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CN101070505B - Anti-wear restoring agent and its preparing method and use - Google Patents

Anti-wear restoring agent and its preparing method and use Download PDF

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Publication number
CN101070505B
CN101070505B CN2006100787328A CN200610078732A CN101070505B CN 101070505 B CN101070505 B CN 101070505B CN 2006100787328 A CN2006100787328 A CN 2006100787328A CN 200610078732 A CN200610078732 A CN 200610078732A CN 101070505 B CN101070505 B CN 101070505B
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agent
abrasion resistance
serpentine
powder
repairing abrasion
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CN101070505A (en
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韩永存
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Dongguan Guoding Energy Saving Technology Co ltd
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Abstract

This invention relates to the chemical domain, publicizes one kind wearresistant repair agent preparation method and its application, its characteristic lies in the wearresistant repair agent including the phyllo-silicate mineral smalls which ferric oxide content is smaller than 2%, six sides boron nitride, the dispersing agent, base oil, among them, the ferric oxide content of phyllo-silicate mineral smalls is smaller than 1%, its granularity request is D97 ( 1 micron; Six sides boron nitride granularity request is D97 (1 micron; This invention has also publicized the preparation method and application of the wearresistant repair agent. The wearresistant repair agent have good dispersible stability, and it can willfully mix with the lubricating oil, it enable the lubricating oil to have the function of compensating the attrition. After using the wearresistant repair agent, it can obtain the lubricating ability carbon oxide film in the friction surface, this carbon oxide film has high hardness, high degree of finish, low friction coefficient, low rate of wear, self-compensated, self-healed, self-repair ability, it provides the exempt dismantling repair possibility of equipment maintenance.

Description

A kind of agent for repairing abrasion resistance and its production and application
Technical field:
The present invention relates to chemical field, particularly nanotechnology and machinery exempt to tear open maintenance and lubricating grease technical field, particularly a kind of agent for repairing abrasion resistance and its production and application.
Background technology:
In mechanical means, the existence of friction has consumed portion of energy, has reduced the efficient of equipment; The generation of wearing and tearing can make component reduce dimensional precision gradually and lose efficacy, even causes equipment scrapping.For reducing or the inhibition frictional wear, except that carrying out rational tribology Design, also must take the measure of various anti-attrition anti-friction, the mode of employing has following several: the one, and minimizing or control cause the condition of wearing and tearing, as corrosion and fatigue, adhesion, erosion, abrasive wear etc.; The 2nd, the wear resisting property of raising surface of friction, as surface alloying, sulfurizing, boronising etc., or make material have self-organization, self-healing ability; The 3rd, in process of friction and wear, remedy wearing and tearing by forming new layer of compensation.And above three kinds of measures can be by to lubricating oil product Formula Design and utilize fricative physics chemical action to realize.
Because the influence of factors vary such as the temperature that produces when the physico-chemical property of lubricating oil, lubricating grease is subjected to the surface of friction motion or during environmental change, pressure is difficult to effectively lubricating and control wearing and tearing.For remedying the defective of lubricating oil, lubricating grease, method commonly used at present is to wherein adding various organic and inorganic compound additives, and these materials roughly can be classified as following a few class:
1. organometallic compound is as zinc dialkyl dithiophosphate etc.;
2. the organic compound of sulfur-bearing, phosphorus, chlorine isoreactivity element is as sulfide isobutene etc.;
3. the solid lubricant that has special constructions such as stratiform is as molybdenumdisulphide etc.;
4. micron, nano level soft metal are as copper etc.
Above-mentioned 1. 2. the class material mostly be oil-soluble compounds, under boundary lubrication and mixed lubrication condition, by modes such as thermolysiss, form adsorption film, reaction film or permeable membrane, thereby improve the lubricating status of surface of friction on the surface of metal mill spot.But when friction Temperature Rise was higher, adsorption film can decompose, or some degradation production of these compounds can have corrosive nature to metallic substance, and the decomposition and consumption when high temperature reduces its performance simultaneously.3. the class material can be easy to take place crystal-plane slip frying in shallow oil under the shear force effect, thereby reduces wearing and tearing, but its lubricity deficiency at a lower temperature.More than three class materials all can not repair occurring wear.Though 4. the class material can infiltrate the metallic surface in friction process, or be filled in the depression of friction surface, can improve the loaded area of surface of friction, ability with certain reparation wearing and tearing, but the new reparation surface that forms does not often have original surface more wear-resisting, reduce in oiling system with material, its repairing effect is with very fast disappearance.
In addition, up-to-date method is to utilize wear-resistant, the anti-attrition of oxide compound.Because a large amount of mechanical means is operated in the atmospheric environment, no matter be in lubricated, metal to-metal contact, particularly under hot conditions, its friction surface will inevitably oxidation, and oxide compound will participate in process of friction and wear.Oxidative wear will become the leading mechanism of wearing and tearing under certain condition.And friction oxidation has the different of essence with thermooxidizing, this be since under the andfrictional conditions solid mechanical interaction cause due to the structural changes and physical change of solid surface, friction makes metal produce various defectives, temperature rising, plastoelastic deformation, surface enlarge, bring out electronics etc., thereby rate of oxidation is accelerated, and can be produced the resultant different with thermal oxidative reaction.Along with deepening continuously of oxide compound anti-attrition and wear-resisting phenomenon research, the structure of the spontaneous oxide film that discovery forms under common lubricating condition is also stable inadequately, and oxide film breakdown can take place; Thickness deficiency, effectively bearing load; Compactness deficiency, hardness are not high, can not effectively reduce adhesive wear; Formation speed is low, can not provide effective anti-attrition during less than wear rate.Therefore utilize the oxide compound anti-attrition never to be widely used.
Summary of the invention:
The objective of the invention is to overcome that existing oxide compound is wear-resistant, the deficiency of anti-attrition technology, a kind of agent for repairing abrasion resistance of obtaining at friction surface oilness oxidation of coal film and its production and application that is used for is provided.
One of prerequisite of utilizing the oxide compound anti-attrition is: the formation speed of oxide film must be greater than the removal speed of its mechanical wear, so must find a kind of particularly can the film formed material of promote the oxidation under the situation that has lubricant medium to exist, be the key that addresses this problem.
By a large amount of tests, we find that layered silicate material has katalysis to the formation of oxidation of coal film, it can discharge oxygen freely in friction process, and carbon and other light elements (nitrogen, boron) that can quicken the lubricating oil decomposition ooze to the metal friction surface expansion, and then form oilness oxidation of coal film.
Technical scheme of the present invention is as follows:
Invent a kind of anti-mechanical wear renovation agent, it is characterized in that comprising layer silicate mineral powder, hexagonal boron nitride, dispersion agent, the base oil of iron oxide content<2%, wherein layer silicate mineral powder degree requires to be D 97<1 micron; The granularity requirements of hexagonal boron nitride is D 97<1 micron.
As further improvement, described agent for repairing abrasion resistance is characterized in that iron oxide content<1% in the described layer silicate mineral powder.
Described agent for repairing abrasion resistance, its feature are that also described dispersion agent is one or more mixtures in dodecyl sodium sulfonate calcium, sodium laurylsulfonate, potassium oleate, lithium 12-hydroxy stearate, neutral calcium mahogany sulfonate, sorbitan mono-laurate, aliphatic amine polyoxyethylene ether, alkylphenol polyoxyethylene, the polyoxyethylene glycol.
Described agent for repairing abrasion resistance, the granularity requirements that it is characterized in that layered silicate mine is D 97<100 nanometers, the granularity requirements of hexagonal boron nitride are D 97<200 nanometers.
Described agent for repairing abrasion resistance, the weight ratio that it is characterized in that hexagonal boron nitride and layered silicate is 0.1: 1~10: 1, the weight sum of hexagonal boron nitride and layered silicate and the weight ratio of dispersion agent are 0.1: 1~5: 1.
Described agent for repairing abrasion resistance, its feature is 0.8: 1~2: 1 at described hexagonal boron nitride and layered silicate weight ratio.
