CN109537271A - A kind of flame-retardant textile and preparation method thereof that the graphene aerogel based on microvesicle templated sol gel method is modified - Google Patents
A kind of flame-retardant textile and preparation method thereof that the graphene aerogel based on microvesicle templated sol gel method is modified Download PDFInfo
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- CN109537271A CN109537271A CN201811508184.7A CN201811508184A CN109537271A CN 109537271 A CN109537271 A CN 109537271A CN 201811508184 A CN201811508184 A CN 201811508184A CN 109537271 A CN109537271 A CN 109537271A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
Abstract
The present invention provides a kind of flame-retardant textile and preparation method thereof that the graphene aerogel based on microvesicle templated sol gel method is modified, comprising the following steps: alkyl polyglycoside and lauryl sodium sulfate are added in deionized water, obtain foam precursor solution；It will be added in DL-cysteine in graphene oxide solution, pre-add thermal reduction obtains the graphene oxide hydrosol of prereduction；Foam precursor solution and the graphene oxide hydrosol of prereduction are mixed, fabric is placed in one, high speed shear, stable foam is formed in fabric surface, takes out fabric, is rapidly frozen, foam film is split, and the graphene oxide liquid crystal porous material of partial reduction is prepared；The graphene oxide liquid crystal porous material of partial reduction is thawed at room temperature, heating reduction, then be freeze-dried, obtain the modified flame-retardant textile of graphene aerogel.Graphene aerogel is attached to the inside and surface of fabric by the present invention, light specific gravity, insoluble not molten, excellent fireproof performance textile fabric is prepared.
Description
Technical field
The invention belongs to textile material technical fields, and in particular to a kind of graphene based on microvesicle templated sol gel method
The modified flame-retardant textile and preparation method thereof of aeroge.
Background technique
Graphene is the two-dimentional carbon nano-structured material with fullerene and carbon nanotube for allotrope, graphene uniqueness
Two-dimensional nano stacking carbon structure make it have superhigh specific surface area, conduction, thermally conductive, antibacterial and mechanical property, therefore by graphite
Alkene can assign the functions such as textile far infrared, uvioresistant, antibacterial bacteriostatic, the enhancing of fire-retardant and mechanics as additive, improve
The surcharge of textile.
The inflammability of textile is always the primary raw material for causing fire, therefore has flame-proof treatment to prevention textile
Fire is very necessary.There is graphene the wrong layer structure of two dimension to make it have lamella barrier action, can delay heat
It transmitting, the diffusion of thermal decomposition product and the diffusion of spilling and oxygen and mixes, and graphene low toxic and environment-friendly Halogen, therefore through stone
The modified flame retardant textiles of black alkene have good market prospects.
A kind of preparation enhancing fire-retardant regenerative polyester staple fiber based on graphene disclosed in Chinese patent CN104630928B
Method is handled graphene by sulfonic acid surfactant radical functino, with polyvinyl alcohol, polyvinylpyrrolidone, four cyanogen for diformazan
The mixing of base benzoquinones, it is agitated, disperse, be added in polyester powder, graphene master batch is made using twin-screw prilling；It will be anti-
Phosphorus series non-halogen fire-retardant master granule is made through screw rod prilling after answering the phosphorus series non-halogen fire retardant of type to mix with polyester powder；Then will
Graphene master batch and phosphorus series non-halogen fire-retardant master granule and recycled polyester raw material carry out vacuum combination drying at 90~140 DEG C, will do
Raw material after dry melted under screw extruder effect after melt be pumped to through melt in homogeneous removal of impurities blender carry out it is uniform
It eliminates and lives together reason, then secondary filter is pumped to through melt, after filtered melt is set the blend melt on pipeline
Into 275~278 DEG C of spinning manifold, the fiber after spinning is carried out drawing-off processing to get fire-retardant recycled polyester is enhanced by spinning
Fiber, the graphene used in this method have humidification not only for polyester fiber, effectively improve the mechanical property of fiber
(fibre strength improves 0.5~1.2cN/dtex), thermal stability, flame retarding efficiency is high, can cooperate with phosphorus series non-halogen fire retardant
Fire retardation effectively reduces the additive amount of fire retardant, reduces cost.Chinese patent CN106996035A is disclosed to have conductive resistance
The fabric and preparation method thereof for firing coating, is coated to fabric surface for the graphene oxide hydrosol of 20-30mg/mL, 60
It is dried at DEG C -120 DEG C, obtains the fabric with graphite oxide ene coatings, then will soaked with the fabric of graphite oxide ene coatings
Stain issues raw reduction reaction at 80-95 DEG C, makes graphite oxide in the aqueous solution of sodium hydrosulfite and/or L-AA reducing agent
Alkene is reduced into graphene, obtains the fabric with conductive flame retardant coating.By the above-mentioned prior art it is found that by the way that graphene is added
To fibrous inside or it is coated on textile surface, can assign textile certain anti-flammability.Graphene aerogel is stone
The three-dimensional network that black alkene is formed by connecting has the characteristics that extremely-low density, macropore volume, high-specific surface area, insoluble insoluble, the present invention
Textile is arranged using graphene aerogel as flame-retardant additive, is more preferably weaved in the hope of flame retardant property is prepared
Product.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of graphene aerogels based on microvesicle templated sol gel method
Modified flame-retardant textile and preparation method thereof, the present invention, as template, make oxidation go back graphene on the surface of microvesicle using microvesicle
Microstructure is spontaneously formed, then graphene oxide microstructure is preserved by quick freezing technology, makes fabric surface
Forming large scale, uniformly graphene aerogel and fabric perfect combination are prepared complete graphene aerogel structure
Modified fabric light specific gravity, less soluble not meltable, excellent fireproof performance also retains certain elasticity.
