CN103525507A - Metal surface alloying agent and preparation method thereof - Google Patents
Metal surface alloying agent and preparation method thereof Download PDFInfo
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- CN103525507A CN103525507A CN201310473282.2A CN201310473282A CN103525507A CN 103525507 A CN103525507 A CN 103525507A CN 201310473282 A CN201310473282 A CN 201310473282A CN 103525507 A CN103525507 A CN 103525507A
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Abstract
The invention discloses a metal surface alloying agent, which is prepared from the following components by weight: 80-92% of vegetable oil, 2-8% of metal compounds and 5-15% of a catalyst. The metal compounds include an aluminum-containing compound, a calcium-containing compound, a boron-containing compound, a magnesium-containing compound, a titanium-containing compound and a molybdenum-containing compound. Amount of each metal compound realizes the following mass fraction of metal atoms in the metal surface alloying agent: 0.01-0.3% of aluminum atoms, 0.01-0.5% of titanium atoms, 0.1-0.5% of boron atoms, 0.5-2% of calcium atoms and 0.5-3% molybdenum atoms. The invention also discloses a preparation method of the alloying agent. The metal surface alloying agent does not contain sulfur, chlorine or phosphorus, meets the requirements of environmental protection and has good extreme pressure antiwear performance and antioxidant properties.
Description
Technical field
The present invention relates to high energy mechanical alloying process field, particularly relate to a kind of metal surface alloy agent and preparation method thereof.
Background technology
According to internal authority mechanism statistics, Material Wear, corrosion and fatigue three lossies account for 30% of gross industrial output value.Frictional wear is ubiquitous spontaneous phenomenon, frictionloss the primary energy source in the world approximately 1/3rd, wearing and tearing are to cause one of three kinds of topmost forms of material and damage of facilities and inefficacy, lubricated be the effective technology that reduces friction, reduces or avoid wearing and tearing.Development has good wear resistance, high bearing capacity, wear surface is had to the lubrication technology of certain repairing effect, environmentally safe or less contamination, is one of important topic of contemporary chemistry and Materials science and tribology.
The efficient extreme pressure anti-wear additives of zinc dialkyl dithiophosphate (ZDDP) has been the indispensable interpolation component of oil engine wet goods oil product since 20 middle of century always, and be also widely applied in gear oil, hydraulic pressure wet goods technical oils, but, the needs that it has seemed and has been difficult to adapt to the situation development now.This be because: the phosphorous converted product of (1) ZDDP can be used in the poisoning of catalyst in the three way catalytic converter that reduces the noxious gas emissions such as oxynitride (NOx) in vehicle exhaust and affect oxygen sensor; (2) ZDDP can produce ash content, stops up filtering system, to the particle trapper of diesel engine, can produce detrimentally affect; (3) element Zn can make some alloy bearing (mainly referring to argentiferous, plumbous parts) produce galvanic corrosion; (4) under the operating mode higher than 160 degree, can lose anti-oxidant and extreme pressure and antiwear behavior because sharply decomposing.
Chinese patent patent of invention ZL200910067880.3 discloses a kind of cermet couplant, this couplant is the wear preventive additive containing magnesium, aluminium, boron and titanium ceramic metal, mixture for each component, in order to guarantee good suspension and dispersiveness, its dispersion agent used is chloride, has potential safety and environmental protection risk.
Chinese patent ZL200710143950.X discloses a kind of nano-stage ceramic metal mixture additive for lubricating oil, fat, and this additive is for including boron nitride, molybdenum, the composition liquid of copper powder body; This boron nitride, molybdenum, copper powder body powder is the spherical solid particulate matter of a kind of nano level that boron nitride and molybdenum form with coordinate bond structure with covalent bond structure, copper; Boron nitride is spherical skeleton, and molybdenum is coated on it with lamellar, and copper is combined with the lattice defect place of spheroid with point, sheet; In this powder, the ratio of boron nitride, molybdenum and the shared component of copper is 7～8.5: 1～1.5: 0.5～1, and the shortcoming of this additive is that oil soluble is poor, easily produces precipitation.
In sum, there is following shortcoming in existing metal surface alloy agent:
(1) sulfur-bearing, phosphorus and zinc, easily produce burn into and poison and high temperature failure; (2) contain chlorine, can produce corrosion; (3) oil soluble is poor, easily produces precipitation.
Summary of the invention
An object of the present invention is to provide the objectionable impuritiess such as a kind of not sulfur-bearing, phosphorus, zinc, chlorine, oil soluble is good, wear resistance is high metal surface alloy agent.
Another object of the present invention is to provide a kind of method of preparing above-mentioned metal surface alloy agent.
For this reason, technical scheme of the present invention is as follows:
An agent, is prepared from by the component of following mass percent:
Vegetables oil: 80-92%
Metallic compound: 2-8%
Catalyzer: 5-15%,
Wherein, described metallic compound comprises aluminum contained compound, calcium containing compound, boron-containing compound, magnesium-containing compound, titanium-containing compound and molybdate compound, and the consumption of each compound is respectively the massfraction of atoms metal in prepared metal surface alloy agent:
Aluminium atom: 0.01-0.3%,
Titanium atom: 0.01-0.5%,
Boron atom: 0.1-0.5%,
Calcium atom: 0.5-2%,
Molybdenum atom: 0.5-3%.
Preferably, described vegetables oil be in peanut oil, soybean oil, oleum lini, plam oil, Oleum Cocois, Viscotrol C, rape seed oil one or more with arbitrarily than mixture.
Described catalyzer is ammoniacal liquor, hydrochloric acid, bicarbonate of ammonia, hydrogen peroxide or potassium permanganate.
Described aluminum contained compound be aluminum isopropylate, Aluminate, Tai-Ace S 150, aluminum nitrate and aluminium powder one or more with arbitrarily than mixture.
Described calcium containing compound be in calcium hydroxide, calcium oxide, organic sulfonic acid calcium, calcium carbonate and alkyl sodium salicylate one or more with arbitrarily than mixture.
Described boron-containing compound be a kind of in boric acid, boron oxide, boric acid ester or wherein multiple with arbitrarily than mixture.
Described magnesium-containing compound be in magnesium oxide, magnesium hydroxide, magnesium nitrate, organic sulfonic acid magnesium one or more with arbitrarily than mixture.
Described titanium-containing compound be in titanic acid ester, titanium oxide, titanium tetrachloride, titanium isopropylate, titanium sulfate one or more with arbitrarily than mixture.
Described molybdate compound be in molybdenum oxide, ammonium molybdate, organic-molybdenum one or more with arbitrarily than mixture.
A preparation method for above-mentioned metal surface alloy agent, comprises the following steps:
1) preparation of metallic compound:
Under agitation condition, according to formula, in reactor, add aluminum contained compound, titanium-containing compound, calcium containing compound, boron-containing compound, magnesium-containing compound and molybdate compound, stir 1～4 hour, obtain brown viscous liquid;
2) preparation of metal surface alloy agent:
The above-mentioned brown liquid that obtains is moved in autoclave, by formula, add vegetables oil and hydrochloric acid, then seal autoclave, pass into carbonic acid gas to supercritical pressure 72.9atm, be warming up to 31.26 ℃ of supercritical temperatures, under agitation condition, react after 3～6 hours, cooling, separatory, vacuum-drying dehydration, obtain oil soluble transparent liquid or viscous liquid.
The method that metal surface alloy agent utilization chemistry of the present invention and physical metallurgy combine changes metal material surface chemical composition and weave construction, thereby makes material surface obtain the technological process of the performance that requires.Take lubricant as carrier, utilize fricative heat, by thermo-chemical treatment technology, can improve material hardness, corrosion-resistant and resistance toheat on the one hand, can also improve on the other hand the wear resistance of material.
Metal surface alloy agent of the present invention is the multi-element compounds of boracic, calcium, molybdenum, aluminium and magnesium, itself is sulfur-bearing, chlorine and phosphorus not, meets the GF-4 of environmental protection and API (API), the low-sulfur of GF-5, phosphorus requires and have good extreme pressure and antiwear behavior and antioxidant property.
Accompanying drawing explanation
Fig. 1 is that the metal surface alloy agent that embodiment 3 makes joins the electronic spectrum of the surface of friction pair element recording in lubricating oil in the ratio of 0.5wt%.
Embodiment
Below in conjunction with specific embodiment, method of the present invention is elaborated.
Embodiment 1
A preparation method for metal surface alloy agent, comprises the following steps:
(1) preparation of metallic compound:
In reactor, under agitation condition, add successively 10g aluminum isopropylate, 15g titanic acid ester, 20g organic sulfonic acid calcium, 10g boric acid, 25g organic sulfonic acid magnesium and 5g ammonium molybdate, stir 1 hour, obtain brown viscous liquid.
(2) preparation of metal surface alloy agent:
The brown liquid that 5g step (1) is made moves in autoclave, add respectively 70g plam oil and 5g hydrochloric acid, then capping still, pass into carbonic acid gas to supercritical pressure 72.9atm, be warming up to 31.26 ℃ of supercritical temperatures, under agitation condition, react after 4 hours, after cooling, separatory, vacuum-drying dehydration, obtain oil soluble transparent liquid or viscous liquid.
Embodiment 2
A preparation method for metal surface alloy agent, comprises the following steps:
(1) preparation of metallic compound:
In reactor, under agitation condition, add successively 12g Aluminate, 13g titanium isopropylate, 24g alkyl sodium salicylate, 12g boric acid, 21g magnesium nitrate and 3g organic-molybdenum, stir 1 hour, obtain brown viscous liquid.
(2) preparation of metal surface alloy agent:
The brown liquid that 5g step (1) is made moves in autoclave, add respectively 60g plam oil and 2g potassium permanganate, then capping still, pass into carbonic acid gas to supercritical pressure 72.9atm, be warming up to 31.26 ℃ of supercritical temperatures, under agitation condition, react after 4 hours, after cooling, separatory, vacuum-drying dehydration, obtain oil soluble transparent liquid or viscous liquid.
The brown liquid that 5g embodiment 1 step (1) is made moves in autoclave, add respectively 60g Oleum Cocois and 2g potassium permanganate, then capping still, pass into carbonic acid gas to supercritical pressure 72.9atm, be warming up to 31.26 ℃ of supercritical temperatures, under agitation condition, react after 4 hours, after cooling, separatory, vacuum-drying dehydration, obtain oil soluble transparent liquid or viscous liquid.
The above-mentioned metal surface alloy agent making is joined in lubricating oil in the ratio of 0.5wt%, and the electronic spectrum (EDX) of the surface of friction pair element recording as shown in Figure 1.
Following table is the resistance to compression abrasion resistance test result of the metal surface alloy agent that makes of above-mentioned 3 embodiment under different loads.
From above-mentioned experimental data, metal surface alloy agent prepared by the embodiment of the present invention does not contain the objectionable impuritiess such as sulphur, phosphorus, zinc, chlorine, has the better extreme pressure and antiwear behavior than ZDDP simultaneously, and frictional coefficient declines 70%, and wear scar diameter declines more than 80%.The energy spectrum analysis of Fig. 1 surface of friction pair can prove, this metal surface alloy agent long-term use in lubricating oil can form in metallic surface boracic, magnesium, molybdenum, iron, the alloy layer structure of titanium.
Claims (10)
1. a metal surface alloy agent, is characterized in that being prepared from by the component of following mass percent:
Vegetables oil: 80-92%
Metallic compound: 2-8%
Catalyzer: 5-15%,
Wherein, described metallic compound comprises aluminum contained compound, calcium containing compound, boron-containing compound, magnesium-containing compound, titanium-containing compound and molybdate compound, and the consumption of each compound is respectively the massfraction of atoms metal in prepared metal surface alloy agent:
Aluminium atom: 0.01-0.3%,
Titanium atom: 0.01-0.5%,
Boron atom: 0.1-0.5%,
Calcium atom: 0.5-2%,
Molybdenum atom: 0.5-3%.
2. metal surface alloy agent according to claim 1, is characterized in that: described vegetables oil be in peanut oil, soybean oil, oleum lini, plam oil, Oleum Cocois, Viscotrol C, rape seed oil one or more with arbitrarily than mixture.
3. metal surface alloy agent according to claim 1, is characterized in that: described catalyzer is ammoniacal liquor, hydrochloric acid, bicarbonate of ammonia, hydrogen peroxide or potassium permanganate.
4. metal surface alloy agent according to claim 1, is characterized in that: described aluminum contained compound be aluminum isopropylate, Aluminate, Tai-Ace S 150, aluminum nitrate and aluminium powder one or more with arbitrarily than mixture.
5. metal surface alloy agent according to claim 1, is characterized in that: described calcium containing compound be in calcium hydroxide, calcium oxide, organic sulfonic acid calcium, calcium carbonate and alkyl sodium salicylate one or more with arbitrarily than mixture.
6. metal surface alloy agent according to claim 1, is characterized in that: described boron-containing compound for for a kind of in boric acid, boron oxide, boric acid ester or wherein multiple with arbitrarily than mixture.
7. metal surface alloy agent according to claim 1, is characterized in that: described magnesium-containing compound be in magnesium oxide, magnesium hydroxide, magnesium nitrate, organic sulfonic acid magnesium one or more with arbitrarily than mixture.
8. metal surface alloy agent according to claim 1, is characterized in that: described titanium-containing compound be in titanic acid ester, titanium oxide, titanium tetrachloride, titanium isopropylate, titanium sulfate one or more with arbitrarily than mixture.
9. metal surface alloy agent according to claim 1, is characterized in that: described molybdate compound be in molybdenum oxide, ammonium molybdate, organic-molybdenum one or more with arbitrarily than mixture.
10. a preparation method for metal surface alloy agent described in claim 1, is characterized in that comprising the following steps:
1) preparation of metallic compound:
Under agitation condition, according to formula, in reactor, add successively aluminum contained compound, titanium-containing compound, calcium containing compound, boron-containing compound, magnesium-containing compound and molybdate compound, stir 1～4 hour, obtain brown viscous liquid;
2) preparation of metal surface alloy agent:
The above-mentioned brown liquid that obtains is moved in autoclave, by formula, add vegetables oil and hydrochloric acid, then seal autoclave, passing into carbonic acid gas to supercritical pressure is 72.9atm, be warming up to 31.26 ℃ of supercritical temperatures, under agitation condition, react after 3～6 hours, cooling, separatory, vacuum-drying dehydration, obtain oil soluble transparent liquid or viscous liquid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106281582A (en) * | 2015-05-26 | 2017-01-04 | 深圳中嘉能源有限公司 | A kind of repairing type lubricant |
| CN113355147A (en) * | 2021-07-06 | 2021-09-07 | 清研检测（天津）有限公司 | Friction improver, preparation method thereof and lubricating oil containing friction improver |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967419A (en) * | 2010-11-02 | 2011-02-09 | 天津东方舜能润滑材料有限公司 | Ceramic alloy lubricating oil special for dredging workboat engine and preparation method thereof |
| CN103302286A (en) * | 2013-06-18 | 2013-09-18 | 江苏和昊激光科技有限公司 | Cobalt-based metal ceramic alloy powder exclusively used in laser cladding of turning tool |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967419A (en) * | 2010-11-02 | 2011-02-09 | 天津东方舜能润滑材料有限公司 | Ceramic alloy lubricating oil special for dredging workboat engine and preparation method thereof |
| CN103302286A (en) * | 2013-06-18 | 2013-09-18 | 江苏和昊激光科技有限公司 | Cobalt-based metal ceramic alloy powder exclusively used in laser cladding of turning tool |
Non-Patent Citations (1)
| Title |
|---|
| 施利毅等: "《纳米科技基础》", 30 September 2005, 华东理工大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106281582A (en) * | 2015-05-26 | 2017-01-04 | 深圳中嘉能源有限公司 | A kind of repairing type lubricant |
| CN113355147A (en) * | 2021-07-06 | 2021-09-07 | 清研检测（天津）有限公司 | Friction improver, preparation method thereof and lubricating oil containing friction improver |
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