CN103554141B - A kind of core-shell rare-earth complexes and its preparation method and application - Google Patents
A kind of core-shell rare-earth complexes and its preparation method and application Download PDFInfo
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- CN103554141B CN103554141B CN201310480330.0A CN201310480330A CN103554141B CN 103554141 B CN103554141 B CN 103554141B CN 201310480330 A CN201310480330 A CN 201310480330A CN 103554141 B CN103554141 B CN 103554141B
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Abstract
The invention discloses a kind of core-shell rare-earth complexes and its preparation method and application, this core-shell rare-earth complexes is with stearic acid rare-earth salts for core, and amide compound is wrapped in core periphery by Coordination Adsorption and forms shell; Preparation method first prepares rare-earth salts, then is obtained by reacting with stearic acid and amide compound successively by rare-earth salts; This preparation method is simple, and cost is low, and obtained core-shell rare-earth complexes good stability, as lubricant applications in powder metallurgical technique, has outstanding lubricant effect.
Description
Technical field
The present invention relates to a kind of core-shell rare-earth complexes and its preparation method and application, belong to powder metallurgical technology.
Background technology
Metal-powder, as iron powder, comminuted steel shot, is usually used for preparing small-sized, accurate complex parts, as gear.Adopt powder metallurgical technique to prepare this type component and comprise following three typical process processes: 1, the preparation of premixing flour: powder metal and the additive such as lubricant, caking agent are mixed to get a kind of mixture; 2, die mould: the mixed powder obtained is poured in a mould, suppress under the high pressure of 200 ~ 1000MPa, then the pressed compact of desired shape is obtained from mold ejection, 3, sinter: pyroprocessing is carried out with the additive such as lubricant, caking agent decomposed and described in removing to pressed compact, and makes metal powder sinteredly reach metallurgical binding and obtain required component.
Add present two aspects of acting body of lubricant before compaction, on the one hand, in the compacting process of pressed compact, the internal friction between each metallic particles can be reduced, obtain the pressed compact of high-density and high strength; On the other hand, the ejection process of pressed compact from mould, reduce the total energy of knockout press and the demoulding.Lack of lubrication can cause pressed compact in knockout course because excessive friction leaves wearing and tearing and cut on mould, thus causes the damage of mould.The problem that lack of lubrication brings can adopt two kinds of methods to solve, or increases the usage quantity of lubricant, or selects more effective lubricant.But adopt the method improving lubricant quantity to have side effects, because increase by better lubricating the density obtained, the volume of lubricated dose of meeting increases and weakened.Therefore, better selecting is exactly select more efficiently lubricant.
At present, what the lubricant use that powder metallurgy is used was maximum is stearic acid and derivative, amides and waxy compound etc.Along with the development of powder metallurgy industry technology, also more and more higher to the requirement of its lubricant, simple stearic acid, amides and wax series lubricant agent closely can not meet the requirement of technical development, and much novel combined lubricant is applied to powder metallurgy industry.Chinese patent CN1402772A, US Patent No. P6413919 disclose the method preparing lubricant compositions, comprise the steps: selection first lubricant and the second lubricant; Mix this lubricant, and make described mixture stand to bond to form the process with the condition of the lubricant compositions of the aggregated particles of the first lubricant core on the second lubricant particle to the first particle, the surface of described core is coated by the second lubricant particle institute.Chinese patent CN102227274A discloses the preparation method of compounded lubricant particle, and core is had more than 18 by least one of 10 ~ 60% weight that the primary fatty acids acid amides of no more than 24 carbon atoms and at least one fatty acid bis-amides of 40 ~ 90% weight form; Described core has the nano particle of adhesion at least one metal oxide thereon.Japanese Patent JP2005-105323 discloses a kind of lubricant compositions: the core material of low melting point, and described core material surfaces is coated by high-melting-point lubricant particle.World Intellectual Property Organization international office patent WO2007078228 discloses another lubricant compositions, and lubricant core material material surface is coated by particulate carbon material.All these lubricant compositions all show good lubricity, but the core material of these lubricant compositions and Surface coating material mainly rely on physical force to combine, unstable in storage, use procedure, cause degradation.
Summary of the invention
The rare earth organic complex that the present invention is directed to single stearic acid of the prior art and derivative or amide compound mainly combines with secondary or physical bond, exist in storage, use procedure unstable, the defect of lubricant effect difference is used as lubricant, object is to provide a kind of constitutionally stable core-shell rare-earth complexes, this title complex, as the lubricant of powder metallurgical technique, has outstanding lubricant effect.