In order to solve the above technical problems, the technical scheme is that
A kind of preparation method for the flame-retardant textile that the graphene aerogel based on microvesicle templated sol gel method is modified, including
Following steps:
(1) alkyl polyglycoside and lauryl sodium sulfate are added in deionized water, are uniformly dispersed, obtain foam precursor
Solution；
(2) it will be added in DL-cysteine in graphene oxide solution, pre-add thermal agitation obtains the oxidation stone of prereduction
The black alkene hydrosol；
(3) graphene oxide of the foam precursor solution of step (1) preparation and the prereduction of step (2) preparation is water-soluble
Glue mixing, fabric is placed in one, and high speed shear forms stable foam in fabric surface, takes out fabric, is rapidly frozen, bubble
Foam film is split, and the graphene oxide liquid crystal porous material of partial reduction is prepared；
(4) the graphene oxide liquid crystal porous material by the partial reduction of step (3) preparation thaws at room temperature, and heating is also
Original, then be freeze-dried, obtain the modified flame-retardant textile of graphene aerogel.
As a preferred embodiment of the above technical solution, in the step (1), the content of alkyl polyglycoside in foam precursor solution
For 0.3-0.4%, the content of lauryl sodium sulfate is 0.1-0.15%.
As a preferred embodiment of the above technical solution, in the step (2), the temperature of pre-add thermal agitation is 50-60 DEG C, stirring
Rate is 600-2500r/min, time 15-30min.
As a preferred embodiment of the above technical solution, in the step (2), the amount ratio of graphene oxide and DL-cysteine
For 1:5-8, the content of graphene oxide is 1-2.5mg/mL.
As a preferred embodiment of the above technical solution, in the step (3), the revolving speed of high speed shear is 15000-20000r/
Min, time 30-60min.
As a preferred embodiment of the above technical solution, in the step (3), the height of foam is 80-100 μm, density 500-
850/cm2.
As a preferred embodiment of the above technical solution, in the step (3), the temperature of fast freezing is -10~-20 DEG C, the time
For 2-4h.
As a preferred embodiment of the above technical solution, in the step (3), the graphene oxide liquid crystal porous material of partial reduction
Size be 80-100cm, with a thickness of 8-15mm, aperture is 84-110 μm, and the wall thickness of porous material is 3-10 μm.
As a preferred embodiment of the above technical solution, in the step (4), the temperature of heating reduction is 70-80 DEG C, and the time is
1-2h。
The present invention also provides a kind of the fire-retardant of graphene aerogel modification based on microvesicle templated sol gel method
Fabric.
Compared with prior art, the invention has the following advantages:
(1) graphene aerogel gos deep into the interior of fabric in the modified flame-retardant textile of graphene aerogel prepared by the present invention
Portion, and large scale uniformly complete graphene aerogel structure, graphene aerogel prepared by the present invention are formed in fabric surface
Structure is combined using distribution reduction method with templated sol gel method, and the obtained graphene aerogel of preparation not only advise by structure
It is whole, and elasticity is good, compressible 70-80% is simultaneously sprung back, and improves the usable range and comfort property of fabric.
(2) graphene aerogel is using microvesicle conduct in the modified flame-retardant textile of graphene aerogel prepared by the present invention
Template spontaneously forms graphene oxide on the surface of microvesicle using the graphene oxide characteristic regular in micro-dimension flowering structure
Then graphene oxide microstructure is preserved by quick freezing technology, fabric surface is made to form big ruler by microstructure
Very little uniformly complete graphene aerogel structure, by graphene aerogel and fabric perfect combination, make to be prepared fire-retardant is knitted
Object light specific gravity, less soluble not meltable, excellent fireproof performance also retains certain elasticity.
