CN106746673B - A kind of Co-Ni co-doped corrosion-resistant glass and its preparation and use method - Google Patents

Abstract

The invention discloses a Co-Ni co-doped corrosion-resistant glass and its preparation and use method. The raw materials are composed of B ₂ O ₃ , SiO ₂ , Na ₂ O, K ₂ O, Co ₂ O ₃ and Ni ₂ O ₃ , the molar ratio is 0~15:20~40:10~30:10~30:5~25:5~25. Add high-concentration Na ₂ O and K ₂ O to improve the compatibility between glass and concrete, increase the thermal expansion coefficient of glass, and significantly reduce the sealing temperature of glass; the inverse network based on SiO ₂ improves the corrosion resistance of glass and react with CaO in concrete to form a dense CaSiO ₃ layer on the surface of the steel bar to prevent the corrosion of the steel bar; high concentrations of Co ₂ O ₃ and Ni ₂ O ₃ in the glass form a solid solution with a spinel structure, and the oxide layer on the surface of the steel bar Tight lap, significantly enhance the adhesion of glass and steel. The invention has low raw material price, stable process and meets the conditions of practicality and industrialization.

Description

A kind of Co-Ni co-doped corrosion-resistant glass and its preparation and use method

technical field

The invention belongs to the field of glass coatings for metal components, and in particular relates to a Co-Ni co-doped corrosion-resistant glass and a preparation and use method thereof.

Background technique

Reinforced concrete structure is a composite material composed of steel bars and concrete with completely different mechanical properties. It effectively utilizes the tensile properties of steel bars and the compressive properties of concrete, and is widely used in actual construction. However, the corrosion of steel bars in reinforced concrete structures will seriously affect the mechanical properties of steel bars, reduce the bonding force between steel bars and concrete, cause cracking and cracking of concrete, and bring serious safety hazards. At present, researchers at home and abroad mainly reduce the electrochemical corrosion of steel bars in concrete by improving the compactness of reinforced concrete and concrete. Recent studies at home and abroad have also shown that the glass coating on the surface of steel bars can effectively isolate the corrosion of steel bars by concrete. However, how to apply a dense glass coating on the surface of steel bars and maintain good interfacial bonding during long-term service is an urgent problem to be solved in the application process. In addition, the coating itself tends to corrode in concrete, losing its protective effect on the reinforcement.

Contents of the invention

In order to solve the above problems, the present invention provides a Co-Ni co-doped corrosion-resistant glass and its preparation and use method, by adding high-concentration Na ₂ O and K ₂ O and keeping the concentration of the two at 1:1, fully exerting The mixed alkali effect can not only maintain the high alkalinity of the glass and improve its compatibility with concrete, but also increase the thermal expansion coefficient of the glass, reduce the difference between the thermal expansion coefficient of the coating and the steel bar, and significantly reduce the sealing temperature of the glass . The reverse glass network composed of SiO ₂ can not only improve the corrosion resistance of glass, but also react with CaO in concrete to form a dense CaSiO ₃ layer on the surface of the steel bar to further prevent the corrosion of the steel bar. The high concentration of Co ²⁺ and Ni ²⁺ in the glass prepared by melting and quenching can not only act as a reducing agent, effectively prevent the carbonization and excessive oxidation of the steel bar during the sealing process, but also form concentration fluctuations at the sealing interface to promote the formation of spinel The solid solution (Co, Ni) ₂ O ₃ of the stone structure forms a coherent interface with the oxide layer (Fe ₂ O ₃ ) on the surface of the steel bar, which significantly enhances the adhesion between the glass and the steel bar. The preparation raw materials selected by the invention are cheap, the process is stable, and the conditions of practicality and industrialization are met.

The present invention is implemented through the following technical solutions:

A Co-Ni co-doped corrosion-resistant glass is composed of B ₂ O ₃ , SiO ₂ , Na ₂ O, K ₂ O, Co ₂ O ₃ and Ni ₂ O ₃ in a molar ratio of 0~15:20 ~40:10~30:10~30:5~25:5~25, wherein the molar ratio of Na ₂ O and K ₂ O is 1:1; the preferred molar ratio is 0~10:20~30:15~ 25:15~25:10~20:10~20, wherein the molar ratio of Na ₂ O and K ₂ O is 1:1.

The method for preparing the above-mentioned Co-Ni co-doped corrosion-resistant glass comprises the following steps:

(1) Mix the raw materials evenly; melt at 880-1100°C and hold for 1-4 hours; quench the melted glass to obtain a glass frit; then crush the glass frit, grind it or ball mill it , to obtain glass powder after sieving;

(2) Mix glass powder with binder, dispersant and solvent to form a slurry, and disperse evenly by ball milling in a ball mill; tape casting, natural drying, and then cutting into the desired shape of the embryo body.

The binder in the step (2) is one or a mixture of epoxy resin, methyl cellulose, polyvinyl butyral and polyvinyl alcohol.

The dispersant in the step (2) is one or a mixture of fish oil, polyacrylic acid, polyvinyl alcohol and polyacrylamide.

The solvent in the step (2) is one or a mixture of water, ethanol, isopropanol, n-butanol, toluene, xylene and acetone.

Place the embryo body at the part to be sealed, raise the temperature in an electric furnace at a rate of 1-5°C/min, keep it at 300-400°C for 0.5-2 hours, and then raise the temperature to 550-650°C at a rate of 1-5°C/min Treat for 0.5-2 hours.

Significant advantage of the present invention is:

(1) By adding high-concentration Na ₂ O and K ₂ O and keeping the concentration of the two at 1:1, the mixed alkali effect can be fully exerted, which can not only maintain the high alkalinity of the glass and improve its compatibility with concrete, but also can Increase the thermal expansion coefficient of the glass, reduce the difference between the thermal expansion coefficient of the coating and the steel bar, and significantly reduce the sealing temperature of the glass;

(2) The reverse glass network composed of SiO ₂ can not only improve the corrosion resistance of glass, but also react with CaO in concrete to form a dense CaSiO ₃ layer on the surface of the steel bar to further prevent the corrosion of the steel bar;

(3) The high concentration of Co ²⁺ and Ni ²⁺ in the glass prepared by melting and quenching can not only act as a reducing agent to effectively prevent the carbonization and excessive oxidation of steel bars during the sealing process, but also form concentration fluctuations at the sealing interface to promote the formation of The solid solution (Co, Ni) ₂ O ₃ with spinel structure forms a coherent interface with the oxide layer (Fe ₂ O ₃ ) on the surface of the steel bar, which significantly enhances the adhesion between the glass and the steel bar;

(4) High concentration of Ni ₂ O ₃ can reduce the surface tension of the coating, improve the sealing performance, and further improve the adhesion between glass and steel bars;

(5) The preparation raw materials selected in the present invention are cheap, the process is stable, and the conditions for practical and industrialization are met.

Detailed ways

A Co-Ni co-doped corrosion-resistant glass is composed of B ₂ O ₃ , SiO ₂ , Na ₂ O, K ₂ O, Co ₂ O ₃ and Ni ₂ O ₃ in a molar ratio of 0~15:20 ~40:10~30:10~30:5~25:5~25.

The method for preparing the above-mentioned Co-Ni co-doped corrosion-resistant glass comprises the following steps:

(1) Mix the raw materials evenly; melt at 880-1100°C and hold for 1-4 hours; quench the melted glass to obtain a glass frit; then crush the glass frit, grind it or ball mill it , to obtain glass powder after sieving;

(2) Mix glass powder with binder, dispersant and solvent to form a slurry, and disperse evenly by ball milling in a ball mill; tape casting, natural drying, and then cutting into the desired shape of the embryo body.

The binder in the step (2) is one or a mixture of epoxy resin, methyl cellulose, polyvinyl butyral and polyvinyl alcohol.

The dispersant in the step (2) is one or a mixture of fish oil, polyacrylic acid, polyvinyl alcohol and polyacrylamide.

The solvent in the step (2) is one or a mixture of water, ethanol, isopropanol, n-butanol, toluene, xylene and acetone.

Place the embryo body at the part to be sealed, raise the temperature in an electric furnace at a rate of 1-5°C/min, keep it at 300-400°C for 0.5-2 hours, and then raise the temperature to 550-650°C at a rate of 1-5°C/min Treat for 0.5-2 hours.

Table 1 is the sealing glass composition table (mol percentage) in embodiment 1-4

Embodiment 1: Preparation and sealing of materials

According to the ratio of each component in Example 1 in Table 1, weigh a certain amount of analytically pure raw materials (B ₂ O ₃ , SiO ₂ , Na ₂ O, K ₂ O, Co ₂ O ₃ and Ni ₂ O ₃ ) , mixed evenly with a planetary ball mill for 24 hours; then put the powder into a platinum crucible, place it in the air atmosphere of a box-type resistance furnace, heat it to 1100°C at 3°C/min, and keep it warm for 1 hour; then, take out the crucible, put The melt is poured into deionized water for rapid cooling, and dried to obtain fragments of the glass melt; ground and passed through a 100-mesh sieve to obtain glass powder. Mix glass powder with polyvinyl alcohol, fish oil, ethanol and toluene (80%, 2%, 1%, 10%, 7% by weight) to form a slurry, and disperse evenly in a ball mill; tape casting, natural Dry, then cut into the embryo body of the desired shape; place the embryo body on the part to be sealed, heat up in an electric furnace at a rate of 2°C/min, keep it at 400°C for 1 hour, and then heat up at a rate of 2°C/min to 650°C for 2 hours. This example is a preferred composition. Pour the heat-preserved melt into a preheated stainless steel abrasive tool to obtain a glass cylinder with Φ=10mm and d=25mm, and test it on a NETZSCH DIL 402EP thermal dilatometer at a heating rate of 10°C/min to obtain the glass line Coefficient of expansion. Co ₂ O ₃ and Ni ₂ O ₃ are both added in an amount of 10%, and the linear expansion coefficient of the glass is 1.09×10 ^-5 /K. The glass cylinder undergoes accelerated corrosion in cement at 80°C, and the corrosion rate is 0.048%/day. The pull-off method test shows that the interface bonding force between the glass coating and the steel bar is 43MPa.

Embodiment 2: Preparation and sealing of materials

According to the ratio of each component in Example 2 in Table 1, weigh a certain amount of analytically pure raw materials (B ₂ O ₃ , SiO ₂ , Na ₂ O, K ₂ O, Co ₂ O ₃ and Ni ₂ O ₃ ) , mixed evenly with a planetary ball mill for 24 hours; then put the powder into a platinum crucible, place it in the air atmosphere of a box-type resistance furnace, heat it to 1020°C at 3°C/min, and keep it warm for 1 hour; then, take out the crucible, put The melt is poured into deionized water for rapid cooling, and dried to obtain fragments of the glass melt; ground and passed through a 100-mesh sieve to obtain glass powder. Mix glass powder with methylcellulose, polyvinyl alcohol, n-butanol and acetone (82%, 2%, 2%, 8%, 6% by weight) to form a slurry, and disperse evenly in a ball mill; Stretching, drying naturally, and then cutting the embryo body into the desired shape; placing the embryo body on the part to be sealed, heating it in an electric furnace at a rate of 2°C/min, keeping it at 380°C for 1 hour, and then heating it at 2°C/min The rate of min was raised to 620°C for 1 hour. This example is a preferred composition. Pour the heat-preserved melt into a preheated stainless steel abrasive tool to obtain a glass cylinder with Φ=10mm and d=25mm, and test it on a NETZSCH DIL 402EP thermal dilatometer at a heating rate of 10°C/min to obtain the glass line Coefficient of expansion. Co ₂ O ₃ and Ni ₂ O ₃ are both added in an amount of 12.5%, and the linear expansion coefficient of the glass is 1.19×10 ^-5 /K. The glass cylinder undergoes accelerated corrosion in cement at 80°C, and its corrosion rate is 0.047%/day. The pull-off method test shows that the interface bonding force between the glass coating and the steel bar is 45MPa.

Embodiment 3: Preparation and sealing of materials

According to the ratio of each component in Example 3 in Table 1, weigh a certain amount of analytically pure raw materials (B ₂ O ₃ , SiO ₂ , Na ₂ O, K ₂ O, Co ₂ O ₃ and Ni ₂ O ₃ ) , mixed evenly with a planetary ball mill for 24 hours; then put the powder into a platinum crucible, place it in the air atmosphere of a box-type resistance furnace, heat it to 960°C at 3°C/min, and keep it warm for 1 hour; then, take out the crucible, put The melt is poured into deionized water for rapid cooling, and dried to obtain fragments of the glass melt; ground and passed through a 100-mesh sieve to obtain glass powder. Mix glass powder with epoxy resin, polyacrylamide, isopropanol and toluene (84%, 1.5%, 0.5%, 9%, 5% by weight) to form a slurry, and disperse evenly in a ball mill; casting Shaping, drying naturally, and then cutting into the embryo body of the desired shape; place the embryo body on the part to be sealed, heat up at a rate of 2°C/min in an electric furnace, keep it at 360°C for 1 hour, and then heat it at 2°C/min The rate of heating was raised to 580°C for 1 hour. This example is a preferred composition. Pour the heat-preserved melt into a preheated stainless steel abrasive tool to obtain a glass cylinder with Φ=10mm and d=25mm, and test it on a NETZSCH DIL 402EP thermal dilatometer at a heating rate of 10°C/min to obtain the glass line Coefficient of expansion. Co ₂ O ₃ and Ni ₂ O ₃ are both added in an amount of 15%, and the linear expansion coefficient of the glass is 1.37×10 ^-5 /K. The glass cylinder undergoes accelerated corrosion in cement at 80°C, and the corrosion rate is 0.026%/day. The pull-off method test shows that the interface bonding force between the glass coating and the steel bar is 49MPa.

Embodiment 4: Preparation and sealing of materials

According to the ratio of each component in Example 4 in Table 1, weigh a certain amount of analytically pure raw materials (B ₂ O ₃ , SiO ₂ , Na ₂ O, K ₂ O, Co ₂ O ₃ and Ni ₂ O ₃ ) , mixed evenly with a planetary ball mill for 24 hours; then put the powder into a platinum crucible, place it in the air atmosphere of a box-type resistance furnace, heat it to 880°C at 3°C/min, and keep it warm for 1 hour; then, take out the crucible, put The melt is poured into deionized water for rapid cooling, and dried to obtain fragments of the glass melt; ground and passed through a 100-mesh sieve to obtain glass powder. Mix glass powder with polyvinyl butyral, polyacrylic acid, isopropanol and acetone (83%, 2%, 1%, 9%, 5% by weight) to form a slurry, and disperse evenly in a ball mill; Tape casting, dry naturally, and then cut into the embryo body of the desired shape; place the embryo body on the part to be sealed, heat up in an electric furnace at a rate of 2 °C/min, keep it at 340 °C for 1 hour, and then heat it at 2 °C /min rate to 550°C for 1 hour. This example is a preferred composition. Pour the heat-preserved melt into a preheated stainless steel abrasive tool to obtain a glass cylinder with Φ=10mm and d=25mm, and test it on a NETZSCH DIL 402EP thermal dilatometer at a heating rate of 10°C/min to obtain the glass line Coefficient of expansion. Co ₂ O ₃ and Ni ₂ O ₃ are both added in an amount of 20%, and the linear expansion coefficient of the glass is 1.42×10 ^-5 /K. The glass cylinder undergoes accelerated corrosion in cement at 80°C, and the corrosion rate is 0.015%/day. The pull-off method test shows that the interface bonding force between the glass coating and the steel bar is 52MPa.

The present invention obtains glass that can be sealed at low temperature through the above implementation. Its remarkable effect is mainly reflected in the good corrosion resistance and excellent interfacial bonding force of glass in cement.

The above descriptions are only preferred embodiments of the present invention, and all equivalent changes and modifications made according to the scope of the patent application of the present invention shall fall within the scope of the present invention.

Claims (4)

1. the anti-corrosion glass that a kind of Co-Ni is co-doped with, it is characterised in that: raw material group becomes B₂O₃、SiO₂、Na₂O、K₂O、Co₂O₃With Ni₂O₃, molar ratio is 0 ~ 10:20 ~ 30:15 ~ 25:15 ~ 25:10 ~ 20:10 ~ 20；Wherein Na₂O and K₂The molar ratio of O is 1:1； The preparation method of the anti-corrosion glass that the Co-Ni is co-doped with the following steps are included:

(1) raw material is uniformly mixed；It is melted by 880-1100 DEG C, soaking time 1-4 hours；To the glass metal melted, into Row chilling obtains glass frit；Then, glass frit is crushed, grinding or ball milling obtain glass powder after sieving；

(2) glass powder and binder, dispersing agent and solvent are mixed into slurry, ball milling disperses in the ball mill；Curtain coating Molding spontaneously dries, is then cut into the green body of required shape.

2. the anti-corrosion glass that Co-Ni according to claim 1 is co-doped with, it is characterised in that: the binder of the step (2) is The mixture of one or more of epoxy resin, methylcellulose, polyvinyl butyral and polyvinyl alcohol.

3. the anti-corrosion glass that Co-Ni according to claim 1 is co-doped with, it is characterised in that: the dispersing agent of the step (2) is The mixture of one or more of fish oil, polyacrylic acid, polyvinyl alcohol and polyacrylamide.

4. the anti-corrosion glass that Co-Ni according to claim 1 is co-doped with, it is characterised in that: the solvent of the step (2) is The mixture of one or more of water, ethyl alcohol, isopropanol, n-butanol, toluene, dimethylbenzene and acetone.