Another object of the present invention is to provide a kind of technique simply, processing ease, the method for the described core-shell rare-earth complexes of preparation that raw material sources are wide.
A further object of the invention is the application being to provide described core-shell rare-earth complexes, and described core-shell rare-earth complexes has excellent lubricant effect as lubricant applications in powder metallurgical technique.
The invention provides a kind of core-shell rare-earth complexes, this core-shell rare-earth complexes is with stearic acid rare-earth salts for core, and amide compound is wrapped in core periphery by Coordination Adsorption and forms shell; Wherein, the mol ratio of stearic acid rare-earth salts and amide compound is 1:1 ~ 2; Described amide compound is one or more in amine hydroxybenzene, erucicamide, stearic amide, ethylene bis stearic acid amide, the two amine hydroxybenzene of ethylene.
Described stearic acid rare-earth salts and the mol ratio of amide compound are preferably 1:1.
Described stearic acid rare-earth salts Rare Earth Ion is preferably one or more in lanthanum ion, praseodymium ion, neodymium ion, samarium ion, europium ion, gadolinium ion, terbium ion, dysprosium ion, holmium ion, erbium ion, ytterbium ion, thulium ion, lutetium ion, ruthenium ion, scandium ion.
Present invention also offers a kind of preparation method of described core-shell rare-earth complexes, the method is that after rare earth oxide is dissolved in hydrochloric acid or nitric acid, solvent evaporated, adds anhydrous alcohol solution, obtains the ethanolic soln of Rare Earths salt or nitrate; The stearic acid solution that pH value is 5 ~ 7 is dripped, at 60 ~ 80 DEG C of stirring reaction 1 ~ 5h in the Rare Earths salt of gained or the ethanolic soln of nitrate; Add amide compound solution again, continue reaction 1 ~ 5h; Leave standstill, filter, washing, after drying, to obtain final product.
Described stearic acid solution is stearic ethanolic soln.
Described amide compound solution is the methyl alcohol of amide compound, ethanol, chloroform, methyl-sulphoxide, DMF, tetrahydrofuran (THF), dioxane, pimelinketone, toluene, toluene(mono)chloride or cyclohexane solution.
Described Rare Earths salt or nitrate and stearic mol ratio are 1:3 or 1:4.
The mol ratio of described Rare Earths salt or nitrate and amide compound is 1:1 ~ 2; Be preferably 1:1.
Present invention also offers a kind of application of described core-shell rare-earth complexes, this application is as lubricant applications in powder metallurgical technique using described core-shell rare-earth complexes.
The preparation method of core-shell rare-earth complexes of the present invention comprises the following steps:
1, rare earth oxide is dissolved in hydrochloric acid or nitric acid, is heated to 20 ~ 80 DEG C, stir, until rare earth oxide dissolves completely; Then slow evaporate to dryness solution, obtained Rare Earths salt or nitrate, then add dehydrated alcohol, stirring and dissolving, obtain the ethanolic soln of Rare Earths salt or nitrate; Wherein, the add-on of churning time and hydrochloric acid or nitric acid is to guarantee that rare earth oxide fully dissolves;
2, stearic acid is dissolved in dehydrated alcohol, and with after ammoniacal liquor or sodium hydroxide or potassium hydroxide solution adjust ph to 5 ~ 7, dropwise join in the Rare Earths salt of step 1 gained or the ethanolic soln of nitrate, be warming up to 60 ~ 80 DEG C, pH value of reaction system is kept to be 5 ~ 7, stirring reaction 1 ~ 5h;
3, after amide compound being dissolved in solvent, join in the reaction system of step 2, continue reaction 1 ~ 5h; Described solvent selected from methanol, ethanol, chloroform, methyl-sulphoxide, DMF, tetrahydrofuran (THF), dioxane, pimelinketone, toluene, toluene(mono)chloride or hexanaphthene;
4, after step 3 has been reacted, hold over night, filters, and with ethanolic soln washing 1 ~ 3 time, 100 ~ 140 DEG C of vacuum-dryings, obtain rare earth compounding.