Described agent for repairing abrasion resistance is characterized in that described hexagonal boron nitride and layered silicate weight ratio are 1: 1, and the weight sum of hexagonal boron nitride and layered silicate and the weight ratio of dispersion agent are 1.5: 1.
Described agent for repairing abrasion resistance, its feature are that also layered silicate can be one or more the mixture in chlorite, serpentine, cronstedtite, the violent ore deposit of kidney silicon.
Described a kind of agent for repairing abrasion resistance is characterized in that described layered silicate is a serpentine.
The present invention also provides the preparation method of a kind of agent for repairing abrasion resistance of the present invention, and is as follows:
The preparation method of described any agent for repairing abrasion resistance is characterized in that may further comprise the steps:
(1) selected laminar silicic acid salt mine is processed into granularity for less than 10 microns superfine powder through pulverizing, magnetic separation, ball milling, flotation, ultrasonic, magnetic separation, oven dry, ball milling, powder I;
(2) use high energy ball mill that powder I is processed, be 1~20 hour process period; Ratio of grinding media to material is 5: 1~20: 1, and being processed into granularity is nano level powder II;
(3) hexagonal boron nitride is processed in protective atmosphere with high energy ball mill, be 1~18 hour process period, preferred 12 hours; Ratio of grinding media to material is 5: 1~20: 1, gets powder III;
(4) use planetary ball mill that powder II and powder III are got powder IV by the formulating of recipe mixed, add dispersion agent processing 10~60 minutes, get solution I; The mass ratio of powder IV and dispersion agent is 0.1: 1~5: 1.
(5) use high energy ball mill with the base oil mixing post-treatment of solution I with suitable proportion, can flow naturally on the abrading-ball surface with mixture is as the criterion, and be 1~20 hour process period, gets solution II; Ratio of grinding media to material is 5: 1~25: 1.
(6) solution II is put into the ultra-sonic dispersion machine and carried out sonic oscillation, the time is 30~60 minutes.
The preparation method of described a kind of agent for repairing abrasion resistance is characterized in that in the described step (2), preferred 6 hours of process period; Preferred 10: 1 of ratio of grinding media to material, in the step (3), preferred 12 hours of process period; Ratio of grinding media to material, preferred 10: 1; In the step (4), add preferred 50 minutes of the process period of dispersion agent; The mass ratio of powder IV and dispersion agent is 0.1: 1~5: 1, preferred 1.5: 1; In the step (5), preferred 8 hours of process period, preferred 15: 1 of ratio of grinding media to material; In the step (6), preferably the sonic oscillation time is 50 minutes.
The preparation method of described a kind of agent for repairing abrasion resistance is characterized in that described protection gas is: nitrogen.
The preparation method of described a kind of agent for repairing abrasion resistance is characterized in that described protection gas is: argon gas.
Agent for repairing abrasion resistance of the present invention is used as follows:
Described any agent for repairing abrasion resistance adds lubricating oil to, makes specific lubricating oil.
Described specific lubricating oil is characterized in that the concentration of layer silicate mineral powder in lubricating oil is 0.01g/L~2g/L
Described specific lubricating oil is characterized in that the concentration of layer silicate mineral powder in lubricating oil is 0.1g/L.
Described any agent for repairing abrasion resistance adds in the lubricating grease, makes special lubricating grease.
Described special lubricating grease is characterized in that the concentration of layer silicate mineral powder in lubricating oil is 0.01g/kg~10g/kg.
Described special lubricating grease is characterized in that the concentration of layer silicate mineral powder in lubricating oil is 0.5g/kg.
Owing to after the agent for repairing abrasion resistance engaging friction pair of the present invention, under the effect of certain friction environment and frictional energy, complicated mechanical, chemistry friction reaction will take place, form the oilness oxidation of coal film of one deck densification at friction surface.And then making the chemical ingredients of surface of friction pair, thing reaches micro texture mutually and changes.
