CN113149429B - High borosilicate glass containing metal nanoparticles and preparation method thereof - Google Patents
High borosilicate glass containing metal nanoparticles and preparation method thereof Download PDFInfo
- Publication number
- CN113149429B CN113149429B CN202110211821.XA CN202110211821A CN113149429B CN 113149429 B CN113149429 B CN 113149429B CN 202110211821 A CN202110211821 A CN 202110211821A CN 113149429 B CN113149429 B CN 113149429B
- Authority
- CN
- China
- Prior art keywords
- parts
- borosilicate glass
- high borosilicate
- glass containing
- metal nanoparticles
- 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.)
- Active
Links
- 239000005388 borosilicate glass Substances 0.000 title claims abstract description 59
- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title description 7
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000011521 glass Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 230000001681 protective effect Effects 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000000137 annealing Methods 0.000 claims abstract description 3
- 230000001678 irradiating effect Effects 0.000 claims abstract 2
- 238000002156 mixing Methods 0.000 claims abstract 2
- 101710134784 Agnoprotein Proteins 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 239000000156 glass melt Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims 2
- 239000004327 boric acid Substances 0.000 claims 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 8
- 239000005361 soda-lime glass Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 4
- 229910018626 Al(OH) Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- -1 soda lime silicate series Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/102—Glass compositions containing silica with 40% to 90% silica, by weight containing lead
- C03C3/105—Glass compositions containing silica with 40% to 90% silica, by weight containing lead containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
Description
(一)技术领域(1) Technical field
本发明涉及一种含金属纳米颗粒的高硼硅玻璃复合材料及其制备方法。The invention relates to a high borosilicate glass composite material containing metal nanoparticles and a preparation method thereof.
(二)背景技术(2) Background technology
金属纳米颗粒(如Au、Ag、Cu等)因其具有独特的表面等离子体共振效应、量子尺寸效应和局域场效应而受到特别关注。将金属纳米颗粒引人到玻璃基质中，由于其表面等离子体振子的激发引起局部场强的增加，能够产生较好的非线性光学性质，在特定光功能的光学器件领域有广泛的应用前景。Metal nanoparticles (such as Au, Ag, Cu, etc.) have received special attention due to their unique surface plasmon resonance effects, quantum size effects, and localized field effects. The introduction of metal nanoparticles into the glass matrix can produce better nonlinear optical properties due to the increase of local field strength caused by the excitation of its surface plasmons, and has broad application prospects in the field of optical devices with specific optical functions.
研究发现，金属纳米颗粒尺寸、粒度分布、结晶程度等对该类材料非线性光学性质影响较大，另外玻璃基体的类型也对其影响较多。目前，玻璃基体的选择一般都是光学、热学及力学性能都比较差的普通钠钙硅酸盐系列玻璃，限制了材料的效果和应用范围。而高硼硅玻璃具有优异的性能(例如良好的透明性、低玻璃化转变温度(Tg)、高密度、高热膨胀系数(容易地制造光纤)、合适带宽、良好的红外透射率等)，更适合作为含金属纳米颗粒的玻璃材料的基体。在传统网络结构松散的钠钙硅玻璃中生成金属纳米颗粒常用的方法有离子注入法、离子交换法、溶胶-凝胶法和熔融热处理法等，但由于高硼硅玻璃的网络结构致密，传统工艺合成纳米颗粒均匀性差、稳定性及可控性多都不好。The study found that the size, particle size distribution, and degree of crystallization of metal nanoparticles have a great influence on the nonlinear optical properties of this type of material, and the type of glass matrix also has a great influence on it. At present, the choice of glass substrate is generally ordinary soda lime silicate series glass with poor optical, thermal and mechanical properties, which limits the effect and application range of the material. And high borosilicate glass has excellent properties (such as good transparency, low glass transition temperature (Tg), high density, high thermal expansion coefficient (easy to manufacture optical fibers), suitable bandwidth, good infrared transmittance, etc.), more Suitable as a matrix for glass materials containing metal nanoparticles. The commonly used methods to generate metal nanoparticles in soda-lime-silica glass with loose network structure include ion implantation, ion exchange, sol-gel method, and fusion heat treatment. However, due to the dense network structure of high borosilicate glass, traditional The process of synthesizing nanoparticles has poor uniformity, stability and controllability.
