CN111073446A - Novel nano titanium powder/epoxy resin based heavy-duty anticorrosive paint and preparation method thereof - Google Patents
Novel nano titanium powder/epoxy resin based heavy-duty anticorrosive paint and preparation method thereof Download PDFInfo
- Publication number
- CN111073446A CN111073446A CN201911199013.5A CN201911199013A CN111073446A CN 111073446 A CN111073446 A CN 111073446A CN 201911199013 A CN201911199013 A CN 201911199013A CN 111073446 A CN111073446 A CN 111073446A
- Authority
- CN
- China
- Prior art keywords
- powder
- epoxy resin
- titanium powder
- nano titanium
- atmosphere
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0881—Titanium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention belongs to the technical field of heavy-duty anticorrosive coatings, and provides a novel nano titanium powder/epoxy resin basis weight anticorrosive coating and a preparation method thereof. Firstly, titanium powder with micron-sized or above is placed in an atmosphere furnace in a hydrogen atmosphere, heating is carried out to ensure that titanium is hydrogen-embrittled, then a sand mill is utilized to sand the powder, and then the powder is heated in the atmosphere furnace in an argon atmosphere to ensure that the powder is dehydrogenated to obtain nano titanium powder; and then carrying out expression modification treatment on the titanium powder, adding the titanium powder, a curing agent and an accelerator into epoxy resin, and curing to obtain the nano titanium powder/epoxy resin based heavy-duty anticorrosive coating. The heavy anti-corrosion coating prepared by the invention has uniform microstructure and excellent comprehensive performance, and meanwhile, the synthesis process of the heavy anti-corrosion coating is simple and easy to operate, the process is environment-friendly and pollution-free, the cost is low, and the popularization and the implementation are easy.
Description
Technical Field
The invention belongs to the field of heavy-duty anticorrosive coatings, and particularly relates to a novel nano titanium powder/epoxy resin basis weight anticorrosive coating and a preparation method thereof.
Background
With the mass production and use of metal materials in the scientific and technological progress, the corrosion problem seriously threatens the development of a plurality of related industries, and seriously hinders the development of industries which use a large amount of metal materials in severe environments such as emerging ocean engineering, energy industry and large-scale industrial enterprises. Incomplete statistics show that the worldwide loss caused by corrosion is up to more than 1 trillion dollars every year, and the annual consumption of heavy anticorrosive paint in China is up to more than 320 trillion tons, which accounts for more than 40% of the worldwide consumption. Therefore, the research and development of novel high-efficiency environment-friendly heavy-duty anticorrosive paint has very important practical significance for the development of national economy and national defense industry in China.
Titanium is a metal with very strong corrosion resistance and high temperature resistance, and the heavy-duty anticorrosion performance of the paint can be further improved by adding the titanium nano modified polymer into the anticorrosion paint. Therefore, through structural design and process optimization, the synthesized nano titanium powder/epoxy resin heavy-duty anticorrosive coating has extremely wide applicability and very obvious economic benefit.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a novel nano titanium powder/epoxy resin basis weight anticorrosive paint and a preparation method thereof.
The technical scheme of the invention is as follows:
the novel nano titanium powder/epoxy resin based heavy-duty anticorrosive paint is prepared from 0.5-3 parts of nano titanium powder, 20-30 parts of curing agent, 0.03-0.05 part of accelerator, 1-10 parts of auxiliary agent and 50 parts of epoxy resin.
Furthermore, the nano titanium powder is heated in a hydrogen atmosphere to ensure that the metal titanium is hydrogen-embrittled, and the particle diameter is about 50 nm.
The preparation method of the novel nano titanium powder/epoxy resin based heavy-duty anticorrosive paint comprises the following steps:
the method comprises the following steps:
firstly, cleaning, filtering and centrifuging purchased common titanium powder (with the size of more than micron level) by using distilled water, and then drying by using a vacuum oven at a certain temperature; then spreading titanium powder on the corundum plate into a thin layer, placing the thin layer in an atmosphere furnace, and heating the titanium powder in a hydrogen atmosphere according to a certain heating process to ensure that the titanium powder is hydrogen-embrittled in the hydrogen atmosphere;
step two:
placing the titanium powder cooled to room temperature in the step one in a container of a nano sand mill, performing sand milling treatment on the powder after hydrogen embrittlement according to a certain sand milling process, cleaning, filtering and centrifuging the powder after sand milling, and drying the powder at a certain temperature by using a vacuum oven; spreading the powder on a corundum plate into a thin layer, placing the thin layer in an atmosphere furnace, and heating the powder in an argon atmosphere to dehydrogenate the powder to obtain hydrogen-embrittled nano titanium powder;
step three:
placing the nano titanium powder and the silane coupling agent obtained in the step two in absolute ethyl alcohol according to a certain proportion, respectively performing ultrasonic dispersion and magnetic stirring for a period of time, and then filtering and drying to obtain surface-modified nano titanium powder;
step four:
and then adding a certain mass of the surface-modified nano powder into epoxy resin (EP) which is electrically stirred at a certain temperature, continuously stirring for a period of time, adding an accelerator, an accelerator and a curing agent, continuously stirring, and finally performing film coating and curing treatment to obtain the epoxy resin basis weight anticorrosive paint.