This oxidation of coal film component is with the oxide compound (Fe of iron 3O 4, Fe 2O 3, FeO) be main, oxygen level is inwardly reduced gradually by the surface, thickness can reach 10 microns; Also comprise free C and Fe 3C, carbon content is inwardly reduced gradually by the surface, also can comprise nitride, boride;
This oxidation of coal film and matrix are combined closely, and have very high bonding strength, can not be subjected to influence of temperature change and come off;
This oxidation of coal film has the hardness higher than matrix, and its microhardness can reach Hv 600~1400;
This oxidation of coal film has the coefficientoffriction 0.001~0.005 lower than film lubrication;
The formation of oxidation of coal film is played the compensation repair to wearing and tearing.
Obviously oilness oxidation of coal film has different significantly with the friction oxidation film.
Therefore, contain agent for repairing abrasion resistance of the present invention and have bigger advantage at aspects such as anti-attrition anti-friction and wearing and tearing selfreparings, and can protect friction surface automatically in equipment automatic formation in service, reduce frictional coefficient automatically, wearing and tearing etc. are repaired in compensation automatically.
A kind of agent for repairing abrasion resistance of the present invention can steady in a long-termly be preserved, and also can mix use with lubricating oil, lubricating grease, and the lubricating oil that is applied is not had any detrimentally affect; The mechanical means field widespread use of various frictional wears can related to.Agent for repairing abrasion resistance of the present invention can promote the generation of friction surface oilness oxide film, and then obtains more excellent anti-friction surface, and to the automatic compensation repairing effect of wear surface also clearly; Through nano material stable dispersion in system of modification parcel, not reunite, do not precipitate, this also is the key that the present invention can achieve success.It is raw material that common mineral, industrial preparation are selected in the preparation of product of the present invention for use, and preparation technology is simple, and is with low cost, and all powder courses of processing are all finished environmentally safe in enclosed space.
Description of drawings
Fig. 1 does not carry out the SEM picture of test specimen under the HT200 of wear test for using agent for repairing abrasion resistance of the present invention
Fig. 2 carries out the SEM picture of test specimen under the HT200 of wear test for using agent for repairing abrasion resistance of the present invention
Fig. 3 uses the SEM picture of oxidation of coal film on the steam jacket surface of the small-sized shipping diesel vehicle after the special lubricating oil work of having added agent for repairing abrasion resistance of the present invention
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1 selects for use 100 gram powders that chlorite and serpentine mixed mineral obtain through pulverizing, magnetic separation, ball milling, flotation, ultrasonic, magnetic separation, oven dry, ball milling processing with high-energy ball milling processing 6 hours; 10 gram hexagonal boron nitrides were processed in nitrogen 8 hours with high energy ball mill, mixed 50 minutes at planetary ball mill with dispersion agent dodecyl sodium sulfonate calcium, each 40 gram of sodium laurylsulfonate; Add base oil 126 grams and in high-energy ball milling, processed 8 hours, in ultrasonic, disperse to obtain in 50 minutes agent for repairing abrasion resistance of the present invention then.
Embodiment 2 selects for use 50 gram powders that serpentine minerals obtains through pulverizing, magnetic separation, ball milling, flotation, ultrasonic, magnetic separation, oven dry, ball milling processing with high-energy ball milling processing 5 hours; 50 gram hexagonal boron nitrides were processed in nitrogen 8 hours with high energy ball mill; Mixed 50 minutes at planetary ball mill with dispersion agent dodecyl sodium sulfonate calcium 20 grams, each 20 gram of sodium laurylsulfonate, aliphatic amine polyoxyethylene ether 10 grams, alkylphenol polyoxyethylene 10 grams; Add base oil 125 grams and in high-energy ball milling, processed 10 hours, in ultrasonic, disperse then also can make agent for repairing abrasion resistance of the present invention in 50 minutes.
Embodiment 3 takes by weighing 1.5 grams with the agent for repairing abrasion resistance of the present invention of embodiment 1 preparation, measures 10 milliliters of Triton X-100s, and 300 milliliters of 15W40/SJ engine oils mix the back and use ultra-sonic oscillation 24 hours.The result shows that resulting renovation agent has good dispersion stabilization.
