CN1556065A - BaO-B2O3-SiO2 precusor collosol and its preparaton method - Google Patents

BaO-B2O3-SiO2 precusor collosol and its preparaton method Download PDF

Info

Publication number
CN1556065A
CN1556065A CNA2004100157606A CN200410015760A CN1556065A CN 1556065 A CN1556065 A CN 1556065A CN A2004100157606 A CNA2004100157606 A CN A2004100157606A CN 200410015760 A CN200410015760 A CN 200410015760A CN 1556065 A CN1556065 A CN 1556065A
Authority
CN
China
Prior art keywords
alkoxide
bao
sio
liquid
boron
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
Application number
CNA2004100157606A
Other languages
Chinese (zh)
Other versions
CN1224591C (en
Inventor
杜永娟
规
谷上嘉规
夏方
赵东辉
熊野聪
陈国荣
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
East China University of Science and Technology
Nihon Yamamura Glass Co Ltd
Original Assignee
East China University of Science and Technology
Nihon Yamamura Glass Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by East China University of Science and Technology, Nihon Yamamura Glass Co Ltd filed Critical East China University of Science and Technology
Priority to CN 200410015760 priority Critical patent/CN1224591C/en
Publication of CN1556065A publication Critical patent/CN1556065A/en
Application granted granted Critical
Publication of CN1224591C publication Critical patent/CN1224591C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Landscapes

  • Glass Melting And Manufacturing (AREA)
  • Glass Compositions (AREA)

Abstract

A process for preparing the sol of BaO-B2O3-SiO2 precursor, used as the sintering and ceramics, is prepared from the raw materials (barium acetate and organic alkoxide of Si and B), the complexing agent chosen from acetylacetone, dimethyl formamide and aceti acid, the cosolvent (inorganic acid) and solvent (water and alcohol). It contains BaO (20-75 wt.%), B2O3 (5-20) and SiO2 (15-70). Its advantages are high stability (45 days), and high solid content (18%).

