CN101857192B - Titanium/rare earth hybrid nanomaterial and method for preparing same - Google Patents
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Abstract
The invention discloses a titanium/rare earth hybrid nanomaterial and a method for preparing the same. The method comprises the following steps of: preparing rare earth oxide nanopowder from rare earth inorganic salt, a solvent, an organic gel forming agent and a surfactant; placing titanium powder in a hybridization reactor; sequentially adding a dispersing agent and a protective agent into the reactor; introducing a protective gas into the reactor; performing high-energy ball milling on the mixture; adding a hybridization reactant into the mixture to produce black nanopaste; volatilizing the organic matter from the nanopaste in an inert atmosphere; and drying the nanopaste under vacuum to obtain the black titanium/rare earth hybrid nanomaterial. The titanium/rare earth hybrid nanomaterial comprises a ternary system of the titanium, the rare earth oxide and the organic matter, wherein the titanium and the rare earth oxide are combined with the organic matter by chemical bonds to form a hybrid system. The material is well compatible with high molecules, is easy to prepare the titanium/rare earth organic matter hybrid functional nanocoating and has the characteristics of integrated network structure, high compactness, high corrosion resistance, high wear resistance and high comprehensive performance. The hybrid nanomaterial also contains the elements of titanium and rare earth and has attractive application prospect in corrosion resistance and various industrial fields when serving as a nanoadditive.
Description
Technical field:
The present invention relates to a kind of preparation method of titanium/rare earth hybrid nanomaterial, this nano material belongs to novel organic matter and macromolecule sodium rice material, belongs to rare metal, rare earth element processing new material technology field.
Background technology:
Rare metal titanium, titanium alloy and rare earth material have purposes widely at industrial circles such as space flight, the energy, electronics, chemical industry.Rare earth element has the magician's of high-tech material title, and it is widely used in each field of industry and defence and military industry, and its function in the anticorrosion field has obtained confirming (" Shanghai non-ferrous metal ", calendar year 2001 the 22nd is rolled up the 1st phase 14-18 page or leaf).Titanium or titanium alloy has the excellent corrosion resistance of wide spectrum, wearability, reaches combination property, but it costs an arm and a leg, and has limited its large-scale application at heavy corrosion-resistant field.A kind of nm-class Ti polymer and titanium alloy nano material are proposed respectively in patent CN1306047 and CN1689731; Be added in the anticorrosive paint as nanometer additive; Form the high corrosion resistance coating at metal and alloy surface; Embody the performance that is superior to traditional anticorrosive paint, will be and have the price of the common metal base material of this high corrosion resistance coating far below the price of Titanium and titanium alloy base material, but defective can appear in this kind coating in application and long-term use or corrosive medium final sum base material comes in contact; The titanium particle here can cause the accelerated corrosion of contacted with it ferrous metals base material at this moment, forms the local corrosion of metal base.
Summary of the invention:
The objective of the invention is to overcome the deficiency of above-mentioned prior art and a kind of have excellent corrosion resistance, wearability and combination property, the preparation method of the titanium/rare earth hybrid nanomaterial that cost is low be provided.
The object of the invention can reach through following measure: a kind of titanium/rare earth hybrid nanomaterial is characterized in that it is the nano-hybrid material that contains titanium, rare earth element dual element and organic high molecular polymer or oligomer; Wherein the titanium weight portion 60～95, rare earth oxide weight portion 0.1～30; This nano powder is pressed the X-ray diffraction method and is measured grain size: titanium 10～30 nanometers, rare earth oxide 10～20 nanometers.
A kind of preparation method of titanium/rare earth hybrid nanomaterial is characterized in that it comprises the steps:
First step: preparation nanometer rare earth oxide powder:
(1) at room temperature inorganic salt of rare earth is added and be stirred well in the solvent that to form the concentration of rare earth ion in solution be the clear solution of 0.3M～1.2M;
(2) in above-mentioned clear solution, add surfactant, the addition of surfactant is 1～5% of rare earth oxide by weight percentage;
(3) add organic gelling agent, put into 20～60 ℃ stirred in water bath after mixing immediately and reacted 0.5～2 hour, the addition of organic gelling agent is 1～12 times of rare earth ion molar concentration;
(4) reacted colloidal sol is obtained xerogel 50～100 ℃ of following dryings;
(5) calcining of 400～700 ℃ of xerogel was ground after 0.5～2 hour can obtain the nanometer rare earth oxide powder;
Second step: preparation titanium/rare earth hybrid nanomaterial:
Titanium valve, nanometer rare earth oxide powder are put into the hydridization reactor, successively add dispersant, protective agent, get rid of the air in the reactor and feed protective gas; Behind the high-energy ball milling; Add the hydridization reactant, produce product black nano slurry, organic matter in the volatilization nanometer slurry in inert atmosphere; Dry under vacuum, obtain the black titanium/rare earth hybrid nanomaterial.
