CN110862703A - Nano fireproof heat-insulating anticorrosive paint and preparation method thereof - Google Patents
Nano fireproof heat-insulating anticorrosive paint and preparation method thereof Download PDFInfo
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- 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
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- 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
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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
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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Abstract
The invention provides a nano fireproof heat-insulating anticorrosive coating and a preparation method thereof, wherein the coating comprises 3-9 wt% of nano titanium dioxide microspheres, 2-7 wt% of nano yttrium oxide microspheres, 15-20 wt% of nano zirconium oxide hydrosol, 30-50 wt% of nano rare earth hydrosol, 0.5-2 wt% of modifier, 1-5 wt% of film-forming assistant, 1-6 wt% of polysilazane, 1-1.5 wt% of GTO nano powder, 2-12 wt% of tungsten bronze whiskers and 1-7 wt% of high-strength nano silica aerogel. The coating is designed into an ultralow-thermal-conductivity crosslinking system, the flame-retardant and fire-resistant heat insulation of the coating is formed by utilizing the fire-resistant and high-temperature-resistant high-reflection nano crosslinking substances, the thermal resistance framework is formed by utilizing the ultralow-thermal-conductivity aerogel, the strength and the tear resistance are improved by utilizing the whiskers, and the impact resistance of the coating is stabilized by utilizing the ultrahigh strength of the inorganic sol and polysilazane hybrid film forming system. Through the mode, the anticorrosive wear-resistant impact-resistant protective functional coating with ultralow heat conductivity coefficient can be obtained.
Description
Technical Field
The invention belongs to the technical field of nano high-strength heat-insulating anticorrosive coatings, and particularly relates to a nano fire-resistant heat-insulating anticorrosive coating and a preparation method thereof.
Background
In special industries, flammable and explosive materials need to be applied, stored, moved and the like, most of the containers are made of steel shells or spaces, so that firstly, the fire safety is solved, and particularly, the safety is more important when the containers are used in military affairs.
The traditional method adopts the scheme of multilayer composite heat insulation (such as fire-proof plates) and the like besides coating common fire-proof coatings, but for a large cabin body (cabin body), the traditional fire-proof structure is feasible, but for small containers such as an elastomer and the like, the traditional scheme cannot be implemented, the thickness of the coating is limited due to the restriction of various factors, generally, the thickness of the dry film of the coating cannot exceed 1 mm, the heat conductivity coefficient of the common fire-proof coating is not as low as required, and inflammable and explosive materials are sensitive to temperature and can explode when reaching a certain temperature critical point, so that the purpose of long-time safe fire resistance cannot be achieved even if the common fire-proof coating is coated.
The fire-resistant and heat-insulating performance is only one aspect, and the corrosion resistance and the collision resistance required by long-term storage and transportation cannot be achieved by the common fireproof coating.
Although some functional high-temperature-resistant heat-insulating anticorrosive coatings exist at present, the coatings have insufficient strength and poor breakage resistance either due to temperature difference resistance, and are not suitable for being used in small-sized, mobile, frequently-worn and bumped environments.
Therefore, an anticorrosive functional coating which has long-time fire resistance (1200 ℃), ultralow heat conductivity coefficient, super-strong wear resistance and impact resistance is urgently needed.
Disclosure of Invention
The invention aims to solve the performance defects of the traditional fireproof coating, and provides a high-strength fire-resistant heat-insulating anticorrosive coating with an ultralow heat conductivity coefficient, which adopts a film-forming material with high temperature resistance (over 1200 ℃), wear resistance and crack resistance to be combined with an inorganic nano heat-insulating and fire-resistant system in a crosslinking way, so that the problems of fire resistance, heat insulation, corrosion resistance, water resistance and wear resistance are solved.