Description

A kind of BaO-B 2O 3-SiO 2Precursor colloidal sol and preparation method thereof
Technical field
The present invention relates to a kind of BaO-B 2O 3-SiO 2Colloidal sol, specifically, relate to a kind of can be used for preparing film, ultrafine powder and as the precursor of ceramic post sintering auxiliary agent.
Background technology
Collosol and gel is the new technology that development in recent years is got up, and is widely used in preparation new inorganic material and organic/inorganic composite material.High-purity, compositing range changes greatly because the material of preparation has, high reactivity, sintering temperature and low, also can prepare some material that traditional method can not prepare, sol-gel method is at the preparation low-dimensional materials, film for example, fiber and ultrafine powder aspect show huge advantage.As BaO-B 2O 3-SiO 2Precursor, by the colloidal sol that corresponding metal alkoxide and organic acid salt are formed, because its composition is in very large range adjustable, viscosity and surface tension are adjustable, except can preparing the thin-film material and preparation ultrafine powder that matrix and no matrix are arranged, can also be as the matrix material of ceramic body.Form by regulating, can under lower temperature, promptly form glass metal, can promote the sintering of base substrate, reduce sintering temperature by liquid phase substance.More can reduce volumetric shrinkage and void content than organic binder bond.
The raw material that sol-gel method often uses is the organic alkoxide of corresponding metal, organic acid salt and inorganic acid salt, and solvent commonly used is an alcohol.The BaO-B that the present invention relates to 2O 3-SiO 2System's precursor colloidal sol, because the alkoxide of silicon and the hydrolysis of alkoxide speed of boron differs greatly, and the former can not directly dissolve each other with water, to its sensitivity of water electrode, hydrolysis rate is high again for the latter.And barium do not have suitable alkoxide, and unique safe available is the barium acetate that is insoluble to alcohol, how to prepare long, the higher BaO-B of solid content stationary phase 2O 3-SiO 2System's precursor colloidal sol is a difficult problem always.
One of technical issues that need to address of the present invention are to disclose to film and as the BaO-B that reduces sintering temperature a kind of can the preparation 2O 3-SiO 2Precursor colloidal sol is to overcome the short and not high defective of solid content stationary phase that prior art exists.
Two of the technical issues that need to address of the present invention are open preparation methods, with not easy, the defective that should not go that overcomes that traditional method exists.
Design of the present invention is as follows:
The hydrolysis rate of the metal alkoxide of silicon will will make the hydrolysis rate of these two kinds of alkoxide suitable far below the hydrolysis rate of the alkoxide of boron, to obtain uniformly containing B with molecularity or with what three-dimensional-Si-O-B-latticed form existed 2O 3-SiO 2The solution of binary precursor must or be accelerated the hydrolysis of silicon alkoxide or the hydrolysis of slow boron alkoxide.The present invention uses the complexing agent (claiming stablizer again) and the pure salt formation complex compound macromole of boron to protect it not to be subjected to the effect of aqueous vapor, slows down hydrolysis rate.
Another technological difficulties are that barium acetate is only water-soluble, are insoluble to acid, and in the sour water binary solution, the solubleness of barium acetate can obviously reduce owing to the existence of alcohol, must seek to improve the cosolvent of solubleness.
The said BaO-B of the present invention 2O 3-SiO 2The composition of precursor colloidal sol and weight percent content are:
BaO：20-75％，B 2O 3：5-20％，SiO 2：15-70％；
Optimum scope is:
BaO：25-70％，B 2O 3：10-18％，SiO 2：15-65％。
Preparation method of the present invention comprises the steps:
(1) pure and mild cosolvent is added the alkoxide of the silicon of said ratio amount, it is standby to obtain A liquid, and complexing agent is added the alkoxide of boron, obtains B liquid;
The general structure of the alkoxide of said silicon is: Si (OR) 4, be to introduce SiO 2Raw material;
Wherein: R represents C 1～C 4Alkyl; That the most frequently used is Si (OCH 3) 4Or Si (OC 2H 5) 4
The general structure of the alkoxide of said boron is: B (OR 1) 3, for introducing B 2O 3Raw material;
Wherein: R 1Represent C 1～C 4Alkyl, that the most frequently used is B (OC 2H 5) 3Or B (OCH 3) 3
Said alcohol is C 1～C 3Unit alcohol, the mol ratio R of alcohol and the alkoxide of silicon sBe 0～5, best 0～3;
Said complexing agent comprises one or more in methyl ethyl diketone, dimethyl formamide, etheric acid second fat, Glacial acetic acid, the diacetylmethane, to stablize the alkoxide of boron;
The mole number of the alkoxide of the mole number/boron of Rc=complexing agent=1～9, best 1～6, depend on the content of BaO, BaO content height, R cBe advisable greatly;
(2) under the vigorous stirring, B liquid is dropwise joined in the A liquid, stir, the aqueous solution with barium acetate drips in the mixed solution of AB under vigorous stirring then, use inorganic acid for adjusting pH value scope 1.5～4.5 during this time, best 2～3.5, and add suitable quantity of water, it is as clear as crystal that solution is become, and promptly obtains BaO-B of the present invention 2O 3-SiO 2Precursor colloidal sol.
Barium acetate is for introducing the raw material of BaO.
Said mineral acid comprises HCl or HNO 3
The add-on R of water wWith the mol ratio of all oxides amount be 12～32, depend primarily on barytic content, the increase of barium oxide content will cause R TWIncrease, be preferably 15～28.
The alkoxide of silicon, the alkoxide of boron and the consumption of barium acetate can calculate according to the scope of the composition of precursor colloidal sol to be determined.
Be a few hours to 45 day the steady time of the colloidal sol that the present invention obtains, and the solid content of colloidal sol changes in 10-18%, but relevant with steady time, and steady time is long, and then solid content is lower.
