阅读说明：本技术 一种含二氧化锡的纳米微晶玻璃及其制备方法 (Tin dioxide-containing nano microcrystalline glass and preparation method thereof ) 是由 郑书培 方再金 于 2020-07-01 设计创作，主要内容包括：本发明提供了一种含二氧化锡的纳米微晶玻璃及其制备方法,属于无机发光材料技术领域。所述的含二氧化锡的纳米微晶玻璃的制备方法,包括如下步骤：多孔玻璃溶液掺杂；初次热处理；酸处理；二次热处理。本申请发明人意外发现去除二氧化锡晶体外的发光离子,只让二氧化锡内部的离子发光反而整体发光更强,即：将多孔玻璃依次经含有锡离子和发光离子的混合溶液掺杂、初次热处理后,再经过酸处理能有效提高玻璃透明度,改善高硅氧玻璃的发光性能。本申请所述方法突破了本行业人员追求活性离子均匀分布来提高玻璃整体发光效果这种惯性认识。(The invention provides tin dioxide-containing nano microcrystalline glass and a preparation method thereof, belonging to the technical field of inorganic luminescent materials. The preparation method of the tin dioxide-containing nano microcrystalline glass comprises the following steps: doping a porous glass solution; primary heat treatment; acid treatment; and (5) secondary heat treatment. The inventor of the present application surprisingly found that removing luminescent ions outside the tin dioxide crystal only allows ions inside the tin dioxide to emit light and overall emit light more strongly, namely: after the porous glass is doped by a mixed solution containing tin ions and luminescent ions, subjected to primary heat treatment and subjected to acid treatment, the transparency of the glass can be effectively improved, and the luminescent property of the high silica glass can be improved. The method breaks through the inertial recognition that the industry pursues the uniform distribution of active ions to improve the integral luminous effect of the glass.)

1. A preparation method of tin dioxide-containing nano microcrystalline glass is characterized by comprising the following steps:

doping a porous glass solution; primary heat treatment; acid treatment; and (5) secondary heat treatment.

2. The method according to claim 1, wherein the porous glass solution doping is dipping the porous glass into the solution;

the porous glass is porous silica glass; further porous high silica glass with nano micropores uniformly distributed inside;

The aperture of the porous glass is 4-1000 nm.

3. The method according to claim 2, wherein the porous glass is immersed in the solution for a period of time ranging from 20 minutes to 24 hours.

4. The method according to claim 1, wherein the solution is a mixed solution containing tin ions and luminescent ions;

the concentration of tin ions in the solution is 0.1-2 mol/L;

the concentration of the luminescent ions in the solution is 0.05-1 mol/L.

5. The method according to claim 4, wherein the luminescent ions comprise at least one or more of europium ion, chromium ion, manganese ion, erbium ion, nickel ion, cerium ion, terbium ion, ytterbium ion, neodymium ion, thulium ion, praseodymium ion, and copper ion.

6. The method of claim 1, wherein the primary heat treatment is performed under the following conditions: the temperature is 400-900 ℃, and the time is not less than 20 minutes.

7. The method according to claim 1, wherein the acid in the acid treatment comprises at least one of hydrochloric acid, nitric acid and sulfuric acid.

8. The production method according to claim 7,

H of the acid in the acid treatment⁺The concentration is 0.1-5 mol/L;

the time of the acid treatment is not less than 1 h.

9. The method according to claim 1, wherein the secondary heat treatment is sintering treatment of the porous glass after the acid treatment;

the conditions of the secondary heat treatment are as follows: the temperature is 900-1300 ℃, and the time is 0.5-5 h.

10. A tin dioxide-containing nano microcrystalline glass, which is characterized by being prepared by the preparation method of any one of claims 1-9.

Technical Field

The invention belongs to the technical field of inorganic luminescent materials, and particularly relates to tin dioxide-containing nano microcrystalline glass and a preparation method thereof.

Background

The quartz and high silica glass basal bodies have high transparency, thermal shock resistance and good acid-base chemical corrosion resistance. The active ion doped high silica glass has important application value in the fields of photoluminescence and lasers. Methods for preparing active ion-doped high silica glass mainly include porous glass doping and Sol-Gel method (Sol-Gel). The luminescent glass prepared by adopting the porous glass has the advantages that the nano-pores which are communicated and distributed provide huge specific surface area for active ions, so that the porous glass can adsorb enough active ions, and the cluster of the luminescent active agent is effectively prevented without undergoing a melting process in subsequent sintering, so that the prepared luminescent glass has certain luminescent property. There are many patents relating to reactive ion doped high silica glasses.

Patent publication No. CN100378020C discloses a method for producing high silica blue light emitting glass; patent publication No. CN100503498C discloses a luminescent glass; patent publication No. CN102320746B discloses a method for producing a high silica glass emitting white light; these methods seek to uniformly distribute active ions in glass and improve luminescence properties. This concept continues for tin dioxide and Indium Tin Oxide (ITO) doped microcrystalline (nanocrystalline) glasses.