Further, the conditions for centrifuging the common titanium powder in the step one are as follows: the rotation speed is 8000 r/min, and the centrifugation time is 5 min.
Further, the heating process of the atmosphere furnace in the step one comprises the following steps: under the atmosphere of hydrogen, the specific heating process of the atmosphere furnace is as follows: the first step is to heat the mixture from room temperature to 150 ℃ at 5 ℃/min, the temperature is kept for 120min, the second step is to heat the mixture to 550-650 ℃ at 3 ℃/min, the temperature is kept for 240min, and the third step is to naturally cool the mixture to room temperature under the hydrogen atmosphere.
Further, the powder sanding process after hydrogen embrittlement in the second step comprises the following steps: firstly setting the rotating speed of the sand mill to be 1000 r/min, sanding for 1h, and then increasing the rotating speed of the sand mill to 3000r/min, and sanding for 2 h.
Further, the dehydrogenation process of the powder in the second step comprises the following steps: in the argon atmosphere, the temperature is increased from room temperature to 150 ℃ at 5 ℃/min in the first step, the temperature is maintained for 120min, the temperature is increased to 650-750 ℃ at 3 ℃/min in the second step, the temperature is maintained for 240min, and the natural cooling is carried out to the room temperature in the hydrogen atmosphere in the third step.
Further, the mass-volume ratio of the nano powder prepared in the third step to the anhydrous ethanol to the silane coupling agent is 5-10 g: 50 ml: 1-2 ml; the silane coupling agent is selected from one or more of KH550, KH560 and KH570, but is not limited to the above-mentioned ones.
Further, in the fourth step, the epoxy resin is one of E-51 type phenolic propane polyester resin, E-44 type epoxy resin, bisphenol a type epoxy resin, bisphenol F type epoxy resin and Novolac epoxy resin, the curing agent is one of aliphatic and alicyclic, the accelerator is 2-ethyl-4-methylimidazole, and the assistant is: one or more of a drier, an anti-skinning agent, a leveling agent, a defoamer, or a thickener.
The invention has the beneficial effects that:
firstly, the invention realizes the control of the size factor and the appearance of a metal dispersion phase by designing and regulating the embrittlement condition of a metal material, the rotating speed and the time in the external field and the nano sanding process, and prepares the nano metal powder with regular size and shape; the titanium nano-particles can play the volume effect, the surface effect, the corrosion resistance effect and the high temperature resistance of the nano-material in the polymer. The titanium nano modified polymer can effectively fill micropores in the coating and increase the adhesive force between the coating and a matrix interface, so that the corrosion resistance of the coating can be greatly improved.
The preparation method and the required equipment are simple, the cost is low, the environment is protected, no pollution is caused, and the popularization and the implementation are easy.
Drawings
FIG. 1 is a scanning electron micrograph of a cross section of a 3wt.% Ti @ EP heavy duty coating prepared in example 3;
FIG. 2 is an XRD physical phase diagram of the heavy duty coating prepared in examples 3, 4 and 5.
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Example 1
The novel nano titanium powder/epoxy resin based heavy-duty anticorrosive paint is prepared from 0.5-3 parts of nano titanium powder, 20-30 parts of curing agent, 0.03-0.05 part of accelerator, 1-10 parts of auxiliary agent and 50 parts of epoxy resin.
A novel nano titanium powder/epoxy resin basis weight anticorrosive paint and a preparation method thereof comprise the following steps:
the method comprises the following steps:
firstly, cleaning, filtering and centrifuging purchased common titanium powder (with the size of more than micron level) by using distilled water, and then drying by using a vacuum oven at a certain temperature; then spreading titanium powder on the corundum plate into a thin layer, placing the thin layer in an atmosphere furnace, and heating the titanium powder in a hydrogen atmosphere according to a certain heating process to ensure that the titanium powder is hydrogen-embrittled in the hydrogen atmosphere;
step two:
placing the titanium powder cooled to room temperature in the step one in a container of a nano sand mill, performing sand milling treatment on the powder after hydrogen embrittlement according to a certain sand milling process, cleaning, filtering and centrifuging the powder after sand milling, and drying the powder at a certain temperature by using a vacuum oven; spreading the powder on a corundum plate into a thin layer, placing the thin layer in an atmosphere furnace, and heating the powder in an argon atmosphere to dehydrogenate the powder to obtain hydrogen-embrittled nano titanium powder;
step three:
placing the nano titanium powder and the silane coupling agent obtained in the step two in absolute ethyl alcohol according to a certain proportion, respectively performing ultrasonic dispersion and magnetic stirring for a period of time, and then filtering and drying to obtain surface-modified nano titanium powder;
step four:
and then adding a certain mass of the surface-modified nano powder into epoxy resin which is electrically stirred at a certain temperature, continuously stirring for a period of time, adding an accelerator and a curing agent, continuously stirring, and finally performing film coating and curing treatment to obtain the epoxy resin basis weight anticorrosive paint.
Example 2
The novel nano titanium powder/epoxy resin based heavy-duty anticorrosive paint is prepared from 0.5-3 parts of nano titanium powder, 20-30 parts of curing agent, 0.03-0.05 part of accelerator, 1-10 parts of auxiliary agent and 50 parts of epoxy resin.
A novel nano titanium powder/epoxy resin basis weight anticorrosive paint and a preparation method thereof are characterized in that the preparation method comprises the following steps:
the method comprises the following steps:
firstly, cleaning purchased common titanium powder (with the size of more than micron level) for 3-5 times by using distilled water, centrifuging for 5 min under the condition that the rotating speed is 8000 r/min after filtering, and then drying for 12 h at 80 ℃ by using a vacuum oven. (ii) a Then spreading titanium powder on the corundum plate into a thin layer, and placing the thin layer in an atmosphere furnace, wherein the specific heating process of the atmosphere furnace under the hydrogen atmosphere is as follows: the first step is to heat the mixture from room temperature to 150 ℃ at 5 ℃/min, the temperature is kept for 120min, the second step is to heat the mixture to 550-650 ℃ at 3 ℃/min, the temperature is kept for 240min, and the third step is to naturally cool the mixture to room temperature under the hydrogen atmosphere. (ii) a
Step two:
placing the titanium powder cooled to room temperature in the step one in a container of a nano sand mill, sanding for 1h at the rotating speed of 1000 r/min, then increasing the rotating speed of the sand mill to 3000r/min, sanding for 2h, then cleaning the sanded powder for 3-5 times by using distilled water, filtering, centrifuging for 10 min at the rotating speed of 10000r/min, and drying for 12 h at 80 ℃ by using a vacuum oven; and then spreading the powder on a corundum plate into a thin layer, placing the thin layer in an atmosphere furnace, heating the thin layer in an argon atmosphere to dehydrogenate the powder, wherein the specific heating process comprises the steps of firstly heating the powder from room temperature to 150 ℃ at a heating rate of 5 ℃ per minute, preserving heat for 120min, secondly heating the powder to 650 plus 750 ℃ at 3 ℃ per minute, preserving heat for 240min, and thirdly naturally cooling the powder to room temperature in a hydrogen atmosphere. (ii) a
Step three:
and (3) placing the nano titanium powder and the silane coupling agent obtained in the step (II) into absolute ethyl alcohol according to a certain proportion, wherein the mass volume ratio of the nano powder to the absolute ethyl alcohol to the silane coupling agent is 5-10 g: 50 ml: 1-2 ml, then ultrasonic dispersing and magnetic stirring for a period of time, filtering and drying to obtain surface-modified nano titanium powder, wherein the silane coupling agent is selected from one or more of KH550, KH560 and KH570, but not limited to the above-mentioned ones;
step four:
then adding a certain mass of the nano powder subjected to surface modification into epoxy resin which is electrically stirred at a certain temperature, wherein the epoxy resin is one of E-51 type phenolic propane polyester resin, E-44 type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin and Novolac epoxy resin; after continuously stirring for a period of time, adding an accelerator, an auxiliary agent and a curing agent, and continuously stirring, wherein the curing agent is one of aliphatic and alicyclic, the accelerator is 2-ethyl-4-methylimidazole, and the auxiliary agent is: one or more of a drier, an anti-skinning agent, a leveling agent, a defoaming agent or a thickener; finally, the epoxy resin basis weight anticorrosive paint is obtained through film coating and curing treatment.
Example 3
The novel nano titanium powder/epoxy resin based heavy-duty anticorrosive paint is prepared from 0.5 part of nano titanium powder, 20-30 parts of curing agent, 0.03-0.05 part of accelerator, 1-10 parts of auxiliary agent and 50 parts of epoxy resin.
A novel nano titanium powder/epoxy resin basis weight anticorrosive paint and a preparation method thereof are characterized in that the preparation method comprises the following steps:
the method comprises the following steps:
firstly, cleaning purchased common titanium powder (with the size of more than micron level) for 3-5 times by using distilled water, centrifuging for 5 min under the condition that the rotating speed is 8000 r/min after filtering, and then drying for 12 h at 80 ℃ by using a vacuum oven. (ii) a Then spreading titanium powder on the corundum plate into a thin layer, and placing the thin layer in an atmosphere furnace, wherein the specific heating process of the atmosphere furnace under the hydrogen atmosphere is as follows: the first step is to heat the mixture from room temperature to 150 ℃ at 5 ℃/min, the temperature is kept for 120min, the second step is to heat the mixture to 550-650 ℃ at 3 ℃/min, the temperature is kept for 240min, and the third step is to naturally cool the mixture to room temperature under the hydrogen atmosphere. (ii) a
Step two:
placing the titanium powder cooled to room temperature in the step one in a container of a nano sand mill, sanding for 1h at the rotating speed of 1000 r/min, then increasing the rotating speed of the sand mill to 3000r/min, sanding for 2h, then cleaning the sanded powder for 3-5 times by using distilled water, filtering, centrifuging for 10 min at the rotating speed of 10000r/min, and drying for 12 h at 80 ℃ by using a vacuum oven; and then spreading the powder on a corundum plate into a thin layer, placing the thin layer in an atmosphere furnace, heating the thin layer in an argon atmosphere to dehydrogenate the powder, wherein the specific heating process comprises the steps of firstly heating the powder from room temperature to 150 ℃ at a heating rate of 5 ℃ per minute, preserving heat for 120min, secondly heating the powder to 650 plus 750 ℃ at 3 ℃ per minute, preserving heat for 240min, and thirdly naturally cooling the powder to room temperature in a hydrogen atmosphere. (ii) a
Step three:
and (3) placing the nano titanium powder and the silane coupling agent obtained in the step (II) into absolute ethyl alcohol according to a certain proportion, wherein the mass volume ratio of the nano powder to the absolute ethyl alcohol to the silane coupling agent is 5-10 g: 50 ml: 1-2 ml, then ultrasonic dispersing and magnetic stirring for a period of time, filtering and drying to obtain surface-modified nano titanium powder, wherein the silane coupling agent is selected from one or more of KH550, KH560 and KH570, but not limited to the above-mentioned ones;
step four:
then adding a certain mass of the nano powder subjected to surface modification into epoxy resin which is electrically stirred at a certain temperature, wherein the epoxy resin is one of E-51 type phenolic propane polyester resin, E-44 type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin and Novolac epoxy resin; after continuously stirring for a period of time, adding an accelerator, an auxiliary agent and a curing agent, and continuously stirring, wherein the curing agent is one of aliphatic and alicyclic, the accelerator is 2-ethyl-4-methylimidazole, and the auxiliary agent is: one or more of a drier, an anti-skinning agent, a leveling agent, a defoaming agent or a thickener; finally, the epoxy resin basis weight anticorrosive paint is obtained through film coating and curing treatment.
Example 4
The novel nano titanium powder/epoxy resin based heavy-duty anticorrosive coating and the preparation method thereof are characterized in that 1.5 parts of nano titanium powder, 20-30 parts of curing agent, 0.03-0.05 part of accelerator, 1-10 parts of auxiliary agent and 50 parts of epoxy resin are contained in the heavy-duty anticorrosive coating prepared under the condition of low filling content.
A novel nano titanium powder/epoxy resin basis weight anticorrosive paint and a preparation method thereof are characterized in that the preparation method comprises the following steps:
the method comprises the following steps:
firstly, cleaning purchased common titanium powder (with the size of more than micron level) for 3-5 times by using distilled water, centrifuging for 5 min under the condition that the rotating speed is 8000 r/min after filtering, and then drying for 12 h at 80 ℃ by using a vacuum oven. (ii) a Then spreading titanium powder on the corundum plate into a thin layer, and placing the thin layer in an atmosphere furnace, wherein the specific heating process of the atmosphere furnace under the hydrogen atmosphere is as follows: the first step is to heat the mixture from room temperature to 150 ℃ at 5 ℃/min, the temperature is kept for 120min, the second step is to heat the mixture to 550-650 ℃ at 3 ℃/min, the temperature is kept for 240min, and the third step is to naturally cool the mixture to room temperature under the hydrogen atmosphere. (ii) a
Step two:
placing the titanium powder cooled to room temperature in the step one in a container of a nano sand mill, sanding for 1h at the rotating speed of 1000 r/min, then increasing the rotating speed of the sand mill to 3000r/min, sanding for 2h, then cleaning the sanded powder for 3-5 times by using distilled water, filtering, centrifuging for 10 min at the rotating speed of 10000r/min, and drying for 12 h at 80 ℃ by using a vacuum oven; and then spreading the powder on a corundum plate into a thin layer, placing the thin layer in an atmosphere furnace, heating the thin layer in an argon atmosphere to dehydrogenate the powder, wherein the specific heating process comprises the steps of firstly heating the powder from room temperature to 150 ℃ at a heating rate of 5 ℃ per minute, preserving heat for 120min, secondly heating the powder to 650 plus 750 ℃ at 3 ℃ per minute, preserving heat for 240min, and thirdly naturally cooling the powder to room temperature in a hydrogen atmosphere. (ii) a
Step three:
and (3) placing the nano titanium powder and the silane coupling agent obtained in the step (II) into absolute ethyl alcohol according to a certain proportion, wherein the mass volume ratio of the nano powder to the absolute ethyl alcohol to the silane coupling agent is 5-10 g: 50 ml: 1-2 ml, then ultrasonic dispersing and magnetic stirring for a period of time, filtering and drying to obtain surface-modified nano titanium powder, wherein the silane coupling agent is selected from one or more of KH550, KH560 and KH570, but not limited to the above-mentioned ones;
step four:
then adding a certain mass of the nano powder subjected to surface modification into epoxy resin which is electrically stirred at a certain temperature, wherein the epoxy resin is one of E-51 type phenolic propane polyester resin, E-44 type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin and Novolac epoxy resin; after continuously stirring for a period of time, adding an accelerator, an auxiliary agent and a curing agent, and continuously stirring, wherein the curing agent is one of aliphatic and alicyclic, the accelerator is 2-ethyl-4-methylimidazole, and the auxiliary agent is: one or more of a drier, an anti-skinning agent, a leveling agent, a defoaming agent or a thickener; finally, the epoxy resin basis weight anticorrosive paint is obtained through film coating and curing treatment.
Example 5
The novel nano titanium powder/epoxy resin based heavy-duty anticorrosive paint is prepared from 0 part of nano titanium powder, 20-30 parts of curing agent, 0.03-0.05 part of accelerator, 1-10 parts of auxiliary agent and 50 parts of epoxy resin.
A novel nano titanium powder/epoxy resin basis weight anticorrosive paint and a preparation method thereof are characterized in that the preparation method comprises the following steps:
the method comprises the following steps:
firstly, cleaning purchased common titanium powder (with the size of more than micron level) for 3-5 times by using distilled water, centrifuging for 5 min under the condition that the rotating speed is 8000 r/min after filtering, and then drying for 12 h at 80 ℃ by using a vacuum oven. (ii) a Then spreading titanium powder on the corundum plate into a thin layer, and placing the thin layer in an atmosphere furnace, wherein the specific heating process of the atmosphere furnace under the hydrogen atmosphere is as follows: the first step is to heat the mixture from room temperature to 150 ℃ at 5 ℃/min, the temperature is kept for 120min, the second step is to heat the mixture to 550-650 ℃ at 3 ℃/min, the temperature is kept for 240min, and the third step is to naturally cool the mixture to room temperature under the hydrogen atmosphere. (ii) a
Step two:
placing the titanium powder cooled to room temperature in the step one in a container of a nano sand mill, sanding for 1h at the rotating speed of 1000 r/min, then increasing the rotating speed of the sand mill to 3000r/min, sanding for 2h, then cleaning the sanded powder for 3-5 times by using distilled water, filtering, centrifuging for 10 min at the rotating speed of 10000r/min, and drying for 12 h at 80 ℃ by using a vacuum oven; and then spreading the powder on a corundum plate into a thin layer, placing the thin layer in an atmosphere furnace, heating the thin layer in an argon atmosphere to dehydrogenate the powder, wherein the specific heating process comprises the steps of firstly heating the powder from room temperature to 150 ℃ at a heating rate of 5 ℃ per minute, preserving heat for 120min, secondly heating the powder to 650 plus 750 ℃ at 3 ℃ per minute, preserving heat for 240min, and thirdly naturally cooling the powder to room temperature in a hydrogen atmosphere. (ii) a
Step three:
and (3) placing the nano titanium powder and the silane coupling agent obtained in the step (II) into absolute ethyl alcohol according to a certain proportion, wherein the mass volume ratio of the nano powder to the absolute ethyl alcohol to the silane coupling agent is 5-10 g: 50 ml: 1-2 ml, then ultrasonic dispersing and magnetic stirring for a period of time, filtering and drying to obtain surface-modified nano titanium powder, wherein the silane coupling agent is selected from one or more of KH550, KH560 and KH570, but not limited to the above-mentioned ones;
step four:
then adding a certain mass of the nano powder subjected to surface modification into epoxy resin which is electrically stirred at a certain temperature, wherein the epoxy resin is one of E-51 type phenolic propane polyester resin, E-44 type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin and Novolac epoxy resin; after continuously stirring for a period of time, adding an accelerator, an auxiliary agent and a curing agent, and continuously stirring, wherein the curing agent is one of aliphatic and alicyclic, the accelerator is 2-ethyl-4-methylimidazole, and the auxiliary agent is: one or more of a drier, an anti-skinning agent, a leveling agent, a defoaming agent or a thickener; finally, the epoxy resin basis weight anticorrosive paint is obtained through film coating and curing treatment.
Fig. 1 is a scanning electron microscope image of a cross section of the epoxy resin based heavy-duty anticorrosive coating with the doping content of 3wt.% of the nano titanium powder prepared in example 4, and it can be seen from the image that the nano titanium powder is uniformly distributed in the epoxy resin, no obvious agglomeration and defects exist, meanwhile, the inorganic particles have high compatibility with the epoxy resin matrix, and no air gap exists at the interface of two phases.
FIG. 2 is an XRD phase diagram of the Ti, 1wt.% Ti @ EP, 3wt.% Ti @ EP and EP materials prepared in examples 3, 4 and 5, from which it can be seen that the characteristic diffraction front of Ti in epoxy based weight anti-corrosive coatings becomes increasingly apparent with the filling of nano Ti powder, and it can also be seen that the introduction of Ti does not disrupt the basic physical structure of the epoxy, and the two phases are merely physically mixed.
Claims (9)
1. The novel nano titanium powder/epoxy resin based heavy-duty anticorrosive coating is characterized in that 0.5-3 parts of nano titanium powder, 20-30 parts of curing agent, 0.03-0.05 part of accelerator, 1-10 parts of auxiliary agent and 50 parts of epoxy resin are contained in the heavy-duty anticorrosive coating prepared under the condition of low filling content.
2. The novel nano titanium powder/epoxy resin based heavy-duty anticorrosive coating according to claim 1, wherein the nano titanium powder is heated in a hydrogen atmosphere to cause hydrogen embrittlement of metallic titanium, and the particle diameter is about 50 nm.
3. A preparation method of a novel nano titanium powder/epoxy resin based heavy-duty anticorrosive paint is characterized by comprising the following steps:
the method comprises the following steps:
firstly, cleaning, filtering and centrifuging purchased common titanium powder (with the size of more than micron level) by using distilled water, and then drying by using a vacuum oven at a certain temperature; then spreading titanium powder on the corundum plate into a thin layer, placing the thin layer in an atmosphere furnace, and heating the titanium powder in a hydrogen atmosphere according to a certain heating process to ensure that the titanium powder is hydrogen-embrittled in the hydrogen atmosphere;
step two:
placing the titanium powder cooled to room temperature in the step one in a container of a nano sand mill, performing sand milling treatment on the powder after hydrogen embrittlement according to a certain sand milling process, cleaning, filtering and centrifuging the powder after sand milling, and drying the powder at a certain temperature by using a vacuum oven; spreading the powder on a corundum plate into a thin layer, placing the thin layer in an atmosphere furnace, and heating the powder in an argon atmosphere to dehydrogenate the powder to obtain hydrogen-embrittled nano titanium powder;
step three:
placing the nano titanium powder and the silane coupling agent obtained in the step two in absolute ethyl alcohol according to a certain proportion, respectively performing ultrasonic dispersion and magnetic stirring for a period of time, and then filtering and drying to obtain surface-modified nano titanium powder;
step four:
and then adding a certain mass of the surface-modified nano powder into epoxy resin (EP) which is electrically stirred at a certain temperature, continuously stirring for a period of time, adding an accelerator and a curing agent, continuously stirring, and finally performing film coating and curing treatment to obtain the epoxy resin based heavy-duty anticorrosive paint.
4. The preparation method of the novel nano titanium powder/epoxy resin based heavy-duty anticorrosive paint according to claim 3, characterized in that the conditions for centrifuging the common titanium powder in the step one are as follows: the rotation speed is 8000 r/min, and the centrifugation time is 5 min.
5. The preparation method of the novel nano titanium powder/epoxy resin basic weight anticorrosive paint according to claim 3, characterized in that the heating process of the atmosphere furnace in the step one is as follows: under the atmosphere of hydrogen, the specific heating process of the atmosphere furnace is as follows: the first step is to heat the mixture from room temperature to 150 ℃ at 5 ℃/min, the temperature is kept for 120min, the second step is to heat the mixture to 550-650 ℃ at 3 ℃/min, the temperature is kept for 240min, and the third step is to naturally cool the mixture to room temperature under the hydrogen atmosphere.
6. The preparation method of the novel nano titanium powder/epoxy resin based heavy-duty anticorrosive paint according to claim 3, characterized in that the powder sanding process after hydrogen embrittlement in the second step is as follows: firstly setting the rotating speed of the sand mill to be 1000 r/min, sanding for 1h, and then increasing the rotating speed of the sand mill to 3000r/min, and sanding for 2 h.
7. The preparation method of the novel nano titanium powder/epoxy resin basis weight anticorrosive paint according to claim 3, characterized in that the dehydrogenation process of the powder in the second step is as follows: in the argon atmosphere, the temperature is increased from room temperature to 150 ℃ at 5 ℃/min in the first step, the temperature is maintained for 120min, the temperature is increased to 650-750 ℃ at 3 ℃/min in the second step, the temperature is maintained for 240min, and the natural cooling is carried out to the room temperature in the hydrogen atmosphere in the third step.
8. The preparation method of the novel nano titanium powder/epoxy resin based heavy-duty anticorrosive paint according to claim 3, characterized in that the mass-to-volume ratio of the nano powder, the anhydrous ethanol and the silane coupling agent in the third step is 5-10 g: 50 ml: 1-2 ml; the silane coupling agent is selected from one or more of KH550, KH560 and KH570, but is not limited to the above-mentioned ones.
9. The method for preparing the novel nano titanium powder/epoxy resin based heavy duty anticorrosive paint according to claim 3, characterized in that in the fourth step, the epoxy resin is one of E-51 type phenolic propane polyester resin, E-44 type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin and Novolac epoxy resin, the curing agent is one of aliphatic and alicyclic, the accelerator is 2-ethyl-4-methylimidazole, and the auxiliary agent is: one or more of a drier, an anti-skinning agent, a leveling agent, a defoamer, or a thickener.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911199013.5A CN111073446A (en) | 2019-11-29 | 2019-11-29 | Novel nano titanium powder/epoxy resin based heavy-duty anticorrosive paint and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911199013.5A CN111073446A (en) | 2019-11-29 | 2019-11-29 | Novel nano titanium powder/epoxy resin based heavy-duty anticorrosive paint and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111073446A true CN111073446A (en) | 2020-04-28 |
Family
ID=70312404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911199013.5A Pending CN111073446A (en) | 2019-11-29 | 2019-11-29 | Novel nano titanium powder/epoxy resin based heavy-duty anticorrosive paint and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111073446A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6168644B1 (en) * | 1996-07-30 | 2001-01-02 | Toho Titanium Co., Ltd. | Titanium-base powders and process for production of the same |
| CN1404949A (en) * | 2002-10-25 | 2003-03-26 | 中国科学院上海微系统与信息技术研究所 | Preparation of nanometal material by hydrogenation ball-milling method |
| CN1718644A (en) * | 2004-07-09 | 2006-01-11 | 中国科学院金属研究所 | A kind of nanometer Ti particle organic protection coating and preparation method of few additive |
| CN101164723A (en) * | 2007-10-11 | 2008-04-23 | 宝鸡富士特钛业有限公司 | Method for preparing high-purification ultrafine titanium powder for aviation |
| CN102407337A (en) * | 2011-11-24 | 2012-04-11 | 李宝干 | Method for manufacturing titanium and titanium alloy powder metallurgy special-shaped pieces |
| CN103275601A (en) * | 2013-05-28 | 2013-09-04 | 胜利油田金岛实业有限责任公司 | Nano titanium polymer inner wall anticorrosion oil pipe |
| CN104511595A (en) * | 2014-12-30 | 2015-04-15 | 中南大学 | Preparation method of high-purity titanium powder |
| CN104530912A (en) * | 2015-01-06 | 2015-04-22 | 李梦 | Nano titanium modified epoxy resin aircraft coating for electromagnetic shielding |
| CN106893441A (en) * | 2015-12-17 | 2017-06-27 | 中国科学院金属研究所 | A kind of epoxy resin-nano-titanium surface chemistry bonding anticorrosive paint and preparation method |
-
2019
- 2019-11-29 CN CN201911199013.5A patent/CN111073446A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6168644B1 (en) * | 1996-07-30 | 2001-01-02 | Toho Titanium Co., Ltd. | Titanium-base powders and process for production of the same |
| CN1404949A (en) * | 2002-10-25 | 2003-03-26 | 中国科学院上海微系统与信息技术研究所 | Preparation of nanometal material by hydrogenation ball-milling method |
| CN1718644A (en) * | 2004-07-09 | 2006-01-11 | 中国科学院金属研究所 | A kind of nanometer Ti particle organic protection coating and preparation method of few additive |
| CN101164723A (en) * | 2007-10-11 | 2008-04-23 | 宝鸡富士特钛业有限公司 | Method for preparing high-purification ultrafine titanium powder for aviation |
| CN102407337A (en) * | 2011-11-24 | 2012-04-11 | 李宝干 | Method for manufacturing titanium and titanium alloy powder metallurgy special-shaped pieces |
| CN103275601A (en) * | 2013-05-28 | 2013-09-04 | 胜利油田金岛实业有限责任公司 | Nano titanium polymer inner wall anticorrosion oil pipe |
| CN104511595A (en) * | 2014-12-30 | 2015-04-15 | 中南大学 | Preparation method of high-purity titanium powder |
| CN104530912A (en) * | 2015-01-06 | 2015-04-22 | 李梦 | Nano titanium modified epoxy resin aircraft coating for electromagnetic shielding |
| CN106893441A (en) * | 2015-12-17 | 2017-06-27 | 中国科学院金属研究所 | A kind of epoxy resin-nano-titanium surface chemistry bonding anticorrosive paint and preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106189719B (en) | A kind of graphene anticorrosive paint and preparation method thereof | |
| US11878909B2 (en) | Method for preparing modified graphene and method for preparing slurry containing the modified graphene | |
| CN111644615A (en) | Preparation method for realizing high strength and toughness of TC4 titanium alloy by co-strengthening method | |
| CN101892004A (en) | Ultraviolet-cured heat-resistant coating and preparation and application methods thereof | |
| CN112457698A (en) | Graphene-modified zinc powder, preparation method and application of graphene-modified zinc powder in zinc-rich anticorrosive coating | |
| CN112961571A (en) | Epoxy zinc-rich anticorrosive paint containing graphene oxide/black talc composite material and preparation method thereof | |
| CN110607104B (en) | High-dispersion high-stability graphene resin dispersion liquid and preparation method and application thereof | |
| CN116970295A (en) | Corrosion-resistant phosphate composite coating with 'brick-mud' layered structure and preparation method and application thereof | |
| CN103357867B (en) | A kind of Scale-like multi-component zinc aluminum silicon alloy powder and preparation method thereof | |
| CN112920687B (en) | Single-component flake type epoxy zinc-rich anti-corrosive primer and preparation method thereof | |
| WO2023070644A2 (en) | Environmentally friendly spray quick-drying chrome-free fingerprint-resistant liquid and preparation method therefor | |
| CN111073446A (en) | Novel nano titanium powder/epoxy resin based heavy-duty anticorrosive paint and preparation method thereof | |
| CN114054762A (en) | Graphene/metal matrix composite material preparation method based on graphene defect regulation | |
| CN111253790B (en) | Preparation method of thin composite nano flake coating | |
| CN108219622A (en) | It is a kind of based on the aluminium alloy of graphene low-density anticorrosive paint and preparation method thereof | |
| CN113333759B (en) | Recycling method of phosphated neodymium iron boron waste | |
| CN105039793A (en) | Nano-featured enhanced aluminum-based composite and preparing method thereof | |
| CN115449278A (en) | Graphene-loaded titanium dioxide composite anticorrosive paint and preparation method thereof | |
| CN103406539B (en) | Scale-like multi-component zinc aluminum silicon alloy powder containing Ce and Pr and preparation method thereof | |
| CN117143497A (en) | Preparation method of high-corrosion-resistance wear-resistance neodymium-iron-boron magnet anticorrosive paint | |
| CN110003776B (en) | Water-based epoxy zinc-rich anticorrosive paint and preparation method and application thereof | |
| CN111808489B (en) | Production process of waterborne toughening paint containing metal nanowires | |
| CN109943194A (en) | A kind of waterborne anti-corrosive primer and preparation method thereof | |
| CN103409662B (en) | Scale-like multi-component zinc aluminum silicon alloy powder containing Ce and Nd and preparation method thereof | |
| CN103433482B (en) | Scale-like multi-component zinc aluminum silicon alloy powder containing La and Ce and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200428 |
|
| WD01 | Invention patent application deemed withdrawn after publication |