State after the thermal treatment: the state of the xerogel after drying and the thermal treatment depends on composition, regulates its composition and can obtain vitreous state after 1000 ℃ of thermal treatment, also can be the powder of light-burned knot.
BaO-B of the present invention 2O 3-SiO 2Precursor colloidal sol has long stationary phase and higher solid content, and whole process of preparation is continuously one and a half hours, neither needs heating, the alkoxide of silicon does not need reflux prehydrolysis yet, and the preparation method is easy than traditional method technology, fast, should go, equipment is simple, is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is 30BaO-20B after 1000 ℃ of calcinings 2O 3-50SiO 2XRD ray diffraction collection of illustrative plates.
Fig. 2 is 70BaO-14B after 1000 ℃ of calcinings 2O 3-16SiO 2XRD ray diffraction collection of illustrative plates.
Embodiment
Embodiment 1～5
By forming 1 alkoxide that takes by weighing the silicon of the oxide aggregate that is equivalent to 0.1 mole, add alcohol according to the ratio of alcohol and alkoxide, and add inorganic acid for adjusting pH, place in the container, stirred fast 30 minutes.The alkoxide that takes by weighing the boron of metering in another container adds complexing agent, stirs 20 minutes.The latter dropwise is added drop-wise among the former goes, vigorous stirring added the back restir 15 minutes simultaneously.Take by weighing the barium acetate of metering in the 3rd container, add essential deionized water, constantly stir it is dissolved fully, add 1.5ml water again.Then the aqueous solution is added under vigorous stirring in the mixing solutions of silicon and boron, stir with dropwise adding water, get transparently fully until solution becomes, clarify by regulating pH value.Use the plastics film sealed vessel, observe its gel time and calculate solid content.Table 1 is composition and highest stabilizing phase and the solid content of embodiment 1～5.The raw material that table 2 is adopted for embodiment 1～5, table 3 are processing condition.Table 4 is 30BaO-20B 2O 3-50SiO 2(wt%) relation of experiment parameter and stationary phase and solid content.Table 5 is 70BaO-14B 2O 3-16SiO 2(wt%) relation of the experiment parameter of the colloidal sol of Zu Chenging and stationary phase and solid content.
The composition of table 1 example 1-5 and highest stabilizing phase and solid content
????NO ????BaO ????B 2O 3 ????SiO 2 Stationary phase Solid content (%)
????1 ????30 ????20 ????50 45 days ????12
????2 ????45 ????15 ????40 28 days ????12
????3 ????64 ????10 ????26 31 days ????13
????4 ????50 ????5 ????45 26 days ????14
????5 ????70 ????14 ????16 40 days ????18
Table 2
Embodiment The alkoxide of silicon The alkoxide of boron Alcohol Complexing agent Mineral acid
????1 ????Si(OCH 3) 4 ??B(OC 2H 5) 3 Ethanol Methyl ethyl diketone ??HCl
????2 ????Si(OC 2H 5) 4 ??B(OC 2H 5) 3 Ethanol Diacetylmethane ??HNO 3
????3 ????Si(OCH 3) 4 ??B(OCH 3) 3 Methyl alcohol Methyl aceto acetate ??HCl
????4 ????Si(OC 3H 7) 4 ??B(OC 2H 5) 3 Virahol Glacial acetic acid ??HCl
????5 ????Si(OC 2H 5) 4 ??B(OC 2H 5) 3 Ethanol The dimethyl formamide Glacial acetic acid ??HCl
Table 3
Embodiment The alkoxide of silicon (mol) The alkoxide of boron (mol) Barium acetate (mol) Alcohol (mol) Complexing agent (mol) Water (mol) ????????pH
????1 ??0.0633 ?0.0436 ?0.0149 ?0～0.19 ?0.044～0 ?.131 ??1.2～2. ??0 ????1.5～3.0
????2 ??0.0567 ?0.0366 ?0.0250 ?0～0.19 ?8 ?0.055～0 ?.22 ??1.3～2. ??8 ????2.0～3.5
????3 ??0.0436 ?0.0290 ?0.0419 ?0～0.13 ?1 ?0.044～0 ?.174 ??1.4～3. ??0 ????2.0～4.0
????4 ??0.0653 ?0.0126 ?0.0284 ?0～0.24 ?8 ?0.038～0 ?.076 ??1.3～3. ??0 ????2.0～4.5
????5 ??0.0289 ?0.0434 ?0.0494 ?0～0.07 ?5 ?0.065～0 ?.326 ??1.5～3. ??2 ????1.5～4.5
Table 4 example 1 30BaO-20B 2O 3-50SiO 2(wt%) experiment parameter and stationary phase and solid content relation
Sequence number Complexing agent ??R c ??R s ???R w ??pH Gel time Solid content
????1 Methyl ethyl diketone ??3 ??2.8 ??18 ??1.5 45 days ????10
????2 Methyl ethyl diketone ??3 ??2.3 ??15 ??2 40 days ????11
????3 Methyl ethyl diketone ??3 ??1.4 ??16 ??2 31 days ????11.5
????4 Methyl ethyl diketone ??1 ??2.3 ??15 ??2 39 days ????11
????5 Methyl ethyl diketone ??3 ??0 ??12 ??3 13 days ????11.3
The experiment parameter of the colloidal sol that table 5 70BaO-14B2O3-16SiO forms and the relation of stationary phase and solid content
Sequence number Complexing agent ????R c ????R s ???R w ??pH Gel time Solid content
????1 Dimethyl formamide ????1.5 ????1.5 ????22 ????2 13 hours ????16
????2 Dimethyl formamide ????3 ????1.5 ????23 ????2 20 days ????12.5
????3 Dimethyl formamide ????6 ????2.5 ????30 ????1.5 40 days ????11.2
????4 Dimethyl formamide ????3 ????1.0 ????23 ????3.5 40 hours ????14.0
????5 Methyl aceto acetate ????3 ????1.5 ????26 ????2 10 days ????12.9
????6 Glacial acetic acid ????3 ????1.0 ????15 ????2 20 days ????14.5
????7 Glacial acetic acid ????3 ????0 ????16 ????4.5 12 hours ????18
????8 Dimethyl formamide ????3 ????0 ????22 ????2 20 days ????14.5
Embodiment 6
The colloidal sol of embodiment 1 is after condensing, and drying is 3 days under the room temperature, moves into drying in oven 4 days, be warming up to 350 ℃ of insulation 3hr with 300 ℃ speed per hour then, again with per hour 150 ℃ be warming up to 500 ℃ the insulation 3hr, with per hour 120 ℃ be warming up to 800 ℃ the insulation 3hr, obtain xerogel.Again with per hour 120 ℃ be warming up to temperature requiredly, insulation preset time observe the state high temperature under then, or the thing phase of the composition of cool to room temperature after calcining with XRD analysis.
Embodiment 1 be slight agglomerating powder 1000 ℃ of calcinings behind the 3hr, and Fig. 1 composes for this XRD figure of forming after 1000 ℃ of calcinings, and collection of illustrative plates demonstration powder contains the low temperature cristobalite crystalline phase of a great deal of.
Embodiment 7
Form 5 gel through to form 1 similar thermal treatment and 1000 ℃ of calcinings after, high temperature is low viscous glass metal down, and is as clear as crystal fully.The XRD material phase analysis that carries out after the cooling is indicated as glassy phase, and XRD figure is shown in Fig. 2.
The glass powder of this composition has carried out the DTA analysis, and the result shows its T gTemperature is about 590 ℃, T fTemperature is about 670 ℃.

Claims (10)

1. BaO-B 2O 3-SiO 2Precursor colloidal sol is characterized in that, composition and weight percent content are;
BaO：20-75％，B 2O 3：5-20％，SiO 2：15-70％。
2. BaO-B according to claim 1 2O 3-SiO 2Precursor colloidal sol is characterized in that, composition and weight percent content are:
BaO：25-70％，B 2O 3：10-18％，SiO 2：15-65％。
3. claim 2 or 3 described BaO-B 2O 3-SiO 2The preparation method of precursor colloidal sol is characterized in that comprising the steps:
(1) pure and mild cosolvent is added the alkoxide of the silicon of said ratio amount, it is standby to obtain A liquid, and complexing agent is added the alkoxide of boron, obtains B liquid;
Said complexing agent comprises one or more in methyl ethyl diketone, dimethyl formamide, etheric acid second fat, Glacial acetic acid, the diacetylmethane;
R cThe mole number of the alkoxide of the mole number/boron of=complexing agent=1～9;
(2) B liquid is dropwise joined in the A liquid, the aqueous solution with barium acetate drips in the mixed solution of AB then, during with inorganic acid for adjusting pH value scope 1.5～4.5, and add entry, promptly obtain BaO-B 2O 3-SiO 2Precursor colloidal sol, the mol ratio R of the add-on of water and all oxides amount wBe 12～32.
4. method according to claim 3 is characterized in that, the general structure of the alkoxide of said silicon is: Si (OR) 4, R represents C 1～C 4Alkyl.
5. method according to claim 4 is characterized in that, the alkoxide of silicon is Si (OCH 3) 4Or Si (OC 2H 5) 4
6. method according to claim 3 is characterized in that, the general structure of the alkoxide of said boron is: B (OR 1) 3, R 1Represent C 1～C 4Alkyl.
7. method according to claim 6 is characterized in that, the alkoxide of boron is B (OC 2H 5) 3Or B (OCH 3) 3
8. method according to claim 3 is characterized in that, said alcohol is C 1～C 3Unit alcohol, the mol ratio R of alcohol and the alkoxide of silicon sBe 0～5.
9. method according to claim 3 is characterized in that, under the vigorous stirring, B liquid is dropwise joined in the A liquid, and the aqueous solution with barium acetate drips in the mixed solution of AB under vigorous stirring then.
10. according to each described method of claim 3～9, it is characterized in that said mineral acid comprises HCl or HNO 3
CN 200410015760 2004-01-12 2004-01-12 BaO-B2O3-SiO2 precusor collosol and its preparaton method Expired - Fee Related CN1224591C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 200410015760 CN1224591C (en) 2004-01-12 2004-01-12 BaO-B2O3-SiO2 precusor collosol and its preparaton method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 200410015760 CN1224591C (en) 2004-01-12 2004-01-12 BaO-B2O3-SiO2 precusor collosol and its preparaton method