The invention specifically adopts the following technical scheme:
the invention provides a nanometer fire-resistant heat-insulating anticorrosive coating which comprises 3-9 wt% of nanometer titanium dioxide microspheres, 2-7 wt% of nanometer yttrium oxide microspheres, 15-20 wt% of nanometer zirconium oxide hydrosol, 30-50 wt% of nanometer rare earth hydrosol, 0.5-2 wt% of a modifier, 1-5 wt% of a film-forming assistant, 1-6 wt% of polysilazane, 1-1.5 wt% of GTO nanometer powder, 2-12 wt% of tungsten bronze whiskers and 1-7 wt% of high-strength nanometer silica aerogel.
Based on the technical scheme, the particle size of the nano-scale titanium dioxide microspheres is preferably 500-2000 nm.
Based on the technical scheme, preferably, the particle size of the nano yttrium oxide microspheres is 200 nm-600 nm
Based on the technical scheme, preferably, the nano zirconia hydrosol and the nano rare earth hydrosol are film-forming hydrosols.
Based on the technical scheme, preferably, the modifier is a KH-570 silane coupling agent.
Based on the technical scheme, the film-forming aid is preferably boric acid and sodium tripolyphosphate in a mass ratio of 1: 2.
Based on the technical scheme, preferably, the tungsten bronze whiskers have the diameter of 0.1-0.6 um and the length of 3-20 um; .
Based on the technical scheme, preferably, the high-strength nano silica aerogel has a particle size of 500-1000 nm and a compressive strength of more than 1 mpa.
Based on the technical scheme, preferably, the solid content of the zirconia hydrosol is 8 wt%; the rare earth hydrosol is lanthanum-cerium mixed oxide hydrogel; in the lanthanum-cerium mixed oxide, the lanthanum oxide accounts for 20-40 wt%, the cerium oxide accounts for 60-80 wt%, and the content of the lanthanum-cerium mixed oxide in the rare earth hydrosol accounts for 1.3 wt%.
The invention also provides a preparation method of the anticorrosive heat-insulating coating, which comprises the following steps:
step 1: weighing the materials in proportion for later use;
step 2: firstly, liquid materials of nano zirconium oxide hydrosol, nano lanthanum cerium rare earth hydrosol, polysilazane and film forming additive are put into a reaction kettle, dispersed at high speed, the rotating speed is 2000 r/min, dispersed for 30 min, the rotating speed is adjusted to 150 r/min,
and step 3: and (3) sucking GTO nano powder, tungsten bronze whiskers and high-strength nano silicon dioxide aerogel into the reaction kettle in vacuum, regulating the rotation speed to 1200 revolutions per minute, dispersing for 30 minutes, and regulating the rotation speed to 350 revolutions per minute.
And 4, step 4: and (3) sucking the nano titanium dioxide microspheres and the nano yttrium oxide microspheres into the reaction kettle in vacuum, and stirring for 20 minutes.
And 5: diluting the modifier with 10 times of absolute ethyl alcohol, putting into a reaction kettle, and stirring for 60 minutes. Thus obtaining the nano fireproof heat-insulating anticorrosive paint.
Advantageous effects
(1) The invention solves the problem that the traditional ultrathin fireproof coating can not achieve the performances of fire resistance for a long time, collision resistance, corrosion resistance, wear resistance and the like.
(2) The nanometer fireproof heat-insulating anticorrosive paint is environment-friendly and non-toxic, and has no pollution and no emission in the production process.
(3) The coating provided by the invention is designed into an ultralow-thermal-conductivity crosslinking system, the flame-retardant, fire-resistant and temperature-insulating properties of the coating are formed by using the fire-resistant, high-temperature-resistant and high-reflection nano crosslinking substances, the thermal resistance framework is formed by using the ultralow-thermal-conductivity aerogel, the strength and the tear resistance are improved by using the whiskers, and the impact resistance of the coating is stabilized by using the ultrahigh strength of the inorganic sol and polysilazane hybrid film forming system.
Drawings
FIG. 1 is a thermal conductivity curve chart of the anticorrosive and heat-insulating coating of the present invention.
