WO2016045339A1 - 一种金属及类金属的氟氧化亲水处理方法 - Google Patents

一种金属及类金属的氟氧化亲水处理方法 Download PDF

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WO2016045339A1
WO2016045339A1 PCT/CN2015/075292 CN2015075292W WO2016045339A1 WO 2016045339 A1 WO2016045339 A1 WO 2016045339A1 CN 2015075292 W CN2015075292 W CN 2015075292W WO 2016045339 A1 WO2016045339 A1 WO 2016045339A1
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interface
hydrophilic
processing method
fluorine
metals
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吕树申
罗智勇
莫冬传
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Sun Yat Sen University
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    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/32—Anodisation of semiconducting materials

Definitions

  • the invention relates to a fluorine oxidation hydrophilic treatment method for metals and metalloids.
  • hydrophilic interface materials self-cleaning in materials, enhancing boiling heat transfer efficiency, Anti-biofouling and the field of biomedicine are of great significance.
  • the construction of the hydrophilic interface is mainly based on surface roughness and surface chemical composition.
  • 2008 In the year, Wang Hui et al. prepared an ultra-hydrophilic aluminum alloy interface by anodizing and supplementing the liquid phase product (CN101665972); 2012 In the year, Wang Bo et al.
  • Fluorine is a highly electronegative chemical element that reacts with most substances. This determines the universality of fluorine treatment technology to a certain extent. At the same time, due to the existence of such extremely strong electronegativity, Will greatly improve the polarity of the material interface, so that it can have electrons with water, etc. H The substance forms a strong hydrogen bond and greatly enhances the hydrophilic properties of the interface.
  • fluorine-containing chemicals for the modification of hydrophilic interfaces has long been known. 2007, Howarter The fluorine-containing surfactant is bonded to the surface of the glass by an intermediate linking reagent based on the hydroxyl group on the surface of the glass to prepare a glass having good hydrophilic antifogging properties.
  • the fluorine reagent used in this study is a hydrophobic perfluoroalkane, and the realization of hydrophilic properties mainly depends on the cis-trans isomerization of the intermediate linking reagent under external stimulation.
  • a metal or metalloid element with weak electronegativity Ti, Al, Cu, Si, etc., so that the electron cloud can be biased to a large extent by fluorine atoms, so that it can contain electron-deficient H
  • the substances such as water, alcohol, etc.
  • the purpose of the invention is to bond the fluorine group to the surface of the metal and the metalloid by the fluorine oxidation technology, thereby greatly improving the hydrophilicity of the material interface, achieving the super-hydrophilic effect, and preparing for the subsequent self-cleaning applications.
  • a fluorine oxidation hydrophilic treatment method for metals and metalloids comprising the steps of:
  • the material is at 100 °C -1000 °C Calcined in an air atmosphere to form an oxide film on the surface of the material;
  • the step (1) is sanded with a sandpaper and polished with a chemical polishing cloth.
  • the frequency of the ultrasonic cleaning in the step (1) is 50-100 KHZ, and the oven temperature is 10-100 °C. .
  • step (2) 2-10 the time of calcination in step (2) 2-10 In an hour, it is ensured that the surface oxide layer is formed without destroying the substrate.
  • the temperature in the step (3) is constant by a constant temperature water bath, and the reaction vessel is placed in a water bath.
  • the lower fluoride ion concentration in the step (3) means 20% or less, preferably 10%. Below the mass, partial fluorination is ensured to form a stable oxyfluoride.
  • the metal is Ti, Al, Cu, Pb, Fe Common metals and lanthanide metals, etc., are essentially characterized by their small electronegativity, which can form a chemical bond with a strong polarity with a highly electronegative fluorine element, thereby forming a hydrophilic interface; It can react with all substances, so this technology is applicable to all metals that can react with fluorine and oxygen.
  • the metalloid is Si, Ge, As, Sb Etc., mainly due to the fact that these elements are inherently less electronegative and can react with fluorine and oxygen.
  • the non-metallic element is not suitable for the fluorine oxidation treatment mainly because its electronegativity is large, and the chemical bond formed with the fluorine element is not polar enough to form a super-hydrophilic surface.
  • the present invention has the following beneficial effects:
