and magnesium nitrate into water according to the mass concentration ratio in the step (1) to obtain a solution A;
(3) adding sodium silicate into the solution A according to the mass concentration ratio in the step (1) under magnetic stirring to obtain a solution B;
(4) continuously stirring the solution B for 20 minutes, adding sodium hydroxide according to the mass concentration ratio in the step (1), and continuously stirring for 20 minutes to obtain a solution C;
(5) sealing the solution C in a polytetrafluoroethylene hydrothermal kettle, and reacting for 35 hours at 300 ℃;
(6) after the reaction is finished, centrifugally collecting precipitate, and centrifugally washing the precipitate by using ethanol and water in sequence to remove impurity ions possibly existing to obtain Ni 2+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) A nanotube;
modification of metal ion-doped hydroxyl silicate nanotube:
(1) mixing Ni2+Doped magnesium hydroxy silicate(Mg6[Si4O10][OH]8) Dispersing the nanotube C in a monohydric alcohol organic solvent, and heating to 65 ℃;
(2) according to Ni2+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) Adding an aluminate coupling agent into the nanotube and the coupling agent at a concentration ratio of 1:0.06, and continuously stirring for 1.5 hours to obtain a liquid D;
(3) centrifugally separating the liquid D, washing with organic solvent methanol to obtain white precipitate which is oil-soluble Ni2+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) A nanotube.
Preparing layered hydroxyl silicate natural mineral powder:
sepiolite (Mg) made of trioctahedral layered hydroxy silicate8Si12O30(OH)4(OH2)4·8H2O) and dioctahedral phyllosilicate kaolinite (A)14(Si4O10)(OH)8) The combination of two kinds of natural mineral powder is used as base material to synthesize layered hydroxyl silicate natural mineral powder, and the preparation steps are as follows:
(1) mixing two natural mineral powder sepiolite (Mg)8Si12O30(OH)4(OH2)4·8H2O) and kaolinite (A1)4(Si4O10)(OH)8) With cationic polyacrylamide (([ CH)2CH]nCONH2-) and HD-22 silane coupling agent in parts by weight 30:30: 1: 1, grinding the mixture into submicron oil-soluble composite powder by a planetary high-energy ball mill;
(2) adding a redox catalyst cobalt dichloride (CoCl) into submicron oil-soluble composite powder 2) And continuously grinding 3 parts of the mixture to form uniform composition powder, namely solute solid-phase component G.
Preparing a self-nanocrystallized composite preparation for the surface of metal friction and wear:
1) mixing oil soluble Ni2+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) Nanotubes at a concentration of 275X 10-6Adding the mixture into lubricating oil base oil to obtain a liquid phase component Y of the liquid-solid composite phase component of the invention, and using the liquid phase component Y as a solvent for later use.
2) Mixing the prepared solid phase component G at 500X 10-6The concentration ratio of the components is added into the liquid-phase component Y to obtain the liquid-solid composite phase preparation for realizing the self-nanocrystallization of the friction and wear surface of the metal, and the liquid-solid composite phase preparation can be directly added into lubricating oil for use. The concentration ratio of the additive to the lubricating oil is 110 multiplied by 10-6。
The influence test of the engine performance is carried out on 1.6 rows of two passenger cars (one car runs 8 kilometres for the A group, and the other car runs 11 kilometres for the B group), after 3000 kilometres of composite preparation with self-nanocrystallization of the metal friction wear surface is used for running, the result is compared with that when 6000 kilometres of composite preparation with the existing lubricating oil is added for running, the result shows that:
(1) when the self-nanocrystallized composite preparation with the metal friction wear surface runs for 3000km, the cylinder pressure of the engine obviously rises, the group A averagely rises by 5.3 percent, the group B averagely rises by 5.4 percent, and the maximum cylinder pressure rise is 8.6 percent.
(2) When the self-nanocrystallized composite preparation with a metal friction wear surface runs for 3000km, the noise of the engine is obviously reduced, the average of the group A is reduced by 19.73 percent, the average of the group B is reduced by 18.52 percent, and the maximum noise reduction value is 21.2dB (noise in a vehicle).
