CN115319018B - Yttrium sol and its preparation method - Google Patents
Yttrium sol and its preparation method Download PDFInfo
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- CN115319018B CN115319018B CN202210970996.3A CN202210970996A CN115319018B CN 115319018 B CN115319018 B CN 115319018B CN 202210970996 A CN202210970996 A CN 202210970996A CN 115319018 B CN115319018 B CN 115319018B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/18—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents
- B22C1/183—Sols, colloids or hydroxide gels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/02—Sand moulds or like moulds for shaped castings
- B22C9/04—Use of lost patterns
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Abstract
The invention discloses an yttrium sol and a preparation method thereof, wherein the yttrium sol is prepared by alcoholysis and association of yttrium isopropoxide and yttrium tert-butoxide in ethanol solution, and nanometer yttrium sol with different particle size ranges can be obtained by controlling the concentration ratio of solid and liquid. The yttrium sol has the advantages of simple preparation process, low equipment requirement, no need of ammonia water, capability of solving the problem of large smell of the field operation environment, capability of enriching and utilizing generated isopropanol and tertiary butanol after alcoholysis, capability of recycling ethanol, controllable particle size, adjustable viscosity and pH, excellent adhesive property, difficult gelation, normal-temperature storage and service life of 6 months.
Description
Technical Field
The invention relates to yttrium sol and a preparation method thereof. Belongs to the technical field of sol preparation.
Background
The shape of the titanium alloy investment precision casting can be arbitrarily complicated, and can be formed in a near-zero-allowance or even zero-allowance way, but titanium is an extremely active chemical element, liquid titanium almost has different degrees of chemical reaction with all modeling materials, and the refractory material and the binder for casting the titanium alloy are required to have extremely high chemical stability so as to weaken the chemical reaction of the titanium liquid and the model shell and reduce the surface pollution layer.
Currently, adhesives for investment precision casting of titanium alloys generally use silica sol and zirconium sol, but both adhesives react with titanium alloys more or less at high temperatures.
The yttrium sol is a uniform dispersion of nano yttrium hydroxide or yttrium oxide colloidal particles in water, is commonly used as a binder material for casting high-temperature alloys, and is widely applied to the field of investment casting. Yttrium sols are prepared primarily from metal alkoxides, oxides or inorganic salts of yttrium. Yttrium nitrate is mainly adopted to produce yttrium sol in the early stage, but the prepared shell has low strength and cannot form compact shell surface. At present, yttrium sol is mostly prepared by yttrium oxide or inorganic salt, the preparation process is complex, the period is long, and the requirement on equipment is high; the prepared yttrium sol has the problems of harsh storage conditions, short service life, easy gelation and the like.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides yttrium sol and a preparation method thereof, which are simple, have low requirements on equipment and can be stored at normal temperature.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
1. the yttrium sol is prepared through alcoholysis and association of yttrium isopropoxide and yttrium tert-butoxide in absolute ethyl alcohol.
Preferably, the specific steps are as follows:
(1) Firstly, adding polyvinylpyrrolidone into an ethanol solution, and stirring until the polyvinylpyrrolidone is fully dissolved to obtain a base solution;
(2) Adding yttrium isopropoxide and yttrium tert-butoxide into a base solution, stirring for 1-2 hours at room temperature to generate polynuclear alkoxide complexes, carrying out intermolecular association reaction on the alkoxide complexes to crosslink each other to generate high-molecular yttrium salt complexes, and connecting the high-molecular yttrium salt complexes together to form a reticular structure to obtain association mixtures, wherein polyvinylpyrrolidone in the base solution plays a role of bonding bridges;
(3) And finally, adding the association mixture into an ice-water mixture, hydrolyzing for 0.5-1 hour, and concentrating under reduced pressure to obtain the yttrium sol.
More preferably, in the step (1), the mass concentration of polyvinylpyrrolidone in the base liquid is 1 to 2%, and the molecular weight of polyvinylpyrrolidone is 29 to 32k.
Further preferably, in step (2), the polynuclear alkoxide complex is formed according to the following reaction formula:
Y((CH3)2CHO)3+nCH3CH2OH→Y((CH3)2CHO)3-n(CH3CH2O)n+n(CH3)2CHOH
Y((CH3)3CO)3+nCH3CH2OH→Y((CH3)3CO)3-n(CH3CH2O)n+n(CH3)3COH.
Further preferably, in the step (2), the reaction formula for forming the polymer yttrium salt complex is as follows:
Y((CH3)2CHO)3-n(CH3CH2O)n+Y((CH3)3CO)3-n(CH3CH2O)n→
((CH3)2CHO)3-nY-Y((CH3)3CO)3-n+2nCH3CH2OH.