Embodiment 4. takes by weighing 2 grams with the agent for repairing abrasion resistance of the present invention of embodiment 2 preparation, adds in the SJ 15W40 machine oil by 1%, and mechanical stirring 20 minutes is deposited.The result shows to deposit and separated out without any throw out in 1 year, shows that it has good dispersion stabilization.
Embodiment 5. takes by weighing 0.5 gram with the agent for repairing abrasion resistance of embodiment 2 preparations, mix with 100 milliliters of base oils, on vertical omnipotent friction wear testing machine, carry out friction-wear test, selecting No. 45 steel for use is last sample, HT200 is following sample, is carrying out wearing test with the base oil that does not add renovation agent under same test conditions.Fig. 1 is the SEM pictures of common base oil wearing and tearing after 120 hours, and Fig. 2 is for adding agent for repairing abrasion resistance of the present invention, the SEM picture after 120 hours of wearing and tearing, and it is to the repair ability of metal friction surface as can be seen.We have carried out XPS analysis to two test specimen wear surfaces, and with argon ion sputtering 60 minutes, each element atomic percentage conc that instrument detecting arrives was as follows:
Figure GSB00000418988700061
As can be seen, use agent for repairing abrasion resistance increase carbon of the present invention, oxygen, nitrogen, boron in matrix, to expand the degree of depth of oozing, even sputter 60 minutes carbon, oxygen concns still are higher than matrix concentration, the thickness that is to say oilness oxidation of coal film obviously is the generation that renovation agent has quickened the oxidation of coal film greater than sputter thickness.
When finishing, test measures sample wear surface test microhardness and quality change down:
Figure GSB00000418988700062
As seen microhardness has improved 3.5 times, and wear rate has reduced by 80%.
Embodiment 6. is with embodiment 2 preparation agent for repairing abrasion resistance, add in the lubricating oil by 5%, on small-sized shipping diesel vehicle, test, add back traveling 5000 kms, the disintegration engine, disassemble steam jacket, and cut steam jacket and carry out the observation of oxidation of coal film, as shown in Figure 3, form the about 9 microns oxidation of coal film protective layer of thickness on the steam jacket surface, use atomic force microscope to measure its surfaceness and be the Ra:0.0107 micron, belong to the precision sizing precision; The original scuffing of cylinder is repaired.
Embodiment 7. presses the agent for repairing abrasion resistance of embodiment 1 preparation, adds in the lubricating oil by 5%, on Honda Accord type car, test, and 200,000 kms of traveling before this car test, not overhaul is short of power, noise is big, oil consumption is high; Detect after adding agent for repairing abrasion resistance traveling 1000 kms of the present invention, the front and back cylinder pressure is as follows:
State Cylinder 1/ kgf Cylinder 2/ kgf Cylinder 3/ kgf Cylinder 4/ kgf
Before the use 9.7 8.9 9.6 10.5
After the use 12.7 13.6 12.8 13.6
Power obviously promotes behind these car traveling 1000 kms, accelerating ability improves, noise reduces, oil consumption reduces by 12%.
The comprehensive visible agent for repairing abrasion resistance of the present invention of above test result can obtain oilness oxidation of coal film at friction surface, and wear-resistant and selfreparing all has fairly obvious effect to the anti-attrition of mechanical means.

Claims (17)

1. agent for repairing abrasion resistance is characterized in that comprising serpentine, hexagonal boron nitride, dispersion agent, the base oil of iron oxide content<1%, and the granularity requirements of described serpentine is D 97<100 nanometers; The granularity requirements of hexagonal boron nitride is D 97<200 nanometers, the weight ratio of hexagonal boron nitride and serpentine are 0.1: 1~10: 1.
2. agent for repairing abrasion resistance according to claim 1 is characterized in that described dispersion agent is one or more mixtures in dodecyl sodium sulfonate calcium, sodium laurylsulfonate, potassium oleate, lithium 12-hydroxy stearate, neutral calcium mahogany sulfonate, sorbitan mono-laurate, aliphatic amine polyoxyethylene ether, alkylphenol polyoxyethylene, the polyoxyethylene glycol.