鉴于上述问题，开发一种能在高硼硅玻璃中制备出均匀性好，稳定性好的纳米金属颗粒的方法具有重要意义。In view of the above problems, it is of great significance to develop a method for preparing nano-metal particles with good uniformity and good stability in borosilicate glass.
(三)发明内容(3) Contents of the invention
针对上述现有技术存在的问题，本发明提供一种高效简便、性能稳定的含金属纳米颗粒的高硼硅玻璃的合成方法。Aiming at the above-mentioned problems in the prior art, the present invention provides an efficient, simple, stable performance synthesis method of high borosilicate glass containing metal nanoparticles.
为了实现上述目的，本发明采用如下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
本发明提供一种含金属纳米颗粒的高硼硅玻璃的制备方法，所述方法包括如下步骤：The invention provides a method for preparing borosilicate glass containing metal nanoparticles, the method comprising the following steps:
(1)按以下质量份数将各组分混合：940～997份(优选975～994份)的高硼硅玻璃配合料、0.2～10份(优选0.8～5份)的粒径为200～1600目的金属化合物微粉和2～50份(优选5～20份)的还原剂，得到预混物；所述金属化合物微粉的金属化合物为AgNO3、HAuCl4·4H2O、Cu2O中的一种或多种；所述还原剂为SnO、Sb2O5、CeO2中的一种或多种；所述高硼硅玻璃配合料由以下质量份数的各组分组成：780～850份二氧化硅(SiO2)、170～270份硼酸(H3BO3)、68～172份碳酸钠(Na2CO3)、0～76份氢氧化铝(Al(OH)3)和0～90份碳酸钙(CaCO3)；(1) Mix the components according to the following parts by mass: 940 to 997 parts (preferably 975 to 994 parts) of high borosilicate glass batch material, 0.2 to 10 parts (preferably 0.8 to 5 parts) with a particle size of 200 to 1600 meshes of metal compound powder and 2 to 50 parts (preferably 5 to 20 parts) of reducing agent to obtain a premix; the metal compound of the metal compound powder is AgNO 3 , HAuCl 4 .4H 2 O, Cu 2 O One or more; the reducing agent is one or more of SnO, Sb 2 O 5 , CeO 2 ; the high borosilicate glass batch consists of the following components in parts by mass: 780-850 Parts of silicon dioxide (SiO 2 ), 170-270 parts of boric acid (H 3 BO 3 ), 68-172 parts of sodium carbonate (Na 2 CO 3 ), 0-76 parts of aluminum hydroxide (Al(OH) 3 ) and 0 ~90 parts calcium carbonate (CaCO 3 );
(2)将步骤(1)所述预混物在保护气氛A下1450～1800℃熔融热处理1～4h后，将所得玻璃熔体注入模具中置于400～550℃退火保温30～90min，冷却至室温，得到含金属离子的玻璃；(2) After melting and heat-treating the premixture in step (1) at 1450-1800°C for 1-4 hours under protective atmosphere A, pour the obtained glass melt into a mold and place it at 400-550°C for annealing and heat preservation for 30-90 minutes, then cool To room temperature, the glass containing metal ions is obtained;
(3)在室温下对步骤(2)所述含金属离子的玻璃X-射线辐照(CuKα，λ＝0.15416nm，50kV，50mA)30min～120min，再在保护气氛B下400～700℃热处理30min～90min，冷却，即得所述含金属纳米颗粒的高硼硅玻璃。(3) X-ray irradiation (CuKα, λ=0.15416nm, 50kV, 50mA) to the glass containing metal ions described in step (2) at room temperature for 30min to 120min, then heat treatment at 400 to 700°C under protective atmosphere B After cooling for 30 minutes to 90 minutes, the borosilicate glass containing metal nanoparticles is obtained.