Beneficial effect of the present invention: a kind of rare earth compounding of new type structure of hud of design and synthesis of the present invention, the rare earth compounding of this nucleocapsid structure to be combined closely formation core by ionic linkage with rare earth central ion and stearate radical ion, meanwhile, the periphery that amide compound is adsorbed on core by coordinate bond forms shell; And using the rare earth compounding of this nucleocapsid structure as lubricant applications in powder metallurgical technique, find that the lubricant in its hinge structure has better stability and powder property, result of study shows: after rare earth compounding of the present invention mixes with iron-based powder, loose density: 2.98 ~ 3.20gcm
-3, mobility (50g): 20 ~ 29s, compressibility: 7.00gcm
-3~ 7.20gcm
-3, knockout press: 13.20 ~ 19.80Nmm
-2.The rare earth compounding preparation method of nucleocapsid structure of the present invention is simple, and cost is low, meets suitability for industrialized production.
Accompanying drawing explanation
The La(C with nucleocapsid structure that [Fig. 1] is prepared for embodiment 1
18h
35o
2)
3c
18h
35the TEM figure of NO.
Embodiment
Following examples are intended to further illustrate the present invention, instead of the restriction to protection scope of the present invention.
Embodiment 1
By 3.26g(0.01mol) La
2o
3add 50mL, in 10wt% hydrochloric acid, be heated to 60 DEG C, stir 60 minutes, solution becomes limpid, shows La
2o
3dissolve completely.Then slow evaporate to dryness solution, obtained LaCl
3, then add dehydrated alcohol, stirring and dissolving, obtain LaCl
3ethanolic soln 1; By 17.11g(0.06mol) stearic acid is dissolved in 100mL dehydrated alcohol, obtains solution 2, by 5.63g(0.02mol) amine hydroxybenzene is dissolved in 50mL dehydrated alcohol, obtains solution 3; First with ammoniacal liquor by solution 2 adjust ph to 5 ~ 7, dropwise join in solution 1, be warming up to 70 DEG C, remain pH value to 5 ~ 7, after stirring reaction 4h; Add solution 3 again, continue reaction 2 hours, hold over night, filter, do not measure chlorion with 1:1 aqueous ethanolic solution washing to the silver nitrate solution inspection of filtrate acidifying, 130 DEG C of vacuum-drying constant weights, obtain linen powdery product.Measure by analysis, in product, La, C, H content are respectively 11.12%, 67.86%, 10.77%, with chemical formula La(C
18h
35o
2)
3c
18h
35nO conforms to (calculated value of La, C, H is respectively 10.95%, 68.09%, 11.03%).
Nucleocapsid structure TEM schemes (as shown in Figure 1): middle and ambient color is distinguished obviously, in conjunction with preparation method, demonstrates obtained La(C
18h
35o
2)
3c
18h
35nO has nucleocapsid structure, and nucleocapsid structure size is for being about 100 ~ 500nm.
Embodiment 2
According to synthetic method and the condition of enforcement 1, by La
2o
3replace with Pr respectively
6o
11, Nd
2o
3, Sm
2o
3, Eu
2o
3, Gd
2o
3, Tb
4o
7, Dy
2o
3, Ho
2o
3, Er
2o
3, Tm
2o
3, Yb
2o
3, Lu
2o
3, Sc
2o
3, Y
2o
3, can obtain consisting of RE(C
18h
35o
2)
3c
18h
35the gray powdery product of NO (RE represents Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc or Y).
Embodiment 3
According to synthetic method and the condition of enforcement 1, amine hydroxybenzene is replaced with respectively erucicamide, to obtain the first part be stearic acid for stearic amide, ethylene bis stearic acid amide, the two amine hydroxybenzene of ethylene, Ligands is respectively the title complex of Rare Earth Lanthanum of erucicamide, stearic amide, ethylene bis stearic acid amide, the two amine hydroxybenzene of ethylene.
Embodiment 4
According to the method for embodiment 1, by La
2o
3replace with Pr respectively
6o
11, Nd
2o
3, Sm
2o
3, Eu
2o
3, Gd
2o
3, Tb
4o
7, Dy
2o
3, Ho
2o
3, Er
2o
3, Tm
2o
3, Yb
2o
3, Lu
2o
3, Sc
2o
3, Y
2o
3, simultaneously according to the rare earth compounding that amine hydroxybenzene to be replaced with erucicamide by the method for enforcement 3 respectively, stearic amide, ethylene bis stearic acid amide, the two amine hydroxybenzene of ethylene can obtain different rare earth central ion, different Ligands.