It is generally believed that the co-luminescence of the active ions in the glass network and the active ions in the tin dioxide crystal before quenching the concentration makes it possible to obtain a better overall luminescence, i.e. a higher overall luminescent ion content gives a stronger luminescence.

The patent with publication number CN107082571A discloses an ITO nanoparticle-doped up-conversion luminescent glass and a preparation method and application thereof; the patent with application number 201910470821.4 discloses a co-doped Eu³⁺And SnO₂Fluorescent detection of Fe by nanocrystalline glass³⁺The use of in (1), wherein co-doped Eu is described³⁺And SnO₂The active ions doped in the samples and all the samples prepared by the sol-gel method are simultaneously and uniformly distributed on the glass matrix and ITO and SnO ₂In the crystal, the overall luminous effect of the glass material is not good enough, and the application requirement of high brightness cannot be met.

Disclosure of Invention

The first purpose of the application is to provide a preparation method of tin dioxide-containing nano microcrystalline glass.

Another object of the present application is to provide a tin dioxide-containing nanocrystalline glass prepared by the above method.

In order to achieve the purpose, the invention is realized by the following technical scheme:

a preparation method of tin dioxide-containing nano microcrystalline glass comprises the following steps:

doping a porous glass solution; primary heat treatment; acid treatment; and (5) secondary heat treatment.

The porous glass solution doping means that the porous glass is immersed into the solution.

The porous glass is porous silica glass; preferably porous high silica glass with nano-micropores uniformly distributed inside.

The porous glass can be obtained commercially, or can be prepared by a method described in the literature or a method prepared by a self-made method.

The porous glass is preferably prepared by any one of the following literature-described methods or a self-made method as described below:

(1)D.Chen,H.Miyoshi,T.Akai,T.Yazawa,Colorless transparentfluorescence material:sintered porous glass containing rare-earth andtransition-metal ions,Appl.Phys.Lett.86(2005),231908-231908.

(2)Q.Zhang,Y.B.Qiao,B.Qian,G.P.Dong,J.Ruan,X.F.Liu,Q.L.Zhou,Q.X.Chen,J.R.Qiu,D.P.Chen,Luminescence properties of the Eu-doped porous glass andspontaneous reduction of Eu³⁺to Eu²⁺,J.Lumines.129(11),(2009)1393-1397.

(3)Y.Shen,S.Zheng,Q.Sheng,S.Liu,W.Li,D.Chen,Synthesis of nano-colloidal silica particles and their effects on the luminescence propertiesof Eu²⁺-doped High silica glass,Mater.Lett.139,(2015)373-376.

the self-making method of the porous glass comprises the following steps: respectively mix SiO₂、B₂O₃、Al₂O₃、Na₂CO₃Mixing the raw materials with CaO powder according to the weight percentage of (49-53): (28-30): (1.2-2.0): 12-14): 5.0-5.8), firing at 1200-1700 ℃ for 1-3 h, pouring out the molten glass for thinning, putting into a muffle furnace at 400-800 ℃ for heat treatment for 5-72 h for phase separation, Then acid H at 60-150 DEG C⁺Soaking in hot acid with the concentration of 0.2-4 mol/L for more than 8 hours to obtain porous glass; the porous glass is more preferably prepared by the following preparation method: respectively mix SiO₂、B₂O₃、Al₂O₃、Na₂CO₃Mixing the raw materials with CaO powder according to the weight percentage of 51:29:1.6:13:5.4, firing for 2 hours at 1400 ℃, pouring out the molten glass, thinning, putting into a 600 ℃ muffle furnace for heat treatment for 24 hours for phase separation, and then soaking in 1mol/L hot hydrochloric acid at 100 ℃ for 24 hours to obtain the porous glass.

The aperture of the porous glass is 4-1000 nm; preferably 4-100 nm; more preferably 4 to 50 nm.

The time for immersing the porous glass in the solution is preferably 20 minutes to 24 hours; further preferably 20 minutes to 10 hours; more preferably 30 minutes.

The solution is preferably a mixed solution containing tin ions and luminescent ions;

the concentration of tin ions in the solution is preferably 0.1-2 mol/L; more preferably 0.8 mol/L.

The concentration of the luminescent ions in the solution is preferably 0.05-1 mol/L; more preferably 0.4 mol/L.

The luminescent ions preferably comprise at least one or more of europium (Eu) ions, chromium (Cr) ions, manganese (Mn) ions, erbium (Er) ions, nickel (Ni) ions, cerium (Ce) ions, terbium (Tb) ions, ytterbium (Yb) ions, neodymium (Nd) ions, thulium (Tm) ions, praseodymium (Pr) ions and copper (Cu) ions.

The conditions of the primary heat treatment are as follows: the temperature is 400-900 ℃, and the time is not less than 20 minutes; preferably heating for 20 minutes to 10 hours at 400 to 900 ℃; further preferably heating at 500-700 deg.C for 0.5-3 hours; more preferably 500 c for 1 hour. The primary heat treatment is carried out at the temperature, so that on one hand, tin dioxide crystals can be formed in the heating process, and on the other hand, the nano-pores of the porous glass can be prevented from being closed. If the heat treatment temperature is too low, tin dioxide crystals cannot be formed, and tin compounds are also removed during acid treatment; if the heat treatment temperature is too high, the nano-pores of the porous glass are closed, and the doped ions are wrapped and can not be removed by acid any more.

The acid in the acid treatment preferably includes at least one of hydrochloric acid, nitric acid, and sulfuric acid.

H of the acid in the acid treatment⁺The concentration is preferably 0.1-5 mol/L; more preferably 0.1 to 2 mol/L; most preferably 1 mol/L.

The volume of the acid in the acid treatment is preferably more than 5 times of the volume of the glass; further preferably 5 to 50 times; more preferably 20 times.

The acid treatment time is not less than 1 h; preferably 10-72 h; more preferably 10-24 h; most preferably 24 h.

The secondary heat treatment refers to sintering treatment of the porous glass after acid treatment.

The conditions of the secondary heat treatment are preferably as follows: the temperature is 900-1300 ℃, and the time is 0.5-5 h; more preferably 1150 deg.C for 1 h.

The sintering atmosphere is air or oxygen.

The tin dioxide-containing nano microcrystalline glass is prepared by the preparation method.

Compared with the prior art, the method has the following beneficial effects:

(1) generally, it is considered that before the concentration is quenched, the luminescent ions in the glass network and the luminescent ions in the tin dioxide crystal emit light together, so that the overall luminescent effect is better, that is, the more the content of the overall luminescent ions is, the stronger the luminescence is; the inventor of the present application surprisingly found that removing luminescent ions outside the tin dioxide crystal only allows ions inside the tin dioxide to emit light and overall emit light more strongly, namely: porous glass is doped with a mixed solution containing tin ions and luminescent ions, subjected to primary heat treatment and then subjected to acid treatment, so that the absorption of ions with low luminous efficiency is reduced, and the transparency of the glass can be effectively improved, and the luminous performance of the high silica glass is improved. The method breaks through the inertial recognition that the industry pursues the uniform distribution of active ions to improve the integral luminous effect of the glass.

(2) The principle that this application utilized does: 1) in the process of the porous glass doping preparation method, tin ions can generate tin dioxide crystals at 400-900 ℃ and the porous glass can not shrink. 2) The stannic oxide crystal is insoluble in dilute acid, so after acid treatment, the structure and components in the crystal are basically unchanged, and the luminescent ions outside the crystal are leached out, and finally the glass material with the luminescent ions only existing in the stannic oxide crystal is obtained. Based on the principle, the porous glass doping method is easy to operate to achieve the target, and the doped ions and the nanocrystalline particles are always in a wrapped state in the preparation process of the sol-gel, so that the acid treatment operation is not easy to perform.

(3) The method can effectively remove the luminescent ions outside the nanocrystals and control the luminescent ions to be enriched in the tin dioxide nanocrystals, thereby improving the luminescent performance of the glass and obtaining the glass material with stronger luminescence. The transparency of the glass substrate obtained by the application is improved; the tin dioxide nanocrystals provide a suitable crystal field for the active ions, and the tin dioxide, as a semiconductor material, can absorb ultraviolet light and transfer energy to the active ions. The tin dioxide nanocrystals can improve the luminescence of the active ions.

Drawings

FIG. 1 is an X-ray diffraction diagram of samples at various stages in the preparation process of the tin dioxide-containing nano-microcrystalline glass of the present invention.

FIG. 2 is a comparison graph of Eu ion distribution of a conventional doped (acid-free porous glass process) and tin dioxide-containing nano glass ceramics prepared by the method of the present invention; wherein, the graph A is a Eu ion distribution result graph of the nano microcrystalline glass containing tin dioxide obtained by common doping; and the figure B is a diagram of the Eu ion distribution result of the tin dioxide-containing nano microcrystalline glass prepared by the method.

FIG. 3 is a comparison graph of the transmission spectra of the tin dioxide-containing nano microcrystalline glass prepared by the method of the present invention and the common doping (acid-free porous glass treatment).

FIG. 4 is a comparison graph of Eu ion luminescence spectra under 325nm excitation for conventional doped (porous glass acid-free treatment preparation method) and tin dioxide-containing nano microcrystalline glass prepared by the method of the present invention; wherein, the graph A is a Eu ion luminescence spectrum result graph of the nano microcrystalline glass containing tin dioxide obtained by common doping; and the figure B is a Eu ion luminescence spectrum result diagram of the nano microcrystalline glass containing the tin dioxide prepared by the method.

Detailed Description

The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.

The following examples are intended to illustrate the present invention, but are not intended to limit the scope of the present invention, and are not particularly limited to the types of the component materials used in the following specific examples. The starting materials used in the present application are commercially available unless otherwise specified.