优选地，步骤(1)所述高硼硅玻璃配合料组成为788份二氧化硅(SiO2)、226份硼酸(H3BO3)、97份碳酸钠(Na2CO3)、30份氢氧化铝(Al(OH)3)、5份碳酸钙(CaCO3)。Preferably, the high borosilicate glass batch composition in step (1) is 788 parts of silicon dioxide (SiO 2 ), 226 parts of boric acid (H 3 BO 3 ), 97 parts of sodium carbonate (Na 2 CO 3 ), 30 parts Aluminum hydroxide (Al(OH) 3 ), 5 parts calcium carbonate (CaCO 3 ).
优选地，步骤(1)所述金属化合物微粉的金属化合物为AgNO3、Cu2O中的一种或两种，特别优选AgNO3。Preferably, the metal compound of the metal compound micropowder in step (1) is one or both of AgNO 3 and Cu 2 O, particularly preferably AgNO 3 .
优选地，步骤(1)所述还原剂为SnO、CeO2中的一种或两种。Preferably, the reducing agent in step (1) is one or both of SnO and CeO 2 .
优选地，步骤(2)所述的保护气氛A或步骤(3)所述的保护气氛B为氮气或氩气气氛。Preferably, the protective atmosphere A described in step (2) or the protective atmosphere B described in step (3) is a nitrogen or argon atmosphere.
优选地，步骤(2)所述的熔融热处理温度为1500～1750℃，时间为1～2h。Preferably, the melting heat treatment in step (2) has a temperature of 1500-1750° C. and a time of 1-2 hours.
优选地，步骤(3)所述的含金属离子的玻璃粉X-射线辐照时间为30min～60min，在保护气氛B下500～600℃热处理30min～60min。Preferably, the X-ray irradiation time of the metal ion-containing glass frit in step (3) is 30 min to 60 min, and the heat treatment is performed in a protective atmosphere B at 500 to 600° C. for 30 min to 60 min.
与现有技术相比，本发明的有益效果在于：可制备出稳定性好的含金属纳米颗粒的高硼硅玻璃复合材料，且制备工艺高效简便，合适制备多种金属纳米颗粒。Compared with the prior art, the beneficial effect of the present invention is that: a high borosilicate glass composite material containing metal nanoparticles with good stability can be prepared, and the preparation process is efficient and simple, and is suitable for preparing various metal nanoparticles.
(四)附图说明(4) Description of drawings
图1为含0.08％AgNO3和1.5％SnO的高硼硅玻璃在X-射线照射后在400℃退火60min的光学吸收光谱。Fig. 1 is the optical absorption spectrum of high borosilicate glass containing 0.08% AgNO 3 and 1.5% SnO annealed at 400°C for 60 min after X-ray irradiation.
图2为含0.15％AgNO3和1.0％SnO的高硼硅玻璃在X-射线照射后在600℃退火60min的光学吸收光谱。Fig. 2 is the optical absorption spectrum of high borosilicate glass containing 0.15% AgNO 3 and 1.0% SnO annealed at 600°C for 60 min after X-ray irradiation.
图3为含0.08％AgNO3和1.5％SnO的高硼硅玻璃在X-射线照射后在600℃退火60min的光学吸收光谱。Fig. 3 is the optical absorption spectrum of high borosilicate glass containing 0.08% AgNO 3 and 1.5% SnO annealed at 600°C for 60 min after X-ray irradiation.
图4为含Ag+的普通玻璃在X-射线照射后分别经420℃和560℃退火60min的光学吸收光谱。Fig. 4 is the optical absorption spectrum of common glass containing Ag + annealed at 420°C and 560°C for 60min respectively after X-ray irradiation.
