KR20070066731A - Method for preparing graphite coated with titanium hydroxid - Google Patents

Method for preparing graphite coated with titanium hydroxid Download PDF

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KR20070066731A
KR20070066731A KR1020050128194A KR20050128194A KR20070066731A KR 20070066731 A KR20070066731 A KR 20070066731A KR 1020050128194 A KR1020050128194 A KR 1020050128194A KR 20050128194 A KR20050128194 A KR 20050128194A KR 20070066731 A KR20070066731 A KR 20070066731A
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graphite
graphite powder
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titanium alkoxide
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KR100740632B1 (en
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이석근
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재단법인 포항산업과학연구원
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material

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Abstract

A method for preparing graphite coated with titanium hydroxide, which saves energy, prolongs the service life of refractories, and stabilizes ironmaking and steelmaking processes accordingly by coating the surface of graphite powder with titanium hydroxide, thereby reducing thermal conductivity of graphite and enhancing oxidation resistance of graphite, is provided. A method for preparing coated graphite comprises the steps of: mixing 4 to 55 weight parts of graphite powder with 100 weight parts of a solution obtained by dissolving 0.02 to 0.95 mol/L of titanium alkoxide into ethanol to prepare a slurry; filtering the slurry to coat the surface of the graphite powder with the titanium alkoxide; mixing 5 to 65 weight parts of the titanium alkoxide coated graphite powder with 100 weight parts of a solution obtained by dissolving 0.05 to 0.7 mol/L of water into ethanol to pyrolyze the titanium alkoxide on the surface of the graphite powder; and filtering the solution, and drying the filtered solution to coat the surface of the graphite powder with titanium hydroxide.

Description

수산화티타늄이 코팅된 흑연의 제조방법{METHOD FOR PREPARING GRAPHITE COATED WITH TITANIUM HYDROXID}Titanium Hydroxide Coated Graphite Production Method {METHOD FOR PREPARING GRAPHITE COATED WITH TITANIUM HYDROXID}

도 1은 본 발명의 수산화티타늄이 코팅된 흑연의 제조방법에 의해서 제조된 수산화티타늄이 코팅된 흑연분말의 표면을 200배 확대하여 찍은 주사전자현미경 사진.1 is a scanning electron microscope photograph taken by enlarging the surface of the titanium hydroxide coated graphite powder prepared by the method for producing titanium hydroxide coated graphite of the present invention 200 times.

본 발명은 흑연의 코팅 제조방법에 관한 것으로, 더욱 상세하게는 흑연에 수산화티타늄을 코팅하여 저열전도성 및 내산화성을 향상시키는 흑연의 코팅 제조방법에 관한 것이다.The present invention relates to a method for producing a coating of graphite, and more particularly to a method for producing a coating of graphite to improve the low thermal conductivity and oxidation resistance by coating titanium hydroxide on the graphite.

근래에는 에너지 다소비 산업인 제철, 제강산업의 특성상 에너지 절약을 실현하기 위해서는 저열전도성 내화물의 개발이 요구되고 있으며, 이에 대한 연구가 전세계적으로 이루어지고 있다. 특히, 흑연계 내화물의 열전도성을 저감하기 위해서는 무엇보다도 흑연의 높은 열전도율을 낮추는 것이 필요하다.Recently, the development of low thermal conductivity refractory material is required to realize energy saving due to the characteristics of the steel-making industry, which is an energy-saving industry, and research on this is being conducted worldwide. In particular, in order to reduce the thermal conductivity of graphite-based refractory materials, it is necessary to lower the high thermal conductivity of graphite above all.

흑연의 화학성분은 탄소로서, 거의 순수한 탄소로 이루어지며 높은 열전도 도, 낮은 탄성계수, 낮은 열팽창계수와 2700℃까지 온도에 따라 증가하는 비교적 만족할 만한 강도를 가지고 있으며, 또한, 낮은 밀도와 가공의 용이함 등으로 고온구조용 재료로 많은 장점을 지니고 있고, 용강에 대한 내식성이 우수하여 제철 및 제강산업의 내화재료로 이용되는 가장 중요한 물질 중의 하나이다.The chemical composition of graphite is carbon, which is composed of almost pure carbon and has high thermal conductivity, low modulus of elasticity, low coefficient of thermal expansion and relatively satisfactory strength which increases with temperature up to 2700 ° C. Also, low density and ease of processing It has many advantages as a material for high temperature structure, etc., and is excellent in corrosion resistance to molten steel and is one of the most important materials used as a fireproof material in the steel and steel industry.

그러나 상기와 같은 흑연은 약 500℃이상의 고온에서 산소와 반응하여 표면이 마모되고 고온에서 상당한 증발속도를 가지며, 고온기체의 흐름에서 마모 현상이 심하기 때문에 흑연 함유 내화물 수명을 제한하는 원인이 된다. 또한, 판상의 흑연과 산화물 분체와의 균일한 혼합이 어렵고 소수성 표면을 갖기 때문에 제조공정에 수계를 이용할 수 없는 등이 흑연의 응용을 제한하는 가장 큰 문제점으로 지적되어 왔다.However, the graphite as described above reacts with oxygen at a high temperature of about 500 ° C. or more, wears a surface and has a significant evaporation rate at a high temperature, and causes a severe wear phenomenon in the flow of high temperature gas, thereby limiting the graphite-containing refractory life. In addition, it has been pointed out that the uniform problem of plate-like graphite and oxide powder is difficult and the hydrophobic surface cannot be used, so that an aqueous system cannot be used in the manufacturing process.

본 발명은 상기와 같은 문제점을 감안하여 안출한 것으로서, 흑연분말 표면을 수산화티타늄으로 코팅하여 흑연의 열전도도를 감소시켜 에너지 절약시키고, 내산화성 증진에 의한 내화물 수명 연장이 가능하고, 이에 따른 제철 및 제강 조업공정의 안정화가 가능한 수산화티타늄이 코팅된 흑연의 제조방법을 제공하는 것이다.The present invention has been made in view of the above problems, by coating the surface of the graphite powder with titanium hydroxide to reduce the thermal conductivity of the graphite to save energy, it is possible to extend the refractory life by increasing the oxidation resistance, according to steelmaking and It is to provide a method for producing titanium hydroxide coated graphite capable of stabilizing the steelmaking operation process.

상기와 같은 목적을 달성하기 위한 본 발명은 흑연의 코팅 제조방법으로서, 티타늄 알콕사이드를 에탄올에 녹인 용액 100 중량부에 흑연분말을 4 내지 55 중량부를 혼합하여 슬러리를 제조하는 단계와, 상기 슬러리를 필터링하여, 상기 흑연분말 표면에 상기 티타늄 알콕사이드를 코팅하는 단계와, 물을 에탄올에 녹인 용액 100 중량부에 상기 티타늄 알콕사이드가 코팅된 흑연분말을 5 내지 65 중량부를 혼합하여 흑연분말 표면의 티타늄 알콕사이드를 가수분해하는 단계와, 상기 용액을 필터링하고, 건조시켜서 흑연분말 표면에 수산화티타늄을 코팅하는 단계를 포함하는 것을 특징으로 한다.The present invention for achieving the above object is a method for producing a coating of graphite, to prepare a slurry by mixing 4 to 55 parts by weight of graphite powder to 100 parts by weight of a solution of titanium alkoxide dissolved in ethanol, and filtering the slurry The titanium alkoxide is coated on the surface of the graphite powder, and 5 to 65 parts by weight of the titanium alkoxide-coated graphite powder is mixed with 100 parts by weight of a solution of water dissolved in ethanol to add titanium alkoxide to the surface of the graphite powder. Decomposing and filtering the solution, and drying to coat the titanium hydroxide on the surface of the graphite powder.

상기 슬러리를 제조하는 단계는, 상기 에탄올에 혼합되는 티타늄 알콕사이드가 0.02mol/L 내지 0.95mol/L의 농도로 사용되는 것이 바람직하다.In the preparing of the slurry, the titanium alkoxide mixed in the ethanol is preferably used at a concentration of 0.02 mol / L to 0.95 mol / L.

상기 가수분해 단계는, 상기 에탄올에 혼합되는 물이 0.05mol/L 내지 0.7mol/L의 농도로 사용되는 것이 바람직하다.In the hydrolysis step, water mixed with the ethanol is preferably used at a concentration of 0.05 mol / L to 0.7 mol / L.

이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

먼저, 티타늄 알콕사이드를 에탄올에 녹인 용액 100 중량부에 흑연분말을 4 내지 55 중량부를 혼합하여 슬러리를 제조한다.First, a slurry is prepared by mixing 4 to 55 parts by weight of graphite powder to 100 parts by weight of a solution in which titanium alkoxide is dissolved in ethanol.

에탄올에 희석되는 티타늄 알콕사이드는 통상의 티타늄 알콕사이드를 사용할 수 있으며, 균일한 코팅층의 형성과 내산화성의 증진효과를 얻기 위하여 티타늄 테트라 에톡사이드(Ti tetra-Ethoxide)를 사용하는 것이 바람직하다.Titanium alkoxide diluted in ethanol may use a conventional titanium alkoxide, it is preferable to use titanium tetra ethoxide (Ti tetra-Ethoxide) in order to obtain a uniform coating layer formation and enhancement effect of oxidation resistance.

티타늄 알콕사이드가 에탄올 용매에 희석되는 농도는 0.02mol/L 내지 0.95mol/L의 농도로 사용하는 것이 바람직하고, 더욱 바람직하게는 0.10mol/L 내지 0.7mol/L인 것이다. 상기 티타늄 알콕사이드가 0.02mol/L 농도 미만일 경우에는 흑연분말 표면에 코팅되는 수산화티타늄의 양이 너무 적어 코팅 효과가 거의 없다는 문제점이 있으며, 0.95mol/L 농도를 초과할 경우에는 수산화티타늄이 흑연분말 표 면에 불균질하게 코팅되어 코팅공정의 조절이 어려우며, 경제성 또한 나쁘다는 문제점이 있다.The concentration at which the titanium alkoxide is diluted in the ethanol solvent is preferably used at a concentration of 0.02 mol / L to 0.95 mol / L, more preferably 0.10 mol / L to 0.7 mol / L. When the titanium alkoxide is less than 0.02 mol / L concentration, the amount of titanium hydroxide coated on the surface of the graphite powder is too small to have a coating effect. When the titanium alkoxide concentration exceeds 0.95 mol / L, the titanium hydroxide is in the graphite powder table. Inhomogeneous coating on the surface is difficult to control the coating process, there is a problem that the economic efficiency is also bad.

한편, 티타늄 알콕사이드 용액에 혼합되는 흑연분말은 통상의 천연 흑연, 인조 흑연, 또는 시판되고 있는 제품을 사용할 수도 있음은 물론이며, 적당한 크기로 분쇄시켜 사용할 수 있으며, 특정한 형상이나 크기에 제한을 받지 않는다.On the other hand, the graphite powder mixed in the titanium alkoxide solution may be used as a natural graphite, artificial graphite, or commercially available products, of course, can be used by grinding to a suitable size, without being limited to a specific shape or size. .

그리고 흑연분말은 티타늄 알콕사이드 용액 100 중량부에 대하여 4 내지 55 중량부로 포함되는데, 그 함량이 4 중량부 미만일 경우에는 제조 및 생산 효율성이 떨어진다는 문제점이 있으며, 55 중량부를 초과할 경우에는 슬러리의 혼합성이 저하되고 또한 흑연분말 표면에 수산화티타늄의 코팅 양이 적어진다는 문제점이 있다.And the graphite powder is included in the 4 to 55 parts by weight based on 100 parts by weight of titanium alkoxide solution, if the content is less than 4 parts by weight has a problem that the manufacturing and production efficiency is lowered, if it exceeds 55 parts by weight of the slurry mixture There is a problem that the property is lowered and the amount of titanium hydroxide coated on the graphite powder surface is reduced.

다음으로 제조된 슬러리를 필터링하여 용액을 제거하고, 흑연분말 표면에 티타늄 알콕사이드를 코팅한다.Next, the prepared slurry is filtered to remove the solution, and titanium alkoxide is coated on the graphite powder surface.

슬러리에 포함된 용액을 제거하는 방법은 필터를 사용하여 걸러내는 방식의 필터링법 이외에도 원심분리기를 사용하여 각각의 물질로 분리하는 원심분리법 등 여러가지 방법이 있을 수 있으며, 소기의 목적만 달성될 수 있다면 특별히 그 방법을 제한할 필요는 없다.The method of removing the solution contained in the slurry may include various methods such as a centrifugal separation method using a centrifugal separator in addition to the filtering method using a filter, and if the desired purpose can be achieved. There is no need to specifically limit the method.

슬러리를 필터링하여 용액을 제거하면, 티타늄 알콕사이드가 표면에 코팅된 흑연분말이 얻어진다.When the slurry is filtered to remove the solution, graphite powder coated with titanium alkoxide is obtained.

다음으로, 물을 에탄올에 녹인 용액 100 중량부에 상기 티타늄 알콕사이드가 코팅된 흑연분말을 5 내지 65 중량부를 혼합하여, 흑연분말 표면의 티타늄 알콕사 이드를 가수분해한다.Next, 5 to 65 parts by weight of the graphite powder coated with titanium alkoxide is mixed with 100 parts by weight of a solution of water dissolved in ethanol to hydrolyze the titanium alkoxide on the surface of the graphite powder.

흑연분말에 코팅된 티타늄 알콕사이드를 가수분해시키기 위하여 사용되는 물은 에탄올 용매에 희석하여 사용하는데 0.05mol/L 내지 0.7mol/L의 농도로 사용하는데, 그 함량이 0.05mol/L 미만일 경우에는 가수분해 반응이 일어나지 않거나 그 반응속도가 너무 느려 제조 및 생산효율성이 떨어진다는 문제점이 있으며, 0.7mol/L를 초과할 경우에는 가수분해 반응이 너무 빨리 진행되어 코팅성이 나빠지며 결과적으로 흑연 표면에 수산화티타늄을 균일하게 코팅시킬 수가 없다는 문제점이 발생한다.Water used to hydrolyze the titanium alkoxide coated on the graphite powder is diluted in an ethanol solvent and used at a concentration of 0.05 mol / L to 0.7 mol / L. If the content is less than 0.05 mol / L, the hydrolysis is used. There is a problem that the reaction does not occur or the reaction rate is too slow to reduce the production and production efficiency. When it exceeds 0.7 mol / L, the hydrolysis reaction proceeds too fast, resulting in poor coating properties, and consequently titanium hydroxide on the graphite surface. There is a problem that can not be uniformly coated.

한편, 티타늄 알콕사이드가 표면에 코팅된 흑연분말은 물을 에탄올에 녹여 희석한 용액 100 중량부에 대하여 5 내지 65 중량부로 포함되는데, 그 함량이 5 중량부 미만일 경우에는 제조 및 생산 효율성이 떨어진다는 문제점이 있으며, 65 중량부를 초과할 경우에는 슬러리의 혼합성이 저하되고 또한 흑연 표면에 수산화티타늄의 코팅 양이 너무 적어진다는 문제점이 있다.On the other hand, the graphite powder coated on the surface of titanium alkoxide is contained in 5 to 65 parts by weight based on 100 parts by weight of a solution diluted by dissolving water in ethanol, when the content is less than 5 parts by weight, the production and production efficiency is reduced There is a problem that, when it exceeds 65 parts by weight, the slurry's miscibility is lowered and the amount of titanium hydroxide coated on the graphite surface is too small.

마지막으로, 물,에탄올 및 흑연분말이 혼합된 상기 용액을 필터링하여 용매를 제거하고, 건조시켜 흑연분말 표면에 수산화티타늄을 코팅한다.Finally, the solvent mixed with water, ethanol and graphite powder is filtered to remove the solvent and dried to coat titanium hydroxide on the surface of the graphite powder.

흑연분말 표면의 티타늄 알콕사이드를 가수분해한 후 용매를 제거하기 위하여, 상술한 바와 같이 필터링법, 원심분리법 등 여러가지 방법을 사용하여 용매를 제거고 난 뒤 흑연분말을 건조시켜 그 표면에 수산화티타늄을 코팅하는 것이다.In order to remove the solvent after hydrolysis of the titanium alkoxide on the surface of the graphite powder, the solvent is removed by various methods such as filtering and centrifugation as described above, and then the graphite powder is dried to coat titanium hydroxide on the surface. It is.

이하, 본 발명을 하기 실시예를 참조로 하여 설명한다. 그러나, 이들 실시예 는 본 발명을 예시하기 위한 것일 뿐, 본 발명이 이에 제한되는 것은 아니다.Hereinafter, the present invention will be described with reference to the following examples. However, these examples are only for illustrating the present invention, the present invention is not limited thereto.

<실시예><Example>

티타늄 테트라 에톡사이드(0.4mol/L)를 에탄올 1000ml에 녹인 용액에 100g의 흑연분말을 첨가하여 교반하면서 30분간 혼합하였다. 이 슬러리를 필터링하여 용액을 제거함으로써 티타늄 알콕사이드가 코팅된 흑연 분말을 제조하였다. 물(0.25mol/L)을 에탄올에 녹인 용액 1000ml를 교반하면서 상기 티타늄 알콕사이드가 코팅된 흑연분말을 첨가하여 10분간 혼합함으로써 흑연 표면의 티타늄 알콕사이드를 가수분해시켰다. 그 후 필터링하여 잔여 용액를 제거하고 80℃의 열풍으로 2시간 건조시켰다. 100 g of graphite powder was added to a solution of titanium tetra ethoxide (0.4 mol / L) in 1000 ml of ethanol and mixed for 30 minutes while stirring. The slurry was filtered to remove the solution to prepare a titanium alkoxide coated graphite powder. Titanium alkoxide on the graphite surface was hydrolyzed by adding 1000 ml of a solution in which water (0.25 mol / L) was dissolved in ethanol and mixing the titanium alkoxide-coated graphite powder for 10 minutes. Thereafter, the residue was filtered to remove the remaining solution and dried for 2 hours with hot air at 80 ° C.

도 1은 본 실시예에 의해서 수산화티타늄이 코팅된 흑연 분말의 표면을 200배 확대하여 찍은 주사전자현미경(SEM) 사진이다. 도 1에서 보는 바와 같이, 얻어진 흑연 분말의 표면에는 수산화티타늄이 코팅되어 있음을 알 수 있다.1 is a scanning electron microscope (SEM) photograph taken by enlarging a surface of a graphite powder coated with titanium hydroxide 200 times according to the present embodiment. As shown in Figure 1, it can be seen that the surface of the obtained graphite powder is coated with titanium hydroxide.

상기와 같은 본 발명의 탄소질 코팅 방법에 의하면, 흑연분말 표면을 수산화티타늄으로 코팅하여, 저열전도성 및 내산화성을 향상시킬 수 있다.According to the carbonaceous coating method of the present invention as described above, by coating the surface of the graphite powder with titanium hydroxide, it is possible to improve the low thermal conductivity and oxidation resistance.

또한, 흑연의 열전도도를 감소시켜 에너지 절약효과와 함께 내산화성 증진에 의한 내화물 수명 연장이 가능하고, 이에 따른 제철 및 제강 조업공정의 안정화가 가능하다.In addition, by reducing the thermal conductivity of the graphite it is possible to extend the refractory life by improving the oxidation resistance and energy saving effect, thereby stabilizing the steel and steel manufacturing process.

또한, 흑연분말 표면이 친수성으로 개질되어 내화물 생산공정 및 품질을 개선할 수 있고, 내화물 제조공정에 수계를 이용한 혼합 및 성형공정이 적용가능하 고, 부정형 내화물에 응용이 가능하다.In addition, since the surface of the graphite powder is modified to be hydrophilic, it is possible to improve the refractory production process and quality, and the mixing and molding process using an aqueous system is applicable to the refractory manufacturing process, and is applicable to amorphous refractory materials.

Claims (3)

흑연의 코팅 제조방법으로서,As a coating production method of graphite, 티타늄 알콕사이드를 에탄올에 녹인 용액 100 중량부에 흑연분말을 4 내지 55 중량부를 혼합하여 슬러리를 제조하는 단계;Preparing a slurry by mixing 4 to 55 parts by weight of graphite powder to 100 parts by weight of a solution in which titanium alkoxide is dissolved in ethanol; 상기 슬러리를 필터링하여, 상기 흑연분말 표면에 상기 티타늄 알콕사이드를 코팅하는 단계;Filtering the slurry to coat the titanium alkoxide on the graphite powder surface; 물을 에탄올에 녹인 용액 100 중량부에 상기 티타늄 알콕사이드가 코팅된 흑연분말을 5 내지 65 중량부를 혼합하여 흑연분말 표면의 티타늄 알콕사이드를 가수분해하는 단계;Hydrolyzing titanium alkoxide on the surface of the graphite powder by mixing 5 to 65 parts by weight of the titanium alkoxide-coated graphite powder with 100 parts by weight of a solution of water dissolved in ethanol; 상기 용액을 필터링하고, 건조시켜서 흑연분말 표면에 수산화티타늄을 코팅하는 단계를 포함하는 것을 특징으로 하는 흑연의 코팅 제조방법.Filtering the solution and drying to coat titanium hydroxide on the surface of the graphite powder. 제1항에 있어서,The method of claim 1, 상기 슬러리를 제조하는 단계는, 상기 에탄올에 혼합되는 티타늄 알콕사이드가 0.02mol/L 내지 0.95mol/L의 농도로 사용되는 것을 특징으로 하는 흑연의 코팅 제조방법.In the preparing of the slurry, the titanium alkoxide mixed in the ethanol is used at a concentration of 0.02 mol / L to 0.95 mol / L. 제1항에 있어서,The method of claim 1, 상기 가수분해 단계는, 상기 에탄올에 혼합되는 물이 0.05mol/L 내지 0.70mol/L의 농도로 사용되는 것을 특징으로 하는 흑연의 코팅 제조방법.The hydrolysis step, the coating method of the graphite, characterized in that the water mixed in the ethanol is used at a concentration of 0.05 mol / L to 0.70 mol / L.
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CN107754778A (en) * 2017-09-27 2018-03-06 广州市华之特奥因特种材料科技有限公司 The preparation method of the graphene titanium dioxide metal ion composite photo-catalyst aqueous solution
KR20180040749A (en) * 2016-10-12 2018-04-23 (주)제너코트 Method for improving property of graphite surface using liquid coating

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US5167943A (en) * 1989-06-06 1992-12-01 Norton Company Titanium nitride coated silicon carbide materials with an interlayer resistant to carbon-diffusivity
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KR100292998B1 (en) * 1998-06-05 2001-07-12 홍성진 Graphite powder with oxidation-resistance and dispersibility and method for preparing the same
US6309702B1 (en) * 1998-08-31 2001-10-30 Textron Systems Corporation Process for the production of improved boron coatings
DE19845291A1 (en) * 1998-10-01 2000-04-13 Fraunhofer Ges Forschung Process for the deposition of titanium oxide layers using soluble powders

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KR20180040749A (en) * 2016-10-12 2018-04-23 (주)제너코트 Method for improving property of graphite surface using liquid coating
CN107754778A (en) * 2017-09-27 2018-03-06 广州市华之特奥因特种材料科技有限公司 The preparation method of the graphene titanium dioxide metal ion composite photo-catalyst aqueous solution
CN107754778B (en) * 2017-09-27 2020-04-24 广州市华之特奥因特种材料科技有限公司 Preparation method of graphene-titanium dioxide-metal ion composite photocatalyst aqueous solution

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