In order further to realize that the object of the invention, the inorganic salt of rare earth described in the first step are a kind of in rare earth nitrades, rare earth-iron-boron, the rare earth sulfate; Solvent is a kind of in water, methyl alcohol, the ethanol; Organic gelling agent is a kind of in carrene, chloroform, hydroxyethyl methacrylate, hexa, trichloroacetamide, methyl formate, Ethyl formate, epoxy methane, oxirane, the expoxy propane; Surfactant is a kind of in citric acid, neopelex, the polyethylene glycol 1500.
In order further to realize that the object of the invention, described rare earth are a kind of in cerium, praseodymium, the terbium.
In order further to realize the object of the invention, each material described in second step is by weight: titanium valve 60～95, nanometer rare earth oxide powder 0.1～30, dispersant 40～400, protective agent 0.05～2, hydridization reactant 0.5～30.
In order further to realize that the object of the invention, described dispersant are a kind of in ketone, alcohols, ester class, the hydro carbons or their mixture; Protective gas is a kind of in argon gas, carbon dioxide, the nitrogen or their mixture; Protective agent is that an end contains the organic matter that inertia group, an end contain active group; The hydridization reactant is oxygen-containing functional group, contains other the organo-functional group or the organic matter of two keys simultaneously; Dispersant should be compatible with protective agent, hydridization reactant.
For further realize the object of the invention, described protective agent be n-butyl glycidyl ether, to a kind of in tert-butyl-phenyl glycidol ether, this Pan 80, this Pan 85, tween 100, polyoxyethylene (40), nonylplenyl ether, phenyl glycidyl ether, the allyl glycidyl ether or their mixture.
In order further to realize the object of the invention; Described hydridization reactant is bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol A diglycidyl ether, 4; 4 '-methyl diphenylene diisocyanate, poly methylene poly phenyl poly isocyanate, 2,4-toluene di-isocyanate(TDI), silane coupler RSiX
3In a kind of, wherein R representative has affinity or respond organo-functional group with polymer molecule, X represents hydrolyzable alkoxyl.
In order further to realize the object of the invention, in second step titanium valve, nanometer rare earth oxide powder are put into the hydridization reactor, add dispersant, protective agent again, under the flow of 80ml/min-120ml/min, fed protective gas 30-50 minute then; Start high energy ball mill, after high-energy ball milling 80-100 minute, leave standstill, add the hydridization reactant to 35 ℃-45 ℃; Under the flow of 80ml/min-120ml/min, fed protective gas 30-50 minute once more, and shut down after high-energy ball milling 2.5-3.5 hour once more; Treat to take out the product black nano slurry of producing after temperature is reduced to normal temperature; Organic matter during the volatilization nanometer is starched under inert atmosphere protection after high speed centrifugation separates, dry under vacuum, obtain the black titanium/rare earth hybrid nanomaterial.
The present invention compares with prior art can produce following good effect:
(1) it is a kind of titanium/rare earth oxide of rare earth element, organic nano-hybrid material of containing.If organic matter uses macromolecule, belong to the high molecule nano material category.
(2) organic matter (comprising macromolecule and oligomer) and titanium nano particle be with chemical bonding and be wrapped in the particle skin, makes it can be not oxidized and stable existence.
(3) nano particle is a crystalline state under preparation process condition, and grain size is in 10～30 nanometers.The electron microscope picture shows that particle is spherical and less than 30 nanometers.
(4) have the characteristics of chemical bonding between titanium and rare earth oxide and the organic facies, and organic matter contains two functional groups above (containing two) and makes it to be easy to organic and macromolecular material is compatible and form the overall network structure with other.This is its basis that can be used for anticorrosive paint and excellent anticorrosive is arranged, and also makes it can be used as nanometer additive, adds to and forms a kind of new polymer-function material in the macromolecule.This shows that this nano material has tempting application prospect in each field of industry and defence and military industry.
(5) in this hybrid nano-material, there is rare earth atom around the titanium particle, makes it under corrosive environment, can give full play to reparation and the corrosion inhibitive function that the changeable valence rare earth element is had, can improve the corrosion resistance of material greatly.
This titanium/rare earth nano-hybrid material of utilization development is as the additive preparation anticorrosive paint, and does contrast test with the titanium nanometer anticorrosive paint that does not add rare earth oxide, finds salt spray test, corrosion resistance test, the former is more excellent in abrasion test.
