CN112063236B - Carbon monoxide indicating ink and preparation method thereof - Google Patents
Carbon monoxide indicating ink and preparation method thereof Download PDFInfo
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- CN112063236B CN112063236B CN202010940456.1A CN202010940456A CN112063236B CN 112063236 B CN112063236 B CN 112063236B CN 202010940456 A CN202010940456 A CN 202010940456A CN 112063236 B CN112063236 B CN 112063236B
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- 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
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
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- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
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Abstract
The present invention relates to a carbon monoxide indicating ink. The raw materials comprise the following components in parts by mass: 20-50 parts of nano cerium dioxide, 30-60 parts of a connecting material and 10-40 parts of a solvent; wherein, the nano cerium dioxide is doped with metal ion impurities. The nano cerium dioxide can play a catalytic role in the oxidation of carbon monoxide in a relatively low-temperature environment of 100 ℃, and in the process, the color of the ink changes from white to golden yellow due to the reduction of the nano cerium dioxide, so that the existence of carbon monoxide gas is indicated. In addition, the invention also relates to a preparation method of the carbon monoxide indicating ink, which is used for preparing the carbon monoxide indicating ink.
Description
Technical Field
The invention relates to the technical field of printing ink, in particular to carbon monoxide indicating printing ink and a preparation method thereof.
Background
It is known that highly toxic carbon monoxide gas is easily generated when the combustion of a substance is insufficient, and since carbon monoxide gas is colorless and odorless, people cannot distinguish it by visual and olfactory methods. Thus, especially in winter, tragedy events of carbon monoxide poisoning and even death due to fire in a closed room still occur occasionally.
At present, cerium dioxide is used as a catalyst for catalytic reaction of carbon monoxide, but the reaction temperature is as high as 500 ℃, and the application of the cerium dioxide in the field of ink is limited due to the excessively high reaction temperature, so that the prior art has no carbon monoxide indicating ink, and the carbon monoxide can not be indicated by the color change of the ink.
Disclosure of Invention
In view of this, there is a need to provide a carbon monoxide indicating ink that is suitable for use at relatively low temperatures.
In addition, a preparation method of the carbon monoxide indicating ink is also provided.
The carbon monoxide indicating ink comprises the following raw materials in parts by mass:
20-50 parts of nano cerium dioxide;
30-60 parts of a connecting material; and
10-40 parts of a solvent;
wherein the nano cerium dioxide is doped with metal ion impurities.
In one embodiment, the molar ratio of the metal ion to the cerium dioxide is 10 mol% to 20 mol%: 40-60 mol%.
In one embodiment, the metal ions are selected from at least one of nickel ions, copper ions, titanium ions, and zirconium ions.
In one embodiment, the nano ceria has a particle size of 10nm to 200 nm.
In one embodiment, the binder is selected from at least one of a methyl methacrylate-styrene-acrylic acid copolymer or a butyl acrylate-styrene-hydroxyethyl acrylate copolymer.
In one embodiment, the methyl methacrylate-styrene-acrylic acid copolymer has a molar ratio of methyl methacrylate to styrene to acrylic acid of 1:2: 2.
In one embodiment, the butyl acrylate-styrene-hydroxyethyl acrylate copolymer has a molar ratio of butyl acrylate to styrene and hydroxyethyl acrylate of 2:1: 2.
In one embodiment, the paint further comprises 0.1-5 parts of a dispersant.
The carbon monoxide indicating ink has the initial reaction temperature greatly reduced to 100 ℃, after the ink is printed and dried, a large number of micropores are generated among the molecules of the connecting material, carbon monoxide molecules enter the ink layer through the micropores to be contacted with nano cerium dioxide, when the ink is close to a heat source and the temperature reaches 100 ℃, active oxygen atoms on the surface of the cerium dioxide and the carbon monoxide undergo redox reaction, the carbon monoxide obtains oxygen atoms and is oxidized into carbon dioxide, and meanwhile, the oxygen atoms lost by the cerium dioxide are reduced into cerium oxide with oxygen cavities, and in the process, the color of the cerium oxide indicating ink is changed from white to golden yellow. Since the ceria crystal has oxygen holes, it can adsorb oxygen in the air, and when the oxygen holes adsorb oxygen atoms, the ceria is oxidized again to ceria. The nano cerium dioxide has good oxygen storage and release capacity on the surface, and can be used as a catalytic indicator in the indicating ink. When the color-changing indicator is arranged near the heat source, the color-changing reaction can be promoted by using the heat of the heat source, and after the reaction is started, the ink is changed from white to golden yellow, so that whether carbon monoxide gas is generated in a room or not is indicated through visible color change, and whether protective measures are taken or not is determined.