(3) When the self-nanocrystallized composite preparation with the metal friction wear surface runs for 3000km, compared with 6000km without the metal friction wear surface, the CO of the A group vehicle is reduced by 22 percent, and the HC + NOx is reduced by 23 percent; the CO of the B group vehicle is reduced by 20 percent, and the HC + NOx is reduced by 21 percent.
Example 4
Preparing the metal ion doped hydroxyl silicate nanotube:
(1) the chemical reagents used: cobalt chloride, magnesium nitrate, sodium silicate and sodium hydroxide, wherein the mass concentration ratio is as follows: 1:25:20: 300;
(2) dissolving cobalt chloride and magnesium nitrate into water according to the mass concentration ratio in the step (1) to obtain a solution A;
(3) adding sodium silicate into the solution A according to the mass concentration ratio in the step (1) under magnetic stirring to obtain a solution B;
(4) continuously stirring the solution B for 25 minutes, adding sodium hydroxide according to the mass concentration ratio in the step (1), and continuously stirring for 25 minutes to obtain a solution C;
(5) sealing the solution C in a polytetrafluoroethylene hydrothermal kettle, and reacting for 30 hours at 250 ℃;
(6) after the reaction is finished, centrifugally collecting precipitate, and centrifugally washing the precipitate by using ethanol and water in sequence to remove impurity ions possibly existing to obtain Co +Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) A nanotube;
modification of metal ion-doped hydroxyl silicate nanotube:
(1) mixing Co+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) Dispersing the nanotube C in a monohydric alcohol organic solvent, and heating to 60 ℃;
(2) according to Co+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) Adding an aluminate coupling agent into the nanotube and the coupling agent at a concentration ratio of 1:0.08, and continuously stirring for 2 hours to obtain a liquid D;
(3) centrifugally separating the liquid D, washing with organic solvent methanol to obtain white precipitate which is oil-soluble Co+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) A nanotube.
Preparing layered hydroxyl silicate natural mineral powder:
sepiolite (Mg) made of trioctahedral layered hydroxy silicate8Si12O30(OH)4(OH2)4·8H2O) and dioctahedral phyllosilicate kaolinite (A)14(Si4O10)(OH)8) The combination of two kinds of natural mineral powder is used as base material to synthesize layered hydroxyl silicate natural mineral powder, and the preparation steps are as follows:
(1) mixing two natural mineral powder sepiolite (Mg)8Si12O30(OH)4(OH2)4·8H2O) and kaolinite (A1)4(Si4O10)(OH)8) With cationic polyacrylamides((-[CH2CH]nCONH2-) and HD-22 silane coupling agent were added in parts by weight 49.5:49.5: 15: 15, grinding the mixture into submicron oil-soluble composite powder by a planetary high-energy ball mill;
(2) adding a redox catalyst cobalt dichloride (CoCl) into submicron oil-soluble composite powder 2) And continuously grinding 3 parts of the mixture to form uniform composition powder, namely solute solid-phase component G.
Preparing a self-nanocrystallized composite preparation for the surface of metal friction and wear:
1) mixing oil soluble Co+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) Nanotubes at a concentration of 300X 10-6Adding the mixture into lubricating oil base oil to obtain a liquid phase component Y of the liquid-solid composite phase component of the invention, and using the liquid phase component Y as a solvent for later use.
2) Mixing the prepared solid phase component G at 200 × 10-6The concentration ratio of the components is added into the liquid-phase component Y to obtain the liquid-solid composite phase preparation for realizing the self-nanocrystallization of the friction and wear surface of the metal, and the liquid-solid composite phase preparation can be directly added into lubricating oil for use. The concentration ratio of the additive to the lubricating oil is 100 multiplied by 10-6。
The influence test of the engine performance is carried out on 1.6 rows of two passenger cars (one car runs 8 kilometres for the A group, and the other car runs 11 kilometres for the B group), after 3000 kilometres of composite preparation with self-nanocrystallization of the metal friction wear surface is used for running, the result is compared with that when 6000 kilometres of composite preparation with the existing lubricating oil is added for running, the result shows that:
(1) when the self-nanocrystallized composite preparation added with the metal friction wear surface runs for 3000km, the cylinder pressure of the engine obviously rises, the group A averagely rises by 5.2 percent, the group B averagely rises by 5.1 percent, and the maximum cylinder pressure rise is 8.4 percent.