The concrete composition of synthesized rare earth compounding sees the following form 1:
The composition of table 1 synthesizing rare-earth title complex
Embodiment 5
Choose 1,10,32,57,69 samples respectively, also have chosen ethylene bis stearic acid amide (EBS) in contrast.By atomized iron powder, 2% copper powder, the manganese powder of 0.3%, the mix lubricant of the graphite of 0.5% and 0.8% selected, measures the mobility of each powdered mixture, loose density, pressed density (under 600MPa) and knockout press.Result is as shown in table 2.
Powder property is tested:
In order to test the performance of novel lubricant, by lubricant and metal-powder mixing, its suitable scope is 0.1 ~ 5wt%, is preferably 0.3 ~ 1wt%.Described metal-powder is iron-based powder.Described iron-based powder can be the mixture of pure iron powder or straight iron powder and alloying element, and alloying element can be selected from Mn, Cu, Ni, P, Si, W, La, Ce, Pr etc.The composition of described iron-based powder and the content of alloying element are selected according to the end-use of goods.
Powder flowbility: carry out fluidity testing according to the standard of ISO4490-2008.
Loose density: carry out loose density test according to the standard of ISO3923-1-2008.
Compressibility: carry out green density test according to the standard of ISO3927-2011.
Knockout press: knockout press be make green compact from mould remove the static pressure that must overcome.It is out
Begin to remove the business of required load divided by the surface-area gained of green compact and contacting dies, unit is N/mm
2.
The performance of table 2 powder
From the results shown in Table 2, the rare earth compounding novel lubricant prepared by the present invention, compared with common ethylene bis stearic acid amide lubricant, has better powder property, velocity of flow increases, loose density improves, and compression performance improves, and knockout press reduces.
Claims (4)
1. a core-shell rare-earth complexes, is characterized in that, with stearic acid rare-earth salts for core, amide compound is wrapped in core periphery by Coordination Adsorption and forms shell; Wherein, the mol ratio of stearic acid rare-earth salts and amide compound is 1:1; Described amide compound is one or more in amine hydroxybenzene, erucicamide, stearic amide, ethylene bis stearic acid amide, the two amine hydroxybenzene of ethylene.
2. core-shell rare-earth complexes as claimed in claim 1, it is characterized in that, described stearic acid rare-earth salts Rare Earth Ion is one or more in lanthanum ion, praseodymium ion, neodymium ion, samarium ion, europium ion, gadolinium ion, terbium ion, dysprosium ion, holmium ion, erbium ion, ytterbium ion, thulium ion, lutetium ion, ruthenium ion, scandium ion.
3. a preparation method for the core-shell rare-earth complexes as described in right 1 or 2, is characterized in that, after rare earth oxide being dissolved in hydrochloric acid or nitric acid, solvent evaporated, adds anhydrous alcohol solution, obtains the ethanolic soln of Rare Earths salt or nitrate; The stearic acid solution that pH value is 5 ~ 7 is dripped, at 60 ~ 80 DEG C of stirring reaction 1 ~ 5h in the Rare Earths salt of gained or the ethanolic soln of nitrate; Add amide compound solution again, continue reaction 1 ~ 5h; Leave standstill, filter, washing, after drying, to obtain final product.
4. an application for the core-shell rare-earth complexes as described in 1 or 2, is characterized in that, using described core-shell rare-earth complexes as lubricant applications in powder metallurgical technique.
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| CN103554141B true CN103554141B (en) | 2015-10-21 |
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|---|---|---|---|---|
| SE9904367D0 (en) * | 1999-12-02 | 1999-12-02 | Hoeganaes Ab | Lubricant combination and process for the preparation thereof |
| JP4423000B2 (en) * | 2003-09-29 | 2010-03-03 | 株式会社神戸製鋼所 | Lubricant for powder metallurgy and mixed powder for powder metallurgy |
| US7993429B2 (en) * | 2005-12-30 | 2011-08-09 | Höganäs Ab (Publ) | Lubricant for powder metallurgical compositions |
| JP5108319B2 (en) * | 2007-02-01 | 2012-12-26 | 昭和シェル石油株式会社 | Friction modifier comprising organomolybdenum compound and lubricating composition containing the same |
| JP5583139B2 (en) * | 2008-11-26 | 2014-09-03 | ホガナス アクチボラグ （パブル） | Lubricants for powder metallurgy compositions |
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