  • the fluorine-oxidation hydrophilic treatment method for metal and metal-like metal provided by the invention has the advantages of low cost and simple and easy to obtain reagents and materials, and the operation method is also very simple, the variables are easy to control during the operation, and the hydrophilic property of the product after the fluorine oxidation treatment is excellent. Good stability.
  • the invention has wide application in the hydrophilic interface of metals, metal-like metals and their oxides, in self-cleaning of materials, prevention of biological pollution, enhancement of pool boiling heat transfer and the like.
  • Figure 1 is a graph showing the hydrophilic mechanism of fluorine oxidation at the interface between metals and metalloids
  • Figure 2 shows the static contact angle changes before and after Ti, Al and glass fluorine oxidation treatment
  • Figure 3 is: (a) pure titanium sheet; (b) oxidized titanium sheet and oxidized treatment in ethylene glycol solution containing 0.1 wt% NH 4 F, 1 wt% water, 25 ° C, 40 V Under voltage, anodized (c) 0.5h; (d) 1h; (e) 1.5h; (f) SEM image after 2h and contact angle (5ul water droplets);
  • Figure 4 is a plot of the contact angle of 5 ul water droplets at the interface of the titanium sheet and the change in fluorine content with fluorine treatment time.
  • Pretreatment of the material The surface of the Ti material is sanded with a sandpaper and a chemical polishing cloth. The organic and inorganic contaminants on the glass surface were removed by ultrasonic cleaning at 80 KHZ for 30 min with analytically pure acetone, ethanol and deionized water, and dried in an oven at 50 °C.
  • the second step is the oxidation treatment of the material interface: the Ti material is calcined in an air atmosphere at 450 ° C for 4 h. To form an oxide film on the surface of the material.
  • the third step is the fluorination treatment of the material interface: the oxidized sample is reacted at a constant temperature of 25 ° C and an ethylene glycol electrolyte containing 0.1 wt% of NH 4 F and 1 wt% of water at a voltage of 40 V for 2 h to make fluoride ions.
  • the material interface is reached and reacts with the oxide to form a stable oxyfluoride layer with a -F terminal group.
  • the fourth step uses the camera to take a static effect of 5 ul of deionized water on the interface to determine the static contact angle.
  • the resulting workpiece has a surface contact angle of 10°
  • the infiltration tends to be super-hydrophilic, and on this basis, increasing the surface roughness will further enhance the hydrophilic properties of the interface.
  • the first step of the material pretreatment the surface of the Al material is sanded with a sandpaper and a chemical polishing cloth, respectively, using analytically pure acetone, ethanol, deionized water. 80KHZ ultrasonic cleaning for 30min, remove the organic and inorganic contaminants on the glass surface, and dry in an oven at 50 °C.
  • the second step is the fluorine oxidation treatment of the material interface: in a constant temperature condition of 25 ° C and a glycol electrolyte containing 3 wt% HF and 8 wt% water, The reaction is carried out for 1 h at a voltage of 40 V.
  • an oxide layer is formed by the interaction of oxygen ions and an interface, and then the fluoride ion reaches the interface of the material and reacts with the oxide to form a -F.
  • a stable oxyfluoride layer of the terminal group is the fluorine oxidation treatment of the material interface: in a constant temperature condition of 25 ° C and a glycol electrolyte containing 3 wt% HF and 8 wt% water.
  • the third step uses the camera to take a static effect of 5 ul of deionized water on the interface to determine the static contact angle.
  • the obtained workpiece had a surface contact angle of 4°, and the wettability was super-hydrophilic, and the performance was excellent and the stability was excellent. (Figure 2)
  • Pretreatment of the material The glass piece (plain slide) is sequentially analyzed with pure acetone, ethanol and deionized water at 80KHZ. Ultrasonic cleaning for 30 min, remove the organic and inorganic contaminants on the glass surface, and dry in an oven at 50 °C.
  • the second step is the fluorination treatment of the material interface: since the glass itself is an oxide, the oxidation step can be omitted, and the glass piece is left to stand at 2 wt% HF.
  • the reaction was carried out for 140 min in an aqueous solution at a constant temperature of 25 ° C, and the fluorine ions were bonded to the surface of the glass by diffusion.
  • the third step uses the camera to take a static effect of 3 ul of deionized water on the interface to determine the static contact angle.
  • the obtained workpiece has a surface contact angle of 5.5°, and the wettability is super-hydrophilic, and the performance is excellent and the stability is excellent (Fig. 2).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

本发明公开了一种金属及类金属的氟氧化亲水处理方法，包括如下步骤：（ 1）将金属或类金属材料表面打磨干净，依次用丙酮、乙醇、去离子水超声清洗，除去污染物，烘干；（ 2 ）将材料在 100 ℃ -1000 ℃的空气气氛中煅烧，使材料表面形成一层氧化膜；（ 3 ）在 10-50 ℃恒温条件及较低的氟离子浓度下，利用电迁移或自由扩散的方式，形成带有 -F末端基团的氟氧化物层；（ 4 ）所得材料表层氟含量测定以及亲水性能测定。本发明的试剂及材料廉价且简单易得，操作方法也非常简单，操作过程中变量容易控制，氟氧化处理后的产品亲水性能上佳，稳定性较好。通过在金属、类金属及其氧化物的亲水界面构筑，在材料自清洁，防生物污染，增强池沸腾传热等方面具有广泛的应用。

Description

一种金属及类金属的氟氧化亲水处理方法
技术领域
本发明涉及一种金属及类金属的氟氧化亲水处理方法。
背景技术
亲水界面材料的研究成果 , 在材料自清洁 , 增强沸腾换热效率 , 防生物污染以及生物医药领域有着十分重要的意义。亲水界面的构筑，主要从表面粗糙度以及表面化学成分两方面着手。就控制材料表面微观结构而言， 2008 年，王慧等通过阳极氧化并辅以液相乘积，制备出了超亲水的铝合金界面（ CN101665972 ）； 2012 年，王波等利用化学腐蚀的方法，在铝表面刻蚀出微观结构，从而得到亲水性能上佳的界面（ CN102825260A ）； 2013 年，蒋毅坚等在铝表面沉积一层树枝状微结构，从而得到超亲水界面（ CN103668140A ）。另一方面，秦大可等通过利用多种化学物质对玻璃表面进行改性，得到防雾性能显著地超亲水玻璃界面（ CN103482883A ）。亲水界面的研究以及相关工艺技术已经日臻成熟。
氟是一种电负性极强的化学元素，能与大多数物质发生反应，这在一定程度上决定了氟处理技术的普适性；同时，由于这种极强的电负性的存在，将大大提高材料界面的极性，从而可以同水等具有缺电子 H 的物质形成较强的氢键作用，大大提高界面的亲水性能。但是，由于氟元素具有极强的电负性，所以大多数氟化物都是离子型化合物，极易溶于水，这样就大大限制了氟化技术的应用，如何形成含有稳定 -F 末端基团的含氟层成为氟化亲水技术的核心，这是本专利要解决的主要问题，也是主要创新点所在。
含氟的化学物质用于亲水界面的改性早已有之。 2007 年， Howarter 等基于玻璃表面的羟基基团，通过中间连接试剂，将含氟的表面活性剂键接到玻璃表面，从而制备出具有较好的亲水防雾性能的玻璃。但是，该研究所用到的氟试剂为疏水的全氟烷烃，亲水性能的实现主要依托于中间连接试剂在外界刺激下的顺反异构。本工艺中，与氟元素直接相连的是电负性弱的金属或类金属元素（ Ti 、 Al 、 Cu 、 Si 等），从而可以使电子云较大幅度偏向于氟原子，使其能与含有缺电子 H 的物质（如水、醇等）形成较强的氢键作用，大大增强界面的浸润性，同时为了稳定带有 -F 末端基团的氟化物，我们通过氟氧化的方式，形成 -O-M-F 的结构（氟氧化物的稳定性 Albu 在 2008 年已报导），这一结构中，由于 O 元素也具有较强的电负性，所以可以避免电子云过度偏向于氟原子而形成离子型化合物，同时又可以将 -F 末端集团稳定在体系庞大的氧化物网络中，增强亲水界面的稳定性。形成机理如图 1 所示。
发明内容
本发明的目的在于通过氟氧化技术，将氟基团键接在金属及类金属表面，从而大大提高材料界面的亲水程度，达到超亲水效果，为后续的自清洁等应用做准备。
为了实现上述目的，本发明采用如下技术方案：
一种金属及类金属的氟氧化亲水处理方法，其特征在于包括如下步骤：
（ 1 ）材料的前处理：将金属或类金属材料表面打磨干净，依次用丙酮、乙醇、去离子水超声清洗，除去玻璃表面有机以及无机类污染物，烘干；
（ 2 ）材料界面的氧化处理：将材料在 100 ℃ -1000 ℃ 的空气气氛中煅烧，使材料表面形成一层氧化膜；
（ 3 ）材料界面的氟化处理：在 10-50 ℃ 恒温条件及较低的氟离子浓度下，利用电迁移或自由扩散的方式，使氟离子达到材料界面并与氧化物发生反应，形成带有 -F 末端基团的稳定的氟氧化物层；
（ 4 ）所得材料表层氟含量测定以及亲水性能测定：利用 EDS 对材料表层的氟含量进行测定，利用高速摄影仪对水滴在界面上的浸润效果进行表征。
在上述处理方法中，步骤（ 1 ）中采用砂纸进行打磨，并用化学抛光布进行抛光。
在上述处理方法中，步骤（ 1 ）中超声清洗的频率为 50-100KHZ ，烘箱温度为 10-100 ℃ 。
在上述处理方法中，步骤（ 2 ）中煅烧的时间 2-10 小时，能确保形成表层氧化层而不至于破坏基体。
在上述处理方法中，步骤（ 3 ）中温度恒定是通过恒温水浴槽来实现，反应容器置于水浴槽中。
在上述处理方法中，步骤（ 3 ）中所述较低的氟离子浓度是指 20% 质量以下，最好是 10% 质量以下，能确保部分氟化而形成稳定的氟氧化物。
在上述处理方法中，所述金属为 Ti 、 Al 、 Cu 、 Pb 、 Fe 等常见金属以及镧系金属等，其本质在于这些元素本身的电负性小，可以和电负性大的氟元素形成具有很强极性的化学键，从而形成亲水界面；同时由于氟元素几乎可以与所有物质反应，所以该技术对可以与氟、氧进行反应的所有金属都适用。
在上述处理方法中，所述类金属为 Si 、 Ge 、 As 、 Sb 等，主要也归因于这些元素本身电负性较小，又能与氟、氧元素反应的特点。非金属元素不适用于该氟氧化处理主要是因为其电负性较大，与氟元素形成的化学键极性不够，无法形成超亲水表面。
与现有技术相比，本发明具有如下有益效果：
本发明提供的金属及类金属的氟氧化亲水处理方法，试剂及材料廉价且简单易得，操作方法也非常简单，操作过程中变量容易控制，氟氧化处理后的产品亲水性能上佳，稳定性较好。本发明通过在金属、类金属及其氧化物的亲水界面构筑，在材料自清洁，防生物污染，增强池沸腾传热等方面具有广泛的应用。
附图说明
图 1 为金属及类金属界面氟氧化亲水机理分析图；
图 2 为 Ti 、 Al 以及玻璃氟氧化处理前后的静态接触角变化；
图 3 为：（ a ）纯钛片；（ b ）氧化处理后的钛片以及氧化处理后再在含 0.1wt% NH4F ， 1wt% 水的乙二醇电解液中， 25 ℃ 、 40V 的电压下，分别阳极氧化（ c ） 0.5h ；（ d ） 1h ； (e)1.5h ；（ f ） 2h 后的 SEM 图和接触角（ 5ul 水滴）；
图 4 为 5ul 水滴在钛片界面接触角以及氟含量随氟处理时间的变化趋势图。
具体实施方式
实施例 1 ：
第一步 材料的前处理：将 Ti 材料表面分别用砂纸及化学抛光布打磨干净 , 依次用分析纯丙酮、乙醇、去离子水在 80KHZ 超声清洗 30min ，分别除去玻璃表面有机以及无机类污染物，用烘箱在 50 ℃ 烘干。
第二步 材料界面的氧化处理：将 Ti 材料在 450 ℃ 的空气气氛中煅烧 4h ，使材料表面形成一层氧化膜。
第三步 材料界面的氟化处理：氧化处理的样品，在 25 ℃ 恒温条件及含 0.1wt% NH4F ， 1wt% 水的乙二醇电解液中， 40V 的电压下反应 2h ，使氟离子达到材料界面并与氧化物发生反应 , 形成带有 -F 末端基团的稳定的氟氧化物层。
第四步 用摄像仪拍下 5ul 去离子水在界面上的静态效果，以确定静态接触角的大小。
所得工件，表面接触角为 10° ，浸润性趋于超亲水状态，在此基础上增加表面粗糙度，将进一步增强界面的亲水性能。（如图 2 ）
如图 3 所示为（ a ）纯钛片、（ b ）氧化处理后的钛片以及氧化处理后再在含 0.1wt% NH4F ， 1wt% 水的乙二醇电解液中， 25 ℃、 40V 的电压下，分别阳极氧化（ c ） 0.5h ；（ d ） 1h ； (e)1.5h ；（ f ） 2h 后的 SEM 图和 5ul 水滴在界面的静态接触角，从图可知界面微观结构变化不大，而接触角呈下降趋势；对界面进一步的成分分析可知，界面氟含量随氟处理时间的延长而增加，这是界面静态接触角变小的直接原因。（如图 4 ）
实施例 2 ：
第一步 材料的前处理：将 Al 材料表面分别用砂纸及化学抛光布打磨干净，依次用分析纯丙酮、乙醇、去离子水在 80KHZ 超声清洗 30min ，分别除去玻璃表面有机以及无机类污染物，用烘箱在 50 ℃ 烘干。
第二步 材料界面的氟氧化处理：在 25 ℃恒温条件及含 3wt% HF ， 8wt% 水的乙二醇电解液中， 40V 的电压下反应 1h ，先由于氧离子与界面作用形成氧化层 , 再使氟离子达到材料界面并与氧化物发生反应，形成带有 -F 末端基团的稳定的氟氧化物层。
第三步 用摄像仪拍下 5ul 去离子水在界面上的静态效果，以确定静态接触角的大小。
所得工件，表面接触角为 4° ，浸润性为超亲水状态，性能优异，稳定性上佳。（如图 2 ）
实施例 3 ：
第一步 材料的前处理：将玻璃片 ( 普通载玻片 ) 依次用分析纯丙酮、乙醇、去离子水在 80KHZ 超声清洗 30min ，分别除去玻璃表面有机以及无机类污染物，用烘箱在 50 ℃ 烘干。
第二步 材料界面的氟化处理：由于玻璃本身为氧化物，所以氧化步骤可以省略，将玻璃片静置于含有 2wt% HF 的水溶液中反应 140min ，温度恒定为 25 ℃，通过扩散作用，使氟离子键接于玻璃表面。
第三步 用摄像仪拍下 3ul 去离子水在界面上的静态效果，以确定静态接触角的大小。
所得工件，表面接触角为 5.5° ，浸润性为超亲水状态，性能优异，稳定性上佳（如图 2 ）。

Claims (9)

  1. 一种金属及类金属的氟氧化亲水处理方法，其特征在于包括如下步骤：
    （ 1 ）材料的前处理：将金属或类金属材料表面打磨干净，依次用丙酮、乙醇、去离子水超声清洗，除去玻璃表面有机以及无机类污染物，烘干；
    （ 2 ）材料界面的氧化处理：将材料在 100 ℃ -1000 ℃ 的空气气氛中煅烧，使材料表面形成一层氧化膜；
    （ 3 ）材料界面的氟化处理：在 10-50 ℃ 恒温条件及较低的氟离子浓度下，利用电迁移或自由扩散的方式，使氟离子达到材料界面并与氧化物发生反应，形成带有 -F 末端基团的稳定的氟氧化物层；
    （ 4 ）所得材料表层氟含量测定以及亲水性能测定：利用 EDS 对材料表层的氟含量进行测定，利用高速摄影仪对水滴在界面上的浸润效果进行表征。
  2. 如权利要求 1 所述的处理方法，其特征在于步骤（ 1 ）中采用砂纸进行打磨，并用化学抛光布进行抛光。
  3. 如权利要求1所述的处理方法，其特征在于步骤（1）中超声清洗的频率为50-100KHZ，烘箱温度为10-100℃。
  4. 如权利要求1所述的处理方法，其特征在于步骤（2）中煅烧的时间为2-10小时。
  5. 如权利要求1所述的处理方法，其特征在于步骤（3）中温度恒定是通过恒温水浴槽来实现，反应容器置于水浴槽中。
  6. 如权利要求1所述的处理方法，其特征在于步骤（3）中所述较低的氟离子浓度是指20%质量以下。
  7. 如权利要求6所述的处理方法，其特征在于步骤（3）中所述较低的氟离子浓度是指10%质量以下。
  8. 权利要求1所述的处理方法，其特征在于所述金属为Ti、Al、Cu、Pb、Fe或镧系金属。
  9. 如权利要求1所述的处理方法，其特征在于所述类金属为Si、Ge、As或Sb。
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CN103693859A (zh) * 2013-12-11 2014-04-02 中山大学 一种玻璃的防雾处理方法
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