CN1180066C - Anti-friction lubricating oil adding inorganic fluoric acid salt solid lubricant product - Google Patents
Anti-friction lubricating oil adding inorganic fluoric acid salt solid lubricant product Download PDFInfo
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- CN1180066C CN1180066C CNB021208417A CN02120841A CN1180066C CN 1180066 C CN1180066 C CN 1180066C CN B021208417 A CNB021208417 A CN B021208417A CN 02120841 A CN02120841 A CN 02120841A CN 1180066 C CN1180066 C CN 1180066C
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Abstract
The present invention belongs to the preparation field of an abrasion resistant lubrication oil medium for machinery, and is particularly to suitable for the preparation of abrasion resistant lubrication oil for automobile industry, and an inorganic fluorate solid lubrication additive product of the abrasion resistant lubrication oil. The inorganic fluorate solid lubrication additive product is characterized in that the abrasion resistant lubrication oil is composed of the components of 0.5% to 10% of inorganic fluorate solid lubricant product and 90% to 99.5% of carrier liquid lubrication medium. An inorganic fluorate solid lubrication additive in the inorganic fluorate solid lubrication additive product is from 1% to 25%, and the content of the carrier liquid lubrication medium is from 75% to 99%. Compared with the prior art, the abrasion resistant lubrication oil adopting the present invention has the advantages of reasonable composition design, good abrasion resistance, good abrasion reduction performance, good use effect, no corrosion and favorable environmental protection function.
Description
Technical field:
The invention belongs to the preparation field of machinery with the abrasion-proof lubricant oil medium.More be applicable to the preparation of the employed abrasion-proof lubricant oil of automobile industry and this inorganic fluorine Barbiturates solid lubrication additive product.
Technical background:
Lubricating oil (fat) is indispensable integral part in mechanical movement, and in the friction surface role, the lubricated of mechanical component generally can be divided into two types: hydrodynamic lubrication and boundary lubrication according to the working conditions of friction parts and lubricating oil (fat).Under Liquid Lubrication Condition, reduce lubricating oil viscosity and just can reduce friction energy loss, but under condition of boundary lubrication, reducing the effective way that rubs is selection appropriate slip additive--extreme pressure anti-wear additives and friction improver.
Traditional antifriction, anti-wear agent can be divided into two classes: a class is oil soluble organic compound (comprising organometallic compound), and another kind of is the molten solid lubrication additive of non-oil.The oil soluble organic compound comprises: sulfur-bearing in the molecule commonly used, phosphorus, chlorine isoreactivity element are as being not contain the extreme pressure anti-wear additives of active element such as organic boron that developed recently gets up and a kind of recombiner of being made up of dimeracid and alcohol in the extreme pressure anti-wear additives, organic molecule of representative with olefine sulfide, phosphoric acid ester and clorafin; Organometallic compound comprises: simple organometallic compound such as lead naphthenate, be the organometallic compound that contains active element of representative and oil-soluble organic molybdenum etc. with the zinc dialkyl dithiophosphate.The oil soluble organic compound can mix with lubricating oil (fat) in its solubility range equably, effectively improves the quality of lubricating oil (fat).But the oil soluble organic compound is easy decomposition and consumption when comparatively high temps, and supporting capacity is low, and also may corrosive nature be arranged to the bearing of non-ferrous metal (silver, tin).Also easily cause environmental pollution when synthesizing these organic compound additives, make its development be subjected to certain restriction.In addition, when the organic compound that contains active element is made slip additive, sulphur, phosphorus, chlorine are the key elements of lubricate, and the oil base antifriction of sulfur-bearing, phosphorus, chlorine, anti-wear agent are not only harmful, and contaminate environment, as phosphoric the catalytic converter that automobile installs is poisoned, thereby influence the discharging of automobile; The anti-wear agent such as the organic boron additive that do not contain active element are easy to lose lubricating function etc. because of hydrolysis.In addition, along with the raising of countries in the world to environmental requirement, the organometallic compound of some better performances is also put under superseded ranks as lead naphthenate etc.And solid lubrication additive, as MoS2, graphite, PTFE, pottery and some metal-powders, can under conditions such as ultrahigh vacuum(HHV), very low temperature, strong oxidation or reduction, severe radiation, high temperature, high loading, lubricant effect can be arranged, but these solid lubrication additives because particle is big, in lubricating oil (fat) dispersive unstable and and the oil product reasons such as dissolubility difference of holding concurrently, make its effect that really reaches expection then exist more technical difficulty.
