Amorphous film capable of preventing silver discoloration and preparation method and application thereof

文档序号：1717607 发布日期：2019-12-17 浏览：31次中文

阅读说明：本技术 一种能够防止银变色的非晶体薄膜及其制备方法与应用 (Amorphous film capable of preventing silver discoloration and preparation method and application thereof ) 是由李家元谢兆凤于 2019-08-22 设计创作，主要内容包括：本发明公开了一种能够防止银变色的非晶体薄膜及其制备方法与应用,所述非晶体中含有氧化钠(Na2O)结构单元、二氧化硅(SiO2)结构单元和三氧化二硼(B2O3)结构单元且三种氧化物中的硅原子、钠原子、硼原子及氧原子间通过化学键连接形成网络体结构。该非晶体薄膜能够与银致密结合,从而对银工件等金属制品起到良好的防护作用,防止其发生变色等腐蚀现象,在光照、水汽及在气氛下能长期有效地防止腐蚀性介质对银工件的侵蚀作用,维持银工件的金属光泽,具有良好的应用前景。(The invention discloses an amorphous film capable of preventing silver from discoloring, and a preparation method and application thereof, wherein the amorphous film contains sodium oxide (Na) 2 O) structural unit, silicon dioxide (SiO) 2 ) Structural unit and boron trioxide (B) 2 O 3 ) The structural unit is formed by connecting silicon atoms, sodium atoms, boron atoms and oxygen atoms in the three oxides through chemical bonds. The amorphous film can be compactly combined with silver, so that the amorphous film has a good protection effect on metal products such as silver workpieces and the like, prevents the metal products from corrosion phenomena such as color change and the like, can effectively prevent corrosive media from corroding the silver workpieces for a long time under illumination, water vapor and atmosphere, maintains the metal luster of the silver workpieces, and has a good application prospect.)

1. an amorphous thin film capable of preventing discoloration of silver, characterized in that: the amorphous material contains Na₂o structural unit, SiO₂Structural unit and B₂O₃The structural unit is formed by connecting silicon atoms, sodium atoms, boron atoms and oxygen atoms in the three oxides through chemical bonds.

2. the amorphous thin film capable of preventing discoloration of silver according to claim 1, wherein: the amorphous thin film is a transparent amorphous thin film of 30 to 50 nm.

3. The amorphous thin film capable of preventing discoloration of silver according to claim 1, wherein: na in the amorphous₂O、SiO₂And B₂O₃The mass ratio of (10-15): (50-60): (20-25).

4. a method for preparing an amorphous thin film capable of preventing discoloration of silver according to any one of claims 1 to 3, comprising: the method comprises the following steps:

S1, preparation of sol:

s01, mixing TEOS and C₂H₆OH and H₂Mixing the O to obtain a solution A;

S02, adding NaOCH₃And CH₃OH is mixed and then transferred into the solution A to obtain a solution B;

S03, mixing HBO₃Mixing with absolute ethyl alcohol, transferring into the solution B to obtain transparent sol;

S2, drying the sol to obtain a gel layer, and carrying out heat treatment on the gel layer in an air atmosphere to obtain the amorphous film, wherein the temperature gradient in the heat treatment process is set as follows:

Heating the mixture from room temperature to (150-210) DEG C, then heating the mixture to (400-500) DEG C after heat preservation, and cooling the mixture to room temperature after heat preservation again.

5. The method of claim 4, wherein: TEOS, C in said step S01₂H₆OH and H₂O is as follows 1: (8-12): (4-6); preferably, the mixing is in a ratio of 1:10: 5.

6. The method of claim 4, wherein: the weight ratio of sodium methoxide to methanol in step S02 is 1: (4-6); preferably 1: 5.

7. The method of claim 4, wherein: HBO in the step S03₃and C₂H₆the weight ratio of OH is 1 (2-6); preferably 1: 5.

8. The method of claim 4, wherein: in the step S2, the temperature rising rate is (0.2-0.6) DEG C/min, the temperature reduction rate is (0.8-1.2)/min, and the time of the two heat preservation treatments is (50-70 min).

9. An article comprising silver, characterized in that: a silver-containing article having a surface provided with a protective layer comprising an amorphous thin film according to any one of claims 1 to 3.

10. A method of making a silver-containing article, comprising: the method comprises the following steps:

I. Preparing sol:

i. TEOS, C₂H₆OH and H₂Mixing the O to obtain a solution A;

ii. Mixing NaOCH₃and CH₃OH is mixed and then transferred into the solution A to obtain a solution B;

iii mixing HBO₃mixing with absolute ethyl alcohol, transferring into the solution B to obtain transparent sol;

II. Coating of the sol: soaking the silver-containing workpiece in the sol prepared in the step I for 20-35 seconds, taking out, and airing to prepare the silver-containing workpiece with the gel thin layer;

and III, carrying out heat treatment on the silver-containing workpiece with the gel thin layer prepared in the step II in an air atmosphere to obtain the silver-containing product, wherein the parameters in the heat treatment process are set as follows:

Technical Field

The invention relates to the technical field of new materials, in particular to an amorphous film capable of preventing silver from discoloring and a preparation method and application thereof.

Background

Silver is a precious metal material with a long history of use, and its use is started from the beginning of jewelry production and is subsequently widely used in the manufacture of currency, tableware, artware, ornaments and the like. However, when silver and its alloy products are used in atmospheric environment, because the atmosphere contains polluting gases, such as hydrogen sulfide, sulfur dioxide, nitrogen dioxide, hydrogen chloride, ozone and the like, electrolyte is formed on the silver surface, so as to cause atmospheric corrosion, and a dark adhesive film is generated on the surface, namely, the silver discoloration phenomenon is caused, thereby affecting the beauty and the use.

Disclosure of Invention

the first technical problem to be solved by the invention is as follows: provided is an amorphous thin film which has excellent weather resistance and can prevent silver discoloration.

The second technical problem to be solved by the invention is: a method for preparing the amorphous thin film is provided.

The third technical problem to be solved by the invention is: the use of the amorphous thin film described above.

In order to solve the first technical problem, the invention adopts the technical scheme that: an amorphous thin film capable of preventing silver discoloration, said amorphous film comprising sodium oxide (Na)₂O) structural unit, silicon dioxide (SiO)₂) Structural unit and boron trioxide (B)₂O₃) The structural unit is formed by connecting silicon atoms, sodium atoms, boron atoms and oxygen atoms in the three oxides through chemical bonds.

Preferably, the amorphous thin film is a transparent amorphous thin film of 30 to 50 nm.

further, Na in the amorphous body₂O、SiO₂and B₂O₃The mass ratio of (10-15): (50-60): (20-25).

Preferably SiO in amorphous₂From Tetraethyl orthosilicate (TEOS) precursor.

Preferably, B in amorphous₂O₃From boric acid (HBO)₃) The precursor is converted to obtain.

preferably Na in the amorphous₂o from sodium methoxide (NaOCH)₃) The precursor is converted to obtain.

The invention has the beneficial effects that: the amorphous film can be compactly combined with silver, so that a good protection effect is achieved on metal products such as silver workpieces and the like, and corrosion phenomena such as color change and the like are prevented; the amorphous film contains silicon oxide, sodium oxide and boron oxide, does not contain heavy metal elements, is environment-friendly and economical, and is combined with silicon, sodium, oxygen and boron through chemical bonds to form a net structure, so that the film is good in flexibility, can be bent and folded, can be combined with silver compactly all the time, is wear-resistant and scratch-resistant, can effectively prevent corrosive media from corroding silver workpieces for a long time under illumination, water vapor and atmosphere, maintains the metallic luster of the silver workpieces, and has a good application prospect.

In order to solve the second technical problem, the invention adopts the technical scheme that: a method for preparing an amorphous thin film capable of preventing silver discoloration, comprising the steps of:

S1, preparation of sol:

S01, mixing TEOS and ethanol (C)₂H₆OH) and water (H)₂O) mixing to obtain a solution A;

s02, adding sodium methoxide (NaOCH)₃) With methanol (CH)₃OH) mixing, and transferring to the solution A to obtain a solution B;

S03 preparation of boric acid (HBO)₃) And anhydrous ethanol (C)₂H₆OH) mixing, and transferring the mixture into the solution B to obtain transparent sol;

S2, drying the sol to obtain a gel layer, and carrying out heat treatment on the gel layer in an air atmosphere to obtain the amorphous film, wherein the parameters in the heat treatment process are as follows:

Further, TEOS, C in the step S01₂H₆OH and H₂O is as follows 1: (8-12): (4-6); preferably, the mixing is in a ratio of 1:10: 5.

Further, step S01 includes mixing TEOS and C₂H₆OH and H₂Mixing O, and standing at room temperature to obtain a solution A; preferably, the reaction time of the standing treatment is (25-40) min; preferably 30 min.

Further, in the step S02, the weight ratio of sodium methoxide to methanol is 1: (4-6); preferably 1: 5.

Further, HBO in the step S03₃And C₂H₆The weight ratio of OH is 1 (2-6); preferably 1: 5.

Further, the temperature rise procedure during the heat treatment is as follows:

Heating from room temperature to 180-220 ℃ at the speed of 0.2-0.8 ℃/min, and then preserving heat for 50-70 min; then heating to 400-500 ℃ at the speed of 0.2-0.8 ℃/min, and then preserving heat for 50-70 min; finally, the temperature is reduced to the room temperature at the speed of 0.8-1.2℃/min.

Preferably, the parameters during the heat treatment are set as follows: heating from room temperature to 200 deg.C at a speed of 0.5 deg.C/min, and maintaining for 60 min; then heating to 450 ℃ at the speed of 0.5 ℃/min, and then preserving heat for 60 min; finally, the temperature is reduced to the room temperature at the speed of 1 ℃/min.

The invention also has the following beneficial effects: the continuous compact transparent amorphous film is prepared through sol-gelation and subsequent heat treatment processes, and when the film is sintered on the surface of metal, the film can be tightly combined with metal so as to avoid the erosion effect of light, water vapor and pollutants in the atmosphere on the metal workpiece.

In order to solve the third technical problem, the invention adopts the technical scheme that: a silver-containing article having a protective layer comprising the amorphous thin film provided on the surface thereof.

Preferably, the silver-containing article comprises at least one of a pure silver article, a silver alloy article, or a silver-plated article.

The preparation method of the silver-containing product comprises the following steps:

I. preparing sol:

i. TEOS, ethanol (C)₂H₆OH) and water (H)₂O) mixing to obtain a solution A;

ii. Sodium methoxide (NaOCH)₃) With methanol (CH)₃OH) mixing, and transferring to the solution A to obtain a solution B;

iii, mixing boric acid (HBO)₃) And anhydrous ethanol (C)₂H₆OH) mixing, and transferring the mixture into the solution B to obtain transparent sol;

And III, carrying out heat treatment on the silver-containing workpiece with the gel thin layer prepared in the step II in an air atmosphere to obtain the silver-containing product, wherein the parameters in the heat treatment process are set as follows: heating the mixture from room temperature to (150-210) DEG C, then heating the mixture to (400-500) DEG C after heat preservation, and cooling the mixture to room temperature after heat preservation again.

further, the temperature rise procedure during the heat treatment is as follows:

the invention also has the following beneficial effects: the film provided by the scheme of the invention is arranged on the surface of a silver-containing workpiece, and can play a good role in protecting silver and other precious metals from corrosion and discoloration.

Detailed Description

In order to explain the technical content, the objects and the effects of the present invention in detail, the following description will be given with reference to the embodiments.

The embodiment 1 of the invention is as follows: an amorphous thin film capable of preventing silver discoloration, the amorphous being formed of SiO₂、Na₂O and B₂O₃three structural units, wherein, SiO₂、Na₂o and B₂O₃The weight ratio of (A) to (B) is 60: 10: 20.

The specific preparation process comprises the following steps:

1. sol preparation: 208.05g TEOS, 2080g C were weighed₂H₆OH and 1040g H₂o, mixing in a 5000ml beaker, and fully hydrolyzing for 30min at room temperature to obtain a solution A; 17.43g of NaOCH₃And 87.16g CH₃Evenly mixing OH, and transferring the OH into the solution A to obtain a transparent solution B; 35.51g of HBO₃And 177.6g C₂H₆And OH is evenly mixed and then transferred into the solution B to obtain transparent sol.

2. coating sol: and (3) soaking the pure silver workpiece in the sol for 30s, then taking out, and naturally airing for 24h to obtain the pure silver workpiece with the gel thin layer attached to the surface.

3. Gel heat treatment: placing the pure silver workpiece attached with the gel thin layer in a well type furnace, and carrying out heat treatment according to the following heat treatment curve under the air atmosphere condition to obtain a pure silver product:

Heating from room temperature to 200 deg.C at a speed of 0.5 deg.C/min, holding for 60min, heating from 200 deg.C to 450 deg.C at a speed of 0.5 deg.C/min, holding for 60min, and cooling to room temperature at a speed of 1 deg.C/min.

The pure silver product coated with the continuous and dense transparent amorphous film obtained by the heat treatment can maintain the metallic luster for a long time even if the pure silver product is placed in corrosive media such as atmospheric atmosphere, hydrogen sulfide atmosphere, sulfur dioxide atmosphere and the like.

In addition, the untreated pure silver and the pure silver product prepared by the operation are soaked in 0.1mol/L sodium sulfide solution, the untreated pure silver is oxidized and discolored after 1min, and the pure silver product plated with the film of the scheme of the invention is not discolored after being placed for 1 month.

The embodiment 2 of the invention is as follows: an amorphous thin film capable of preventing silver discoloration, the amorphous being formed of SiO₂、Na₂O and B₂O₃Three structural units, wherein, SiO₂、Na₂O and B₂O₃The weight ratio of (A) to (B) is 60: 10: 25.

The specific preparation process comprises the following steps:

1. Sol preparation: 208.05g TEOS, 2080g C were weighed₂H₆OH and 1040g H₂o, mixing in a 5000ml beaker, and fully hydrolyzing for 30min at room temperature to obtain a solution A; 17.43g of NaOCH₃And 87.16g CH₃Evenly mixing OH, and transferring the OH into the solution A to obtain a transparent solution B; 44.38g HBO₃And 221.9g C₂H₆And OH is evenly mixed and then transferred into the solution B to obtain transparent sol.

2. Coating sol: and soaking the silver-plated workpiece in the sol for 30sec, taking out, and naturally drying for 24h to obtain the silver workpiece with the gel thin layer attached to the surface.

3. Gel heat treatment: placing the silver-plated workpiece attached with the gel thin layer in a well type furnace, and carrying out heat treatment according to the following heat treatment curve under the air atmosphere condition:

The silver product coated with the continuous and dense transparent amorphous film obtained by the heat treatment is placed in a corrosive medium such as an atmospheric atmosphere, a hydrogen sulfide atmosphere, a sulfur dioxide atmosphere, or the like, and maintains metallic luster for a long time.

The embodiment 3 of the invention is as follows: an amorphous thin film capable of preventing silver discoloration, the amorphous being formed of SiO₂、Na₂O and B₂O₃three structural units, wherein, SiO₂、Na₂O and B₂O₃The weight ratio of (A) to (B) is 60: 15: 20.

The specific preparation process comprises the following steps:

1. Sol preparation: 208.05g TEOS, 2080g C were weighed₂H₆OH and 1040g H₂O, mixing in a 5000ml beaker, and fully hydrolyzing for 30min at room temperature to obtain a solution A; 26.15g of NaOCH₃And 130.74g CH₃Evenly mixing OH, and transferring the OH into the solution A to obtain a transparent solution B; 35.51g of HBO₃And 177.6g C₂H₆And OH is evenly mixed and then transferred into the solution B to obtain transparent sol.

2. coating sol: and soaking the silver-plated workpiece in the sol for 30sec, taking out, and naturally drying for 24h to obtain the silver workpiece with the gel thin layer attached to the surface.

The embodiment 4 of the invention is as follows: an amorphous thin film capable of preventing silver discoloration, the amorphous being formed of SiO₂、Na₂O and B₂O₃Three structural units, wherein, SiO₂、Na₂O and B₂O₃The weight ratio of (A) to (B) is 60: 15: 25.

the specific preparation process comprises the following steps:

1. Sol preparation: 208.05g TEOS, 2080g C were weighed₂H₆OH and 1040g H₂O, mixing in a 5000ml beaker, and fully hydrolyzing for 30min at room temperature to obtain a solution A; 26.15g of NaOCH₃And 130.74g CH₃Evenly mixing OH, and transferring the OH into the solution A to obtain a transparent solution B; 44.38g HBO₃And 221.9g C₂H₆And OH is evenly mixed and then transferred into the solution B to obtain transparent sol.

2. Coating sol: and (3) soaking the pure silver workpiece in the sol for 30sec, then taking out, and naturally airing for 24h to obtain the silver workpiece with the gel thin layer attached to the surface.

The embodiment 5 of the invention is as follows: an amorphous thin film capable of preventing silver discoloration, the amorphous being formed of SiO₂、Na₂O and B₂O₃Three structural units, wherein, SiO₂、Na₂O and B₂O₃The weight ratio of (A) to (B) is 60: 10: 20.

The specific preparation process comprises the following steps:

1. sol preparation: 173.38g TEOS, 1734g C were weighed₂H₆OH and 1040g H₂O, mixing in a 5000ml beaker, and fully hydrolyzing for 30min at room temperature to obtain a solution A; 17.43g of NaOCH₃And 87.16g CH₃Evenly mixing OH, and transferring the OH into the solution A to obtain a transparent solution B; 35.51g of HBO₃And 177.6g C₂H₆and OH is evenly mixed and then transferred into the solution B to obtain transparent sol.

The embodiment 6 of the invention is as follows: an amorphous thin film capable of preventing silver discoloration, the amorphous being formed of SiO₂、Na₂O and B₂O₃Three structural units, wherein, SiO₂、Na₂O and B₂O₃The weight ratio of (A) to (B) is 60: 10: 25.

The specific preparation process comprises the following steps:

1. preparation of solPreparing: 173.38g TEOS, 1734g C were weighed₂H₆OH and 1040g H₂O, mixing in a 5000ml beaker, and fully hydrolyzing for 30min at room temperature to obtain a solution A; 17.43g of NaOCH₃and 87.16g CH₃Evenly mixing OH, and transferring the OH into the solution A to obtain a transparent solution B; 44.38g HBO₃And 221.9g C₂H₆And OH is evenly mixed and then transferred into the solution B to obtain transparent sol.

2. Coating sol: and (3) soaking the silver-cerium alloy workpiece in the sol for 30sec, then taking out, and naturally airing for 24h to obtain the silver workpiece with the gel thin layer attached to the surface.

3. gel heat treatment: placing the silver-cerium alloy workpiece attached with the gel thin layer in a well type furnace, and carrying out heat treatment according to the following heat treatment curve under the air atmosphere condition:

heating from room temperature to 200 deg.C at a speed of 0.5 deg.C/min, holding for 60min, heating from 200 deg.C to 450 deg.C at a speed of 0.5 deg.C/min, holding for 60min, and cooling to room temperature at a speed of 1 deg.C/min.

The embodiment 7 of the invention is as follows: an amorphous thin film capable of preventing silver discoloration, the amorphous being formed of SiO₂、Na₂O and B₂O₃Three structural units, wherein, SiO₂、Na₂O and B₂O₃The weight ratio of (A) to (B) is 60: 15: 20.

the specific preparation process comprises the following steps:

1. Sol preparation: 173.38g TEOS, 1734g C were weighed₂H₆OH and 1040g H₂O, mixing in a 5000ml beaker, and fully hydrolyzing for 30min at room temperature to obtain a solution A; 26.15g of NaOCH₃And 130.74g CH₃Evenly mixing OH, and transferring the OH into the solution A to obtain a transparent solution B; 35.51g of HBO₃And 177.6g C₂H₆And OH is evenly mixed and then transferred into the solution B to obtain transparent sol.

2. Coating sol: and soaking the silver-plated workpiece in the sol for 30sec, taking out, and naturally drying for 24h to obtain the silver workpiece with the gel thin layer attached to the surface.

the embodiment 8 of the invention is as follows: an amorphous thin film capable of preventing silver discoloration, the amorphous being formed of SiO₂、Na₂O and B₂O₃Three structural units, wherein, SiO₂、Na₂o and B₂O₃The weight ratio of (A) to (B) is 60: 15: 25.

the specific preparation process comprises the following steps:

1. Sol preparation: 173.38g TEOS, 1734g C were weighed₂H₆OH and 1040g H₂O, mixing in a 5000ml beaker, and fully hydrolyzing for 30min at room temperature to obtain a solution A; 26.15g of NaOCH₃And 130.74g CH₃Evenly mixing OH, and transferring the OH into the solution A to obtain a transparent solution B; 44.38g HBO₃And 221.9g C₂H₆And OH is evenly mixed and then transferred into the solution B to obtain transparent sol.

2. Coating sol: and soaking the silver-plated workpiece in the sol for 30sec, taking out, and naturally drying for 24h to obtain the silver workpiece with the gel thin layer attached to the surface.

In conclusion, the amorphous film has good weather resistance and the capability of durably preventing silver discoloration, and can effectively prevent the silver from being corroded by corrosive media for a long time, so that the silver can keep metallic luster for a long time.

the above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or directly or indirectly applied to the related technical field are included in the scope of the present invention.

8页详细技术资料下载

Amorphous film capable of preventing silver discoloration and preparation method and application thereof

相关技术

网友询问留言