(五)具体实施方式(5) Specific implementation methods
下面通过具体实施例对本发明作进一步的说明，但本发明的保护范围并不仅限于此。以下示例中选用的高硼硅玻璃配合料引入各组的原料的方法是选用试剂级SiO2、H3BO3、Na2CO3、Al(OH)3和CaCO3，称取788g SiO2、226g H3BO3、97g Na2CO3、30g Al(OH)3和5gCaCO3，混匀得高硼硅玻璃配合料。高硼硅玻璃理论质量组成(wt％)为SiO2:78.8；B2O3:12.8；Na2O:5.7；Al2O3:2.0；CaO:0.3。The present invention will be further described below through specific examples, but the protection scope of the present invention is not limited thereto. The method of introducing the borosilicate glass batch selected in the following examples into the raw materials of each group is to use reagent grade SiO 2 , H 3 BO 3 , Na 2 CO 3 , Al(OH) 3 and CaCO 3 , and weigh 788g of SiO 2 , 226g of H 3 BO 3 , 97g of Na 2 CO 3 , 30g of Al(OH) 3 and 5g of CaCO 3 , mixed well to obtain a high borosilicate glass batch. The theoretical mass composition (wt%) of borosilicate glass is SiO 2 : 78.8; B 2 O 3 : 12.8; Na 2 O : 5.7; Al 2 O 3 : 2.0; CaO: 0.3.
实施例1：Example 1:
一种在高硼硅玻璃中合成金属纳米颗粒的方法，其特征在于：该制备方法包括以下步骤：A method for synthesizing metal nanoparticles in borosilicate glass, characterized in that: the preparation method comprises the following steps:
(1)将98.42g的高硼硅玻璃配合料与0.1259g的AgNO3，再加入1.7g的SnO还原剂等比例混合，在陶瓷研钵中研磨混合30min，得到99.1g混合物；(1) Mix 98.42g of high borosilicate glass batch material with 0.1259g of AgNO 3 , and then add 1.7g of SnO reducing agent in equal proportions, grind and mix in a ceramic mortar for 30min, and obtain 99.1g of the mixture;
(2)再对上述混合物在氮气气氛下，进行1700℃下熔融热处理1h，在模具中浇筑成玻璃，然后退火冷却处理，550℃保温60min，冷却至室温，得到含金属离子(Ag+)的高硼硅玻璃。(2) The above mixture is melted and heat-treated at 1700°C for 1 hour under a nitrogen atmosphere, cast into a glass in a mold, then annealed and cooled, kept at 550°C for 60 minutes, and cooled to room temperature to obtain a metal ion (Ag + ) High borosilicate glass.
(3)最后对得到的含金属离子(Ag+)的高硼硅玻璃在室温下，进行X-射线(CuKα，λ＝0.15416nm，50kV，50mA)辐照30min，再在氮气气氛下进行400℃高温热处理60min，再冷却至室温，即得到61.8g含金属纳米颗粒的高硼硅玻璃。用紫外-可见吸收光谱表征产生的金属纳米颗粒，如图1所示，可以发现光谱曲线呈现出金属纳米粒子的特征峰，波长稳定，大约400nm处的吸收带，在该条件下可在高硼硅玻璃中制备出稳定性好的金属纳米颗粒。(3) Finally, the obtained high borosilicate glass containing metal ions (Ag + ) was irradiated with X-rays (CuKα, λ=0.15416nm, 50kV, 50mA) for 30min at room temperature, and then 400 minutes under nitrogen atmosphere. ℃ high temperature heat treatment for 60 minutes, and then cooled to room temperature to obtain 61.8 g of borosilicate glass containing metal nanoparticles. The metal nanoparticles produced are characterized by ultraviolet-visible absorption spectrum, as shown in Figure 1, it can be found that the spectral curve presents the characteristic peak of metal nanoparticles, the wavelength is stable, and the absorption band at about 400nm can be used in high boron under this condition. Metal nanoparticles with good stability were prepared in silica glass.