Description of drawings:
Fig. 1 is the X-ray diffractogram of the nano cerium oxide that makes, from figure, can judge the diffraction maximum into pure phase oxidation cerium, and grain size can calculate according to the Scherrer formula and be about 16 nanometers.
Fig. 2 is the X-ray diffractogram of titanium/cerium oxide organic hybrid nano powder of making, and 1 is titanium; 2 is cerium oxide.Two kinds of crystal grain diffraction maximums of clearly visible existence among the figure: Titanium and cerium oxide, their grain sizes can calculate according to the Scherrer formula: titanium is about 15 nanometers, and cerium oxide is about 16 nanometers.
Fig. 3 is the electron micrograph of titanium/cerium oxide organic hybrid nano powder, can find out among the figure that particle is spherical, and particle size is below 30 nanometers.
The specific embodiment: followingly technical scheme of the present invention is described in further detail, but protection scope of the present invention is not limited in this through embodiment:
The core technology content of the said titanium/rare earth nano-hybrid material of the present invention is the preparation method of nanometer rare earth oxide particle and the prescription and its preparation process of titanium/rare earth nano-hybrid material.
Embodiment 1:
The first step: preparation nano cerium oxide:
At room temperature cerium chloride is added and be stirred well in the ethanol that to form the concentration of cerium ion in solution be the clear solution of 0.3M; Add the polyethylene glycol 1500 that accounts for product cerium oxide weight 1% then; Adding and cerium ion molar ratio are 1 hexa again; Putting into 20 ℃ stirred in water bath after mixing immediately reacted 0.5 hour; With the colloidal sol that obtains 50 ℃ of dryings until obtaining xerogel, the nano cerium oxide that obtains loosening after 400 ℃ of calcinings are ground after 0.5 hour gently.
Second step: preparation titanium/cerium hybrid nano-material:
The titanium valve of 60 weight portions and the nano cerium oxide of 0.1 weight portion are joined in the reactor, add the cyclohexanone of 40 weight portions again, and add the phenyl glycidyl ether of 0.05 weight portion, under the flow of 80ml/minn, fed argon gas 30 minutes then; Leave standstill after 80 minutes to 35 ℃ at high-energy ball milling; Add 5 weight portions γ-glycidyl trimethoxy silane, under flow 80ml/min, fed argon gas 30 minutes once more, and high-energy ball milling was shut down after 2.5 hours once more; Treat to take out the black slurry after temperature is reduced to normal temperature; Organic matter during the volatilization nanometer is starched under the inert gas argon shield after high speed centrifugation separates is dried to pressed powder under vacuum, obtain the black titanium/rare earth hybrid nanomaterial; It is measured the titanium grain size through X-ray diffraction and is about 21 nanometers, and cerium oxide crystal grain size is about 16 nanometers.
Embodiment 2:
The first step: preparation praseodymium oxide nano powder:
At room temperature praseodymium nitrate is added and be stirred well in the methyl alcohol that to form the concentration of praseodymium ion in solution be the clear solution of 0.8M; Add the citric acid that accounts for product praseodymium oxide weight 3% then; Adding and praseodymium ion molar ratio are 5 oxirane again; Putting into 40 ℃ stirred in water bath after mixing immediately reacted 1 hour; With the colloidal sol that obtains 75 ℃ of dryings until obtaining xerogel, the praseodymium oxide nano powder that obtains loosening after 550 ℃ of calcinings are ground after 1 hour gently.
Second step: preparation titanium/praseodymium hybrid nano-material:
The titanium valve of 75 weight portions and the praseodymium oxide nano powder of 15 weight portions are joined in the reactor, add the butyl acetate of 150 weight portions again, and add the nonylplenyl ether of 1 weight portion, under the flow of 100ml/min, fed nitrogen 40 minutes then; Leave standstill to 40 ℃ after about 90 minutes at high-energy ball milling, add 15 weight portions 4,4 '-methyl diphenylene diisocyanate; Under flow 100ml/min n, fed nitrogen 40 minutes once more; And high-energy ball milling was shut down after 3 hours once more, treated to take out the black slurry after temperature is reduced to normal temperature organic matter during the volatilization nanometer is starched under the inert nitrogen gas protection after high speed centrifugation separates; Under vacuum, be dried to pressed powder, obtain the black titanium/rare earth hybrid nanomaterial; It is measured the titanium grain size through X-ray diffraction and is about 21 nanometers, and the praseodymium oxide grain size is about 16 nanometers.
Embodiment 3:
The first step: preparation terbium oxide nano powder:
At room temperature the sulfuric acid terbium is added and be stirred well in the entry that to form the concentration of rare earth ion in solution be the clear solution of 1.2M; Add the neopelex that accounts for product terbium oxide weight 5% then; Adding and terbium ion molar ratio are 12 methyl formate again; Putting into 60 ℃ stirred in water bath after mixing immediately reacted 2 hours; With the colloidal sol that obtains 100 ℃ of dryings until obtaining xerogel, the terbium oxide nano powder that obtains loosening after 700 ℃ of calcinings are ground after 2 hours gently.
Second step: preparation titanium/terbium hybrid nano-material:
The titanium valve of 95 weight portions and the terbium oxide nano powder of 30 weight portions are joined in the reactor, add the n-butanol of 250 weight portions and the butanone of 150 weight portions again, and add this Pan 80 of 2 weight portions; Under the flow of 120ml/min, feed argon gas 20 minutes then, fed carbon dioxide 30 minutes; Leave standstill to 45 ℃ after 100 minutes at high-energy ball milling, add 30 weight portion bisphenol f type epoxy resins, under flow 120ml/min n, fed argon gas 20 minutes once more; Fed carbon dioxide 30 minutes; And high-energy ball milling was shut down after 3.5 hours once more, treated to take out the black slurry after temperature is reduced to normal temperature organic matter during the volatilization nanometer is starched under the inert gas argon shield after high speed centrifugation separates; Under vacuum, be dried to pressed powder, obtain the black titanium/rare earth hybrid nanomaterial; It is measured the titanium grain size through X-ray diffraction and is about 20 nanometers, and the terbium oxide grain size is about 15 nanometers.
Can adopt planetary high-energy ball mill in preparation method's of the present invention second step; It can repack the ball grinder that has in the planetary high-energy ball mill into reactor; Two needle valves promptly are housed in ball grinder; An inlet valve, an outlet valve enable to feed the gas of protectiveness, and control flow; A charging valve is housed simultaneously, can adds material in case of necessity.Reactor can be equipped with thermosensitive probe (thermometric degree temperature-sensitive element), can the remote measurement temperature of reactor.With titanium, rare-earth oxidation sodium rice corpuscles, contain oxygen organo-functional group organic matter (comprising macromolecular compound or oligomer) and put into reactor; Reactor is in anaerobic and the inert atmosphere, adds dispersant and abrading-ball, whole system is in the air-tight state high-energy ball milling, detects and the control reaction temperature.The surface of titanium particle, rare earth oxide nano particle constantly produces nascent state titanium atom and rare earth atom in the reactor, and both have extremely strong binding ability with oxygen atom.They run foul of each other under the high temperature oxygen-free atmosphere and with organic facies molecule high-frequency, abrading-ball and three friction simultaneously, extruding, collision.Under this condition; The titanium particle of nascent state surface titanium atom and rare earth oxide particle surface rare earth atom be easy to organic facies in contain the reaction of oxygen organo-functional group generation chemical bonding, a kind of combination hybrid between formation titanium, rare earth, the organic matter (comprising macromolecule or oligomer).The existence of this hybrid systems can be confirmed through sign: product (nanometer slurry) is dry under vacuum, obtain black powder, and its X-ray diffraction is measured (referring to Fig. 2) and is shown and have titanium and rare earth oxide simultaneously that grain size is about 15 nanometers; Its electron micrograph (referring to Fig. 3) shows that particle size is below 30 nanometers; The x-ray photoelectron spectroscopy analysis shows that this nano material top layer exists Ti-O-C, Re-O-C key, has hydrocarbon key, phenyl ring simultaneously, and this shows the existence of organic layer and the existence of titanium, rare earth atom and organic matter oxygen-containing functional group chemical bonding.
In addition from the quantitative analysis test angle also hydridization bonding performance of this new material of susceptible of proof: a certain amount of sample is put into cable type extractor according, extract with the strong solvent of the organic matter (protective agent, hydridization reactant) that adds in the preparation; Change the solid after extracting over to the ultracentrifuge centrifuge tube, add the strong solvent washing, then centrifugation; Discard the solvent phase; Add new strong solvent once more, after centrifuge tube washs, be centrifugal, discard the solvent phase; Three times so repeatedly, can guarantee that so the unreacted organic facies in the sample is all washed off; Sample vacuum drying constant weight with the wash-out dissolved organic matter; This sample accurate quantification is measured the content of titanium and rare earth oxide; The percentage composition behind deduction titanium and the rare earth oxide and the organic facies of adding are coincide; The organic matter that this confirms to add again and the titanium and the rare earth atom of particle surface are chemical bondings, and can not be by wash-out.