(2) When the self-nanocrystallized composite preparation with a metal friction wear surface runs for 3000km, the noise of the engine is obviously reduced, the average of the group A is reduced by 19.73 percent, the average of the group B is reduced by 18.62 percent, and the maximum noise reduction value is 21.7dB (noise in a vehicle).
(3) When the self-nanocrystallized composite preparation with the metal friction wear surface runs for 3000km, compared with the time when the self-nanocrystallized composite preparation is not filled for 6000km, the CO of the A group vehicle is reduced by 22 percent, and the HC + NOx is reduced by 22 percent; the CO of the B group vehicle is reduced by 20 percent, and the HC + NOx is reduced by 20 percent.
Example 5
Preparing the metal ion doped hydroxyl silicate nanotube:
(1) the chemical reagents used: ferrous chloride, magnesium nitrate, sodium silicate and sodium hydroxide, wherein the mass concentration ratio is as follows: 1:30:20: 300;
(2) dissolving ferrous chloride and magnesium nitrate into water according to the mass concentration ratio in the step (1) to obtain a solution A;
(3) adding sodium silicate into the solution A according to the mass concentration ratio in the step (1) under magnetic stirring to obtain a solution B;
(4) continuously stirring the solution B for 25 minutes, adding sodium hydroxide according to the mass concentration ratio in the step (1), and continuously stirring for 25 minutes to obtain a solution C;
(5) sealing the solution C in a polytetrafluoroethylene hydrothermal kettle, and reacting for 30 hours at 250 ℃;
(6) after the reaction is finished, centrifugally collecting precipitate, and centrifugally washing the precipitate by using ethanol and water in sequence to remove impurity ions possibly existing to obtain Fe 3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) A nanotube;
modification of metal ion-doped hydroxyl silicate nanotube:
(1) mixing Fe3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) Dispersing the nanotube C in a monohydric alcohol organic solvent, and heating to 65 ℃;
(2) according to Fe3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) Adding an aluminate coupling agent into the nanotube and the coupling agent at a concentration ratio of 1:0.04, and continuously stirring for 2 hours to obtain liquid D;
(3) centrifugally separating the liquid D, and washing with organic solvent methanol to obtain white precipitate which is oil-soluble Fe3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) A nanotube.
Preparing layered hydroxyl silicate natural mineral powder:
sepiolite (Mg) made of trioctahedral layered hydroxy silicate8Si12O30(OH)4(OH2)4·8H2O) and dioctahedral phyllosilicate kaolinite (A)14(Si4O10)(OH)8) The combination of two kinds of natural mineral powder is used as base material to synthesize layered hydroxyl silicate natural mineral powder, and the preparation steps are as follows:
(1) mixing two natural mineral powder sepiolite (Mg)8Si12O30(OH)4(OH2)4·8H2O) and kaolinite (A1)4(Si4O10)(OH)8) With cationic polyacrylamide (([ CH)2CH]nCONH2-) and an HD-22 silane coupling agent in a weight ratio of 40:40: 2.5: 2.5, grinding the mixture into submicron oil-soluble composite powder by a planetary high-energy ball mill;
(2) adding an oxidation reducing agent cobalt dichloride (CoCl) into submicron oil-soluble composite powder 2)0.05 part of the mixture is continuously ground to form uniform composition powder, namely solute solid-phase component G.
Preparing a self-nanocrystallized composite preparation for the surface of metal friction and wear:
1) mixing oil soluble Fe3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) Nanotubes at a concentration of 400X 10-6Adding the mixture into lubricating oil base oil to obtain a liquid phase component Y of the liquid-solid composite phase component of the invention, and using the liquid phase component Y as a solvent for later use.
2) Mixing the prepared solid phase component G at 200 × 10-6The concentration ratio of the components is added into the liquid-phase component Y to obtain the liquid-solid composite phase preparation for realizing the self-nanocrystallization of the friction and wear surface of the metal, and the liquid-solid composite phase preparation can be directly added into lubricating oil for use. The concentration ratio of the additive to the lubricating oil is 100 multiplied by 10-6。
The influence test of the engine performance is carried out on 1.6 rows of two passenger cars (one car runs 8 kilometres for the A group, and the other car runs 11 kilometres for the B group), after 3000 kilometres of composite preparation with self-nanocrystallization of the metal friction wear surface is used for running, the result is compared with that when 6000 kilometres of composite preparation with the existing lubricating oil is added for running, the result shows that:
(1) when the self-nanocrystallized composite preparation added with the metal friction wear surface runs for 3000km, the cylinder pressure of the engine obviously rises, the group A averagely rises by 6.2 percent, the group B averagely rises by 6.1 percent, and the maximum cylinder pressure rise is 10.3 percent.
(2) When the self-nanocrystallized composite preparation with a metal friction wear surface runs for 3000km, the noise of the engine is obviously reduced, the average of the group A is reduced by 20.13%, the average of the group B is reduced by 20.22%, and the maximum noise reduction value is 22.5dB (noise in the vehicle).
(3) When the self-nanocrystallized composite preparation with the metal friction wear surface runs for 3000km, compared with the time when the self-nanocrystallized composite preparation is not filled for 6000km, the CO of the A group vehicle is reduced by 25 percent, and the HC + NOx is reduced by 28 percent; the CO of the B group vehicle is reduced by 27 percent, and the HC + NOx is reduced by 29 percent.
Example 6
Preparing the metal ion doped hydroxyl silicate nanotube:
(1) the chemical reagents used: ferrous chloride, magnesium nitrate, sodium silicate and sodium hydroxide, wherein the mass concentration ratio is as follows: 1:25:30: 300;
(2) dissolving ferrous chloride and magnesium nitrate into water according to the mass concentration ratio in the step (1) to obtain a solution A;
(3) adding sodium silicate into the solution A according to the mass concentration ratio in the step (1) under magnetic stirring to obtain a solution B;
(4) continuously stirring the solution B for 25 minutes, adding sodium hydroxide according to the mass concentration ratio in the step (1), and continuously stirring for 25 minutes to obtain a solution C;
(5) sealing the solution C in a polytetrafluoroethylene hydrothermal kettle to react for 35 hours at 250 ℃;
(6) after the reaction is finished, centrifugally collecting precipitate, and centrifugally washing the precipitate by using ethanol and water in sequence to remove impurity ions possibly existing to obtain Fe 3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) A nanotube;
modification of metal ion-doped hydroxyl silicate nanotube:
(1) mixing Fe3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) Dispersing the nanotube C in a monohydric alcohol organic solvent, and heating to 60 ℃;
(2) according to Fe3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) Adding an aluminate coupling agent into the nanotube and the coupling agent at a concentration ratio of 1:0.08, and continuously stirring for 2 hours to obtain a liquid D;
(3) centrifugally separating the liquid D, and washing with organic solvent methanol to obtain white precipitate which is oil-soluble Fe3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) A nanotube.
Preparing layered hydroxyl silicate natural mineral powder:
sepiolite (Mg) made of trioctahedral layered hydroxy silicate8Si12O30(OH)4(OH2)4·8H2O) and dioctahedral phyllosilicate kaolinite (A)14(Si4O10)(OH)8) The combination of two kinds of natural mineral powder is used as base material to synthesize layered hydroxyl silicate natural mineral powder, and the preparation steps are as follows:
(1) mixing two natural mineral powder sepiolite (Mg)8Si12O30(OH)4(OH2)4·8H2O) and kaolinite (A1)4(Si4O10)(OH)8) With cationic polyacrylamide (([ CH)2CH]nCONH2-) and HD-22 silane coupling agent were added in parts by weight 49.5:49.5: 5:5, grinding the mixture into submicron oil-soluble composite powder by a planetary high-energy ball mill;
(2) adding an oxidation reducing agent cobalt dichloride (CoCl) into submicron oil-soluble composite powder 2) And continuously grinding 3 parts of the mixture to form uniform composition powder, namely solute solid-phase component G.