Publications (2)

Publication Number Publication Date
CN1556065A true CN1556065A (en) 2004-12-22
CN1224591C CN1224591C (en) 2005-10-26

Family

ID=34351502

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 200410015760 Expired - Fee Related CN1224591C (en) 2004-01-12 2004-01-12 BaO-B2O3-SiO2 precusor collosol and its preparaton method

Country Status (1)

Country Link
CN (1) CN1224591C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111097297A (en) * 2019-12-30 2020-05-05 江西师范大学 Boron-doped microporous silicon dioxide membrane and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111097297A (en) * 2019-12-30 2020-05-05 江西师范大学 Boron-doped microporous silicon dioxide membrane and preparation method and application thereof
CN111097297B (en) * 2019-12-30 2021-10-26 江西师范大学 Boron-doped microporous silicon dioxide membrane and application

Also Published As

Publication number Publication date
CN1224591C (en) 2005-10-26

Similar Documents

Publication Publication Date Title
CN100396826C (en) Process for preparing patterning titanium dioxide inverse opal photonic crystal
KR19980045796A (en) Composition for forming a transparent conductive thin film, method for producing a transparent conductive thin film using the same, and surface conductive product
CN112961675B (en) Method for improving stability of perovskite quantum dots through sol-gel passivation
CN109775748A (en) A kind of SnO with gas-sensitive property2The preparation method of graphene aerogel material
JPWO2012105606A1 (en) Method for producing phosphor-dispersed glass and phosphor-dispersed glass
CN1224591C (en) BaO-B2O3-SiO2 precusor collosol and its preparaton method
EP1605010A1 (en) Organic-inorganic hybrid vitreous material and method for producing same
JP2538527B2 (en) Method for producing metal oxide glass film and spherical fine particles
JP4079898B2 (en) Organic inorganic hybrid glassy material
US6408648B1 (en) Method for production of metal oxide glass microspherules at low temperatures
JP5062853B2 (en) Manufacturing method of GRIN lens
JP2635313B2 (en) Method for producing silica glass
JPH054839A (en) Method for preparing thin film by sol-gel method
KR100396370B1 (en) Organic-inorganic hybrid material for gate insulation film of tft-lcd, gate insulation film and its preparation comprising the same
CN113416066A (en) LTCC substrate and preparation method and application thereof
CN1265211C (en) Preparation method of organic-inorganic composite photochromic film material
JP2004300416A (en) Organic-inorganic hybrid glassy material and method for producing the same
US20020013209A1 (en) Erbium-doped multicomponent glasses manufactured by the sol-gel method
JPH0755835B2 (en) Method for producing silica glass
CN102352184A (en) Method for preparing sol for stabilizing properties of anti-reflection film of solar glass
JPS63182222A (en) Production of silica glass
CN117384627A (en) Organic silicon ligand for stabilizing quantum dot, organic silicon modified quantum dot and preparation method thereof
CN110862220A (en) Preparation method of two-dimensional material doped multicomponent gel glass
CN114280889A (en) Inorganic composite anti-reflection film solution and preparation method thereof
JP2005247945A (en) Organic/inorganic hybrid glassy material and method for producing the same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
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