实施例2：Example 2:
一种在高硼硅玻璃中合成金属纳米颗粒的方法，其特征在于：该制备方法包括以下步骤：A method for synthesizing metal nanoparticles in borosilicate glass, characterized in that: the preparation method comprises the following steps:
(1)将98.35g的高硼硅玻璃配合料与0.2361g的AgNO3，再加入1.1g的SnO还原剂等比例混合，在陶瓷研钵中研磨混合30min，得到98.6g混合物；(1) Mix 98.35g of high borosilicate glass batch material with 0.2361g of AgNO 3 , and then add 1.1g of SnO reducing agent in equal proportions, grind and mix in a ceramic mortar for 30min, and obtain 98.6g of the mixture;
(2)再对上述混合物在氮气气氛下，进行1700℃下熔融热处理1h，在模具中浇筑成玻璃，然后退火冷却处理，550℃保温60min，冷却至室温，得到含金属离子(Ag+)的高硼硅玻璃。(2) The above mixture is melted and heat-treated at 1700°C for 1 hour under a nitrogen atmosphere, cast into a glass in a mold, then annealed and cooled, kept at 550°C for 60 minutes, and cooled to room temperature to obtain a metal ion (Ag + ) High borosilicate glass.
(3)最后对得到的含金属离子(Ag+)的高硼硅玻璃在室温下，进行X-射线(CuKα，λ＝0.15416nm，50kV，50mA)辐照30min，再在氮气气氛下进行600℃高温热处理60min，再冷却至室温，即得到57.2g含金属纳米颗粒的高硼硅玻璃。用紫外-可见吸收光谱表征产生的金属纳米颗粒，如图2所示，可以发现光谱曲线呈现出金属纳米粒子的特征峰，波长稳定，大约404nm处的吸收带，在该条件下可在高硼硅玻璃中制备出稳定性好的金属纳米颗粒。(3) Finally, the obtained high borosilicate glass containing metal ions (Ag + ) was irradiated with X-rays (CuKα, λ=0.15416nm, 50kV, 50mA) for 30min at room temperature, and then 600 minutes under a nitrogen atmosphere. ℃ high temperature heat treatment for 60 minutes, and then cooled to room temperature to obtain 57.2 g of borosilicate glass containing metal nanoparticles. The metal nanoparticles produced are characterized by ultraviolet-visible absorption spectrum, as shown in Figure 2, it can be found that the spectral curve presents the characteristic peak of metal nanoparticles, the wavelength is stable, and the absorption band at about 404nm, under this condition, it can be used in high boron Metal nanoparticles with good stability were prepared in silica glass.
实施例3：Example 3:
一种在高硼硅玻璃中合成金属纳米颗粒的方法，其特征在于：该制备方法包括以下步骤：A method for synthesizing metal nanoparticles in borosilicate glass, characterized in that: the preparation method comprises the following steps:
(1)将98.42g的高硼硅玻璃配合料与0.1259g的AgNO3，再加入1.7g的SnO还原剂等比例混合，在陶瓷研钵中研磨混合30min，得到98.5g混合物；(1) Mix 98.42g of high borosilicate glass batch material with 0.1259g of AgNO 3 , and then add 1.7g of SnO reducing agent in equal proportions, grind and mix in a ceramic mortar for 30min, and obtain 98.5g of the mixture;
(2)再对上述混合物在氮气气氛下，进行1700℃下熔融热处理1h，在模具中浇筑成玻璃，然后退火冷却处理，550℃保温60min，冷却至室温，得到含金属离子(Ag+)的高硼硅玻璃。(2) The above mixture is melted and heat-treated at 1700°C for 1 hour under a nitrogen atmosphere, cast into a glass in a mold, then annealed and cooled, kept at 550°C for 60 minutes, and cooled to room temperature to obtain a metal ion (Ag + ) High borosilicate glass.