(3) the uniform complete graphene of coarse scale structures in the modified flame-retardant textile of graphene aerogel prepared by the present invention
Aeroge is stablized using Structure of need, and for the microvesicle of long half time as template, alkyl polyglycoside is one kind by fatty alcohol and Portugal
The nonionic surface active agent of the reproducibilities plant material such as grape sugar synthesis, the present invention is by alkyl polyglycoside and dodecyl sulphur
Sour sodium compounding, is prepared the solution with good foaming properties and spreading property, and foamed material prepared by the present invention without
Malicious, non-stimulated, easily biological-degradable, will not structure to subsequent fabric and performance impact, stability and safety are good.
(4) preparation method of the invention is simple, by simply impregnating and stirring technique, then by freeze drying process,
Controllability is strong, low for equipment requirements, is suitable for industrializing a wide range of production.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be described in detail, herein illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1:
(1) alkyl polyglycoside and lauryl sodium sulfate are added in deionized water, are uniformly dispersed, obtain foam precursor
Solution, wherein the content of alkyl polyglycoside is 0.3% in foam precursor solution, and the content of lauryl sodium sulfate is
0.1%.
It (2) is 1:5 according to graphene oxide and the amount ratio of DL-cysteine, by the graphene oxide solution of 1mg/mL
In middle addition DL-cysteine, at 50 DEG C, with the revolving speed pre-add thermal agitation 15min of 600r/min, the oxidation of prereduction is obtained
The graphene hydrosol.
(3) foam precursor solution and the graphene oxide hydrosol of prereduction are mixed, fabric is placed in one,
High speed shear 30min under the revolving speed of 15000r/min, forms stable foam in fabric surface, wherein the height of foam is 80-
100 μm, density is 500/cm2, takes out fabric, 2h is rapidly frozen at -10 DEG C, foam film is split, and partial reduction is prepared
Graphene oxide liquid crystal porous material, part reduction graphene oxide liquid crystal porous material size be 80-
100cm, with a thickness of 8mm, aperture is 84-110 μm, and the wall thickness of porous material is 3 μm.
(4) the graphene oxide liquid crystal porous material of partial reduction is thawed at room temperature, the heating reduction 1h at 70 DEG C,
It is freeze-dried again, obtains the modified flame-retardant textile of graphene aerogel.
Embodiment 2:
(1) alkyl polyglycoside and lauryl sodium sulfate are added in deionized water, are uniformly dispersed, obtain foam precursor
Solution, wherein the content of alkyl polyglycoside is 0.4% in foam precursor solution, and the content of lauryl sodium sulfate is
0.15%.
It (2) is 1:8 according to graphene oxide and the amount ratio of DL-cysteine, the graphene oxide of 2.5mg/mL is molten
It is added in DL-cysteine in liquid, at 60 DEG C, with the revolving speed pre-add thermal agitation 30min of 2500r/min, obtains prereduction
The graphene oxide hydrosol.
(3) foam precursor solution and the graphene oxide hydrosol of prereduction are mixed, fabric is placed in one,
High speed shear 60min under the revolving speed of 20000r/min, forms stable foam in fabric surface, wherein the height of foam is 80-
100 μm, density is 850/cm2, takes out fabric, 4h is rapidly frozen at -20 DEG C, foam film is split, and partial reduction is prepared
Graphene oxide liquid crystal porous material, part reduction graphene oxide liquid crystal porous material size be 80-
100cm, with a thickness of 15mm, aperture is 84-110 μm, and the wall thickness of porous material is 10 μm.
(4) the graphene oxide liquid crystal porous material of partial reduction is thawed at room temperature, the heating reduction 2h at 80 DEG C,
It is freeze-dried again, obtains the modified flame-retardant textile of graphene aerogel.
Embodiment 3:
(1) alkyl polyglycoside and lauryl sodium sulfate are added in deionized water, are uniformly dispersed, obtain foam precursor
Solution, wherein the content of alkyl polyglycoside is 0.35% in foam precursor solution, and the content of lauryl sodium sulfate is
0.12%.
It (2) is 1:6 according to graphene oxide and the amount ratio of DL-cysteine, the graphene oxide of 1.5mg/mL is molten
It is added in DL-cysteine in liquid, at 53 DEG C, with the revolving speed pre-add thermal agitation 20min of 1200r/min, obtains prereduction
The graphene oxide hydrosol.
(3) foam precursor solution and the graphene oxide hydrosol of prereduction are mixed, fabric is placed in one,
High speed shear 45min under the revolving speed of 18000r/min, forms stable foam in fabric surface, wherein the height of foam is 80-
100 μm, density is 650/cm2, takes out fabric, 3h is rapidly frozen at -15 DEG C, foam film is split, and partial reduction is prepared
Graphene oxide liquid crystal porous material, part reduction graphene oxide liquid crystal porous material size be 80-
100cm, with a thickness of 12mm, aperture is 84-110 μm, and the wall thickness of porous material is 5 μm.