Claims (4)
1. the preparation method of a titanium/rare earth hybrid nanomaterial is characterized in that it comprises the steps:
First step: preparation nanometer rare earth oxide powder:
(1) at room temperature inorganic salt of rare earth is added and be stirred well in the solvent that to form the concentration of rare earth ion in solution be the clear solution of 0.3M～1.2M;
(2) in above-mentioned clear solution, add surfactant, the addition of surfactant is 1～5% of rare earth oxide by weight percentage;
(3) add organic gelling agent, put into 20～60 ℃ stirred in water bath after mixing immediately and reacted 0.5～2 hour, the addition of organic gelling agent is 1～12 times of rare earth ion molar concentration;
(4) reacted colloidal sol is obtained xerogel 50～100 ℃ of following dryings;
(5) calcining of 400～700 ℃ of xerogel was ground after 0.5～2 hour can obtain the nanometer rare earth oxide powder;
Second step: preparation titanium/rare earth hybrid nanomaterial:
Titanium valve, nanometer rare earth oxide powder are put into the hydridization reactor, add dispersant, protective agent again, under the flow of 80ml/min-120ml/min, fed protective gas 30-50 minute then; Start high energy ball mill, after high-energy ball milling 80-100 minute, leave standstill, add the hydridization reactant to 35 ℃-45 ℃; Under the flow of 80ml/min-120ml/min, fed protective gas 30-50 minute once more, and shut down after high-energy ball milling 2.5-3.5 hour once more; Treat to take out the product black nano slurry of producing after temperature is reduced to normal temperature; Organic matter during the volatilization nanometer is starched under inert atmosphere protection after high speed centrifugation separates, dry under vacuum, obtain the black titanium/rare earth hybrid nanomaterial;
Described inorganic salt of rare earth is a kind of in rare earth nitrades, rare earth-iron-boron, the rare earth sulfate; Solvent is a kind of in water, methyl alcohol, the ethanol; Organic gelling agent is a kind of in carrene, chloroform, hydroxyethyl methacrylate, hexa, trichloroacetamide, methyl formate, Ethyl formate, epoxy methane, oxirane, the expoxy propane; Surfactant is a kind of in citric acid, neopelex, the polyethylene glycol 1500;
Described rare earth is a kind of in cerium, praseodymium, the terbium;
Described dispersant is a kind of in ketone, alcohols, ester class, the hydro carbons or their mixture; Protective gas is a kind of in argon gas, carbon dioxide, the nitrogen or their mixture; Protective agent is that an end contains the organic matter that inertia group, an end contain active group; The hydridization reactant is oxygen-containing functional group, contains other the organo-functional group or the organic matter of two keys simultaneously; Dispersant should be compatible with protective agent, hydridization reactant.
2. the preparation method of a kind of titanium/rare earth hybrid nanomaterial according to claim 1 is characterized in that each material described in second step is by weight: titanium valve 60～95, nanometer rare earth oxide powder 0.1～30, dispersant 40～400, protective agent 0.05～2, hydridization reactant 0.5～30.
3. the preparation method of a kind of titanium/rare earth hybrid nanomaterial according to claim 1, it is characterized in that described protective agent be n-butyl glycidyl ether, to a kind of in tert-butyl-phenyl glycidol ether, this Pan 80, this Pan 85, tween 100, polyoxyethylene (40), nonylplenyl ether, phenyl glycidyl ether, the allyl glycidyl ether or their mixture.
4. the preparation method of a kind of titanium/rare earth hybrid nanomaterial according to claim 1; It is characterized in that described hydridization reactant is bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol A diglycidyl ether, 4; 4 '-methyl diphenylene diisocyanate, poly methylene poly phenyl poly isocyanate, 2; A kind of among 4-toluene di-isocyanate(TDI), the silane coupler RSiX3 or their mixture; Wherein the R representative has affinity or respond organo-functional group with polymer molecule, and X represents hydrolyzable alkoxyl.
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| CN1306047A (en) * | 2000-12-14 | 2001-08-01 | 薛峻峰 | Nm-class Ti polymer paint |
| CN1689731A (en) * | 2004-04-23 | 2005-11-02 | 许德成 | Preparation method of rare metal alloy nanometer powder |
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| CN1306047A (en) * | 2000-12-14 | 2001-08-01 | 薛峻峰 | Nm-class Ti polymer paint |
| CN1689731A (en) * | 2004-04-23 | 2005-11-02 | 许德成 | Preparation method of rare metal alloy nanometer powder |
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