(3)最后对得到的含金属离子(Ag+)的高硼硅玻璃在室温下，进行X-射线(CuKα，λ＝0.15416nm，50kV，50mA)辐照30min，再在氮气气氛下进行600℃高温热处理60min，再冷却至室温，即得到55.7g含金属纳米颗粒的高硼硅玻璃。用紫外-可见吸收光谱表征产生的金属纳米颗粒，如图3所示，可以发现光谱曲线呈现出金属纳米粒子的特征峰，波长稳定，大约400nm处的吸收带，在该条件下可在高硼硅玻璃中制备出稳定性好的金属纳米颗粒。(3) Finally, the obtained high borosilicate glass containing metal ions (Ag + ) was irradiated with X-rays (CuKα, λ=0.15416nm, 50kV, 50mA) for 30min at room temperature, and then 600 minutes under a nitrogen atmosphere. ℃ high temperature heat treatment for 60 minutes, and then cooled to room temperature to obtain 55.7 g of borosilicate glass containing metal nanoparticles. The metal nanoparticles produced are characterized by ultraviolet-visible absorption spectrum, as shown in Figure 3, it can be found that the spectral curve presents the characteristic peaks of metal nanoparticles, the wavelength is stable, and the absorption band at about 400nm can be used in high boron under this condition. Metal nanoparticles with good stability were prepared in silica glass.
实施例4：Example 4:
一种在高硼硅玻璃中合成金属纳米颗粒的方法，其特征在于：该制备方法包括以下步骤：A method for synthesizing metal nanoparticles in borosilicate glass, characterized in that: the preparation method comprises the following steps:
(1)将98.8g的高硼硅玻璃配合料与0.5589g的Cu2O，再加入0.6g的CeO2还原剂，在陶瓷研钵中研磨混合30min，得到97.9g混合物；(1) 98.8g of high borosilicate glass batch material and 0.5589g of Cu 2 O, then add 0.6g of CeO 2 reducing agent, grind and mix in a ceramic mortar for 30min, to obtain 97.9g of the mixture;
(2)再对上述混合物在氩气气氛下，进行1750℃下熔融热处理1.5h，在模具中浇筑成玻璃，然后退火冷却处理，550℃保温70min，冷却至室温，得到含金属离子(Cu+)的高硼硅玻璃。(2) The above mixture is subjected to melting heat treatment at 1750°C for 1.5 hours under an argon atmosphere, poured into a mold to form glass, then annealed and cooled, kept at 550°C for 70 minutes, and cooled to room temperature to obtain a metal ion (Cu + ) of borosilicate glass.
(3)最后对得到的含金属离子(Cu+)的高硼硅玻璃在室温下，进行X-射线(CuKα，λ＝0.15416nm，50kV，50mA)辐照40min，再在氩气气氛下进行700℃高温热处理50min，再冷却至室温，即得到62.4g含金属纳米颗粒的高硼硅玻璃。用紫外-可见吸收光谱表征产生的金属纳米颗粒，可以发现光谱曲线呈现出金属纳米粒子的特征峰，峰形稳定，在该条件下可在高硼硅玻璃中制备出稳定性好的金属纳米颗粒。(3) Finally, the obtained high borosilicate glass containing metal ions (Cu + ) was irradiated with X-rays (CuKα, λ=0.15416nm, 50kV, 50mA) for 40min at room temperature, and then irradiated under an argon atmosphere. After heat treatment at 700°C for 50 minutes, and then cooling to room temperature, 62.4 g of borosilicate glass containing metal nanoparticles was obtained. The produced metal nanoparticles were characterized by ultraviolet-visible absorption spectrum. It can be found that the spectral curve presents the characteristic peaks of metal nanoparticles, and the peak shape is stable. Under this condition, metal nanoparticles with good stability can be prepared in high borosilicate glass. .
对比例1：Comparative example 1:
本对比例采用普通钠钙硅玻璃，引入各组的原料选用试剂级SiO2，Na2CO3，CaCO3和Al(OH)3，称量732gSiO2、261gNa2CO3、181gCaCO3和19gAl(OH)3，混合得到钠钙硅玻璃配合料。钠钙硅玻璃理论质量组成(wt％)为SiO2:73.2，Na2O:15.3，CaO:10.2，Al2O3:1.3。In this comparative example, ordinary soda-lime-silica glass was used. The raw materials introduced into each group were reagent grade SiO 2 , Na 2 CO 3 , CaCO 3 and Al(OH) 3 , and 732g SiO 2 , 261gNa 2 CO 3 , 181g CaCO 3 and 19gAl( OH) 3 , mixed to obtain soda lime silica glass batch material. The theoretical mass composition (wt%) of soda lime silica glass is SiO 2 : 73.2, Na 2 O: 15.3, CaO: 10.2, Al 2 O 3 : 1.3.
将99.92g的普通钠钙硅玻璃配合料与0.1259g的AgNO3，在陶瓷研钵中研磨混合30min，得到97.3g混合物；在1400℃下熔融热处理3h，在模具中浇筑成玻璃，然后退火冷却处理，550℃保温70min，冷却至室温，得到含金属离子(Ag+)的钠钙硅玻璃。Grind and mix 99.92g of common soda-lime-silica glass batch material and 0.1259g of AgNO 3 in a ceramic mortar for 30 minutes to obtain 97.3g of mixture; melt heat treatment at 1400°C for 3 hours, cast into glass in a mold, and then anneal and cool Treatment, heat preservation at 550° C. for 70 minutes, and cooling to room temperature to obtain soda lime silica glass containing metal ions (Ag + ).
含Ag+普通钠钙硅玻璃在X-射线(CuKα，λ＝0.15416nm，50kV，50mA)辐照30min后，生成Ag原子，再加热到420℃保温60min，得到68.7g含Ag纳米颗粒的钠钙硅玻璃，玻璃在405nm左右有明显的吸收峰。如图4所示，普通钠钙硅玻璃中，420℃生成Ag纳米颗粒，玻璃出现特征的黄色，但在560℃左右加热，Ag纳米颗粒会消失，405nm左右有明显的吸收峰会消退。Ag + ordinary soda-lime-silica glass is irradiated with X-rays (CuKα, λ=0.15416nm, 50kV, 50mA) for 30 minutes to generate Ag atoms, and then heated to 420°C for 60 minutes to obtain 68.7g of sodium particles containing Ag nanoparticles. Lime silica glass, the glass has an obvious absorption peak around 405nm. As shown in Figure 4, in ordinary soda-lime-silica glass, Ag nanoparticles are formed at 420°C, and the glass has a characteristic yellow color, but when heated at about 560°C, the Ag nanoparticles will disappear, and the obvious absorption peak at about 405nm will disappear.
通过实施例2和对比例1对比可见，含Ag纳米颗粒的高硼硅玻璃的Ag纳米颗粒的物化性质和特征吸收峰更稳定。From the comparison of Example 2 and Comparative Example 1, it can be seen that the physicochemical properties and characteristic absorption peaks of the Ag nanoparticles of the high borosilicate glass containing Ag nanoparticles are more stable.
虽然本发明已通过参考优选的实施例进行了描述，但是，本领域普通技术人员应当了解，可以不限于上述实施例的描述，在权利要求书的范围。Although the present invention has been described with reference to preferred embodiments, those of ordinary skill in the art will appreciate that it may not be limited to the description of the above-described embodiments, and is within the scope of the claims.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110211821.XA CN113149429B (en) | 2021-02-25 | 2021-02-25 | High borosilicate glass containing metal nanoparticles and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110211821.XA CN113149429B (en) | 2021-02-25 | 2021-02-25 | High borosilicate glass containing metal nanoparticles and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113149429A CN113149429A (en) | 2021-07-23 |
| CN113149429B true CN113149429B (en) | 2023-03-31 |
Family
ID=76883407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110211821.XA Active CN113149429B (en) | 2021-02-25 | 2021-02-25 | High borosilicate glass containing metal nanoparticles and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113149429B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115043644B (en) * | 2022-04-13 | 2023-03-24 | 山东电盾科技股份有限公司 | Ceramic hand mold with anti-static function and preparation process thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004001729B4 (en) * | 2004-01-13 | 2006-01-12 | Schott Ag | Process for the preparation of a red-colored borosilicate glass |
| CN100453484C (en) * | 2006-03-21 | 2009-01-21 | 武汉理工大学 | A preparation method of a colorless transparent glass material capable of forming a purple-red three-dimensional pattern inside |
| JP5569942B2 (en) * | 2009-10-27 | 2014-08-13 | 学校法人東京理科大学 | Luminescent glass, light-emitting device provided with the luminescent glass, and method for producing the luminescent glass |
| CN104817268B (en) * | 2015-04-21 | 2017-07-11 | 同济大学 | Low concentration AgNO3Fluorescent glass of the controllable Ag nano particles of yardstick and preparation method thereof is efficiently separated out under doping condition |
| WO2019071324A1 (en) * | 2017-10-13 | 2019-04-18 | The University Of Adelaide | Method for controlling the formation of metallic nanoparticles in glass and products thereof |
| CN111168079B (en) * | 2020-01-15 | 2023-01-10 | 浙江工业大学 | Method for synthesizing metal nanoparticles based on glass surface |
-
2021
- 2021-02-25 CN CN202110211821.XA patent/CN113149429B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113149429A (en) | 2021-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112456806B (en) | Glass ceramics, glass ceramics product and manufacturing method thereof | |
| US10391039B2 (en) | Al2O3-free lithium silicate glass composition | |
| US11414340B2 (en) | High strength lithium silicate glass ceramic having high shielding property | |
| CN102730970A (en) | Red silicate glass and preparation method thereof | |
| WO2023035704A1 (en) | Preparation method for fluorescent lithium silicate glass ceramic | |
| WO2022151610A1 (en) | Colored microcrystalline glass and preparation method therefor | |
| CN115772001A (en) | A kind of color transparent glass composition, glass ceramics and preparation method thereof | |
| CN113149429B (en) | High borosilicate glass containing metal nanoparticles and preparation method thereof | |
| CN108529876A (en) | A kind of high temperature resistant tempered glass and preparation method thereof | |
| CN113831021B (en) | Crystallized glass and preparation method thereof, glass protective layer, glass cover plate and electronic device | |
| CN113754288B (en) | Fluorescent lithium silicate glass ceramic enhanced by ion exchange and preparation method thereof | |
| CN112811821B (en) | Rare earth doped YAG high-crystallinity transparent glass ceramics and preparation method thereof | |
| CN112723748B (en) | A preparation method of high-strength lithium disilicate glass-ceramic material | |
| CN114538780B (en) | Front tooth facing ceramic material and preparation method thereof | |
| CN112174533B (en) | White high-aluminum microcrystalline glass and preparation method thereof | |
| CN108623154B (en) | A surface-strengthened transparent glass | |
| CN114455842A (en) | Precipitated Bi2GeO5 nanocrystalline high-density bismuth germanate glass-ceramic and preparation method thereof | |
| CN113698101A (en) | Glass ceramic finished product with gradually changed color, preparation method and application thereof | |
| CN118388140B (en) | Transparent magnesium aluminum silicon microcrystalline glass with high hardness and high indentation fracture toughness and preparation method thereof | |
| CN110002742B (en) | An electronic device panel and electronic device including the same | |
| CN108423996A (en) | A kind of gear division devitrified glass and preparation method thereof that Ce, V, Tb are co-doped with | |
| CN113998895B (en) | Controllable crystallization method of lithium disilicate glass ceramics | |
| CN119118506A (en) | A kind of high borosilicate glass and preparation method thereof | |
| CN112592066B (en) | A kind of method for preparing jadeite glass-ceramic | |
| CN107759078A (en) | A kind of heat-insulated coloured glass of antiultraviolet and its production technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |