CN1354056A - Metal copper nano granules, its preparation method and application - Google Patents
Metal copper nano granules, its preparation method and application Download PDFInfo
- Publication number
- CN1354056A CN1354056A CN 01135662 CN01135662A CN1354056A CN 1354056 A CN1354056 A CN 1354056A CN 01135662 CN01135662 CN 01135662 CN 01135662 A CN01135662 A CN 01135662A CN 1354056 A CN1354056 A CN 1354056A
- Authority
- CN
- China
- Prior art keywords
- formula
- nano particle
- compound
- metal copper
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The present invention discloses a kind of metal copper nano particles compound as multifunctional lubricant additive. Its preparation method includes the following steps: using organic compound containing thiophosphate as modifying agent and making it react with soluble cupric acetate for 2-12 hr. at 50-80 deg.c in the presence of reaction medium hydrated hydrazine so as to obtain the invented product.
Description
Affiliated field
The present invention relates to a kind of organic compound modified metal copper nano granules of sulfo-phosphorus and preparation method thereof and purposes of containing.
Background technology
Nano material is owing to its unique physics and chemical property have obtained paying attention to widely.In recent years, the preparation of nano particle, performance and applied research have become the forward position research field of multidisciplinary intersection.Inorganic nano-particle has the character of many uniquenesses, yet is restricted owing to its non-oil soluble and easy oxidation make its application in lubricated field.
Summary of the invention
The object of the present invention is to provide a kind of new organic compound modified metal copper nano granules that can in organic medium, lubricated wet goods, have the stable dispersion performance.
Further aim of the present invention provides a kind of preparation method who contains the organic compound modified metal copper nano granules of sulfo-phosphoric acid salt.
Another object of the present invention provides the purposes of metal copper nano granules in lubricated field.
The present invention realizes by following measure:
The novel phosphatic organic compound modified metal copper nano granules of sulfo-that contains is found, and its structure is represented with general formula (I):
R is C in the formula (I)
8～C
18The straight or branched alkyl.
M represents the atom number of metallic copper in the nano particle, is 100-900; N represents the molecule number of left-half in the nano particle formula (I), is 10-800.
In formula (I) compound, preferred R is a hexadecyl.
Preparation method of the present invention may further comprise the steps:
A) use alkyl chain length to be C
8-C
18Straight or branched contain thiophosphatephosphorothioate organic compound as modifier, make it and solubility neutralized verdigris Cu (AC)
2H
2The O reaction;
B) in the presence of the reaction medium hydrazine hydrate;
C) 50～80 ℃ were reacted 2-12 hour down.
Preparation contains in the method for the organic compound modified metal copper nano granules of sulfo-phosphoric acid salt, and the mol ratio of modifier and neutralized verdigris is 1: 10～10: 1.
Product of the present invention has good dispersiveness in organic solvent and lubricating oil.The copper of modifying through thiophosphatephosphorothioate has good dispersiveness in organic mediums such as chloroform, toluene, benzene, whiteruss, it is brown that solution is, and dispersity is little in ethanol isopolarity organic medium; The nanometer copper of modifying without thiophosphatephosphorothioate all can not disperse in polarity and non-polar solvent.
Nano particle of the present invention adds in the lubricating grease can obtain good wear-resistant, antifriction performance, also has very high supporting capacity simultaneously.
Nano particle of the present invention can be used as a kind of multifunctional lubricant fat additives and uses.
The nanometer copper that thiophosphatephosphorothioate is modified is 1～5.0% of lubricating grease weight as the addition of lubricating oil and grease additive.
Description of drawings
Fig. 1 is the frictional coefficient variation relation curve in time of phosphorus substituted phosphate decorated nanometer Cu, unmodified nanometer Cu, zinc dialkyl dithiophosphate (ZDDP) and paraffin oil.
Fig. 2 is the relation curve between thiophosphoric acid decorated nanometer Cu and ZDDP content of additive and the wear scar diameter.
Embodiment:
In order to understand the present invention better, describe by example.
Embodiment 1:
Get 200ml distilled water and ethanol mixed solvent (V
Water: V
Ethanol=1: 1), inject the reactor have the constant temperature jacket layer, constant temperature to 50 ℃ adds 0.01 mole of two (hexadecyl) phosphorodithioate and excessive hydrazine hydrate.At this moment solution clear, the PH ≈ 9-10 of solution, under the magnetic force vigorous stirring, logical high-purity N
2After 20 minutes, 0.05 mole has dissolved neutralized verdigris Cu (AC) completely
2H
2O once adds, solution by the clarification change into very soon brick-red change into again brown transparent, slowly there is brown flocks to occur, reacted 2.0 hours, still aging spending the night, heat filtering, precipitation is washed for several times with hot water, ethanol, acetone successively, to remove inorganic impurity and unreacted thiophosphatephosphorothioate completely, vacuum-drying gets powder.
Its particle diameter of the transmission electron microscope of product (TEM) analysis revealed is about 6 nanometers (nm), is the not too near-spherical of rule, and does not have tangible agglomeration.
Embodiment 2:
Get 100ml distilled water and ethanol mixed solvent (V
Water: V
Ethanol=1: 1), inject the reactor have the constant temperature jacket layer, constant temperature to 50 ℃ adds a certain amount of hydrazine hydrate, makes the PH ≈ 9-10 of solution, under the magnetic force vigorous stirring, and logical high-purity N
2After 20 minutes, 0.05 mole has dissolved neutralized verdigris Cu (AC) completely
2H
2O once adds, reacted 3 hours, and still aging spending the night, heat filtering, precipitation is washed for several times with hot water, ethanol, acetone successively, and to remove inorganic impurity, vacuum-drying must not have the copper nanoparticle body that organic modifier is modified.
The particle diameter of transmission electron microscope (TEM) the analysis revealed unmodified nanometer copper of example 1 and example 2 products is about 40 nanometers (nm), and the particle diameter of thiophosphatephosphorothioate decorated nanometer copper is about 6 nanometers (nm).
Embodiment 3:
Get 200ml distilled water and ethanol mixed solvent (V
Water: V
Ethanol=1: 1), inject the reactor have the constant temperature jacket layer, constant temperature to 50 ℃ adds 0.01 mole of two (dodecyl) phosphorodithioate and excessive hydrazine hydrate.At this moment solution clear, the PH ≈ 9-10 of solution, under the magnetic force vigorous stirring, logical high-purity N
2After 20 minutes, 0.02 mole has dissolved neutralized verdigris Cu (AC) completely
2H
2O once adds, solution by the clarification change into very soon brick-red change into again brown transparent, slowly there is brown flocks to occur, reacted 2.5 hours, still aging spending the night, heat filtering, precipitation is washed for several times with three water, ethanol, acetone of heat successively, to remove inorganic impurity and unreacted thiophosphatephosphorothioate completely, vacuum-drying gets powder.
Embodiment 4:
Get 200ml distilled water and ethanol mixed solvent (V
Water: V
Ethanol=1: 1), inject the reactor have the constant temperature jacket layer, constant temperature to 50 ℃ adds 0.01 mole of dioctyl phosphorodithioate and excessive hydrazine hydrate.At this moment solution clear, the PH ≈ 9-10 of solution, under the magnetic force vigorous stirring, logical high-purity N
2After 20 minutes, 0.01 mole has dissolved neutralized verdigris Cu (AC) completely
2H
2O once adds, solution by the clarification change into very soon brick-red change into again brown transparent, slowly there is brown flocks to occur, reacted 3.0 hours, still aging spending the night, heat filtering, precipitation is washed for several times with three water, ethanol, acetone of heat successively, to remove inorganic impurity and unreacted thiophosphatephosphorothioate completely, vacuum-drying gets powder.
With the resultant thiophosphatephosphorothioate surface ornament Cu nanoparticulate dispersed that contains at analytically pure paraffin oil, at the wear scar diameter of having measured on the four-ball tester under different load.Testing used four-ball tester is the vertical omnipotent friction wear testing machine of MMW-1 type that Jinan trier factory produces, and used steel ball is the secondary standard steel ball (φ 12.7mm, GCr15 bearing steel, HRc are 59-61) that Lanzhou Berings Factory produces.Test is at room temperature carried out, and addition is 1wt.%, and rotating speed is 1450 rev/mins, and test period is 30 minutes, the results are shown in Figure 1.As seen from the figure, unmodified Cu nanoparticle and commercial lubricating oil additive ZDDP have high and unsettled friction curve, all fail to reduce the frictional coefficient of base oil.No matter load is 300N or 1500N and contain thiophosphatephosphorothioate modification Cu nanoparticle, and friction curve is highly stable, and presents certain antifriction ability under the 300N load, has excellent antifriction quality under the 1500N high loading.This explanation contains thiophosphatephosphorothioate modification Cu nanoparticle and has formed firmly and the low surface film of shearing resistance at friction surface.
Table 1 has provided embodiment 1, embodiment 2, embodiment 3, embodiment 4 products therefroms four-ball test result under similarity condition.As can be seen, compare with the base oil whiteruss, prepared nano copper particle all can reduce the wearing and tearing of moving parts, and wherein the nanometer copper of thiophosphatephosphorothioate modification has better effect than unmodified nanometer copper.In the nanometer copper that the sulphur phosphoric acid ester of three kinds of prepared different alkyl structures is modified, the nanometer copper of modifying with the hexadecyl thiophosphatephosphorothioate has minimum wear scar diameter.
The evaluation result of table 1 wear scar diameter (mm)
(four-ball tester, additive concentration are 1wt%, 300N, 1450r/min, 30min, 25 ℃)
| Additive | Wear scar diameter (mm) |
| Whiteruss | ????0.72 |
| Example 1 | ????0.42 |
| Example 2 | ????0.61 |
| Example 3 | ????0.45 |
| Example 4 | ????0.47 |
Table 2 shows hexadecyl thiophosphatephosphorothioate decorated nanometer Cu, without the bearing capacity and the resistance to abrasion of decorated nanometer Cu, ZDDP and paraffin oil, the wearing test condition is when long: load 300N, test period 30min, rotating speed 1450r/min.The result shows that unmodified Cu nanoparticle has certain resistance to abrasion, bearing capacity to base oil does not have obvious influence, and the ZDDP additive has good resistance to abrasion, has improved the extreme pressure property of base oil significantly, and thiophosphoric acid decorated nanometer Cu compares with ZDDP, its bearing capacity (P
B) high 100N, sintering load (P
D) high 2.8 times, and wear scar diameter (WSD) is less.This shows that thiophosphoric acid decorated nanometer Cu compares with commercial additive ZDDP, has more superior tribological property.
The bearing capacity of table 2 additive and resistance to abrasion
Samples contg wt% P
B/ N P
D/ N WSD/mm
LP??????????100????????372?????568??????0.72
Unmodified
1??????????412?????618??????0.61
Nanometer Cu
ZDDP????????4??????????715?????1960?????0.48
Sulphur phosphoric acid is repaiied
4??????????813?????5500?????0.40
Decorations nanometer Cu
Fig. 2 shows the relation curve between hexadecyl thiophosphatephosphorothioate decorated nanometer Cu additive and ZDDP additive level and the wear scar diameter, and test condition is: load 300N, time 30min, rotating speed 1450r/min.Wherein not containing the neat liquid paraffin of the additive wear scar diameter under lubricated is 0.72mm.Can see, in the concentration range of being tested, thiophosphoric acid decorated nanometer Cu and ZDDP can both make the resistance to abrasion of base oil significantly improve, wherein thiophosphoric acid decorated nanometer Cu has better resistance to abrasion than ZDDP, increase with concentration, the wear scar diameter of thiophosphoric acid decorated nanometer Cu constantly reduces, and reaches optimum value when 2wt.% adds concentration, and tends towards stability with the increase of concentration.And the ZDDP additive reaches optimum value when 4wt.%, and with the further increase of concentration, wear scar diameter constantly increases.
ZDDP is a kind of traditional organic compound lubricating oil additive, its mechanism of action is to rely on adsorption film or its polymer deposition film of ZDDP to work under underload, under higher load, rely on S, P element to work, when load surpasses surperficial film strength, reach the load that lost efficacy at the inorganic reaction film that friction surface generates.Not only contain S, P element in the sulphur phosphoric acid decorated nanometer Cu additive, and have a Cu nanoparticle, its mechanism of action is than under the underload, the surface film that is formed by S, P plays main antifriction antiwear effect, therefore, thiophosphoric acid decorated nanometer Cu and ZDDP additive are approaching than the tribological property under the underload.Under high loading, a large amount of nano-particle of copper deposit at friction surface, and the surface film that forms low shearing resistance is sprawled in melting under the High Temperature High Pressure of zone of action, what at this moment direct support loads was isolated the matrix contact is the Cu nanoparticle, because metal Cu has lower shearing resistance, therefore under high loading, present good anti-wear and wear-resistant performance.
Claims (6)
1. metal copper nano granules is characterized in that being general formula (I) compound:
R is C in the formula
8～C
18The straight or branched alkyl, m represents the atom number of metallic copper in the nano particle, is 100-900; N represents the molecule number of left-half in the nano particle formula (I), is 10-800.
2. compound according to claim 1 is characterized in that R is a hexadecyl in general formula (I) compound.
3. the formula of a metal copper nano granules (I) compounds process for production thereof,
R is C in the formula
8～C
18The straight or branched alkyl, m represents the atom number of metallic copper in the nano particle, is 100-900; N represents the molecule number of left-half in the nano particle formula (I), is 10-800, it is characterized in that this method may further comprise the steps:
A) use alkyl chain length to be C
8-C
18The straight or branched alkyl contain the thiophosphatephosphorothioate organic compound as modifier, make it and solubility neutralized verdigris Cu (AC)
2H
2The O reaction;
B) in the presence of the reaction medium hydrazine hydrate;
C) 50-80 ℃ was reacted 2-12 hour down.
4. method as claimed in claim 3 is characterized in that reaction medium is distilled water and ethanol mixed solvent.
5. method as claimed in claim 3, the mol ratio that it is characterized in that modifier and neutralized verdigris is 1: 10～10: 1.
6. the formula of a metal copper nano granules (I) compound,
R is C in the formula
8～C
18The straight or branched alkyl, m represents the atom number of metallic copper in the nano particle, is 100-900; N represents the molecule number of left-half in the nano particle formula (I), is 10-800, it is characterized in that compound uses as the multifunctional lubricant fat additives, and addition is the 1-5.0% of lubricating grease weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01135662 CN1184037C (en) | 2001-10-12 | 2001-10-12 | Metal copper nano granules, its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01135662 CN1184037C (en) | 2001-10-12 | 2001-10-12 | Metal copper nano granules, its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1354056A true CN1354056A (en) | 2002-06-19 |
| CN1184037C CN1184037C (en) | 2005-01-12 |
Family
ID=4673242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01135662 Expired - Fee Related CN1184037C (en) | 2001-10-12 | 2001-10-12 | Metal copper nano granules, its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1184037C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100441340C (en) * | 2005-03-02 | 2008-12-10 | 河南大学 | Phosphorus-containing organic compound modified low-melting-point alloy nano particles and method for preparing same |
| CN101612667B (en) * | 2009-05-31 | 2011-01-26 | 河南大学 | Method for preparing surface modification oil solubility nanometer copper |
| CN102554217A (en) * | 2012-02-24 | 2012-07-11 | 河南大学 | Water-soluble nano-copper and preparation method thereof |
| CN101090785B (en) * | 2004-11-26 | 2013-03-20 | 首尔国立大学工业基金会 | Novel methods of large scale production of monodisperse nano grain |
| EP3091065A1 (en) | 2015-04-20 | 2016-11-09 | China Petroleum&Chemical Corporation | Lubricant composition, and preparation method and use thereof |
| CN110744068A (en) * | 2019-10-21 | 2020-02-04 | 河南大学 | Oil-soluble nano copper and preparation method thereof |
-
2001
- 2001-10-12 CN CN 01135662 patent/CN1184037C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101090785B (en) * | 2004-11-26 | 2013-03-20 | 首尔国立大学工业基金会 | Novel methods of large scale production of monodisperse nano grain |
| CN100441340C (en) * | 2005-03-02 | 2008-12-10 | 河南大学 | Phosphorus-containing organic compound modified low-melting-point alloy nano particles and method for preparing same |
| CN101612667B (en) * | 2009-05-31 | 2011-01-26 | 河南大学 | Method for preparing surface modification oil solubility nanometer copper |
| CN102554217A (en) * | 2012-02-24 | 2012-07-11 | 河南大学 | Water-soluble nano-copper and preparation method thereof |
| CN102554217B (en) * | 2012-02-24 | 2014-12-17 | 河南大学 | Water-soluble nano-copper and preparation method thereof |
| EP3091065A1 (en) | 2015-04-20 | 2016-11-09 | China Petroleum&Chemical Corporation | Lubricant composition, and preparation method and use thereof |
| US9944883B2 (en) | 2015-04-20 | 2018-04-17 | China Petroleum & Chemical Corporation | Lubricant composition, and preparation method and use thereof |
| CN110744068A (en) * | 2019-10-21 | 2020-02-04 | 河南大学 | Oil-soluble nano copper and preparation method thereof |
| CN110744068B (en) * | 2019-10-21 | 2021-01-26 | 河南大学 | Oil-soluble nano copper and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1184037C (en) | 2005-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wu et al. | Tribological properties of oleic acid-modified zinc oxide nanoparticles as the lubricant additive in poly-alpha olefin and diisooctyl sebacate base oils | |
| Tang et al. | A review of recent developments of friction modifiers for liquid lubricants (2007–present) | |
| Liu et al. | An investigation of the tribological behaviour of surface-modified ZnS nanoparticles in liquid paraffin | |
| Bakunin et al. | Synthesis and application of inorganic nanoparticles as lubricant components–a review | |
| US4990271A (en) | Antiwear, antioxidant and friction reducing additive for lubricating oils | |
| Kang et al. | Synthesis and tribological property study of oleic acid-modified copper sulfide nanoparticles | |
| CN1184037C (en) | Metal copper nano granules, its preparation method and application | |
| CN106103670A (en) | Lubricant compositions based on metal nanoparticle | |
| Zhang et al. | Preparation of water-soluble lanthanum fluoride nanoparticles and evaluation of their tribological properties | |
| CN1618799A (en) | Metal coppor nano-particle and its preparation process and use | |
| US4465604A (en) | Lubricating compositions and process using complex metal chalcogenides | |
| Bakunin et al. | Surface‐capped molybdenum sulphide nanoparticles—a novel type of lubricant additive | |
| WO2021012754A1 (en) | Preparation method of self-dispersing nano copper with long organice carbon chain, nano copper preparation and application thereof | |
| Kumara et al. | Organic-modified ZnS nanoparticles as a high-performance lubricant additive | |
| CN1769404A (en) | Rare earth trifluoride nanometer particle, its preparation method and uses | |
| US20220259516A1 (en) | Polyphenol shelled nanoparticles lubricating composition and method | |
| WO2022139853A1 (en) | Tribotechnical compositions from self-assembled carbon nanoarchitectonics, and applications thereof | |
| CN1173982C (en) | Sulphur-containing organic compound modified metal-chalocogenide nm particles, its prepn. and application | |
| Wang et al. | Using a novel disulphide compound containing boron as a potential substitute for sulphurized olefins in lubricants | |
| CN1044248C (en) | Ternary complex of rare-earth (N,N-dialkyl dithio-amino formic acid)--(1,10-ortho-phenanthroline) | |
| KR102115607B1 (en) | Nanofluid lubricant for rotating machines using surface-treated alumina nanoparticles | |
| CN114231334B (en) | Polyether calcium phosphate quantum dot and preparation method thereof | |
| Verma | Abstract available in content. Investigations on reduced graphene Oxide-based nanchybrids as friction and Wear modifiers | |
| Li et al. | A study of the tribological behaviour of dialkyldithiophosphate esters as additives in rape seed oil | |
| JP2566618B2 (en) | Method of manufacturing solid lubricant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |