Low-melting-point glass-based inorganic anticorrosive coating with excellent conductivity and preparation method of low-melting-point glass-based inorganic anticorrosive coating

Abstract

The invention discloses a low-melting-point glass-based inorganic anticorrosive coating with excellent conductivity and a preparation method of the low-melting-point glass-based inorganic anticorrosive coating. The inorganic anticorrosive conductive coating material comprises 80-99.5 parts of a glass base material and 0.5-20 parts of conductive phase powder dispersed in the glass base material, wherein the conductive phase powder adopts a conductive oxide; the preparation process comprises the following steps: 1) mixing glass base materials; 2) melting into molten glass; 3) crushing and introducing a conductive phase; 4) sintering into blocks; 5) crushing and screening the sample; (6) preparing slurry; (7) paint spraying; and 8) sintering and cooling to obtain the paint. The method is simple in process, low in cost, corrosion-resistant, high-temperature-resistant and good in conductivity; after the conductive phase is added, the surface resistivity of the coating is reduced to 102-109 ohms, and the minimum value of the surface resistivity is far higher than that of an existing system.

Description

Technical Field

[0001] The present invention belongs to the field of construction engineering, and particularly relates to a glass-based inorganic anti-corrosion coating with excellent conductivity and a preparation method thereof. Background Art

[0002] In recent years, with the continuous development of industries such as petrochemical and electric power energy in China, the scale of related infrastructure construction has continued to expand. Along with the increase in the level of facilities, the problems of electrochemical corrosion and static electricity accumulation have become increasingly severe. Conducting anti-corrosion and static electricity treatment on relevant important infrastructure will provide important guarantees for the safe operation of infrastructure and energy consumption reduction. Therefore, the development of anti-corrosion and conductive coating materials with excellent multifunctions such as static electricity conduction and anti-corrosion has become the core technical requirement for ensuring facility safety and reducing operation and maintenance costs.

[0003] Currently, the research and development of anti-corrosion and conductive coatings can be mainly divided into two categories: organic and inorganic coating materials. The organic coating system is mainly based on polymer systems such as epoxy resin, polyaniline, and polyacetylene, and has advantages such as excellent conductivity, good flexibility, and easy construction. The latest research shows that the surface resistivity of a 30wt% conductive aniline / epoxy resin anti-static coating can be as low as 4.1×10 7 Ω. However, organic coatings have poor thermal stability and are prone to softening and decomposition in scenarios such as refining pipelines (200~400℃), resulting in resistivity fluctuations and serious risks such as environmental pollution. In the inorganic system, the intrinsic coating materials without doped conductive phases are mainly composed of nitrides, metal alloys, and compounds, and have conductivity similar to that of metals, but the preparation cost is high and it is difficult to be actually applied. The composite inorganic coatings doped with conductive phases generally use insulating systems such as silicates as the substrate and incorporate metals as the conductive phase. Although inorganic materials have strong high-temperature resistance and corrosion resistance, their conductivity is poor, and the process difficulty and cost are extremely high (the sintering temperature is usually >1200℃). After adding the conductive phase, on the one hand, common Ni, Zn powders, and graphite powders are easily oxidized at high temperatures and have poor compatibility with most inorganic oxide substrates and cannot be completely incorporated, making it difficult to meet the requirements of the coating in terms of mechanics, thermology, etc.

[0004] Based on the above problems, the existing technology lacks a low-melting-point glass-based inorganic anti-corrosion and conductive coating doped with conductive oxides that simultaneously takes into account excellent corrosion resistance and excellent static electricity conduction ability. Summary of the Invention

[0005] In order to overcome the deficiencies of the existing technology, the present invention provides a glass-based inorganic anti-corrosion coating with excellent conductivity and a preparation method thereof. A low-melting-point glass-based composite conductive oxide is used as the conductive phase, so as to take into account anti-corrosion and static electricity conduction ability as well as a coating material with relatively low preparation cost. At the same time, a coating process is set, which has excellent corrosion resistance and excellent static electricity conduction ability.

[0006] The technical solution adopted by the present invention to solve its technical problems is as follows:

[0007] I. An all-inorganic composite conductive coating material based on low-melting glass:

[0008] The inorganic anti-corrosion conductive coating material includes a low-melting glass base material and conductive phase powders dispersed in the low-melting glass base material, and the conductive phase powders are made of conductive oxides.

[0009] The material of the all-inorganic composite conductive coating mainly consists of the following components by mass percentage wt%: 80 - 99.5 parts of the low-melting glass base material, 0.5 - 20 parts of the conductive phase powders.

[0010] The low-melting glass base material mainly consists of the following components (wt%): 0.01 - 50 parts of P2O5, 10 - 50 parts of Na2O, 0.01 - 70 parts of Bi2O3, 0.01 - 70 parts of TeO2, 0.01 - 50 parts of PbO2, 0.01 - 50 parts of WO3, 5 - 50 parts of B2O3, 0.01 - 20 parts of K2O, 0.01 - 30 parts of SiO2, and 0.01 - 10 parts of a modification component; the modification component is one or a combination of more of CaF2, NaF, ZnO, ZrO2, Li2O, Al2O3, CaO, NiO, CoO. The above overall glass base material is of low melting point, and the melting point is 300 - 600 °C.

[0011] The main components of the glass base material are a combination of multiple of P2O5, Na2O, Bi2O3, TeO2, PbO2, WO3, B2O3, K2O, SiO2, ensuring that the glass base material can be melted at a relatively low temperature (400 - 800 °C). The remaining components, such as one or more of aF2, NaF, ZnO, ZrO2, Li2O, Al2O3, CaO, NiO, CoO, are used as modification components, which can be used to adjust the physical and chemical stability properties such as impact resistance and corrosion resistance of the base material. In specific implementation, for example, the addition of ZrO2 and Al2O3 can significantly increase the mechanical properties of the material, but the melting point of the glass base will increase to some extent.

[0012] Preferably, Na2O, B2O3, K2O, and CaO in the low-melting glass base material are respectively replaced by salt substances such as Na2CO3, H3BO3, K2CO3, CaCO3 (the mass relationship of the corresponding cations remains unchanged after replacement), and they can be decomposed into the corresponding oxides by themselves during the sintering and melting process.

[0013] The conductive oxide is one of doped tin oxide (such as SnO2:F, indicating SnO2 doped with fluorine, denoted as SnO2:F, abbreviated as FTO, the same below), doped indium oxide (such as In2O3:Sn), doped zinc oxide (such as ZnO:Al), doped cadmium oxide (such as CdO:Yb), and conductive titanium oxide. The total mass fraction of the conductive oxide in the all-inorganic composite conductive coating is 0.5-20%.

[0014] Preferably, the doped mass percentages of the conductive oxide powders are respectively: ITO: 90% In2O3 + 10% SnO2, ATO: 90% SnO2 + 10% Sb2O3, AZO: 90% ZnO + 10% Al2O3, doped cadmium oxide: 95% CdO + 5% Yb2O3, and conductive titanium oxide: Ti2O3, Ti4O7, etc.

[0015] The particle size of the low-melting-point glass base material is 102-104 nm, and the particle size of the conductive phase powder is 10-104 nm.

[0016] Preferably, after the prepared mixed powder meets the requirements of antistatic ability, the proportion of the conductive phase should be reduced as much as possible to ensure that other properties of the glass base material are not modified and at the same time reduce the cost.

[0017] II. A preparation method of an inorganic anti-corrosion conductive coating:

[0018] The preparation process of the coating material of the present invention includes the following steps: 1) mixing the glass base material; 2) melting into glass liquid; 3) pulverizing and introducing the conductive phase; 4) sintering into a block; 5) pulverizing and sieving the sample. In addition, the present invention also discloses the coating process of the inorganic anti-corrosion conductive coating, including: 1) making into a slurry; 2) spraying paint; 3) sintering and cooling into paint.

[0019] The method is specifically divided into:

[0020] 1) First, prepare the coating powder, including the following steps:

[0021] 1.1) Ball-mill and mix the glass base material with a ball mill.

[0022] 1.2) Melt the ball-milled and mixed glass base material at a higher temperature for a longer time to make glass liquid.

[0023] 1.3) Pour out the molten glass liquid, pulverize it, add the conductive phase powder, and then use the ball mill to ball-mill and mix again to form a mixture with the conductive phase evenly dispersed.

[0024] 1.4) Melt the mixture at a lower temperature for a shorter time to make a whole solid, which is used as the block mixture.

[0025] 1.5) Take out the bulk mixture for crushing, and screen out the powder within a specific particle size range for standby;

[0026] 2) First, perform the coating process of the coating powder, including the following steps:

[0027] 2.1) Mix the prepared powder with absolute ethanol and stir evenly to form a gel-like slurry;

[0028] 2.2) Fill the gel-like slurry into a high-atomization pneumatic spray gun, and use the high-atomization pneumatic spray gun to evenly spray the gel-like slurry on a clean sample plate;

[0029] 2.3) After the sprayed sample plate is subjected to high-temperature sintering and then cooled, it is completed.

[0030] In the process step 2.1), the powder containing only the conductive phase of conductive oxides is mixed with absolute ethanol in a ratio of 20:9 to make the dispersion effect more uniform.

[0031] After the inorganic anti-corrosion conductive coating is prepared, it presents the characteristics of being smooth, firm, having strong adsorption ability, and no cracks as a whole. A slight granularity does not affect the performance and application.

[0032] Preferably, the thickness of the coating is preferably several tens to two hundred microns, and the spraying time needs to be controlled.

[0033] In the step 1):

[0034] The ball milling and mixing treatment time for the steps 1.1) and 1.3) is 1 - 5h;

[0035] The melting temperature for the step 1.2) is 400 - 800 °C, and the melting treatment time is 1 - 4h;

[0036] The melting temperature for the step 1.4) is 400 - 500 °C, and the melting treatment time is 0.5 - 1h;

[0037] And the melting temperature of the step 1.2) is higher than that of the step 1.4), and the melting time of the step 1.2) is longer than that of the step 1.4);

[0038] In the step 1.5), the powder with a particle size ≤ 75μm is screened out, and specifically, a 200-mesh sieve can be used for screening treatment.

[0039] In the preparation method step 1.2), it only needs to be completely melted into a liquid state, and it does not need to be a clarified glass liquid. Crystallization after pouring out does not affect the preparation process.

[0040] In step 1.4) of the preparation method, it is only necessary to sinter into a block-like solid with a smooth surface, and it does not need to be melted into a liquid state. To ensure the completeness of the internal sintering, the insulation time can be extended, but the reaction temperature needs to be controlled to ensure that the conductive oxide does not chemically react. For example, if the ITO conductive phase is added and sintered at above 550°C, ITO reacts with the glass base material, greatly reducing the conductivity. If the sintering temperature is lower than 400°C, it may not be sintered into a block, and the sample is always in a rough powder state, resulting in insufficient adsorption capacity of the coating and easy discoloration. Therefore, the sintering temperature can be selected as 450°C.

[0041] Preferably, the crucible used in the sintering and melting process is a SiO2 ceramic crucible or a quartz crucible.

[0042] Preferably, the sintering may be performed as the furnace is heated up or the heating furnace may be preheated to a specified temperature before being placed in the furnace.

[0043] In the step 2):

[0044] The step 2.1) is to mix the powder and anhydrous ethanol in a mass ratio of 20:9 and stir evenly;

[0045] The step 2.3) is to place the sample in an environment of 400-500° C., sinter it into a smooth coating, then take it out, and then cool it down to prepare the coating.

[0046] The thickness of the inorganic anti-corrosion conductive coating is 10 2 ~10 3 μm, the surface resistivity is 10 2 ~10 9 Ω, can withstand high temperature within 400℃.

[0047] It is used as both anti-corrosion and high temperature resistant material.

[0048] The inorganic anti-corrosion conductive coating has both certain electrical conductivity and excellent anti-corrosion and high temperature resistance of inorganic materials, which can effectively prevent problems such as corrosion and static electricity accumulation, and achieve long-term protection of important infrastructure in my country such as substation grounding grids, oil storage tanks, and oil pipelines.

[0049] The coating material of the present invention innovatively proposes a method of doping an inorganic conductive oxide conductive phase into a purely inorganic low-melting point glass base material, which not only retains the original corrosion resistance and high temperature resistance advantages of the inorganic material, but is also prepared through a gradient melting process (400-800°C → 400-500°C), and the conductive phase is introduced while ensuring its integrity (no reaction with the substrate) and uniformity.

[0050] The beneficial effects of the present invention are:

[0051] (1) Using a low-melting glass base material enables the coating powder to be prepared at a lower temperature, avoiding the phenomenon that conductive oxides easily react with the substrate at high temperatures and ensuring the integrity of the conductive phase;

[0052] (2) The conductive oxides bring excellent electrical conductivity, and under the protection of the inorganic coating, the corrosion resistance is also higher than that of the organic coating;

[0053] (3) The lower melting temperature and the preparation method of gradient melting greatly reduce the construction cost;

[0054] (4) The surface resistivity is 10 2 ~10 9 Ω; it can withstand high temperatures below 400°C.

[0055] The process of the present invention is simple, low-cost, corrosion-resistant, high-temperature-resistant and has good electrical conductivity; after adding the conductive phase, the surface resistivity of the coating is reduced to 10 2 ~10 9 Ω, and its lowest value has far exceeded the existing systems (organic antistatic coatings and carbon-based / organic composite coatings), providing a new solution and idea for the research and development of inorganic anti-corrosion conductive coatings and the long-term protection of important infrastructure. Specific embodiments

[0056] In order to enable those skilled in the art to better understand the solution of the present invention, the technical solutions in the embodiments of the invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments.

[0057] Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0058] The embodiments of the present invention are as follows:

[0059] Example 1

[0060] (1) Preparation of a low-melting glass-based inorganic anti-corrosion coating with excellent electrical conductivity, including the following steps:

[0061] 1) Weigh 20 g of P2O5, 17.7 g of H3BO3, 10.3 g of K2CO3, 34.2 g of Na2CO3, 29.5 g of Bi2O3, 0.01 g of TeO2, 0.01 g of PbO2, 0.01 g of WO3, 0.01 g of K2O, 0.01 g of SiO2, 1.7 g of CoO, 2.3 g of NiO, and 1 g of ZrO as the glass base material, and 5 g of the conductive oxide ITO (doping concentration: 90% by mass of In2O3 + 10% by mass of SnO2) powder as the conductive phase.

[0062] 2) Mix the glass powders together and grind them in a planetary ball mill for 2 h to obtain a uniform glass base material;

[0063] 3) Pour the mixed glass base material into a ceramic crucible and place it in a box furnace preheated to 700 °C for melting treatment for 1 h;

[0064] 4) Quickly take out the glass base material melted into a blue-black liquid, pour it on an iron plate, and cool it until it solidifies into a glass (or glass-ceramic that has crystallized) sample;

[0065] 5) Use a pulverizer to grind the above glass sample into powder, add 5 g of ITO powder, and grind the mixture in a ball mill for 2 h to obtain a mixed coating material with uniformly dispersed conductive phase;

[0066] 6) Place the mixture in a ceramic crucible and place it in a box furnace preheated to 450 °C for melting treatment for 0.5 h to obtain a smooth blue-black solid sample melted into one piece;

[0067] 7) Grind the solid sample into powder in a pulverizer and sieve it with a 200-mesh sieve to obtain the coating powder for standby.

[0068] (II) Coating process of a low-melting-point glass-based inorganic anti-corrosion coating with excellent conductivity, including the following steps:

[0069] 1) Take 30 g of the above standby coating powder, mix it with 13.5 g of absolute ethanol, stir evenly, and pour it into a high-atomization pneumatic spray gun;

[0070] 2) Spray the coating on the sample plate, and the spraying time is about 5 s;

[0071] 3) Place the sample plate in a box furnace preheated to 400 °C for sintering for 20 min, and obtain a smooth anti-corrosion conductive coating after cooling.

[0072] Example 2

[0073] (I) Preparation of a low-melting-point glass-based inorganic anti-corrosion coating with excellent conductivity, including the following steps:

[0074] 1) Weigh 20.6 g of P2O5, 18.3 g of H3BO3, 10.6 g of K2CO3, 35.2 g of Na2CO3, 30.5 g of Bi2O3, 0.01 g of TeO2, 0.01 g of PbO2, 0.01 g of WO3, 0.01 g of K2O, 0.01 g of SiO2, 1.8 g of CoO, 2.4 g of NiO, and 1 g of ZrO as the glass base material, and 2 g of the conductive oxide ITO (doping concentration: 90% by mass of In2O3 + 10% by mass of SnO2) powder as the conductive phase.

[0075] 2) Mix the glass powders together and grind them in a planetary ball mill for 2 h to obtain a uniform glass base material.

[0076] 3) Pour the mixed glass base material into a ceramic crucible and place it in a box furnace preheated to 700 °C for melting treatment for 1 h.

[0077] 4) Quickly take out the glass base material melted into a blue-black liquid and pour it on an iron plate to cool until it solidifies into a glass (or glass-ceramic that has crystallized) sample.

[0078] 5) Use a pulverizer to grind the above glass sample into powder, add 5 g of ITO powder, and grind the mixture in a ball mill for 2 h to obtain a mixed coating material with uniformly dispersed conductive phase.

[0079] 6) Place the mixture in a ceramic crucible and put it in a box furnace preheated to 450 °C for melting treatment for 0.5 h to obtain a smooth blue-black solid sample melted into one piece.

[0080] 7) Grind the solid sample into powder in a pulverizer and sieve it with a 200-mesh sieve to obtain the coating powder for standby.

[0081] (II) Coating process of a low-melting-point glass-based inorganic anti-corrosion coating with excellent conductivity, including the following steps:

[0082] 1) Take 30 g of the above standby coating powder, mix it with 13.5 g of absolute ethanol, stir evenly, and pour it into a high-atomization pneumatic spray gun.

[0083] 2) Spray the coating on the sample plate, and the spraying time is about 5 s.

[0084] 3) Place the sample plate in a box furnace preheated to 400 °C for sintering for 20 min, and obtain a smooth anti-corrosion conductive coating after cooling.

[0085] Example 3

[0086] (I) Preparation of a low-melting-point glass-based inorganic anti-corrosion coating with excellent conductivity, including the following steps:

[0087] 1) Weigh 16.8 g of P2O5, 14.9 g of H3BO3, 8.7 g of K2CO3, 28.7 g of Na2CO3, 24.8 g of Bi2O3, 0.01 g of TeO2, 0.01 g of PbO2, 0.01 g of WO3, 0.01 g of K2O, 0.01 g of SiO2, 1.4 g of CoO, 1.9 g of NiO, and 0.8 g of ZrO as the glass base material, and 20 g of the conductive oxide ITO (doping concentration: 90% by mass of In2O3 + 10% of SnO2) powder as the conductive phase.

[0088] 2) Mix the glass powders together and grind them in a planetary ball mill for 2 h to obtain a uniform glass base material.

[0089] 3) Pour the mixed glass base material into a ceramic crucible and place it in a box furnace preheated to 700 °C for melting treatment for 1 h.

[0090] 4) Quickly take out the glass base material melted into a blue-black liquid, pour it on an iron plate, and cool it until it solidifies into a glass (or glass-ceramic that has crystallized) sample.

[0091] 5) Use a pulverizer to grind the above glass sample into powder, add 5 g of ITO powder, and grind the mixture in a ball mill for 2 h to obtain a mixed coating material with uniformly dispersed conductive phase.

[0092] 6) Place the mixture in a ceramic crucible and put it in a box furnace preheated to 450 °C for melting treatment for 0.5 h to obtain a blue-black solid sample with a smooth surface and melted into one piece.

[0093] 7) Grind the solid sample in a pulverizer and sieve it with a 200-mesh sieve to obtain the coating powder for standby.

[0094] (II) Coating process of the low-melting-point glass-based inorganic anti-corrosion coating with excellent conductivity, including the following steps:

[0095] 1) Take 30 g of the above standby coating powder, mix it with 13.5 g of absolute ethanol, stir evenly, and pour it into a high-atomization pneumatic spray gun.

[0096] 2) Spray the coating on the sample plate, and the spraying time is about 5 s.

[0097] 3) Place the sample plate in a box furnace preheated to 400 °C for sintering for 20 min, and after cooling, a smooth anti-corrosion conductive coating is obtained.

[0098] Example 4

[0099] (I) Preparation of the low-melting-point glass-based inorganic anti-corrosion coating with excellent conductivity, including the following steps:

[0100] 1) Weigh 20 g of P2O5, 17.7 g of H3BO3, 10.3 g of K2CO3, 34.2 g of Na2CO3, 29.5 g of Bi2O3, 0.01 g of TeO2, 0.01 g of PbO2, 0.01 g of WO3, 0.01 g of K2O, 0.01 g of SiO2, 1.7 g of CoO, 2.3 g of NiO, and 1 g of ZrO as the glass base material, and 5 g of conductive oxide AZO (doping concentration: 90% ZnO + 10% Al2O3 by mass fraction) powder as the conductive phase.

[0101] 2) Mix the glass powders together and grind them in a planetary ball mill for 2 h to obtain a uniform glass base material.

[0102] 3) Pour the mixed glass base material into a ceramic crucible and place it in a box furnace preheated to 700 °C for melting treatment for 1 h.

[0103] 4) Quickly take out the glass base material melted into a blue-black liquid and pour it on an iron plate to cool until it solidifies into a glass (or glass-ceramic that has crystallized) sample.

[0104] 5) Use a pulverizer to grind the above glass sample into powder, add 5 g of ITO powder, and grind the mixture in a ball mill for 2 h to obtain a mixed coating material with uniformly dispersed conductive phase.

[0105] 6) Put the mixture into a ceramic crucible and place it in a box furnace preheated to 450 °C for melting treatment for 0.5 h to obtain a blue-black solid sample with a smooth surface and fused into one piece.

[0106] 7) Grind the solid sample into powder in a pulverizer and sieve it with a 200-mesh sieve to obtain the coating powder for standby.

[0107] (II) Coating process of a low-melting-point glass-based inorganic anti-corrosion coating with excellent conductivity, including the following steps:

[0108] 1) Take 30 g of the above standby coating powder, mix it with 13.5 g of absolute ethanol, stir evenly, and pour it into a high-atomization pneumatic spray gun.

[0109] 2) Spray the coating on the sample plate, and the spraying time is about 5 s.

[0110] 3) Put the sample plate into a box furnace preheated to 400 °C for sintering for 20 min, and obtain a smooth anti-corrosion conductive coating after cooling.

[0111] Example 5

[0112] (I) Preparation of a low-melting-point glass-based inorganic anti-corrosion coating with excellent conductivity, including the following steps:

[0113] 1) Weigh 20 g of P2O5, 17.7 g of H3BO3, 10.3 g of K2CO3, 34.2 g of Na2CO3, 29.5 g of Bi2O3, 0.01 g of TeO2, 0.01 g of PbO2, 0.01 g of WO3, 0.01 g of K2O, 0.01 g of SiO2, 1.7 g of CoO, 2.3 g of NiO, and 1 g of ZrO as the glass base material, and 5 g of the conductive oxide ATO (doping concentration: 90% by mass SnO2 + 10% Sb2O5) powder as the conductive phase.

[0114] 2) Mix the glass powders together and grind them in a planetary ball mill for 2 h to obtain a uniform glass base material.

[0115] 3) Pour the mixed glass base material into a ceramic crucible and place it in a box furnace preheated to 700 °C for melting treatment for 1 h.

[0116] 4) Quickly take out the glass base material melted into a blue-black liquid and pour it on an iron plate to cool until it solidifies into a glass (or glass-ceramic that has crystallized) sample.

[0117] 5) Use a pulverizer to grind the above glass sample into powder, add 5 g of ITO powder, and grind the mixture in a ball mill for 2 h to obtain a mixed coating material with uniformly dispersed conductive phase.

[0118] 6) Put the mixture into a ceramic crucible and place it in a box furnace preheated to 450 °C for melting treatment for 0.5 h to obtain a blue-black solid sample with a smooth surface and fused into one piece.

[0119] 7) Grind the solid sample into powder in a pulverizer and sieve it with a 200-mesh sieve to obtain the coating powder for standby.

[0120] (2) Coating process of a low-melting-point glass-based inorganic anti-corrosion coating with excellent conductivity, including the following steps:

[0121] 1) Take 30 g of the above standby coating powder, mix it with 13.5 g of absolute ethanol, stir evenly, and pour it into a high-atomization pneumatic spray gun.

[0122] 2) Spray the coating on the sample plate, and the spraying time is about 5 s.

[0123] 3) Put the sample plate into a box furnace preheated to 400 °C for sintering for 20 min, and after cooling, obtain a smooth anti-corrosion conductive coating.

[0124] To verify the improvement of the antistatic ability of the coating material by the doped conductive oxide in the present invention, according to Examples 1-5, a glass base material without adding conductive phase powder was set as Control Group 1, and samples adding undoped pure oxides, namely indium oxide (In2O3), zinc oxide (ZnO) and tin oxide (SnO2), were set as Control Group 2 (1-5).

[0125] To verify the antistatic ability of the present invention, electrochemical tests were carried out. Experiments corresponding to different undoped pure metal oxides were set as controls for comparison. The relationship of the surface resistivity of different components is as follows:

[0126] Table 1: Order of magnitude of surface resistivity of different examples

[0127]

[0128] It can be seen from the above table and situation comparison that adding conductive phases of the point metal oxides ITO, AZO, and ATO can significantly improve the electrical conductivity of the coating. The electrical conductivity of the coating is positively correlated with the content of the added conductive phase. When the content of the added conductive phase reaches 20 wt%, the surface resistivity of the conductive coating is 10 2 Ω. And when the addition amount of these conductive phases such as ITO, AZO, and ATO is 5 wt%, the electrical conductivity of the coating is quite the same. In addition, it can be known from Control Group 1 and Control Group 2 (1-5) that the surface resistivity of the glass base material without adding conductive phase is above 10 12 and can be regarded as an insulator; while adding undoped pure oxides, regardless of the content, cannot change the electrical conductivity of the coating, and the surface resistivity is still above 10 12 and above.

[0129] In summary, based on the bottlenecks of the existing technology (the poor corrosion resistance of organic coatings and the insufficient electrical conductivity of inorganic coatings), this patent innovatively proposes a solution to add a conductive metal oxide as a conductive phase in an inorganic anti-corrosion coating based on a low-melting-point glass base. Combining the results of the examples and the control groups, adding a doped conductive metal oxide significantly improves the electrical conductivity of the inorganic coating, realizes the preparation of a pure inorganic anti-corrosion conductive coating, and can be applied to many important facility constructions with strict requirements for both anti-corrosion and electrical conductivity.

[0130] The above specific embodiments are used to explain and illustrate the present invention, rather than to limit the present invention. Any modifications and changes made to the present invention within the spirit and protection scope of the claims of the present invention fall within the protection scope of the present invention.

Claims

1. An all-inorganic composite conductive coating material based on low-melting glass, characterized in that, The inorganic anti-corrosion conductive coating material includes a low-melting-point glass base material and conductive phase powders dispersed in the low-melting-point glass base material, and the conductive phase powders are made of conductive oxides.

2. The all-inorganic composite conductive coating material based on low-melting-point glass according to claim 1, characterized in that The material of the all-inorganic composite conductive coating mainly consists of the following components by mass percentage wt% Composition: 80 - 99.5 parts of low-melting-point glass base material, 0.5 - 20 parts of conductive phase powders.

3. The inorganic anti-corrosion conductive coating material according to claim 1 or 2, characterized in that: The low-melting-point glass base material mainly consists of the following components (wt%): 0.01 - 50 parts of P2O5, 10 - 50 parts of Na2O, 0.01 - 70 parts of Bi2O3, 0.01 - 70 parts of TeO2, 0.01 - 50 parts of PbO2, 0.01 - 50 parts of WO3, 5 - 50 parts of B2O3, 0.01 - 20 parts of K2O, 0.01 - 30 parts of SiO2 and 0.01 - 10 parts of a modifying component; the modifying component is one or a combination of CaF2, NaF, ZnO, ZrO2, Li2O, Al2O3, CaO, NiO, CoO.

4. The inorganic anti-corrosion conductive coating material according to claim 3, characterized in that: Na2O, B2O3, K2O, and CaO in the low-melting-point glass base material are respectively replaced by salt substances such as Na2CO3, H3BO3, K2CO3, and CaCO3.

5. The inorganic anti-corrosion conductive coating material according to claim 1, characterized in that: The conductive oxide is one of doped tin oxide, doped indium oxide, doped zinc oxide, doped cadmium oxide, and conductive titanium oxide.

6. The inorganic anti-corrosion conductive coating material according to claim 1, characterized in that: The particle size of the low-melting-point glass base material is 102 - 104 nm, and the particle size of the conductive phase powders is 10 - 104 nm.

7. A method for preparing an inorganic anti-corrosion conductive coating applied to the material according to any one of claims 1-6, characterized in that: The method specifically includes: 1) First, prepare the coating powder, including the following steps: 1.1) Ball-mill and mix the glass base material with a ball mill. 1.2) Melt the ball-milled and mixed glass base material at a relatively high temperature for a long time to form a glass liquid. 1.3) Pour out the molten glass liquid, crush it, add the conductive phase powders, and then use the ball mill to ball-mill and mix again to form a mixture. 1.4) Melt the mixture at a relatively low temperature for a short time to form a solid block as the bulk mixture. 1.5) Take out the bulk mixture and crush it, and screen out powders within a specific particle size range. 2) First, perform the coating process of the coating powder, including the following steps: 2.1) Mix the prepared powder with absolute ethanol and stir evenly to form a gel-like slurry. 2.2) Fill the gel-like slurry into a high-atomization pneumatic spray gun, and use the high-atomization pneumatic spray gun to evenly spray the gel-like slurry on a clean sample plate. 2.3) After high-temperature sintering and then cooling the sprayed sample plate, it is prepared.

8. The preparation method of the inorganic anti-corrosion conductive coating according to claim 7, characterized in that: In step 1): The ball milling and mixing treatment time in steps 1.1) and 1.3) is 1-5 h; The melting temperature in step 1.2) is 400-800 °C, and the melting treatment time is 1-4 h; The melting temperature in step 1.4) is 400-500 °C, and the melting treatment time is 0.5-1 h; And the melting temperature in step 1.2) is higher than that in step 1.4), and the melting time in step 1.2) is longer than that in step 1.4); In step 1.5), powders with a particle size ≤ 75 μm are screened out.

9. The preparation method of the inorganic anti-corrosion conductive coating according to claim 7, characterized in that: In step 2): In step 2.1), the powder and absolute ethanol are mixed in a mass ratio of 20:9 and stirred evenly; In step 2.3), the sample plate is placed in an environment of 400-500 °C, sintered into a smooth coating and then taken out, and then cooled to complete the preparation of the coating.

10. Use of the inorganic anti-corrosion conductive coating according to any one of claims 1 to 6 or the inorganic anti-corrosion conductive coating prepared by the preparation method according to any one of claims 7 to 9, characterized in that: Application as both an anti-corrosion and high-temperature resistant material.

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