CN100348706C - Inorganic composite nano intelligent repair agent, and its preparing method - Google Patents
Inorganic composite nano intelligent repair agent, and its preparing method Download PDFInfo
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- CN100348706C CN100348706C CNB2005101311846A CN200510131184A CN100348706C CN 100348706 C CN100348706 C CN 100348706C CN B2005101311846 A CNB2005101311846 A CN B2005101311846A CN 200510131184 A CN200510131184 A CN 200510131184A CN 100348706 C CN100348706 C CN 100348706C
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Abstract
The present invention relates to a nanometer repair agent which uses lubricating oil as a carrier and can automatically repair the worn surface of a mechanical equipment friction pair, and a preparation method of the repair agent. The repair agent of the present invention contains 0.1 to 5 wt% of nanometer additive and uses lubricating oil as a substrate. The nanometer additive is prepared from 18 to 33 wt% of SiO2, 21 to 40 wt% of AL2O3 and 31 to 55 wt% of MgO, wherein the particle diameter of the SiO2 is from 10 to 200 nm, the particle diameter of the Al2O3 is from 10 to 200 nm, and the particle diameter of the MgO is from 30 to 200 nm. The preparation method of the repair agent uses an ultrasonic wave crushing method. The nanometer intelligent repair agent of the present invention has the advantages of high stability, no aggregation, small friction coefficient, strong power performance, low oil consumption and low oil fume discharge amount, and has the function of automatically repairing worn surfaces.
Description
(1) technical field under
The present invention relates to a kind of is the nanometer renovation agent that can repair automatically mechanized equipment friction pair wear surface of carrier with lubricating oil, and the preparation method of above-mentioned renovation agent.
(2) background technology
At present, nanometer has obtained widely using, and as at mechanical field, utilizes nano material to optimize the metallic surface performance, increases the abrasion resistance of metallic surface, reduces frictional coefficient, the friction pair wear surface is repaired automatically etc.What foreign patent was produced forms the protective layer that attracts each other with positron-electron between friction pair, reduce friction loss, poor with the welding property of matrix, could form protective layer when mechanical means turns round; Product with the main component of hydrocarbon polymer is the heat energy that produces when mechanical means turns round, the protective layer that utilizes the mode of " hot activation " to form between friction pair, the loss between the pair of reducing friction.Protective layer disappears immediately when mechanical means shuts down.Mostly there is following problem in above product: (1) under pure oily medium, its frictional coefficient all is not less than 0.003, and under DRY SLIDING greater than 0.003, even lose the effect that should have; (2) high thermal resistance is poor, is difficult to break through 900 ℃ of limit; (3) can't satisfy in high-temperature, ocean environment and the strong acid-base medium and work, especially form tangible interfacial layer or oil film at surface of friction pair after the modification, the slightly degree of making of material surface is difficult to above 14 grades; (4) though on wear-resistant, antifriction effect, can play good effect, be subjected to the restriction of range of application; (5) on the repairing effect to the wearing and tearing surface of a wound, can not keep size for a long time, only the wearing surface in the following degree of depth of several nanometers be had repair.
The patent of invention of Chinese patent 200410099286X, " lubricating oil additive and preparation method thereof " discloses a kind of lubricating oil that mainly is added with silicon-dioxide.Because the simple nano silicon that adds, the effective nanometer film of difficult formation only can be repaired local pair of friction components surface.
(3) summary of the invention
The present invention is in order to overcome the deficiency of above technology, a kind of good stability is provided, do not reunited, the abrasion surface is had the intelligent repair agent of automatic repairing effect.
Another object of the present invention is to provide the preparation method of above-mentioned renovation agent.
The present invention realizes by following measure:
Inorganic composite nano intelligent repair agent of the present invention contains the nanometer additive of 0.1-5% weight, and matrix is lubricating oil, and described nanometer additive is the SiO by 18-33% weight
2, 21-40% weight AL
2O
3, 31-55% weight MgO form SiO wherein
2Particle diameter be 10-200nm Al
2O
3Particle diameter be 10-200nm, the particle diameter of MgO is 30-200nm.
The inorganic composite nano intelligent repair agent of the invention described above, the particle diameter of the best of described nanometer additive is: SiO
2Particle diameter be 50-80nm AL
2O
3Particle diameter be 70-80nm, the particle diameter of MgO is 80-120nm.
The preparation method of the inorganic composite nano intelligent repair agent of the invention described above is:
Take by weighing nanometer additive respectively, be ground into the fine powder of 1-80 micron with the standard machinery machine;
Fine powder is joined in the lubricating oil, mix, adding has in hyperacoustic ultrasonic grinding machine, carries out ultrasonication, makes nano intelligent repair agent of the present invention.
Above-mentioned preparation method of the present invention has water-chilling plant in the described ultrasonic grinding machine, and described frequency of ultrasonic is 20KHz～50KHz.
Inorganic composite nano intelligent repair agent of the present invention makes inorganic nano-particle possess the characteristic of distinctive interface and surface effects and small-size effect.In inorganic composite materials, because nanoparticle SiO
2The serious coordination deficiency in surface has extremely strong activity, huge specific surface, oxygen debt characteristic, bonding action easily takes place, improve intermolecular bonding force, possess a kind of " certainly seek " function, also have wear-resistant, anti-aging simultaneously and improve the effect of material surface smooth finish; Materials A l
2O
3, the nanoparticle formed of MgO, possess good material toughness and heat conductance, the thermal expansivity close with iron alloy arranged, improve melting (welding property) and affine performance with steel matrix, possess simultaneously and nanometer SiO
2The high rigidity of particle, anticorrosive anti-wear performance.
The mechanism of action of renovation agent of the present invention is as follows:
(1) the deposited film mechanism of action: the nanoparticle in the friction process in the oil phase is moved to surface of friction pair by two kinds of factor effect meetings, the one, because of can causing intensity, fricative microcell high temperature is higher than the molecule fluctuation of body phase, the fluctuation of enhanced molecule helps the non-directional migration, and the non-directional migration has increased the chance of nanoparticle to the surface of friction pair migration; The 2nd, because of friction pair produces exoelectron etc. the interface electromagnetic field of surface of friction pair is strengthened, the interface electric field of strengthening can produce the magnetic field of reinforcement, the existence of the faint electromagnetic field in surface is adsorbed with the micromolecular nanoparticle of strong polarity to the surface, can increase its chance in the surface of friction pair enrichment undoubtedly; The 3rd, be in the oil-bound film viscosity that the nanoparticle on the nearly surface of friction pair makes the surface contain nanoparticle and increase, thereby significantly reduced the possibility of it and body phase medium generation exchange of substance.Nanoparticle in the oil-bound film is under repeated friction in this case, be anchored in its surperficial super dispersion stabilizer and small amount of polar small molecules and can produce desorption, thereby the compactness extent and the thickness of the space bit resistance layer of nanoparticle surface are reduced, this has increased particle undoubtedly and has gathered, and and then is deposited on the chance of surface of friction pair.
(2) oil-bound film enhanced mechanism: any lubricating oil all has certain glutinous pressure characteristic, makes its viscosity of time spent when the oil film carry load pressure between friction pair and increases, and oil film can be by multiviscosisty, even becomes the class solid film with suitable thixotroping intensity.Disperse is distributed with the inorganic nano-particle period of the day from 11 p.m. to 1 a.m of surface anchoring polymkeric substance in oil-bound film, and the disperse of nanoparticle in oil film distributes and will make: 1. oil film viscosity increase, thickness increase, and thixotroping intensity rises; 2. the polymkeric substance of particle surface anchoring increases the toughness of oil film and intensity.More than two factors all help improving the antiwear and friction reduction property and the supporting capacity of oil product.Its enhanced mechanism synoptic diagram such as Fig. 1.
(3) repair mechanism: if the surface micro-pit size is the same with nanoparticle also at nano level, deposit or be adsorbed on the nanoparticle in little hole so, or the nanoparticle that is brought into the little hole of nano level in friction process just might be embedded in little hole under the carrying condition, thereby realizes the reparation in the little hole of nano level.For shaggy friction pair, the reparation of nanoparticle is less to tribological property improvement effect, because friction pair contact surface when carrying only accounts for the very little part of whole surface of friction pair, thereby to the contributive reparation of only having only contact surface of tribological property, its repair mechanisms synoptic diagram as shown in Figure 2.Above analysis revealed: 1. surface of friction pair is smooth more smooth, and contact surface is big more during carrying, and the reparation of nanoparticle is big more to improving the tribological property contribution; 2. under the prerequisite that guarantees nanoparticle dispersiveness and dispersion stabilization, the nanoparticle with certain grain size distribution helps filling the little hole of the nano level that varies in size, and realizes condition reparation greatly.
(4) the surface optimization mechanism of action: nanoparticle also can produce the mechanical polishing effect to surface of friction pair in the oily medium in friction process.Slick friction surface, not only frictional coefficient can be lower, and when carrying contact surface pressure stresses can be littler, thereby can correspondingly improve the supporting capacity of oil product.Friction pair for uneven surface, the mechanical polishing effect of nanoparticle can be too unobvious to improving the oil product tribological property, because nanoparticle is with respect to the protruding peak of the nano level on surface and Yan Taixiao, it can only be by producing the protruding peak of nano level of effect polishing surface of friction pair such as atom level elastic failure to surface atom.So more little, the slick more surface of friction pair of surfaceness, the interpolation of nanoparticle is remarkable more to the improvement of its tribological property in the oil product.Need to prove that nanoparticle is a dynamic process to the effect that produces because of wearing and tearing in the polishing action on surface and the friction process, surfaceness is increased, the former is a slow process; To the uneven surface under the harsh friction condition, wearing and tearing can take place rapidly, but the smooth surface less to roughness, harsh especially if not the tribology condition because pressure stresses is little, wearing and tearing also are very slowly.To being added with the oil product of nanoparticle, the friction pair load uses surface appearance, oil product tribological property, the action time of its level of surface roughness and load, friction pair itself after for some time, physical property of nanoparticle or the like relevant.To low load, smooth or ultra-smooth friction pair, be in the rigidity nano spherical particle in the good lubrication medium, be favourable to improving the surface of friction pair planarization.Its surface optimization mechanism of action synoptic diagram is shown in 3.
(5) the smooth or super-smooth surface rolling resistance mechanism of action: after the deposited film mechanism of action, oil-bound film enhanced mechanism, repair mechanism, the surface optimization mechanism of action are finished, R particularly
MaxDuring＜nano particle diameter, the nano spherical particle of lubricating oil camber disperse is realized the rolling resistance of surface of friction pair in certain load range, and its action model as shown in Figure 4.When the preparation nanoparticle, the control nanometer particle size could be realized smooth or the super-smooth surface rolling resistance.For big particle diameter particle, before the rolling resistance of being unrealized, can be excessive because of the stress that big particle diameter particle bears, be pressed into surface of friction pair; And too little that a part of particle of particle diameter also can not participate in rolling lubrication because of the antithesis of contact friction simultaneously.
The inorganic composite nano intelligent repair agent technology is a dynamic self-repair technology of novel original position, and it utilizes the distinctive performance of inorganic materials, and acting on lubricating oil is any mechanized equipment surface of friction pair of carrier.Nanoparticle is scattered in each friction pair contact layer with lubricating oil, under certain temperature, pressure, frictional force effect, surface of friction pair produces violent friction and moulding distortion, nano particle will deposit film forming at friction surface, and with the friction surface effect, when friction surface temperature height arrives certain value, the nano particle strength degradation strengthens lubricated microscopic particles with surface friction and produces eutectic, infiltration, " welding ", fills up surface microscopic cheuch, reparation surface of friction pair.Have superpower hardness, high smooth finish and super attrition resistant selfreparing film in surface of friction pair formation.Reach best running fit tolerance.This moment, effect minimizing, the frictional coefficient of frictional force reduced, and the nanometer repair process is finished.And the nano particle in the lubricating oil is constantly being sought new friction defective, and at the friction surface of ultra-smooth, realize rolling resistance, the effect of the power of reducing friction more reduces frictional coefficient, thereby forms the liquid or solid-state selfreparing film that one deck has the antifriction antiwear effect.
Nano intelligent repair agent of the present invention has good stability, do not reunite, the abrasion surface is had automatic repairing effect, and frictional coefficient is little, and dynamic property is strong, and oil consumption is low, and the oil smoke discharge amount is low.
Adopt preparation method of the present invention, it is little to make renovation agent have granularity, does not reunite good stability.
(4) description of drawings
The two-dimensional model synoptic diagram of Fig. 1 renovation agent nano particle of the present invention composite lubricating film
Fig. 2 renovation agent nano particle of the present invention is repaired the two-dimensional model synoptic diagram of friction pair micropore
Fig. 3 renovation agent surface finish of the present invention synoptic diagram
The rolling resistance action model synoptic diagram of Fig. 4 renovation agent super-smooth surface of the present invention
(5) embodiment
Below in conjunction with the drawings and specific embodiments the present invention is made specific description.
Embodiment 1:
Take by weighing the SiO of 0.3kg
2, 0.35kg AL
2O
3, 0.35kg MgO, be ground into 20 microns fine powder respectively with the standard machinery machine; Above-mentioned fine powder is joined in the 500kg lubricating oil, mix, adding has in hyperacoustic ultrasonic grinding machine, carries out ultrasonication, makes nano intelligent repair agent of the present invention.It is the ultrasonic grinding machine among the embodiment 1 in 200310105421 that above-mentioned ultrasonic grinding machine adopts the patent No..Amount to 19 ultrasonic transmitters, vibrational frequency 35KHz, total power is 1500W.
Materials Academy material analysis laboratory measurement, data such as table 1 are learned by economic Nanjing University.
Table 1 granulometry is table as a result
| Project name | Minimum value | Maximum value | Mean value | Standard variance |
| Feature area (μ m 2) | 0.000 | 0.010 | 0.005 | 0.005 |
| Girth (μ m) | 0.210 | 2.510 | 0.405 | 0.812 |
| 0 degree direction particle diameter (μ m) | 0.020 | 0.110 | 0.041 | 0.036 |
| 90 degree direction particle diameters (μ m) | 0.0180 | 0.150 | 0.050 | 0.039 |
Embodiment 2:
Take by weighing the SiO of 0.2kg
2, 0.25kg AL
2O
3, 0.5kg MgO, be ground into 20 microns fine powder respectively with the standard machinery machine; Above-mentioned fine powder is joined in the 25kg lubricating oil, mix, adding has in hyperacoustic ultrasonic grinding machine, carries out ultrasonication, makes nano intelligent repair agent of the present invention.It is the ultrasonic grinding machine among the embodiment 1 in 200310105421 that above-mentioned ultrasonic grinding machine adopts the patent No..Amount to 19 ultrasonic transmitters, vibrational frequency 25KHz, total power is 500W.
Materials Academy material analysis laboratory measurement, data such as table 2 are learned by economic Nanjing University.
Table 2 granulometry is table as a result
| Project name | Minimum value | Maximum value | Mean value | Standard variance |
| Feature area (μ m 2) | 0.000 | 0.010 | 0.005 | 0.005 |
| Girth (μ m) | 0.570 | 4.980 | 1.685 | 0.889 |
| 0 degree direction particle diameter (μ m) | 0.030 | 0.280 | 0.099 | 0.049 |
| 90 degree direction particle diameters (μ m) | 0.030 | 0.290 | 0.096 | 0.045 |
Embodiment 3:
Take by weighing the SiO of 0.3kg
2, 0.4kg AL
2O
3, 0.45kg MgO, be ground into 20 microns fine powder respectively with the standard machinery machine; Above-mentioned fine powder is joined in the 100kg lubricating oil, mix, adding has in hyperacoustic ultrasonic grinding machine, carries out ultrasonication, makes nano intelligent repair agent of the present invention.It is the ultrasonic grinding machine among the embodiment 1 in 200310105421 that above-mentioned ultrasonic grinding machine adopts the patent No..Amount to 19 ultrasonic transmitters, vibrational frequency 45KHz, total power is 1000W.
Materials Academy material analysis laboratory measurement, data such as table 3 are learned by economic Nanjing University.
Table 3 granulometry is table as a result
| Project name | Minimum value | Maximum value | Mean value | Standard variance |
| Feature area (μ m 2) | 0.000 | 0.010 | 0.005 | 0.005 |
| Girth (μ m) | 0.270 | 2.830 | 0.805 | 0.839 |
| 0 degree direction particle diameter (μ m) | 0.020 | 0.110 | 0.061 | 0.042 |
| 90 degree direction particle diameters (μ m) | 0.020 | 0.180 | 0.076 | 0.037 |
Embodiment 4:
Take by weighing the SiO of 0.25kg
2, 0.25kg AL
2O
3, 0.48kg MgO, be ground into 20 microns fine powder respectively with the standard machinery machine; Above-mentioned fine powder is fed Ar gas make protection gas in exsiccant vacuum material machine, collide mutually with grinding between the body, powder particle is carried out clinkering, fracture, clinkering more repeatedly, make the continuous refinement of crystal by the converted steel abrading-ball that runs up.
After the refinement, Materials Academy material analysis laboratory measurement is learned by economic Nanjing University, and data are as shown in table 4.
Table 4 granulometry is table as a result
| Project name | Minimum value | Maximum value | Mean value | Standard variance |
| Feature area (μ m 2) | 0.000 | 0.010 | 0.005 | 0.005 |
| Girth (μ m) | 0.470 | 3.380 | 1.583 | 0.842 |
| 0 degree direction particle diameter (μ m) | 0.040 | 0.400 | 0.165 | 0.137 |
| 90 degree direction particle diameters (μ m) | 0.040 | 0.450 | 0.174 | 0.141 |
Test case 1:
The hardness test of motorcycle cylinder body: through Shandong University's college of materials science and engineering materialogy lab investigation.
Send the project of testing: the motorcycle cylinder body carries out nanometer protective layer Hv hardness test after renovation agent of the present invention is handled
Testing tool: Tianjin, island microhardness tester
Test operating mode: 10 seconds of Hv50g time
Test result:
Hv HRC
Embodiment 1:769 62.8
Embodiment 2:935 67.8
Embodiment 3:1123 70
Embodiment 4:725 60.2
Disintegration sample testing result without the nanometer additive processing:
Hv HRC
333 33.6
Test case 2: the renovation agent of the present invention with embodiment 2 is an example, carries out motorcycle cylinder body frictional experiment.The result is as follows:
Shandong University's college of materials science and engineering
The report of materialogy laboratory test
Send the product of testing: the disintegration sample that the motorcycle cylinder body is handled through galling nanometer repair additive.
Send the project of testing: the abrasion test.
Trier model: MM200 type wearing test type machine, ultimate load 200kg.
Standard emery wheel size: Ф 40 * 10mm, material: 45
#Steel is without thermal treatment, but handles through galling nanometer repair additive.
Operating condition of test: adopt skimming wear, standard emery wheel rotating speed is 400 rev/mins.
Oil dripping is 10 droplets/minute (20
#Machine oil+galling nanometer repair additive mixed solution).
Process of the test and result are as follows:
Under the normal fuel injection state:
The load moment kg-cm time (hour) coefficient of friction μ
30kg 0.2 1/2h 0.003
50kg 0.3 1/2h 0.003
20kg 0.2 1/2h 0.005
Under the fuel cut-off state:
The load moment kg-cm time (hour) coefficient of friction μ
30kg 0.2 1h 0.003
50kg 0.2 1/4h 0.002
75kg 0.3 1/4h 0.002
100kg 0.4 1/4h 0.002
125kg 0.4 1/4h 0.0016
150kg 12 minutes 0.0066
Conclusion (of pressure testing):
Under the normal fuel injection state
Coefficientoffriction: 0.003～0.005
Under the fuel cut-off state:
Coefficientoffriction: 0.002～0.006
Test case 3: the renovation agent of the present invention with embodiment 2 is an example, carries out the motor vehicle dynamic experiment.The result is as follows:
Claims (4)
1. inorganic composite nano intelligent repair agent contains the nanometer additive of 0.1-5% weight, and matrix is lubricating oil, it is characterized in that: described nanometer additive is the SiO by 18-33% weight
2, 21-40% weight AL
2O
3, 31-55% weight MgO form SiO wherein
2Particle diameter be 10-200nmAL
2O
3Particle diameter be 10-200nm, the particle diameter of MgO is 30-200nm.
2. inorganic composite nano intelligent repair agent according to claim 1 is characterized in that: SiO
2Particle diameter be 50-80nm AL
2O
3Particle diameter be 70-80nm, the particle diameter of MgO is 80-120nm.
3. the preparation method of claim 1 or 2 described inorganic composite nano intelligent repair agents is characterized in that: may further comprise the steps,
Take by weighing nanometer additive, be ground into the fine powder of 1-80 micron with the standard machinery machine;
Fine powder is joined in the lubricating oil, mix, adding has in hyperacoustic ultrasonic grinding machine, carries out ultrasonication, makes nano intelligent repair agent of the present invention.
4. preparation method according to claim 3 is characterized in that: have water-chilling plant in the described ultrasonic grinding machine, described frequency of ultrasonic is 20KHz～50KHz.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| UA104864C2 (en) | 2010-12-24 | 2014-03-25 | Володимир Леонідович Зозуля | Nanostructure revitalizer with stabile nanostructure for and the process for its production |
| CN107384511A (en) * | 2017-06-30 | 2017-11-24 | 太仓宝达齿条有限公司 | A kind of rack surface solid lubricant layer |
| CN108059994A (en) * | 2017-12-05 | 2018-05-22 | 杭州启俄科技有限公司 | It is a kind of to repair secondary composition of friction and its preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1013748B (en) * | 1988-01-28 | 1991-09-04 | 安徽工学院 | Machining method of polycrystalline diamond by using mechano-electrical pull |
| RU2168663C1 (en) * | 2000-06-15 | 2001-06-10 | Сергей Николаевич Александров | Composition for friction pairs treatment |
| US6548454B1 (en) * | 1997-08-29 | 2003-04-15 | Nsk Ltd. | Rolling apparatus containing a liquid fluorinated polymer oil and thickening agent |
| CN1660981A (en) * | 2004-12-29 | 2005-08-31 | 中国石油化工股份有限公司 | Lubricating oil additive and preparation method |
-
2005
- 2005-12-30 CN CNB2005101311846A patent/CN100348706C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1013748B (en) * | 1988-01-28 | 1991-09-04 | 安徽工学院 | Machining method of polycrystalline diamond by using mechano-electrical pull |
| US6548454B1 (en) * | 1997-08-29 | 2003-04-15 | Nsk Ltd. | Rolling apparatus containing a liquid fluorinated polymer oil and thickening agent |
| RU2168663C1 (en) * | 2000-06-15 | 2001-06-10 | Сергей Николаевич Александров | Composition for friction pairs treatment |
| CN1660981A (en) * | 2004-12-29 | 2005-08-31 | 中国石油化工股份有限公司 | Lubricating oil additive and preparation method |
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