Goal of the invention and summary of the invention:
It is reasonable in design to the objective of the invention is to propose a kind of composition, and wear-resistant, antifriction performance and result of use are all good, but also has the abrasion-proof lubricant oil of the interpolation inorganic fluorine Barbiturates solid lubricant product that does not have corrosion and fine environment protection effect.
Can find out according to the object of the invention, the present invention mainly is the hold concurrently disadvantage of dissolubility difference of the solid lubricant that added to overcome in the prior art and oil product, and elements such as the graphite of decontamination environment and metal, the present invention adopts the solid particulate of ultra-fine (micron--nanometer) inorganic fluorine Barbiturates to prepare a kind of lubricating oil additive of wear-resisting, environment-friendly type.Therefore the ultimate principle that will deal with problems of the present invention is according to as follows: by interpolation inorganic fluorine Barbiturates ultrafine solids slip additive proposed by the invention is with the technology of superfine (micron---nanometer) inorganic fluorine Barbiturates particle by stirring or ball milling, above-mentioned powder is scattered in the carrier oil equably and forms stable suspension system.When a small amount of ultra-fine inorganic fluoric acid salt slip additive is added in the plain oil (fat), because these ultrafine solids particulate granularities are very little, very easily enter the mechanical friction surface in the work, these particles are as " ball bearing ", change sliding friction into rolling resistance on the microcosmic, can reduce friction resistance greatly like this.Ultra-fine inorganic fluoric acid salt particulate volume effect and surface effects make it have characteristics such as higher adsorptive power, high diffustivity and easy-sintering.If when the oil film attenuation, when the bossing between friction pair is in contact with one another, ultra-fine inorganic fluoric acid salt slip additive particle will form one deck borderline oil film between friction pair, and generation original position friction chemical reaction forms one deck diffusion layer, reduce direct contact frequency between friction pair, played the antifriction antiwear effect.In addition in abrasion-proof lubricant oil of the present invention, because ultra-fine inorganic fluoric acid salt slip additive particle is to be scattered in the oil (fat) with similar colloidal form, so mistake is missed grease is lost during lubricating oil is using (as strong extruding etc.), and still can play lubrication attached to the ultra-fine grain on the friction surface in for some time of unlubricated carrier oil.Therefore proposed by the invention is a kind of abrasion-proof lubricant oil that adds inorganic fluorine Barbiturates solid lubricant product, and it is characterized in that the composition (weight %) that this abrasion-proof lubricant oil is made up of inorganic fluorine Barbiturates solid lubricant product and carrier fluid lubricant medium is: the addition of inorganic fluorine Barbiturates solid lubricant product is: 0.5%-10%; The lubricating oil add-on is 90%-99.5%; Wherein in inorganic fluorine Barbiturates solid lubricant product, inorganic fluorine Barbiturates solid lubrication additive content is 1%-25%; Carrier fluid lubricant medium content is 75%-99%; In the inorganic fluorine Barbiturates solid lubrication additive that is added, the content of inorganic fluorine Barbiturates solid lubricant, dispersion agent and other salts (weight %) respectively is: inorganic fluorine Barbiturates solid lubricant powder: 1%-24.5%; Dispersion agent: 0.5%-1.5%; Other salts 0-4.5%; Should be in carrier fluid lubricating oil and the carrier fluid lubricating grease any one in the carrier fluid lubricant medium, wherein the content of carrier fluid lubricating oil and carrier fluid lubricating grease respectively (weight %) be: carrier fluid lubricating oil: 85%-99%; Carrier fluid lubricating grease: 75%-99%.Add in the abrasion-proof lubricant oil of inorganic fluorine Barbiturates solid lubricant product in the present invention, other features are to comprise in Sodium tetrafluoroborate, potassium fluoborate, potassium fluozirconate, potassium