Further preferably, in the step (2), the mass ratio of the yttrium isopropoxide to the yttrium tert-butoxide is 1:1, the mass ratio of yttrium isopropoxide to the base solution is 1:1.
Further preferably, in the step (2), nanoparticles with different particle size ranges can be obtained by controlling the concentration ratio of the solid and the liquid, that is, by controlling the n value. When n=an integer between 1 and 10, the particle size of the obtained yttrium sol is 2 to 40nm. The larger the n value, the smaller the particle size of the obtained nanoparticle. When n increases from 1 to 10, the nanoparticle size decreases from 40nm to 2 nm.
Further preferably, yttrium sol with different viscosity and pH value can be obtained by controlling the amount of the ice-water mixture;
when the mass ratio of the mixture to the ice water mixture after association is 1:1, an yttrium sol having a viscosity of 20mpa·s and a ph=7.8 was obtained.
When the mass ratio of the mixture to the ice water mixture after association is 1:2, an yttrium sol having a viscosity of 15 mpa.s and a ph=7.2 was obtained.
Preferably, in the step (3), the vacuum degree during the vacuum concentration is 60-90 kPa, the vacuum concentration time is 1-3 hours, and the obtained yttrium sol has the particle size range of 2-40 nm.
2. The yttrium sol is prepared by the preparation method.
3. The yttrium sol is applied to a binder for precision investment casting of titanium alloy.
The invention has the beneficial effects that:
The yttrium sol prepared by the invention solves the problems that the shell strength is low and a compact shell surface cannot be formed when the yttrium sol is applied to the field of titanium alloy investment casting as an adhesive. The yttrium sol is mainly prepared by alcoholysis and association of yttrium isopropoxide and yttrium tert-butoxide in ethanol solution, and nanometer yttrium sol with different particle size ranges can be obtained by controlling the concentration ratio of the yttrium isopropoxide to the yttrium tert-butoxide. The yttrium sol has the advantages of simple preparation process, low equipment requirement, no need of ammonia water, capability of solving the problem of large smell of the field operation environment, capability of enriching and utilizing generated isopropanol and tertiary butanol after alcoholysis, capability of recycling ethanol, controllable particle size, adjustable viscosity and pH, excellent adhesive property, difficult gelation, good stability, normal-temperature storage and service life of 6 months.
The PVP is a nonionic polymer compound, can be dissolved in water and alcohol, has film forming property and cohesiveness, and is a good polymer adhesive. If PVP is replaced by other polymers such as PVA, PVB and the like, the solubility in the base solution is not good, and the obtained yttrium sol has insufficient adhesive force.
Drawings
FIG. 1 is a comparative shell prepared using yttrium sol, wherein A is a commercially available preparation and B is example 1 preparation.
Detailed Description
The present invention will be further illustrated by the following examples, which are given by way of illustration only and are not intended to be limiting.
The yttrium tert-butoxide, yttrium amyl alcohol and yttrium n-butoxide related by the invention are purchased from Shandong Ying chemical industry Co.
Example 1:
The preparation method of the yttrium sol comprises the following specific steps:
1. preparing base liquid
Polyvinylpyrrolidone (PVP) was added to the ethanol solution and stirred to be sufficiently dissolved, and PVP was 1% by weight of the entire base solution and had a molecular weight of 29k.
2. Alcoholysis and association
10G of yttrium isopropoxide and 10g of yttrium tert-butoxide are weighed and added into 10g of the base solution obtained in the step 1, and the yttrium salt association mixture with the particle size of 40 nanometers is obtained after stirring reaction.
3. Hydrolyzing and concentrating
The yttrium salt association mixture obtained in the step2 is added into 30g of ice water for hydrolysis, and then concentrated under reduced pressure to obtain yttrium sol with the viscosity of 20 MPa.s and the pH value of 7.8.
Example 2:
The preparation method of the yttrium sol comprises the following specific steps:
1. preparing base liquid
Polyvinylpyrrolidone (PVP) is added into the ethanol solution and stirred to be fully dissolved, and the PVP accounts for 1.5 percent of the weight of the whole base solution and has the molecular weight of 30k.
2. Alcoholysis and association
10G of yttrium isopropoxide and 10g of yttrium tert-butoxide are weighed and added into 20g of the base solution obtained in the step 1, and the yttrium salt association mixture with the particle size of 30 nanometers is obtained after stirring reaction.
3. Hydrolyzing and concentrating
The yttrium salt association mixture obtained in the step 2 is added into 80g of ice water for hydrolysis, and then concentrated under reduced pressure to obtain yttrium sol with the viscosity of 15 MPa.s and the pH value of 7.2.
Example 3:
The preparation method of the yttrium sol comprises the following specific steps:
1. preparing base liquid
Polyvinylpyrrolidone (PVP) is added into the ethanol solution and stirred to be fully dissolved, and the PVP accounts for 1.8 percent of the weight of the whole base solution and has the molecular weight of 32k.
2. Alcoholysis and association
10G of yttrium isopropoxide and 10g of yttrium tert-butoxide are weighed and added into 120g of the base solution obtained in the step 1, and the yttrium salt association mixture with the particle size of 4 nanometers is obtained after stirring reaction.
3. Hydrolyzing and concentrating
The yttrium salt association mixture obtained in the step 2 is added into 420g of ice water for hydrolysis, and then concentrated under reduced pressure to obtain yttrium sol with the viscosity of 11 MPa.s and the pH value of 7.0.
Comparative example 1
Yttrium tert-butoxide was omitted and the remainder was the same as in example 1.
Comparative example 2
Yttrium isopropoxide was omitted and the rest was the same as in example 1.
Comparative example 3
The amount of yttrium isopropoxide was 20g, the amount of yttrium tert-butoxide was 10g, and the rest was the same as in example 1.
Comparative example 4
The amount of yttrium isopropoxide was 10g, the amount of yttrium tert-butoxide was 20g, and the rest was the same as in example 1.
Comparative example 5
Yttrium amyl alcohol was used instead of yttrium tert-butoxide, the remainder being the same as in example 1.
Comparative example 6
Yttrium n-butoxide replaces yttrium tert-butoxide, and the rest is the same as in example 1.
The particle diameters, viscosities, pH values and stabilities of the yttrium sols obtained in examples 1 to 3 and comparative examples 1 to 6 were compared, and the results are shown in Table 1.
The particle size is tested by a transmission electron microscope, the viscosity is tested by a rotary viscometer, the pH is measured by a pH meter, the stability is measured by a naked eye observation method, the timing is started after the preparation of yttrium sol is finished, and the time is stabilized once precipitation or gelation occurs and the timing is stopped.
Generally, the smaller the particle size, the smaller the viscosity, and the better the adhesion of the yttrium sol, the closer the pH value to neutrality and the better the stability when the yttrium sol is applied to the field of investment precision casting.
TABLE 1 results of yttrium sol Performance investigation
| Particle size (nm) | Viscosity (mPa. S) | pH | Stability of | |
| Example 1 | 40 | 20 | 7.2 | Not less than 6 months |
| Example 2 | 30 | 15 | 7.2 | Not less than 6 months |
| Example 3 | 4 | 11 | 7.0 | Not less than 6 months |
| Comparative example 1 | 300 | 50 | 8.2 | For 15 days |
| Comparative example 2 | 400 | 58 | 8.2 | For 12 days |
| Comparative example 3 | 35 | 22 | 7.9 | For 30 days |
| Comparative example 4 | 42 | 25 | 7.8 | For 32 days |
| Comparative example 5 | 32 | 50 | 7.8 | For 30 days |
| Comparative example 6 | 35 | 60 | 7.9 | For 20 days |
As is clear from Table 1, the yttrium sols obtained in examples 1 to 3 have small particle size, proper viscosity, proper pH, long shelf life at normal temperature of 6 months, and good stability.
Comparative examples 1 and 2 were used alone with yttrium isopropoxide or yttrium tert-butoxide, comparative examples 3 and 4 were used to adjust the ratio of yttrium isopropoxide to yttrium tert-butoxide, comparative examples 5 and 6 were used to replace yttrium tert-butoxide with yttrium alkoxide, and the stability of the resulting yttrium sol was significantly deteriorated, indicating that the specific combination of yttrium isopropoxide and yttrium tert-butoxide of the present invention had a critical effect on the stability of yttrium sol. This is probably because yttrium tert-butoxide has a very good steric branch steric hindrance structure, and yttrium sol with uniform particle size can be obtained after association hydrolysis, so that the stability time of the yttrium sol is prolonged, and yttrium amyl alcohol and yttrium n-butoxide are very easy to mutually intertwine due to longer branch of an organic functional group, so that the viscosity of the obtained yttrium sol is overlarge, and the stability time is reduced.
The shell strength and the shell compactness were tested using yttrium sol commercial and yttrium sol obtained in example 1 as binders for the shell preparation process of the shell coating, respectively, and the results are shown in table 2 and fig. 1.
The process flow of the preparation of the shell is as follows: forming a wax mould, preparing a surface coating, dipping slurry, sanding, drying, repeating the steps of dipping slurry, sanding and drying, hanging slurry, drying, dewaxing and roasting.
The surface layer density is directly judged by visual observation, the surface compactness without sand holes is good in density, and the surface sand holes and holes are more, so that the density is poor.
TABLE 2 comparative results of Shell Performance
| Shell strength (MPa) | Surface layer density | |
| Commercial products | 25 | Poor quality |
| Example 1 | 35 | Preferably, it is |
As can be seen from Table 2 and FIG. 1, compared with the commercial products, the yttrium sol prepared in example 1 has high strength of the shell, good surface layer compactness and better application prospect in the field of titanium alloy investment casting.
While the foregoing describes the embodiments of the present invention, it is not intended to limit the scope of the present invention, and various modifications or variations may be made by those skilled in the art without the need for inventive effort on the basis of the technical solutions of the present invention.
Claims (7)
1. The preparation method of the yttrium sol is characterized by comprising alcoholysis and association of yttrium isopropoxide and yttrium tert-butoxide in absolute ethyl alcohol;
The method comprises the following specific steps:
(1) Firstly, adding polyvinylpyrrolidone into an ethanol solution, and stirring until the polyvinylpyrrolidone is fully dissolved to obtain a base solution;
(2) Adding yttrium isopropoxide and yttrium tert-butoxide into a base solution, stirring for 1-2 hours at room temperature to generate polynuclear alkoxide complexes, carrying out intermolecular association reaction on the alkoxide complexes to crosslink each other to generate high-molecular yttrium salt complexes, and connecting the high-molecular yttrium salt complexes together to form a reticular structure to obtain association mixtures, wherein polyvinylpyrrolidone in the base solution plays a role of bonding bridges;
(3) Finally, adding the association mixture into an ice-water mixture, hydrolyzing for 0.5-1 hour, and concentrating under reduced pressure to obtain the yttrium sol;
In the step (2), the mass ratio of the yttrium isopropoxide to the yttrium tert-butoxide is 1:1, the mass ratio of yttrium isopropoxide to base solution is 1:1.
2. The process according to claim 1, wherein in the step (1), the mass concentration of polyvinylpyrrolidone in the base solution is 1 to 2% and the molecular weight of polyvinylpyrrolidone is 29 to 32k.
3. The process of claim 1, wherein in step (2), the polynuclear alkoxide complex is formed according to the following reaction scheme:
Y((CH3)2CHO)3+nCH3CH2OH→Y((CH3)2CHO)3-n(CH3CH2O)n+n(CH3)2CHOH
Y((CH3)3CO)3+nCH3CH2OH→Y((CH3)3CO)3-n(CH3CH2O)n+n(CH3)3COH.
4. the process of claim 1, wherein in step (2), the polymer yttrium salt complex is formed according to the following reaction scheme:
Y((CH3)2CHO)3-n(CH3CH2O)n+Y((CH3)3CO)3-n(CH3CH2O)n→
((CH3)2CHO)3-nY-Y((CH3)3CO)3-n+2nCH3CH2OH.
5. the preparation method according to claim 1, wherein yttrium sols with different viscosities and pH values can be obtained by controlling the amount of ice-water mixture;
When the mass ratio of the mixture to the ice water mixture after association is 1:1, obtaining yttrium sol with the viscosity of 20 mPas and the pH=7.8;
When the mass ratio of the mixture to the ice water mixture after association is 1:2, an yttrium sol having a viscosity of 15 mpa.s and a ph=7.2 was obtained.
6. An yttrium sol obtainable by the process of any one of claims 1 to 5.
7. The use of an yttrium sol as defined in claim 6 as a binder for investment casting of titanium alloys.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102527921A (en) * | 2012-01-06 | 2012-07-04 | 武汉市智发科技开发有限公司 | Preparation method of yttrium sol |
| CN107325119A (en) * | 2017-06-18 | 2017-11-07 | 天津大学 | A kind of method that complexing prepares yttrium colloidal sol |
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| EP0204674B1 (en) * | 1985-06-06 | 1991-12-27 | Remet Corporation | Casting of reactive metals into ceramic molds |
| JPH06128033A (en) * | 1992-10-16 | 1994-05-10 | Nippon Shokubai Co Ltd | Yttria-based refractory composition |
| JP3139918B2 (en) * | 1993-12-28 | 2001-03-05 | 株式会社キャディック・テクノロジ−・サ−ビス | Method for producing refractory molded article and binder for refractory molded article |
| DE102004031607A1 (en) * | 2004-06-30 | 2006-02-09 | Shera-Werkstofftechnologie Gmbh & Co. Kg | Ceramic investment materials for the production of precision casting molds for castings of titanium, zirconium or their alloys |
| CN111362693B (en) * | 2020-03-20 | 2020-12-29 | 南京理工宇龙新材料科技股份有限公司 | Preparation method and application of zirconium dioxide porous ceramic material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102527921A (en) * | 2012-01-06 | 2012-07-04 | 武汉市智发科技开发有限公司 | Preparation method of yttrium sol |
| CN107325119A (en) * | 2017-06-18 | 2017-11-07 | 天津大学 | A kind of method that complexing prepares yttrium colloidal sol |
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