3. agent for repairing abrasion resistance according to claim 2 is characterized in that the weight sum of hexagonal boron nitride and serpentine and the weight ratio of dispersion agent are 0.1: 1~5: 1.
4. agent for repairing abrasion resistance according to claim 3 is characterized in that described hexagonal boron nitride and serpentine weight ratio are 0.8: 1~2: 1.
5. agent for repairing abrasion resistance according to claim 4 is characterized in that described hexagonal boron nitride and serpentine weight ratio are 1: 1, and the weight sum of hexagonal boron nitride and serpentine and the weight ratio of dispersion agent are 1.5: 1.
6. according to the preparation method of each described agent for repairing abrasion resistance among the claim 1-5, it is characterized in that may further comprise the steps:
(1) selected serpentine ore is processed into granularity for less than 10 microns superfine powder through pulverizing, magnetic separation, ball milling, flotation, ultrasonic, magnetic separation, oven dry, ball milling, powder I;
(2) use high energy ball mill that powder I is processed, be 1~20 hour process period; Ratio of grinding media to material is 5: 1~20: 1, and being processed into granularity is nano level powder II;
(3) hexagonal boron nitride is processed in protective atmosphere with high energy ball mill, be 1~18 hour process period; Ratio of grinding media to material is 5: 1~20: 1, gets powder III;
(4) use planetary ball mill that powder II and powder III are got powder IV by the formulating of recipe mixed, add dispersion agent processing 10~60 minutes, get solution I; The mass ratio of powder IV and dispersion agent is 0.1: 1~5: 1;
(5) use high energy ball mill with the base oil mixing post-treatment of solution I with suitable proportion, can flow naturally on the abrading-ball surface with mixture is as the criterion, and be 1~20 hour process period, gets solution II; Ratio of grinding media to material is 5: 1~25: 1;
(6) solution II is put into the ultra-sonic dispersion machine and carried out sonic oscillation, the time is 30~60 minutes.
7. the preparation method of a kind of agent for repairing abrasion resistance according to claim 6 is characterized in that in the described step (2), preferred 6 hours of process period; Preferred 10: 1 of ratio of grinding media to material, in the step (3), preferred 12 hours of process period; Ratio of grinding media to material, preferred 10: 1; In the step (4), add preferred 50 minutes of the process period of dispersion agent; The mass ratio of powder IV and dispersion agent is 0.1: 1~5: 1; In the step (5), preferred 8 hours of process period, preferred 15: 1 of ratio of grinding media to material; In the step (6), preferably the sonic oscillation time is 50 minutes.
8. the preparation method of a kind of agent for repairing abrasion resistance according to claim 6 is characterized in that being preferably 12 hours process period in the described step (3).
9. the preparation method of a kind of agent for repairing abrasion resistance according to claim 7 is characterized in that the mass ratio of powder IV and dispersion agent is preferably 1.5: 1 in the described step (4).
10. the preparation method of a kind of agent for repairing abrasion resistance according to claim 7 is characterized in that the described protection gas of step (3) is: nitrogen.
11. weigh the preparation method who asks 7 described a kind of agent for repairing abrasion resistance according to right, it is characterized in that the described protection gas of step (3) is: argon gas.
12. a lubricating oil is characterized in that having added each described agent for repairing abrasion resistance among the claim 1-5.
13. lubricating oil according to claim 12 is characterized in that the concentration of serpentine in lubricating oil is 0.01g/L~2g/L.
14. lubricating oil according to claim 13 is characterized in that the concentration of serpentine in lubricating oil is 0.1g/L.
15. a lubricating grease is characterized in that having added each described agent for repairing abrasion resistance among the claim 1-5.
16. lubricating grease according to claim 15 is characterized in that the concentration of serpentine in lubricating grease is 0.01g/kg~10g/kg.
17. lubricating grease according to claim 16 is characterized in that the concentration of serpentine in lubricating grease is 0.5g/kg.
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