fluotitanate, the zine fluosilicate any one in inorganic fluorine Barbiturates additive in addition, or two kinds and two or more inorganic fluorine Barbiturates are formed.Dispersion agent includes: any one in the salt of (1) long-chain polyamino acid amides, (2) polymer acid fat, (3) long-chain polyamino amidophosphoric acid salt, (4) polymeric polycarboxylic acid salt, (5) glycerin fatty acyl two hexanols.In any one and other salt in above-mentioned inorganic fluorine Barbiturates solid lubrication additive in fluoroboric acid caesium, sodium fluoroaluminate, the strontium fluoride class any one mixture sum form.Carrier fluid lubricating oil is any one lubricating oil in mineral oil, PAO and two fat or their mixing oil.Other features in interpolation inorganic fluorine Barbiturates solid lubricant product abrasion-proof lubricant oil of the present invention are that the powder size of inorganic fluorine Barbiturates additive should be in the 30nm-800nm scope in addition.
By a kind of abrasion-proof lubricant oil that adds inorganic fluorine Barbiturates solid lubricant product proposed by the invention, its preparation method can be found out (seeing accompanying drawing) by this technical process accompanying drawing, at first be will be to the screening and the preparation of inorganic fluorine Barbiturates powder with good wear-resistant, antifriction performance, then superfine powder, dispersion agent (and tensio-active agent) are added in the carrier fluid oil by stirring or ball milling, after liquid stream pulverizing, centrifuging and Performance Detection, can obtain to add the abrasion-proof lubricant oil finished product of ultra-fine inorganic fluoric acid salt solid lubricant.Ultra-fine inorganic fluoric acid salt solid powder can adopt chemical deposition, hydrolysis method, spray drying method for preparation in above technology.Ultra-fine inorganic fluoric acid salt powder includes that potassium fluoborate, potassium fluozirconate, fluoroboric acid are received, in potassium fluotitanate and the zine fluosilicate any one, and the mixture that contains them, accounts for 5%～25% of additive gross weight; Carrier fluid can be the mixture of any one or they in mineral oil, synthetic oil (as polyalphaolefin PAO), the diester.Dispersion agent can adopt any one in salt, long-chain polyamino amidophosphoric acid salt, polymeric polycarboxylic acid salt, glycerin fatty acid phosphoric acid or the diethanolamine of fat acyl etc. of long-chain polyamino acid amides and polymer acid esters.
It is reasonable in design to adopt interpolation inorganic fluorine Barbiturates solid lubricant product abrasion-proof lubricant oil of the present invention to have composition compared with prior art; wear-resistant, antifriction performance and result of use are all good; there are not corrosion and fine environment protection effect but also have; also has stronger stability simultaneously; it is overheated that its good thermal conductivity can guarantee also that when running up machinery can not produce; and can mate with low viscosity oil; the existence that still can keep lubricant film under the condition of high capacity and vibration is particularly suitable for work under heavy duty, high (low) speed, high (low) temperature and vibration condition.In addition, because ultra-fine grain is to be scattered in the oil (fat) with similar colloidal form, so when lubricating oil miss or for a certain reason (as strong extruding etc.) grease is lost, the ultra-fine grain that is deposited on the friction surface still can play lubrication in considerable time.The more important thing is that this product color is pure white, do not contain any heavy metal, sulphur, phosphorus and toxic chemical substance, free from environmental pollution.
Description of drawings
At the abrasion-proof lubricant oil preparation technology schema of accompanying drawing described in the specification sheets of the present invention, in the accompanying drawings: 1. be the inorganic fluorine Barbiturates for interpolation inorganic fluorine Barbiturates solid lubricant product; 2. dispersion agent; 3. be carrier fluid; 4. work in-process; 5. be abrasion-proof lubricant oil, the A. in the technical process is for stirring or ball milling; B. pulverize for liquid stream; C. be centrifuging and Performance Detection.
Embodiment
Abrasion-proof lubricant oil composition scope according to interpolation inorganic fluorine Barbiturates solid lubricant product of the present invention, we have done the test of 8 kinds of component contents altogether, in order to contrast conveniently, we also enumerate two kinds abrasion-proof lubricant oil of the prior art simultaneously, and its contrast composition, simultaneous test condition and contents such as result and physico-chemical analysis are all listed in the contrast table.Sequence number 1-8 is the abrasion-proof lubricant oil of composition of the present invention in table, and sequence number 9,10 is the contrast abrasion-proof lubricant oil.Oil sample sequence number 1,2,3,4,5,6,7,8 is respectively to be prepared into inorganic fluorine Barbiturates slip additive product in different component content ratios in table 1, and be added in the SE15W/40 machine oil, and the contrast experiment who rubs, weares and teares (seeing Table 2) in 5% ratio; The contrast oil sample of sequence number 9 is for adding the SE15W/40 machine oil of the special wear-resisting engine copper plating additive of 5% U.S. (micron order); Sequence number 10 is common SE15W/40 machine oil; The frictional coefficient of simultaneous test is by 120kgf with the drop lubricaton condition is following is surveyed at load value; Be at load value 120kgf perdurability, lubricated after 10 minutes, 10 minutes following survey of condition of oil-break continuity.
Composition and preparation technology's comparison sheet of table 1, embodiment of the invention inorganic fluorine Barbiturates solid lubricant product
| Sample | The inorganic fluorine Barbiturates | Other salts | Carrier fluid | ||||||||
| Main component | Median size (nm) | Component content (%) | Dispersion agent (%) | The preparation method | Main component | Component content (%) | Median size (nm) | Composition | Component content (%) | ||
| 1 | KBF 4 | 96 | 19 | (1) 1 | Sedimentation | / | / | / | Mineral oil | 80 | |
| 2 | KBF 4 | 680 | 19 | (4) 1 | Sedimentation | / | / | / | Mineral oil | 80 | |
| 3 | KBF 4+KZrF 6 | 85 | 15+4 | (1) 1 | Comminuting method | / | / | / | PAO | 80 | |
| 4 | KBF 4 | 77.5 | 4.5 | (2) 0.5 | Spray-drying process | / | / | / | Mineral oil+PAO | 95 | |
| 5 | NaBF 4 | 67 | 14 | (5) 1.5 | Comminuting method | CsBF 4 | 4.5 | 40 | Diester | 80 | |
| 6 | KZrF 6 | 93 | 8.5 | (3) 1.5 | Sedimentation | / | / | Mineral oil+PAO | 90 | ||
| 7 | KTiF 6 | 500 | 14.5 | (1) 1 | Hydrolysis method | Na 3AlF 4 | 4.5 | 66.5 | Mineral oil+two fat | 80 | |
| 8 | ZnSiF 4 | 87 | 16 | (2) 1 | | SrF | 4 | 3 | 98 | Mineral oil+PAO | 80 |
| 9 | Comparative Examples | / | / | / | / | / | / | / | / | 95 | |
| 10 | Comparative Examples | / | / | / | / | / | / | / | / | 100 | |
Annotate: sequence number 9,10 is the Comparative Examples oil sample, and wherein sequence number 9 is that SE15W/40+5% U.S. spy is wear-resisting, and sequence number 10 is SE15W/40.
The friction of the different ultra-fine inorganic salt of table 2. slip additive product, wearing and tearing contrast experiment:
| Oil sample | Four ball formula trier experimental datas | M-200 trier experimental data | |||
| Attrition value | Rupture of oil film intensity PB value (kgf) | Frictional coefficient | Perdurability (min) | ||
| d 30min 60Kg (mm) | d 30min 120Kg(mm) | ||||
| 1 | 0.61 | 1.074 | 106 | 0.115 | 66:54 |
| 2 | 0.65 | 1.462 | 102.5 | 0.118 | 49:32 |
| 3 | 0.62 | 1.177 | 105 | 0.116 | 62:37 |
| 4 | 0.61 | 1.318 | 104 | 0.115 | 36:38 |
| 5 | 0.66 | 1.298 | 104 | 0.117 | 40:51 |
| 6 | 0.66 | 1.387 | 102 | 0.116 | 40:27 |
| 7 | 0.87 | 1.847 | 99.5 | 0.120 | 25:37 |
| 8 | 0.89 | 1.901 | 99.5 | 0.120 | 15:48 |
| 9, contrast oil sample | 0.718 | 2.203 | 102 | 0.119 | 9:50 |
| 10.SE15W/40 machine oil | 0.66 | 2.283 | 98.5 | 0.116 | 7:55 |
The report of table 3. ultra-fine inorganic fluoric acid salt solid lubrication additive physico-chemical analysis
| The | 1 # | 2 # | Analytical procedure |
| Viscosity (mm 2/s) | 105.6(40℃) | 105.6(40 ℃) | GB/T265 |
| Viscosity (mm 2/s) | 14.66(100℃) | 14.68(100 ℃) | GB/T265 |
| Pour point (℃) | -31 | -31 | Gb/T3535 |
| Acid number (mgKOH/g) | 1.78 | 1.78 | Gb/T264 |
| Flash-point (℃) | 230 (opening cup) | 231 (opening cup) | GB/T267 |
| The petroleum products viscosity index | 143 | 143 | GB/T2541 |
Annotate: 1
#Be certain SE15W/40 machine oil; 2
#Be No. 1 oil sample in the table 2.
Friction, the wearing and tearing contrast experiment of the different abrasion-proof lubricant oils of table 4 when 75 ℃ of temperature and 100 ℃:
| Oil sample | The addition of inorganic fluorine Barbiturates solid lubricant product and lubricating oil is (weight %) | Four ball formula trier experimental datas | |||||
| Attrition value (mm) | Frictional coefficient (room temperature) | ||||||
| Inorganic fluorine Barbiturates solid lubrication additive product | Lubricating oil | d 60min 40Kg (75℃) | d 15min 125Kg (75℃) | d 30min 40Kg (100℃) | d 10min 125Kg (100℃) | ||
| 1 | 9 | 91 | 0.411 | 1.42 | 0.425 | 1.41 | 0.114 |
| 2 | 1 | 99 | 0.771 | 1.83 | 0.643 | 2.13 | 0.120 |
| 3 | 3.5 | 96.5 | 0.410 | 1.36 | 0.420 | 1.37 | 0.113 |
| 4 | 0.8 | 99.2 | 0.872 | 1.90 | 0.563 | 1.72 | 0.119 |
| 5 | 6.2 | 93.8 | 0.499 | 1.91 | 0.613 | 2.15 | 0.115 |
| 6 | 5.8 | 94.2 | 0.533 | 1.92 | 0.690 | 2.24 | 0.115 |
Annotate: press the GB/T5096 standard in addition, above 1,2,3, No. 4 oil sample is done copper corrosion, its result is: copper corrosion (100 ℃ 3h) are the 1a level.
As can be seen from Table 2, behind the ultra-fine inorganic fluoric acid salt solid lubricant product of adding 5%, its abrasion-proof lubricant oil fastness to wear increases substantially, the rupture of oil film intensity P of lubricating oil in common SE15W/40 lubricating oil
BValue is brought up to 99～106kgf by original 98.5kgf, attrition value d
30 120Being dropped to below the 1.9mm by 2.283mm, add behind No. 1 the inorganic fluorine Barbiturates solid lubricant product attrition value even 1.074mm is only arranged, is 2.203mm and add the attrition value of other metal additives (Comparative Examples oil sample sequence number 9) this moment; At load value is 120Kgf, lubricated after 10 minutes, under 10 minutes the condition of oil-break continuity, be about 6 minutes the perdurability of plain oil (SE15W/40 machine oil), and add the abrasion-proof lubricant oil of 5% inorganic fluorine Barbiturates solid lubricant product, with regard to same machine oil perdurability generally all more than 15 minutes, reach as high as more than 67 minutes.
The embodiment explanation of tables: each table at the foregoing description is respectively: composition and preparation technology's synopsis of table 1. embodiment of the invention inorganic fluorine Barbiturates solid lubricant product; Table 2. embodiment of the invention is for the different ultra-fine inorganic salt slip additives contrast experiment that rubs, weares and teares; The report of table 3. ultra-fine inorganic fluoric acid salt solid lubrication additive physico-chemical analysis; Friction, the wearing and tearing contrast experiment of the different abrasion-proof lubricant oils of table 4. when 75 ℃ of temperature and 100 ℃.
Claims (2)
1, a kind of abrasion-proof lubricant oil that contains solid lubricant product, it is characterized in that this abrasion-proof lubricant oil is mixed with lubricating oil by inorganic fluorine hydrochlorate solid lubrication additive product forms, wherein the composition weight % of inorganic fluorine hydrochlorate solid lubrication additive product is: 0.5%-10%, and the lubricating oil add-on is 90%-99.5%; In inorganic fluorine hydrochlorate solid lubricant product, the content weight % of inorganic fluorine hydrochlorate solid lubrication additive is 1%-25%, and carrier fluid lubricant medium content is 75%-99%; Wherein the content weight % of inorganic fluorine hydrochlorate solid lubricant, dispersion agent and other salts in the inorganic fluorine hydrochlorate solid lubrication additive is respectively: inorganic fluorine hydrochlorate solid lubricant: 1%-24.5%; Dispersion agent: 0.5%-1.5%; Other salts: 0-4.5%; Component included in above-described composition is respectively:
(1) other salts in inorganic fluorine hydrochlorate solid lubrication additive are to be selected from fluoroboric acid caesium, sodium fluoroaluminate, the strontium fluoride salt any one or a few;
(2) inorganic fluorine hydrochlorate solid lubricant is to be selected from potassium fluoborate, Sodium tetrafluoroborate, potassium fluozirconate, potassium fluotitanate, the zine fluosilicate any one or a few.
(3) in inorganic fluorine hydrochlorate solid lubricant product, dispersion agent is to be selected from the salt that contains long-chain polyamino acid amides, polymer acid fat, long-chain polyamino amidophosphoric acid salt, polymeric polycarboxylic acid salt, glycerin fatty acyl two hexanols any one.
2, according to the described abrasion-proof lubricant oil that contains solid lubricant product of claim 1, the powder size that it is characterized in that being added on the inorganic fluorine hydrochlorate solid lubrication additive in the carrier fluid lubricant medium should be in the 30nm-800nm scope.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021208417A CN1180066C (en) | 2002-06-05 | 2002-06-05 | Anti-friction lubricating oil adding inorganic fluoric acid salt solid lubricant product |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021208417A CN1180066C (en) | 2002-06-05 | 2002-06-05 | Anti-friction lubricating oil adding inorganic fluoric acid salt solid lubricant product |
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| CN1180066C true CN1180066C (en) | 2004-12-15 |
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| CN104946345A (en) * | 2014-03-27 | 2015-09-30 | 南通第五机床有限公司 | Lubricant additive |
| CN104946344A (en) * | 2014-03-27 | 2015-09-30 | 南通第五机床有限公司 | Preparation method of lubricating oil additive |
| CN104611116A (en) * | 2015-01-29 | 2015-05-13 | 安徽铖友汽车零部件制造有限公司 | Microemulsion cutting solution |
| CN107686768A (en) * | 2017-09-29 | 2018-02-13 | 成都新柯力化工科技有限公司 | A kind of abrasion-proof lubricant oil and preparation method thereof |
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