Preparing a self-nanocrystallized composite preparation for the surface of metal friction and wear:
1) mixing oil soluble Fe3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) Nanotube by concentration300×10-6Adding the mixture into lubricating oil base oil to obtain a liquid phase component Y of the liquid-solid composite phase component of the invention, and using the liquid phase component Y as a solvent for later use.
2) Mixing the prepared solid phase component G at 200 × 10-6The concentration ratio of the components is added into the liquid-phase component Y to obtain the liquid-solid composite phase preparation for realizing the self-nanocrystallization of the friction and wear surface of the metal, and the liquid-solid composite phase preparation can be directly added into lubricating oil for use. The concentration ratio of the additive to the lubricating oil is 100 multiplied by 10-6。
The influence test of the engine performance is carried out on 1.6 rows of two passenger cars (one car runs 8 kilometres for the A group, and the other car runs 11 kilometres for the B group), after 3000 kilometres of composite preparation with self-nanocrystallization of the metal friction wear surface is used for running, the result is compared with that when 6000 kilometres of composite preparation with the existing lubricating oil is added for running, the result shows that:
(1) when the self-nanocrystallized composite preparation with the metal friction wear surface runs for 3000km, the cylinder pressure of the engine obviously rises, the group A averagely rises by 6.5 percent, the group B averagely rises by 6.3 percent, and the maximum cylinder pressure rise is 10.6 percent.
(2) When the self-nanocrystallized composite preparation with a metal friction wear surface runs for 3000km, the noise of the engine is obviously reduced, the average of the group A is reduced by 20.54 percent, the average of the group B is reduced by 20.46 percent, and the maximum noise reduction value is 22.9dB (noise in a vehicle).
(3) When the self-nanocrystallized composite preparation with the metal friction wear surface runs for 3000km, compared with the time when the self-nanocrystallized composite preparation is not filled for 6000km, the CO of the A group vehicle is reduced by 28 percent, and the HC + NOx is reduced by 31 percent; the CO of the B group vehicle is reduced by 32 percent, and the HC + NOx is reduced by 31 percent.
Comparative example 1:
preparing the metal ion doped hydroxyl silicate nanotube:
(1) the chemical reagents used: ferrous chloride, magnesium nitrate, sodium silicate and sodium hydroxide, wherein the mass concentration ratio is as follows: 1:10:5: 100;
(2) dissolving ferrous chloride and magnesium nitrate into water according to the mass concentration ratio in the step (1) to obtain a solution A;
(3) adding sodium silicate into the solution A according to the mass concentration ratio in the step (1) under magnetic stirring to obtain a solution B;
(4) continuously stirring the solution B for 25 minutes, adding sodium hydroxide according to the mass concentration ratio in the step (1), and continuously stirring for 25 minutes to obtain a solution C;
(5) sealing the solution C in a polytetrafluoroethylene hydrothermal kettle to react for 55 hours at 500 ℃;
(6) after the reaction is finished, centrifugally collecting precipitate, and centrifugally washing the precipitate by using ethanol and water in sequence to remove impurity ions possibly existing to obtain Fe 3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) A nanotube;
modification of metal ion-doped hydroxyl silicate nanotube:
(1) mixing Fe3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) Dispersing the nanotube C in a monohydric alcohol organic solvent, and heating to 60 ℃;
(2) according to Fe3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) Adding an aluminate coupling agent into the nanotube and the coupling agent at a concentration ratio of 1:0.08, and continuously stirring for 2 hours to obtain a liquid D;
(3) centrifugally separating the liquid D, and washing with organic solvent methanol to obtain white precipitate which is oil-soluble Fe3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) A nanotube.
Preparing layered hydroxyl silicate natural mineral powder:
sepiolite (Mg) made of trioctahedral layered hydroxy silicate8Si12O30(OH)4(OH2)4·8H2O) and dioctahedral phyllosilicate kaolinite (A)14(Si4O10)(OH)8) The combination of two kinds of natural mineral powder is used as base material to synthesize layered hydroxyl silicate natural mineral powder, and the preparation steps are as follows:
(1) mixing two natural mineral powder sepiolite (Mg)8Si12O30(OH)4(OH2)4·8H2O) and kaolinite (A1)4(Si4O10)(OH)8) Harmonizing yangIonic polyacrylamide (([ CH)2CH]nCONH2-) and HD-22 silane coupling agent in parts by weight 50:50: 0.2: 0.2, and grinding the mixture into submicron oil-soluble composite powder by a planetary high-energy ball mill;
(2) adding a redox catalyst cobalt dichloride (CoCl) into submicron oil-soluble composite powder 2)0.01 part of the mixture is continuously ground to form uniform composition powder, namely solute solid-phase component G.
Preparing a self-nanocrystallized composite preparation for the surface of metal friction and wear:
1) mixing oil soluble Fe3+Doped magnesium hydroxy silicate (Mg)6[Si4O10][OH]8) Nanotubes were grown at a concentration of 10X 10-6Adding the mixture into lubricating oil base oil to obtain a liquid phase component Y of the liquid-solid composite phase component of the invention, and using the liquid phase component Y as a solvent for later use.
2) Preparing the solid phase component G according to the ratio of 2 x 10-6The concentration ratio of the components is added into the liquid-phase component Y to obtain the liquid-solid composite phase preparation for realizing the self-nanocrystallization of the friction and wear surface of the metal, and the liquid-solid composite phase preparation can be directly added into lubricating oil for use. The concentration ratio of the additive to the lubricating oil is 100 multiplied by 10-6。
The influence test of the engine performance is carried out on 1.6 rows of two passenger cars (one car runs 8 kilometres for the A group, and the other car runs 11 kilometres for the B group), after 3000 kilometres of composite preparation with self-nanocrystallization of the metal friction wear surface is used for running, the result is compared with that when 6000 kilometres of composite preparation with the existing lubricating oil is added for running, the result shows that:
(1) when the self-nanocrystallized composite preparation added with the metal friction wear surface runs for 3000km, the cylinder pressure of the engine obviously rises, the group A averagely rises by 2.5 percent, the group B averagely rises by 2.3 percent, and the maximum cylinder pressure rise is 3.6 percent.
(2) When the self-nanocrystallized composite preparation with a metal-filled friction wear surface runs for 3000km, the noise of the engine is obviously reduced, the average of the group A is reduced by 10.54 percent, the average of the group B is reduced by 10.46 percent, and the maximum noise reduction value is 11.9dB (noise in a vehicle).
(3) When the self-nanocrystallized composite preparation with the metal friction wear surface is added to run for 3000km, compared with the time when the self-nanocrystallized composite preparation is not added to run for 6000km, the CO of the A group vehicle is reduced by 12 percent, and the HC + NOx is reduced by 15 percent; the CO of the B group vehicle is reduced by 11 percent, and the HC + NOx is reduced by 12 percent.
The solid phase component comprises the following components in parts by weight: 60-99 parts of layered hydroxyl silicate natural mineral powder; 2-30 parts of a surface modifier; the composite preparation with 0.05-3 parts of redox catalyst and self-nanocrystallized surface has better effect, high self-nanocrystallization efficiency and high formation speed of the surface nanocrystalline reinforced protective layer; after the engine runs for a shorter distance (3000 kilometers), the cylinder pressure of the engine obviously rises, the noise of the engine obviously falls and the emission of tail gas pollutants is lower compared with the existing lubricating oil which runs for a longer distance (6000 kilometers); the solid phase component comprises the following components in parts by weight: 80-99 parts of layered hydroxyl silicate natural mineral powder; 5-10 parts of a surface modifier; 0.05-3 parts of redox catalyst; the self-nanocrystallization efficiency is highest, and the forming speed of the surface nanocrystalline reinforced protective layer is higher; the engine cylinder pressure rises the highest, the engine noise falls the biggest, and exhaust pollutant discharges the lowest. The self-nanocrystallization efficiency of the metal friction wear surface self-nanocrystallization composite preparation adopting the process range beyond the process range of the embodiments 1 to 6 is low, the forming speed of the surface nanocrystal reinforced protective layer is slow, and the exhaust emission effects of the cylinder pressure rise amount, the engine noise reduction amount and the exhaust pollutant emission amount of the engine are not as good as those of the embodiments.
The invention introduces a liquid-solid composite phase component into a friction pair system, and a special internal oxidation process different from high-temperature internal oxidation is generated under the action of mechanochemistry. The action mechanism is firstly the internal oxidation of the friction surface of the metal and secondly the thinning and strengthening of the structural deformation under the action of friction and shearing. Because the liquid phase component is introduced, the concentration of the required solid phase component is greatly reduced, and the lubricating oil is only used as a carrier of the preparation and does not participate in any reaction. The internal oxidation is essentially a thermal oxidation reaction of the alloy phase in the metal surface layer, and the reaction layer in the non-friction contact area is the thermal oxidation reaction layer. In addition, the rate of the internal oxidation reaction by the liquid-solid composite phase is higher than that of the mechanical alloying process. Therefore, the self-nanocrystallization efficiency is higher, and the formation speed of the surface nanocrystalline reinforced protective layer is higher.
The above description is only for the preferred embodiment of the present invention and is not intended to limit the scope of the present invention, and all equivalent structural changes made by using the contents of the present specification and the drawings can be directly or indirectly applied to other related technical fields and are included in the scope of the present invention.
Claims (15)
1. A composite preparation for self-nanocrystallization of a metal friction wear surface is characterized by comprising a liquid-phase component and a solid-phase component; the liquid phase component is dissolved in the lubricating oil base oil to form a solvent; the solid phase component is dissolved in a solvent as a solute to prepare a composite preparation;
wherein the liquid phase component comprises metal ion doped hydroxyl silicate nanotubes; the solid phase component is used for generating a protective layer on the friction and wear surface of the metal;
the solid-phase component contains layered hydroxyl silicate natural mineral powder particles;
the metal ions in the metal ion-doped hydroxyl silicate nanotube are ions of VIB group and VIII group metal elements corresponding to the fourth to sixth periods of 3 long periods in the periodic table of elements;
the concentration of the liquid phase component added into the lubricating oil base oil is 50 multiplied by 10 -6 -1000×10 -6；
The concentration of the solid phase component added into the solvent is 10 multiplied by 10-6 -500×10 -6。
2. The self-nanocrystallized composite preparation for metallic frictional wear surface according to claim 1, wherein said layered hydroxyl silicate natural mineral powder is a layered silicate mineral composed of hexagonal network composite ions; the phyllosilicate mineral composed of hexagonal layer network composite ions is one or more of pyrophyllite, talc, mica, kaolinite, serpentine, chlorite, sepiolite and montmorillonite.
3. The self-nanocrystallized composite formulation for metallic frictional wear surface according to claim 1, wherein said solid phase component further comprises a surface modifier and a redox agent; the solid phase component comprises the following components in parts by weight:
30-99 parts of layered hydroxyl silicate natural mineral powder
1-30 parts of surface modifier
0.05-5 parts of redox agent.
4. The self-nanocrystallized composite preparation for a metal frictional wear surface according to claim 3, wherein the solid phase component comprises the following components in parts by weight:
60-99 parts of layered hydroxyl silicate natural mineral powder
2-30 parts of surface modifier
0.05-3 parts of redox agent.
5. The self-nanocrystallized composite preparation for a metal frictional wear surface according to claim 4, wherein the solid phase component comprises the following components in parts by weight:
80-99 parts of layered hydroxyl silicate natural mineral powder
5-10 parts of surface modifier
0.05-3 parts of redox agent.