Detailed Description
The zirconia hydrosol of the invention has a solid content of 8 wt%, and the preparation method refers to patent document CN102531053B (2014); the rare earth hydrosol is lanthanum-cerium mixed oxide hydrosol, and the preparation method refers to patent document CN108311156A (2018); unless otherwise specified, other raw materials of the present invention are commercially available, for example, the silica aerogel is a commercially pure product, and the GTO nanopowder is a commercially available transparent nanomaterial.
The technical scheme of the invention is further described in detail by combining the drawings and the specific embodiments in the specification.
The invention discloses a nano fireproof heat-insulating anticorrosive paint and a preparation method thereof.
The nanometer fireproof heat-insulating anticorrosive paint comprises 3-9 wt% of nanometer titanium dioxide microspheres, 2-7 wt% of nanometer yttrium oxide microspheres, 15-20 wt% of nanometer zirconium oxide hydrosol, 30-50 wt% of nanometer lanthanum cerium rare earth hydrosol, 0.5-2 wt% of modifier, 1-5 wt% of film forming aid, 1-6 wt% of polysilazane, 1-1.5 wt% of GTO nanometer powder, 2-12 wt% of tungsten bronze whiskers and 1-7 wt% of high-strength nanometer silicon dioxide aerogel.
The nano-scale titanium dioxide microspheres have the particle size of 500-2000 nm.
The particle size of the nano yttrium oxide microspheres is 200 nm-600 nm
The nano zirconia hydrosol and the nano lanthanum cerium rare earth hydrosol are film-forming hydrosols.
The modifier is KH-570 silane coupling agent.
The film-forming additive is boric acid and sodium tripolyphosphate in a ratio of 1: 2.
The tungsten bronze crystal whisker has the diameter of 0.1-0.6 um and the length of 3-20 um; .
The high-strength nano silicon dioxide aerogel has the particle size of 500-1000 nm and the compressive strength of more than 1 mpa.
The application also discloses a preparation method of the anticorrosive heat-insulating coating, which comprises the following steps:
step 1: weighing the materials in proportion for later use;
step 2: firstly, liquid materials of nano zirconium oxide hydrosol, nano lanthanum cerium rare earth hydrosol, polysilazane and film forming additive are put into a reaction kettle, dispersed at high speed, the rotating speed is 2000 r/min, dispersed for 30 min, the rotating speed is adjusted to 150 r/min,
and step 3: and (3) sucking GTO nano powder, tungsten bronze whiskers and high-strength nano silicon dioxide aerogel into the reaction kettle in vacuum, regulating the rotation speed to 1200 revolutions per minute, dispersing for 30 minutes, and regulating the rotation speed to 350 revolutions per minute.
And 4, step 4: and (3) sucking the nano titanium dioxide microspheres and the nano yttrium oxide microspheres into the reaction kettle in vacuum, and stirring for 20 minutes.
And 5: diluting the modifier with 10 times of absolute ethyl alcohol, putting into a reaction kettle, and stirring for 60 minutes.
Thus obtaining the nano fireproof heat-insulating anticorrosive paint.
The above technical solution is described in detail by the following specific embodiments.
Example 1
The nanometer fireproof heat-insulating anticorrosive paint comprises 4 wt% of nanometer titanium dioxide microspheres, 7 wt% of nanometer yttrium oxide microspheres, 15 wt% of nanometer zirconium oxide hydrosol, 50 wt% of nanometer lanthanum cerium rare earth hydrosol, 1 wt% of modifier, 5 wt% of film-forming assistant, 1 wt% of polysilazane, 1 wt% of GTO nanometer powder, 12 wt% of tungsten bronze whiskers and 4 wt% of high-strength nanometer silicon dioxide aerogel.
The particle size of the nano titanium dioxide microspheres is 500 nm.
The particle size of the nano yttrium oxide microspheres is 200nm
The nano zirconia hydrosol and the nano lanthanum cerium rare earth hydrosol are film-forming hydrosols.
The modifier is KH-570 silane coupling agent.
The film-forming additive is boric acid and sodium tripolyphosphate in a ratio of 1: 2.
The tungsten bronze crystal whisker has the diameter of 0.1um and the length of 20 um; .
The high-strength nano-silica aerogel has a particle size of 500nm and a compressive strength of more than 1 mpa.
The application also discloses a preparation method of the anticorrosive heat-insulating coating, which comprises the following steps:
step 1: weighing the materials in proportion for later use;
step 2: firstly, liquid materials of nano zirconium oxide hydrosol, nano lanthanum cerium rare earth hydrosol, polysilazane and film forming additive are put into a reaction kettle, dispersed at high speed, the rotating speed is 2000 r/min, dispersed for 30 min, the rotating speed is adjusted to 150 r/min,
and step 3: and (3) sucking GTO nano powder, tungsten bronze whiskers and high-strength nano silicon dioxide aerogel into the reaction kettle in vacuum, regulating the rotation speed to 1200 revolutions per minute, dispersing for 30 minutes, and regulating the rotation speed to 350 revolutions per minute.
And 4, step 4: and (3) sucking the nano titanium dioxide microspheres and the nano yttrium oxide microspheres into the reaction kettle in vacuum, and stirring for 20 minutes.
And 5: diluting the modifier with 10 times of absolute ethyl alcohol, putting into a reaction kettle, and stirring for 60 minutes.
Thus obtaining the nano fireproof heat-insulating anticorrosive paint.
In the embodiment, the components are blended in a formula ratio and at two poles, and the obtained nanometer fireproof, heat-insulating and anticorrosive coating has the following properties:
the thermal conductivity at 1200 ℃ is: 0.068 w/m.k. The highest temperature resistance: 1200 ℃. Peel strength: 1 Mpa; compressive strength: 3Mpa
Example 2
A nanometer fire-resistant heat-insulating anticorrosive paint and a preparation method thereof are characterized in that:
the nanometer fireproof heat-insulating anticorrosive paint comprises 6 wt% of nanometer titanium dioxide microspheres, 7 wt% of nanometer yttrium oxide microspheres, 17 wt% of nanometer zirconium oxide hydrosol, 50 wt% of nanometer lanthanum-cerium-rare earth hydrosol, 1 wt% of modifier, 3 wt% of film forming additive, 3 wt% of polysilazane, 2 wt% of GTO nanometer powder, 5 wt% of tungsten bronze whiskers and 6 wt% of high-strength nanometer silicon dioxide aerogel.
The particle size of the nano titanium dioxide microspheres is 1000 nm.
The particle size of the nano yttrium oxide microspheres is 400nm
The nano zirconia hydrosol and the nano lanthanum cerium rare earth hydrosol are film-forming hydrosols.
The modifier is KH-570 silane coupling agent.
The film-forming additive is boric acid and sodium tripolyphosphate with the mass ratio of 1: 2.
The tungsten bronze crystal whisker has the diameter of 0.4um and the length of 10 um; .
The high-strength nano-silica aerogel has the particle size of 700nm and the compressive strength of more than 1 mpa.
The application also discloses a preparation method of the anticorrosive heat-insulating coating, which is characterized by comprising the following steps:
step 1: weighing the materials in proportion for later use;
step 2: firstly, liquid materials of nano zirconium oxide hydrosol, nano lanthanum cerium rare earth hydrosol, polysilazane and film forming additive are put into a reaction kettle, dispersed at high speed, the rotating speed is 2000 r/min, dispersed for 30 min, the rotating speed is adjusted to 150 r/min,
and step 3: and (3) sucking GTO nano powder, tungsten bronze whiskers and high-strength nano silicon dioxide aerogel into the reaction kettle in vacuum, regulating the rotation speed to 1200 revolutions per minute, dispersing for 30 minutes, and regulating the rotation speed to 350 revolutions per minute.
And 4, step 4: and (3) sucking the nano titanium dioxide microspheres and the nano yttrium oxide microspheres into the reaction kettle in vacuum, and stirring for 20 minutes.
And 5: diluting the modifier with 10 times of absolute ethyl alcohol, putting into a reaction kettle, and stirring for 60 minutes.
Thus obtaining the nano fireproof heat-insulating anticorrosive paint.
In the embodiment, the powder-liquid ratio in the formula is increased, the film forming factor is increased, and the properties of the obtained nano fireproof heat-insulating anticorrosive coating are as follows:
the thermal conductivity at 1200 ℃ is: 0.057 w/m.k. The highest temperature resistance: 1200 ℃. Peel strength: 1.6 Mpa; compressive strength: 7Mpa is used
Example 3
A nanometer fire-resistant heat-insulating anticorrosive paint and a preparation method thereof are characterized in that:
the nanometer fireproof heat-insulating anticorrosive paint comprises 9 wt% of nanometer titanium dioxide microspheres, 7 wt% of nanometer yttrium oxide microspheres, 20 wt% of nanometer zirconium oxide hydrosol, 40 wt% of nanometer lanthanum-cerium-rare earth hydrosol, 2 wt% of a modifier, 5 wt% of a film forming additive, 6 wt% of polysilazane, 1 wt% of GTO nanometer powder, 5 wt% of tungsten bronze whiskers and 5 wt% of high-strength nanometer silicon dioxide aerogel.
The nano-scale titanium dioxide microspheres are graded according to the ratio of 1:1:1, wherein the particle sizes of the nano-scale titanium dioxide microspheres are 500nm, 1000nm and 2000 nm.
The nanometer yttrium oxide microspheres have the grain sizes of 200nm, 400nm and 600nm according to 1:1:1 gradation
The nano zirconia hydrosol and the nano lanthanum cerium rare earth hydrosol are film-forming hydrosols.
The modifier is KH-570 silane coupling agent.
The film-forming additive is prepared from boric acid and sodium tripolyphosphate in a mass ratio of 1: 2.
the tungsten bronze whiskers are 0.1, 0.3 and 0.6um in diameter and 5, 10 and 20um in length and are graded according to a ratio of 1:1: 1; .
The high-strength nano silicon dioxide aerogel has the grain size of 500nm, 700nm and 1000nm which are graded according to the ratio of 1:1:1, and the compressive strength of more than 1 mpa.
The application also discloses a preparation method of the anticorrosive heat-insulating coating, which is characterized by comprising the following steps:
step 1: weighing the materials in proportion for later use;
step 2: firstly, liquid materials of nano zirconium oxide hydrosol, nano lanthanum cerium rare earth hydrosol, polysilazane and film forming additive are put into a reaction kettle, dispersed at high speed, the rotating speed is 2000 r/min, dispersed for 30 min, the rotating speed is adjusted to 150 r/min,
and step 3: and (3) sucking GTO nano powder, tungsten bronze whiskers and high-strength nano silicon dioxide aerogel into the reaction kettle in vacuum, regulating the rotation speed to 1200 revolutions per minute, dispersing for 30 minutes, and regulating the rotation speed to 350 revolutions per minute.
And 4, step 4: and (3) sucking the nano titanium dioxide microspheres and the nano yttrium oxide microspheres into the reaction kettle in vacuum, and stirring for 20 minutes.
And 5: diluting the modifier with 10 times of absolute ethyl alcohol, putting into a reaction kettle, and stirring for 60 minutes.
Thus obtaining the nano fireproof heat-insulating anticorrosive paint.
In the embodiment, various particles with the functions of fire resistance and heat insulation are graded according to the particle size distribution, the film forming factor is adjusted to be maximum, the strength and the corrosion resistance of the coating are enhanced, and the properties of the obtained nano fire-resistant heat-insulating anticorrosive coating are as follows:
the thermal conductivity at 1200 ℃ is: 0.039 w/m.k. The highest temperature resistance: 1200 ℃. Peel strength: 2 Mpa; compressive strength: 8 Mpa.
As shown in fig. 1, it is the thermal conductivity curve characteristic of the nano fire-resistant, heat-insulating and corrosion-resistant coating of example 3 of the present invention.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A nanometer fireproof heat-insulating anticorrosive paint is characterized in that: the titanium dioxide/zirconium oxide composite material comprises 3-9 wt% of titanium dioxide microspheres, 2-7 wt% of yttrium oxide microspheres, 15-20 wt% of zirconium oxide hydrosol, 30-50 wt% of rare earth hydrosol, 0.5-2 wt% of modifier, 1-5 wt% of film forming assistant, 1-6 wt% of polysilazane, 1-1.5 wt% of GTO nano powder, 2-12 wt% of tungsten bronze whiskers and 1-7 wt% of silicon dioxide aerogel.
2. The nano fire-resistant heat-insulating anticorrosive paint according to claim 1, characterized in that: the particle size of the titanium dioxide microspheres is 500-2000 nm.
3. The nano fire-resistant heat-insulating anticorrosive paint according to claim 1, characterized in that: the grain diameter of the yttrium oxide microspheres is 200 nm-600 nm.
4. The nano fire-resistant heat-insulating anticorrosive paint according to claim 1, characterized in that: the nano zirconia hydrosol and the nano rare earth hydrosol are film-forming hydrosols.
5. The nano fire-resistant heat-insulating anticorrosive paint according to claim 1, characterized in that: the modifier is KH-570 silane coupling agent.
6. The nano fire-resistant heat-insulating anticorrosive paint according to claim 1, characterized in that: the film-forming additive is a mixture of boric acid and sodium tripolyphosphate; in the mixture, the mass ratio of boric acid to sodium tripolyphosphate is 1: 2.
7. The nano fire-resistant heat-insulating anticorrosive paint according to claim 1, characterized in that: the diameter of the tungsten bronze whisker is 0.1-0.6 um, and the length is 3-20 um.
8. The nano fire-resistant heat-insulating anticorrosive paint according to claim 1, characterized in that: the particle size of the silicon dioxide aerogel is 500 nm-1000 nm, and the compressive strength of the silicon dioxide aerogel is greater than 1 mpa.
9. The nano fireproof heat-insulating anticorrosive paint as claimed in claim 1, wherein the zirconia hydrosol has a solid content of 8 wt%; the rare earth hydrosol is lanthanum-cerium mixed oxide hydrosol; in the lanthanum-cerium mixed oxide, the content of lanthanum oxide is 20-40 wt%, the content of cerium oxide is 60-80 wt%, and in the rare earth hydrosol, the content of lanthanum-cerium mixed oxide is 1.3 wt%.
10. The preparation method of the nanometer fire-resistant heat-insulating anticorrosive paint as claimed in any one of claims 1 to 9, characterized by comprising the following steps:
step 1: putting the zirconia hydrosol, the rare earth hydrosol, the polysilazane and the film-forming additive into a reaction kettle, dispersing at a high speed at 2000 rpm for 30 minutes, and adjusting the rotating speed to 150 rpm;
step 2: sucking GTO nano powder, tungsten bronze whiskers and nano silicon dioxide aerogel into a reaction kettle in vacuum, regulating the rotation speed to 1200 revolutions per minute, and regulating the rotation speed to 350 revolutions per minute after dispersing for 30 minutes;
and step 3: sucking titanium dioxide and yttrium oxide into the reaction kettle in vacuum, and stirring for 20 minutes;
and 4, step 4: diluting the modifier with 10 times of absolute ethyl alcohol, putting the diluted modifier into a reaction kettle, and stirring for 60 minutes to obtain the nano fireproof heat-insulating anticorrosive paint.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115650679A (en) * | 2022-12-28 | 2023-01-31 | 河北宝廷工程建设有限公司 | Light foam concrete and preparation method thereof |
| CN115650679B (en) * | 2022-12-28 | 2023-03-17 | 河北宝廷工程建设有限公司 | Light foam concrete and preparation method thereof |
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