A method of making a carbon monoxide indicating ink comprising the steps of:
adding 30-60 parts of connecting material into 10-40 parts of solvent, and fully stirring to prepare a first solution;
and adding 20-50 parts of nano cerium dioxide into the first solution, and fully stirring to obtain the carbon monoxide indicating ink, wherein the nano cerium dioxide is doped with metal ion impurities.
In one embodiment, after the step of adding 30 to 60 parts of the binder to 10 to 40 parts of the solvent and fully stirring to prepare the first solution, the step of adding 20 to 50 parts of the nano ceria to the first solution and fully stirring to prepare the carbon monoxide indicating ink further comprises the step of adding 0.1 to 5 parts of a dispersant and stirring.
The preparation method of the carbon monoxide indicating ink is simple to operate, can be completed by common equipment, and is beneficial to reducing the production cost.
Drawings
FIG. 1 is a flow diagram of a method of making a carbon monoxide indicating ink in accordance with one embodiment;
fig. 2 is a flow chart of a method of making another embodiment of a carbon monoxide indicating ink.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In this document, parts of each raw material refer to parts by weight unless otherwise specified.
The carbon monoxide indicating ink of one embodiment comprises the following raw materials in parts by mass:
20-50 parts of nano cerium dioxide;
30-60 parts of a connecting material; and
10-30 parts of a solvent;
wherein the nano cerium dioxide is doped with metal ion impurities.
The nano cerium dioxide plays a role of a catalytic indicator in the carbon monoxide indicating ink, so that the oxidation temperature and the oxidation rate of carbon monoxide gas are greatly improved, and the reaction chemical formula is as follows:
2CeO2+CO=Ce2O3+CO2
2Ce2O3+O2=4CeO2
the cerium dioxide has a crystal structure of a face-centered cubic, and the isotropic structural characteristics of the cerium dioxide make the cerium dioxide not easy to form a one-dimensional or two-dimensional structure and easy to form spherical nanoparticles. At a high temperature higher than 600 ℃, active oxygen atoms on the surface of the cerium dioxide are easy to generate oxidation-reduction reaction with carbon monoxide, and in the oxidation-reduction process, oxygen atoms of the cerium dioxide are lost to be reduced into cerium oxide with oxygen holes, so that carbon monoxide obtains oxygen atoms and is oxidized into carbon dioxide, and in the process, the color of the cerium dioxide is changed from white to golden yellow. Since the ceria crystal has oxygen holes, it can adsorb oxygen in the air, and when the oxygen holes adsorb oxygen atoms, the ceria is oxidized again to ceria. The nano cerium dioxide has good oxygen storage and release capacity on the surface, and can be used as a catalytic indicator in the indicating ink.
Specifically, nano-ceria particles are selected as the catalytic indicator material, and since the smaller the particle size of the particles, the larger the total or sub-surface area of the particles, the greater the discoloration reaction occurs at the surface or sub-surface of the nano-ceria, and thus, the rate of reaction thereof can be accelerated by selecting nano-materials as the catalytic indicator material.
Further, the shapes of particles such as nano microspheres, nano wires and nano rods are selected as catalytic indicator materials, and experiments prove that the shapes of the particles such as the nano microspheres, the nano wires and the nano rods are adopted as catalytic indicator materials at the same temperature, so that the color interval of an ink layer is obviously enlarged and the indicating effect is more obvious in the color change reaction process.
Preferably, the nano cerium dioxide particles are nanowires formed by connecting nano microspheres in series, and the cerium dioxide particles with a nano-wire structure can greatly reduce the redox initiation reaction temperature of the indicating ink due to the special microstructure of the cerium dioxide particles.
In one embodiment, the particle size of the nano cerium dioxide particles is 10 nm-200 nm, so that the carbon monoxide indication ink meets the printability requirements of different printing modes, and in addition, the reduction of the particle size of the cerium dioxide particles is beneficial to enlarging the surface or the sub-surface of the cerium dioxide, thereby promoting the progress of the color change reaction.
Preferably, the particle size of the nano cerium dioxide is 10 nm-30 nm, and by limiting the particle size of the nano cerium dioxide, the printability of the ink can be improved on one hand, and the initial reaction temperature of the indicating ink can be reduced on the other hand.
By doping metal ions, the lattice morphology of cerium dioxide can be changed, and the initial reaction temperature can be further effectively reduced. Different metal ions have different ionic radiuses or different valence states, different coordination conditions are formed in crystal lattices, lattice distortion defects are caused by generating lattice stress, the distortion defects are favorable for forming oxygen cavities, energy required by redox reaction is greatly reduced, and therefore the reaction temperature and the complete conversion temperature are reduced. Experiments prove that compared with pure cerium dioxide particles, the doped nano cerium dioxide particles can reduce the reaction temperature to 100 ℃ and the complete conversion temperature to 300 ℃ by doping metal ions.
Specifically, the molar ratio of the metal ions to the cerium dioxide is 10-20 mol%: 40-60 mol%, in the proportion range, the doping amount of the metal ions is positively correlated with the reaction activity, namely the higher the doping amount is, the lower the initial reaction temperature is, and conversely, the lower the doping amount is, the higher the initial reaction temperature is.
Further, the metal ion is selected from at least one of nickel ion, copper ion, titanium ion, and zirconium ion.
The binder plays a role in forming a film in the indicating ink, can resist high-temperature baking, and does not generate combustion or carbonization reaction at a high temperature of below 500 ℃. So that the carbon monoxide indicating ink can be firmly attached to the surface of an object after being cured.
Specifically, the binder can be dissolved in the solvent, and after the binder is cured, a large number of micropores are generated among molecules of the binder along with the volatilization of the solvent, so that carbon monoxide gas can enter the indicating ink through the micropores to participate in a color change reaction. Since carbon monoxide indicates that the ink has an initial reaction temperature of more than 100 ℃, the binder is required to have good high temperature resistance, which does not undergo a combustion or carbonization reaction at a high temperature of 300 ℃ or less, and preferably, does not undergo a combustion or carbonization reaction at a high temperature of 500 ℃ or less.
In this embodiment, the binder is at least one selected from a methyl methacrylate-styrene-acrylic acid copolymer or a butyl acrylate-styrene-hydroxyethyl acrylate copolymer.
In one embodiment, the methyl methacrylate-styrene-acrylic acid copolymer has a molar ratio of methyl methacrylate to styrene to acrylic acid of 1:2: 2.
In one embodiment, the butyl acrylate-styrene-hydroxyethyl acrylate copolymer has a molar ratio of butyl acrylate to styrene, hydroxyethyl acrylate of 2:1: 2.
In one embodiment, the ratio of methyl methacrylate-styrene-acrylic acid copolymer to butyl acrylate-styrene-hydroxyethyl acrylate copolymer is 1: 1.
It is to be understood that other film-forming materials that are soluble in the solvent and resistant to high temperatures may also be used as binders in the present invention.
The solvent is used for dissolving the binder, so that the carbon monoxide indicating ink has good printability.
Specifically, the solvent is at least one selected from the group consisting of ethanol, ethylene glycol, isopropanol, butanol, pentanol, cyclohexanol, acetone, cyclohexanone, and water.
In this example, the solvent was a 75% ethanol solution.
In one embodiment, the carbon monoxide indicating ink further comprises 0.1-5 parts of a dispersing agent, and the dispersing agent can reduce the interfacial tension between liquid and solid and liquid, improve the compatibility of ink components in the same system, help a solvent to wet the surfaces of particles, prevent the agglomeration of ink component particles, and keep the carbon monoxide indicating ink in an emulsion state.
Specifically, the dispersant may be any of commercially available organic dispersants.
The carbon monoxide indicating ink has the initial reaction temperature greatly reduced to 100 ℃, after the ink is printed and dried, a large number of micropores are generated among the molecules of the connecting material, carbon monoxide molecules enter the ink layer through the micropores to be contacted with nano cerium dioxide, when the ink is close to a heat source and the temperature reaches 100 ℃, active oxygen atoms on the surface of the cerium dioxide and the carbon monoxide undergo redox reaction, the carbon monoxide obtains oxygen atoms and is oxidized into carbon dioxide, and meanwhile, the oxygen atoms lost by the cerium dioxide are reduced into cerium oxide with oxygen cavities, and in the process, the color of the cerium oxide indicating ink is changed from white to golden yellow. Since the ceria crystal has oxygen holes, it can adsorb oxygen in the air, and when the oxygen holes adsorb oxygen atoms, the ceria is oxidized again to ceria. The nano cerium dioxide has good oxygen storage and release capacity on the surface, and can be used as a catalyst in the indicating ink. When the color-changing ink is arranged near a heat source (such as a cooking bench or a stove), the color-changing reaction can be promoted by using the heat of the heat source, and after the reaction is started, the color of the ink is changed from white to golden yellow, so that whether carbon monoxide gas is generated in a room or not is indicated through the visible color change, and whether a protective measure is taken or not is determined.
The carbon monoxide indicating ink disclosed by the invention is simple in component, low in cost and good in high-temperature resistance, the reaction temperature is greatly reduced to 100 ℃, the safety performance is high, and the reaction can repeatedly indicate carbon monoxide gas.
Referring to fig. 1, a method for preparing a carbon monoxide indicating ink according to an embodiment includes the following steps:
s10: adding 30-60 parts of the connecting material into 10-40 parts of the solvent, and fully stirring to prepare a first solution.
Adding 30-60 parts of the binder into 10-40 parts of the solvent, and fully stirring until the binder is completely dissolved to prepare a first solution.
The binder plays a role in forming a film in the indicating ink, can resist high-temperature baking, and does not generate combustion or carbonization reaction at a high temperature of below 500 ℃. So that the carbon monoxide indicating ink can be firmly attached to the surface of an object after being cured.
Specifically, the binder can be dissolved in the solvent, and after the binder is cured, a large number of micropores are generated among molecules of the binder along with the volatilization of the solvent, so that carbon monoxide gas can enter the indicating ink through the micropores to participate in a color change reaction. Since carbon monoxide indicates that the ink has an initial reaction temperature of more than 100 ℃, the binder is required to have good high temperature resistance, which does not undergo a combustion or carbonization reaction at a high temperature of 300 ℃ or less, and preferably, does not undergo a combustion or carbonization reaction at a high temperature of 500 ℃ or less.
In this embodiment, the binder is at least one selected from a methyl methacrylate-styrene-acrylic acid copolymer or a butyl acrylate-styrene-hydroxyethyl acrylate copolymer.
In one embodiment, the methyl methacrylate-styrene-acrylic acid copolymer has a molar ratio of methyl methacrylate to styrene to acrylic acid of 1:2: 2.
In one embodiment, the butyl acrylate-styrene-hydroxyethyl acrylate copolymer has a molar ratio of butyl acrylate to styrene, hydroxyethyl acrylate of 2:1: 2.
In one embodiment, the ratio of methyl methacrylate-styrene-acrylic acid copolymer to butyl acrylate-styrene-hydroxyethyl acrylate copolymer is 1: 1.
It is to be understood that other film-forming materials that are soluble in the solvent and resistant to high temperatures may also be used as binders in the present invention.
The solvent is used for dissolving the binder, so that the carbon monoxide indicating ink has good printability.
Specifically, the solvent is at least one selected from the group consisting of ethanol, ethylene glycol, isopropanol, butanol, pentanol, cyclohexanol, acetone, cyclohexanone, and water.
In this example, the solvent was a 75% ethanol solution.
S30: and adding 20-50 parts of nano cerium dioxide into the first solution, and fully stirring to obtain the carbon monoxide indicating ink, wherein the nano cerium dioxide is doped with metal ion impurities.
And adding 20-50 parts of nano cerium dioxide into the first solution, and fully stirring until the nano cerium dioxide is uniformly dispersed to obtain the carbon monoxide indicating ink.
The nano cerium dioxide plays a role of a catalytic indicator in the carbon monoxide indicating ink, so that the oxidation temperature and the oxidation rate of carbon monoxide gas are greatly improved, and the reaction chemical formula is as follows:
2CeO2+CO=Ce2O3+CO2
2Ce2O3+O2=4CeO2
the cerium dioxide has a crystal structure of a face-centered cubic, and the isotropic structural characteristics of the cerium dioxide make the cerium dioxide not easy to form a one-dimensional or two-dimensional structure and easy to form spherical nanoparticles. At a high temperature higher than 600 ℃, active oxygen atoms on the surface of the cerium dioxide are easy to generate oxidation-reduction reaction with carbon monoxide, and in the oxidation-reduction process, oxygen atoms of the cerium dioxide are lost to be reduced into cerium oxide with oxygen holes, so that carbon monoxide obtains oxygen atoms and is oxidized into carbon dioxide, and in the process, the color of the cerium dioxide is changed from white to golden yellow. Since the ceria crystal has oxygen holes, it can adsorb oxygen in the air, and when the oxygen holes adsorb oxygen atoms, the ceria is oxidized again to ceria. The nano cerium dioxide has good oxygen storage and release capacity on the surface, and can be used as a catalytic indicator in the indicating ink.
Specifically, nano-ceria particles are selected as the catalytic indicator material, and since the smaller the particle size of the particles, the larger the total or sub-surface area of the particles, the greater the discoloration reaction occurs at the surface or sub-surface of the nano-ceria, and thus, the rate of reaction thereof can be accelerated by selecting nano-materials as the catalytic indicator material.
Further, the shapes of particles such as nano microspheres, nano wires and nano rods are selected as catalytic indicator materials, and experiments prove that the shapes of the particles such as the nano microspheres, the nano wires and the nano rods are adopted as catalytic indicator materials at the same temperature, so that the color interval of an ink layer is obviously enlarged and the indicating effect is more obvious in the color change reaction process.
Preferably, the nano cerium dioxide particles are nanowires formed by connecting nano microspheres in series, and the cerium dioxide particles with a nano-wire structure can greatly reduce the redox initiation reaction temperature of the indicating ink due to the special microstructure of the cerium dioxide particles.
In one embodiment, the particle size of the nano cerium dioxide particles is 10 nm-200 nm, so that the carbon monoxide indication ink meets the printability requirements of different printing modes, and in addition, the reduction of the particle size of the cerium dioxide particles is beneficial to enlarging the surface or the sub-surface of the cerium dioxide, thereby promoting the progress of the color change reaction.
Preferably, the particle size of the nano cerium dioxide is 10 nm-30 nm, and by limiting the particle size of the nano cerium dioxide, the printability of the ink can be improved on one hand, and the initial reaction temperature of the indicating ink can be reduced on the other hand.
By doping metal ions, the lattice morphology of cerium dioxide can be changed, and the initial reaction temperature can be further effectively reduced. Different metal ions have different ionic radiuses or different valence states, different coordination conditions are formed in crystal lattices, lattice distortion defects are caused by generating lattice stress, the distortion defects are favorable for forming oxygen cavities, energy required by redox reaction is greatly reduced, and therefore the reaction temperature and the complete conversion temperature are reduced. Experiments prove that compared with pure cerium dioxide particles, the doped nano cerium dioxide particles can reduce the reaction temperature to 100 ℃ and the complete conversion temperature to 300 ℃ by doping metal ions.
Specifically, the molar ratio of the metal ions to the cerium dioxide is 10-20 mol%: 40-60 mol%, in the proportion range, the doping amount of the metal ions is positively correlated with the reaction activity, namely the higher the doping amount is, the lower the initial reaction temperature is, and conversely, the lower the doping amount is, the higher the initial reaction temperature is.
Further, the metal ion is selected from at least one of nickel ion, copper ion, titanium ion, and zirconium ion.
In some embodiments, referring to fig. 2, a step of adding a dispersant is further included after step S10 and before step S30.
Step S20: and adding 0.1-5 parts of a dispersing agent into the first solution, and stirring and dissolving to obtain a second solution.
The dispersing agent can reduce the interfacial tension between liquid and solid, improve the compatibility of the ink components in the same system, help the solvent wet the particle surface, prevent the ink component particles from agglomerating, and enable the carbon monoxide to indicate that the ink keeps the emulsion state. Specifically, the dispersant may be any of commercially available organic dispersants.
It should be noted that step S20 belongs to the preferred step, and thus step S20 may be omitted.
The preparation method of the carbon monoxide indicating ink is simple to operate, can be completed by common equipment, and is beneficial to reducing the production cost.
It is to be understood that the above indicated binders, solvents and doped metal ions suitable for the present carbon monoxide indicating ink are only some of the preferred materials, and that any other material that can be used to form a carbon monoxide indicating ink using the principles described above is also within the scope of the present invention.
The carbon monoxide indicating ink of any one of the above or the method of preparing the carbon monoxide indicating ink of any one of the above has at least the following advantages:
(1) the carbon monoxide indication ink has low reaction temperature, can start catalytic reaction at the temperature of 100 ℃, does not need to be provided with a heat source independently, can be used close to a common heat source, and has low safety risk.
(2) The carbon monoxide indicating ink is prepared from the raw materials which are low in price, and is suitable for being used in a large area in a household space.
(3) After the carbon monoxide indicates that the catalytic reaction of the ink is started, the color of the ink is changed from white to golden yellow, and the indicating effect is obvious and striking.
Specific examples are as follows.
Example 1
Referring to fig. 1, the present embodiment provides a method for preparing a carbon monoxide indicating ink, including the following steps:
(1) 30 parts of methyl methacrylate-styrene-acrylic acid copolymer (binder) was added to 10 parts of ethanol (solvent), and sufficiently stirred until the binder was completely dissolved, to prepare a first solution. Wherein the molar ratio of methyl methacrylate to styrene to acrylic acid of the methyl methacrylate-styrene-acrylic acid copolymer is 1:2: 2.
(2) Adding 20 parts of nickel ion-doped microspherical nano cerium dioxide into the first solution, and fully stirring to obtain the carbon monoxide indicating ink, wherein the nano cerium dioxide is in the shape of nano microspheres, the particle size is 10nm, and the molar ratio of copper ions to cerium dioxide is 10 mol% to 40 mol%.
The carbon monoxide indicating ink prepared in the example 1 is white after being printed, and after the printing is dried, a large number of micropores are generated among the binder molecules, and the carbon monoxide molecules enter the ink layer through the micropores to be contacted with the nano cerium dioxide. Because the cerium dioxide in the indicating ink is doped with nickel ions, different coordination conditions are formed in crystal lattices due to different ionic radiuses or valence states among different metal ions, lattice distortion defects are caused by generating lattice stress, the distortion defects are favorable for forming oxygen cavities, and the energy required by redox reaction is greatly reduced, so that the reaction starting temperature and the complete conversion temperature are reduced, and meanwhile, the initial reaction temperature is favorably reduced by adopting nano microsphere cerium dioxide as an indicating catalyst. In this embodiment, the initial reaction temperature is reduced to 100 ℃, when the temperature of the ink near the heat source reaches 100 ℃, the active oxygen atoms on the surface of the ceria and carbon monoxide undergo redox reaction, and the carbon monoxide obtains oxygen atoms and is oxidized into carbon dioxide, so that the oxygen atoms lost from the ceria are reduced into ceria with oxygen vacancies, and the color of the ceria changes from white to golden yellow in the process. Since the ceria crystal has oxygen holes, it can adsorb oxygen in the air, and when the oxygen holes adsorb oxygen atoms, the ceria is oxidized again to ceria. The nano cerium dioxide has good oxygen storage and release capacity on the surface, and can be used as a catalyst in the indicating ink. When the color-changing ink is arranged near a heat source (such as a cooking bench or a stove), the color-changing reaction can be promoted by using the heat of the heat source, and after the reaction is started, the color of the ink is changed from white to golden yellow, so that whether carbon monoxide gas is generated in a room or not is indicated through the visible color change, and whether a protective measure is taken or not is determined.
The carbon monoxide indicating ink is simple in components, low in cost, good in high-temperature resistance, high in safety and reversible in reaction, and the reaction temperature of the carbon monoxide indicating ink is greatly reduced to 100 ℃.
Example 2
Referring to fig. 1, the present embodiment provides a method for preparing a carbon monoxide indicating ink, including the following steps:
(1) 45 parts of a butyl acrylate-styrene-hydroxyethyl acrylate copolymer (binder) was added to 25 parts of isopropyl alcohol (solvent), and sufficiently stirred until the binder was completely dissolved, to prepare a first solution. Wherein the molar ratio of butyl acrylate of the butyl acrylate-styrene-hydroxyethyl acrylate copolymer to styrene and hydroxyethyl acrylate is 2:1: 2.
(2) Adding 35 parts of copper ion-doped cerium dioxide nano-microspheres into the first solution, and fully stirring to obtain the carbon monoxide indicating ink, wherein the nano-cerium dioxide is a nanowire formed by connecting the nano-microspheres in series, the particle size of the nano-microspheres is 10nm, the length of the nanowire is 200nm, and the molar ratio of the copper ions to the cerium dioxide is 15 mol%: 50 mol%.
The carbon monoxide indicating ink prepared in the embodiment 2 is white after being printed, a large number of micropores are generated among connecting material molecules after being printed and dried, carbon monoxide molecules can enter an ink layer through the micropores to be contacted with tetravalent nano cerium dioxide, copper ions are doped in cerium dioxide in the indicating ink, different coordination conditions are formed in lattices due to different metal ions, lattice distortion defects are caused by lattice stress, the distortion defects are favorable for forming oxygen cavities, energy required by redox reaction is greatly reduced, and therefore the reaction temperature and the complete conversion temperature are reduced. In this embodiment, the initial reaction temperature is reduced to 100 ℃, when the temperature of the ink near the heat source reaches 100 ℃, the active oxygen atoms on the surface of the ceria and carbon monoxide undergo redox reaction, and the carbon monoxide obtains oxygen atoms and is oxidized into carbon dioxide, so that the oxygen atoms lost from the ceria are reduced into ceria with oxygen vacancies, and the color of the ceria changes from white to golden yellow in the process. Since the ceria crystal has oxygen holes, it can adsorb oxygen in the air, and when the oxygen holes adsorb oxygen atoms, the ceria is oxidized again to ceria. The nano cerium dioxide has good oxygen storage and release capacity on the surface, and can be used as a catalyst in the indicating ink. When the color-changing ink is arranged near a heat source (such as a cooking bench or a stove), the color-changing reaction can be promoted by using the heat of the heat source, and after the reaction is started, the color of the ink is changed from white to golden yellow, so that whether carbon monoxide gas is generated in a room or not is indicated through the visible color change, and whether a protective measure is taken or not is determined.
The carbon monoxide indicating ink is simple in components, low in cost, good in high-temperature resistance, high in safety and reversible in reaction, and the reaction temperature of the carbon monoxide indicating ink is greatly reduced to 100 ℃.
Example 3
Referring to fig. 2, the carbon monoxide indicating ink of the present embodiment is prepared by the following steps:
(1) 60 parts of a butyl acrylate-styrene-hydroxyethyl acrylate copolymer (binder) was added to 40 parts of a 75% isopropyl alcohol solution (solvent), and sufficiently stirred until the binder was completely dissolved, to prepare a first solution. Wherein the molar ratio of butyl acrylate of the butyl acrylate-styrene-hydroxyethyl acrylate copolymer to styrene and hydroxyethyl acrylate is 2:1: 2.
(2) 0.1 part of dispersant is added into the first solution, and the mixture is fully stirred to prepare a second solution.
(3) Adding 50 parts of titanium ion-doped cerium dioxide nanowires into the second solution, and fully stirring to obtain the carbon monoxide indicating ink, wherein the nano cerium dioxide is in the shape of a nanorod, the width of the end of the nanorod is 20nm, the length of the nanorod is 150nm, and the molar ratio of the titanium ions to the cerium dioxide is 20 mol%: 60 mol%.
The carbon monoxide indicating ink prepared in the embodiment 3 is white after being printed, a large number of micropores are generated among connecting material molecules after being printed and dried, carbon monoxide molecules can enter an ink layer through the micropores to be contacted with tetravalent nano cerium dioxide, titanium ions are doped in cerium dioxide in the indicating ink, different coordination conditions are formed in crystal lattices due to different metal ions, lattice distortion defects are caused by lattice stress, the distortion defects are favorable for forming oxygen cavities, energy required by redox reaction is greatly reduced, and therefore the reaction temperature and the complete conversion temperature are reduced. In this embodiment, the initial reaction temperature is reduced to 100 ℃, when the temperature of the ink near the heat source reaches 100 ℃, the active oxygen atoms on the surface of the ceria and carbon monoxide undergo redox reaction, and the carbon monoxide obtains oxygen atoms and is oxidized into carbon dioxide, so that the oxygen atoms lost from the ceria are reduced into ceria with oxygen vacancies, and the color of the ceria changes from white to golden yellow in the process. Since the ceria crystal has oxygen holes, it can adsorb oxygen in the air, and when the oxygen holes adsorb oxygen atoms, the ceria is oxidized again to ceria. The nano cerium dioxide has good oxygen storage and release capacity on the surface, and can be used as a catalyst in the indicating ink. When the color-changing ink is arranged near a heat source (such as a cooking bench or a stove), the color-changing reaction can be promoted by using the heat of the heat source, and after the reaction is started, the color of the ink is changed from white to golden yellow, so that whether carbon monoxide gas is generated in a room or not is indicated through the visible color change, and whether a protective measure is taken or not is determined.
The carbon monoxide indicating ink is simple in components, low in cost, good in high-temperature resistance, high in safety and reversible in reaction, and the reaction temperature of the carbon monoxide indicating ink is greatly reduced to 100 ℃.
Example 4
Referring to fig. 2, the present embodiment provides a method for preparing a carbon monoxide indicating ink, including the following steps:
(1) 30 parts of methyl methacrylate-styrene-acrylic acid copolymer (binder) and 30 parts of butyl acrylate-styrene-hydroxyethyl acrylate copolymer (binder) were added to 40 parts of ethylene glycol (solvent), and sufficiently stirred until the binder was completely dissolved, to prepare a first solution.
(2) 2 parts of a dispersant is added into the first solution, and the mixture is fully stirred to prepare a second solution.
(3) And adding 50 parts of cerium dioxide nanowires with particle sizes doped with zirconium ions into the second solution, and fully stirring to obtain the carbon monoxide indicating ink. Wherein, the shape of the nano cerium dioxide is a nanorod, the width of the end of the nanorod is 15nm, the length of the nanorod is 200nm, and the molar ratio of zirconium ions to cerium dioxide is 16 mol%: 50 mol%.
The carbon monoxide indicating ink prepared in the embodiment 4 is white after being printed, a large number of micropores are generated among connecting material molecules after being printed and dried, carbon monoxide molecules can enter an ink layer through the micropores to be contacted with tetravalent nano cerium dioxide, titanium ions are doped in cerium dioxide in the indicating ink, different coordination conditions are formed in crystal lattices due to different metal ions, lattice distortion defects are caused by lattice stress, the distortion defects are favorable for forming oxygen cavities, energy required by redox reaction is greatly reduced, and therefore the reaction temperature and the complete conversion temperature are reduced. In this embodiment, the initial reaction temperature is reduced to 100 ℃, when the temperature of the ink near the heat source reaches 100 ℃, the active oxygen atoms on the surface of the ceria and carbon monoxide undergo redox reaction, and the carbon monoxide obtains oxygen atoms and is oxidized into carbon dioxide, so that the oxygen atoms lost from the ceria are reduced into ceria with oxygen vacancies, and the color of the ceria changes from white to golden yellow in the process. Since the ceria crystal has oxygen holes, it can adsorb oxygen in the air, and when the oxygen holes adsorb oxygen atoms, the ceria is oxidized again to ceria. The nano cerium dioxide has good oxygen storage and release capacity on the surface, and can be used as a catalyst in the indicating ink. When the color-changing ink is arranged near a heat source (such as a cooking bench or a stove), the color-changing reaction can be promoted by using the heat of the heat source, and after the reaction is started, the color of the ink is changed from white to golden yellow, so that whether carbon monoxide gas is generated in a room or not is indicated through the visible color change, and whether a protective measure is taken or not is determined.
The carbon monoxide indicating ink is simple in components, low in cost, good in high-temperature resistance, high in safety and reversible in reaction, and the reaction temperature of the carbon monoxide indicating ink is greatly reduced to 100 ℃.
Example 5
This example provides a carbon monoxide indicating ink similar to that of example 4, except that: (1) the binder of the indicating ink is a mixture of methyl methacrylate-styrene-acrylic acid copolymer and butyl acrylate-styrene-hydroxyethyl acrylate copolymer, the weight percentage is 1:1, and the content of (2) dispersant is 5 parts.
The carbon monoxide indicating ink prepared in the embodiment 5 is white after being printed, a large number of micropores are generated among connecting material molecules after being printed and dried, carbon monoxide molecules can enter an ink layer through the micropores to be contacted with tetravalent nano cerium dioxide, titanium ions are doped in cerium dioxide in the indicating ink, different coordination conditions are formed in crystal lattices due to different metal ions, lattice distortion defects are caused by lattice stress, the distortion defects are favorable for forming oxygen holes, energy required by redox reaction is greatly reduced, and therefore the reaction temperature and the complete conversion temperature are reduced. In this embodiment, the initial reaction temperature is reduced to 100 ℃, when the temperature of the ink near the heat source reaches 100 ℃, the active oxygen atoms on the surface of the ceria and carbon monoxide undergo redox reaction, and the carbon monoxide obtains oxygen atoms and is oxidized into carbon dioxide, so that the oxygen atoms lost from the ceria are reduced into ceria with oxygen vacancies, and the color of the ceria changes from white to golden yellow in the process. Since the ceria crystal has oxygen holes, it can adsorb oxygen in the air, and when the oxygen holes adsorb oxygen atoms, the ceria is oxidized again to ceria. The nano cerium dioxide has good oxygen storage and release capacity on the surface, and can be used as a catalyst in the indicating ink. When the color-changing ink is arranged near a heat source (such as a cooking bench or a stove), the color-changing reaction can be promoted by using the heat of the heat source, and after the reaction is started, the color of the ink is changed from white to golden yellow, so that whether carbon monoxide gas is generated in a room or not is indicated through the visible color change, and whether a protective measure is taken or not is determined.
The carbon monoxide indicating ink is simple in components, low in cost, good in high-temperature resistance, high in safety and reversible in reaction, and the reaction temperature of the carbon monoxide indicating ink is greatly reduced to 100 ℃.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. The carbon monoxide indicating ink is characterized by comprising the following raw materials in parts by mass:
20-50 parts of nano cerium dioxide;
30-60 parts of a connecting material; and
10-40 parts of a solvent;
wherein, the nano cerium dioxide is doped with metal ion impurities, and the molar ratio of the metal ions to the cerium dioxide is 10 mol% to 20 mol%: 40 to 60 mole%, the metal ion is at least one of nickel ion, copper ion, titanium ion and zirconium ion, and the carbon monoxide indicating ink can indicate the carbon monoxide concentration through color change.
2. The carbon monoxide indicating ink as in claim 1, wherein the nano ceria has a particle size of 10nm to 200 nm.
3. The carbon monoxide indicating ink as recited in claim 2, wherein the binder is selected from at least one of methyl methacrylate-styrene-acrylic acid copolymer or butyl acrylate-styrene-hydroxyethyl acrylate copolymer.
4. The carbon monoxide indicating ink as in claim 3, wherein the methyl methacrylate-styrene-acrylic acid copolymer has a molar ratio of methyl methacrylate to styrene to acrylic acid of 1:2: 2.
5. The carbon monoxide indicating ink as in claim 3, wherein the butyl acrylate-styrene-hydroxyethyl acrylate copolymer has a molar ratio of butyl acrylate to styrene and hydroxyethyl acrylate of 2:1: 2.
6. The carbon monoxide indicating ink as defined in claim 1, further comprising 0.1 to 5 parts of a dispersant.
7. A method of preparing a carbon monoxide indicating ink for use in preparing a carbon monoxide indicating ink as claimed in any one of claims 1 to 6, comprising the steps of:
adding 30-60 parts of connecting material into 10-40 parts of solvent, and fully stirring to prepare a first solution;
adding 20-50 parts of nano cerium dioxide into the first solution, and fully stirring to obtain the carbon monoxide indicating ink, wherein the nano cerium dioxide is doped with metal ion impurities, and the molar ratio of the metal ions to the cerium dioxide is 10-20 mol%: 40 to 60 mole%, the metal ion is at least one of nickel ion, copper ion, titanium ion and zirconium ion, and the carbon monoxide indicating ink can indicate the carbon monoxide concentration through color change.
8. The method of claim 7, wherein after the step of adding 30 to 60 parts of the binder to 10 to 40 parts of the solvent and sufficiently stirring to obtain the first solution, the step of adding 20 to 50 parts of the nano ceria to the first solution and sufficiently stirring to obtain the carbon monoxide indicating ink further comprises the step of adding 0.1 to 5 parts of the dispersant and stirring.
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