6. The self-nanocrystallized composite formulation for metallic frictional wear surface according to claim 3, wherein said surface modifier is one or more of a combination of cationic surfactant and coupling agent.
7. The self-nanocrystallized composite formulation for metallic frictional wear surfaces according to claim 6, wherein said cationic surfactant is a combination of one or more of a higher amine salt and a cationic modified amide.
8. The composite formulation for self-nanocrystallization of a metal frictional wear surface according to claim 6, wherein the coupling agent is a combination of one or more of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent.
9. The composite preparation for self-nanocrystallization of a metal frictional wear surface as set forth in claim 3, wherein said redox agent is one or more of a simple substance, an oxide and a chloride of group VIIB and group VIII elements corresponding to the fourth to sixth periods of 3 long periods in the periodic table.
10. The self-nanocrystallized composite formulation for metal frictional wear surfaces according to claim 1, wherein the lubricant base oil is one or more mixtures with the trade name of 150SN, 200SN, 250SN, 350SN, 500 SN.
11. The composite formulation for self-nanocrystallization of a metallic frictional wear surface according to claim 1, wherein the method for producing said metal ion-doped hydroxysilicate nanotubes comprises the steps of:
1) metal chloride, magnesium nitrate, sodium silicate and sodium hydroxide are mixed according to mass concentration: 1 (20-40) (10-30) (200-);
2) dissolving metal chloride and magnesium nitrate into water, and then adding sodium silicate; continuously stirring for 10-30 minutes, adding sodium hydroxide, and continuously stirring for 10-30 minutes to obtain an intermediate solution;
3) Sealing the intermediate solution and placing the intermediate solution in a reaction kettle to react for 20 to 50 hours at the temperature of 200 ℃ and 400 ℃;
4) and after the reaction is finished, centrifugally collecting precipitates, and centrifugally washing the precipitates by using solvents in sequence to obtain the metal ion doped hydroxyl silicate nanotube.
12. The self-nanocrystallized composite formulation for metallic frictional wear surfaces according to claim 11, further comprising the following modification steps:
1) dispersing metal ion doped hydroxyl silicate nanotube in organic solvent, and heating to 45-85 deg.c;
2) adding the coupling agent according to the concentration ratio of the metal ion doped hydroxyl silicate nanotube to the coupling agent of 1 (0.03-1), and continuously stirring for 1-2 hours to obtain liquid to be treated;
3) centrifugally separating the liquid to be treated, and then cleaning the liquid by using an organic solvent to obtain the oil-soluble metal ion doped hydroxyl silicate nanotube.
13. The composite formulation for self-nanocrystallization of a metal frictional wear surface according to claim 12, wherein the silicate hydroxide nanotubes of the modification step 1) are magnesium silicate hydroxide (Mg)6 [Si4O10][OH]8) Nanotube, nickel (Ni) hydroxy silicate3 Si2 O5 (OH)4) Nanotubes or nickel magnesium hydroxy silicate ((Ni, Mg)3 Si2 O5 (OH)4 ) A nanotube.
14. The composite formulation for self-nanocrystallization of a metal frictional wear surface according to claim 12, wherein the organic solvent in the modification step 1) is a monohydric alcohol, and the monohydric alcohol is one of ethanol or propanol.
15. The composite formulation for self-nanocrystallization of a metal frictional wear surface according to claim 12, wherein the coupling agent in the modification step 2) is one or more of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent.
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| CN1858294A (en) * | 2006-04-20 | 2006-11-08 | 金元生 | Preparation for forming protective layer on metal friction and wear-out surface and its preparing method |
| US20100087346A1 (en) * | 2006-03-31 | 2010-04-08 | Honeywell International, Inc. | Solid film lubricated high oxidation temperature rhenium material |
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| US20100087346A1 (en) * | 2006-03-31 | 2010-04-08 | Honeywell International, Inc. | Solid film lubricated high oxidation temperature rhenium material |
| CN1858294A (en) * | 2006-04-20 | 2006-11-08 | 金元生 | Preparation for forming protective layer on metal friction and wear-out surface and its preparing method |
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