(4) the graphene oxide liquid crystal porous material of partial reduction is thawed at room temperature, the heating reduction at 75 DEG C
1.5h, then be freeze-dried, obtain the modified flame-retardant textile of graphene aerogel.
Embodiment 4:
(1) alkyl polyglycoside and lauryl sodium sulfate are added in deionized water, are uniformly dispersed, obtain foam precursor
Solution, wherein the content of alkyl polyglycoside is 0.37% in foam precursor solution, and the content of lauryl sodium sulfate is
0.14%.
It (2) is 1:7.2 according to graphene oxide and the amount ratio of DL-cysteine, by the graphene oxide of 2.1mg/mL
It is added in DL-cysteine in solution, at 57 DEG C, with the revolving speed pre-add thermal agitation 20min of 2300r/min, obtains prereduction
The graphene oxide hydrosol.
(3) foam precursor solution and the graphene oxide hydrosol of prereduction are mixed, fabric is placed in one,
High speed shear 55min under the revolving speed of 19000r/min, forms stable foam in fabric surface, wherein the height of foam is 80-
100 μm, density is 700/cm2, takes out fabric, 2.5h is rapidly frozen at -15 DEG C, and foam film is split, and part is prepared also
Former graphene oxide liquid crystal porous material, the size of the graphene oxide liquid crystal porous material of part reduction are 80-
100cm, with a thickness of 12mm, aperture is 84-110 μm, and the wall thickness of porous material is 7 μm.
(4) the graphene oxide liquid crystal porous material of partial reduction is thawed at room temperature, the heating reduction at 77 DEG C
1.5h, then be freeze-dried, obtain the modified flame-retardant textile of graphene aerogel.
Embodiment 5:
(1) alkyl polyglycoside and lauryl sodium sulfate are added in deionized water, are uniformly dispersed, obtain foam precursor
Solution, wherein the content of alkyl polyglycoside is 0.39% in foam precursor solution, and the content of lauryl sodium sulfate is
0.11%.
It (2) is 1:6 according to graphene oxide and the amount ratio of DL-cysteine, the graphene oxide of 1.8mg/mL is molten
It is added in DL-cysteine in liquid, at 59 DEG C, with the revolving speed pre-add thermal agitation 20min of 2400r/min, obtains prereduction
The graphene oxide hydrosol.
(3) foam precursor solution and the graphene oxide hydrosol of prereduction are mixed, fabric is placed in one,
High speed shear 40min under the revolving speed of 18500r/min, forms stable foam in fabric surface, wherein the height of foam is 80-
100 μm, density is 710/cm2, takes out fabric, 3.5h is rapidly frozen at -17 DEG C, and foam film is split, and part is prepared also
Former graphene oxide liquid crystal porous material, the size of the graphene oxide liquid crystal porous material of part reduction are 80-
100cm, with a thickness of 10mm, aperture is 84-110 μm, and the wall thickness of porous material is 4 μm.
(4) the graphene oxide liquid crystal porous material of partial reduction is thawed at room temperature, the heating reduction 2h at 75 DEG C,
It is freeze-dried again, obtains the modified flame-retardant textile of graphene aerogel.
Embodiment 6:
(1) alkyl polyglycoside and lauryl sodium sulfate are added in deionized water, are uniformly dispersed, obtain foam precursor
Solution, wherein the content of alkyl polyglycoside is 0.3% in foam precursor solution, and the content of lauryl sodium sulfate is
0.15%.
It (2) is 1:5 according to graphene oxide and the amount ratio of DL-cysteine, the graphene oxide of 2.5mg/mL is molten
It is added in DL-cysteine in liquid, at 50 DEG C, with the revolving speed pre-add thermal agitation 15min of 2500r/min, obtains prereduction
The graphene oxide hydrosol.
(3) foam precursor solution and the graphene oxide hydrosol of prereduction are mixed, fabric is placed in one,
High speed shear 30min under the revolving speed of 20000r/min, forms stable foam in fabric surface, wherein the height of foam is 80-
100 μm, density is 850/cm2, takes out fabric, 4h is rapidly frozen at -10 DEG C, foam film is split, and partial reduction is prepared
Graphene oxide liquid crystal porous material, part reduction graphene oxide liquid crystal porous material size be 80-
100cm, with a thickness of 8mm, aperture is 84-110 μm, and the wall thickness of porous material is 10 μm.
(4) the graphene oxide liquid crystal porous material of partial reduction is thawed at room temperature, the heating reduction 2h at 70 DEG C,
It is freeze-dried again, obtains the modified flame-retardant textile of graphene aerogel.
Through detecting, the graphene aerogel of embodiment 1-6 preparation modified flame-retardant textile and untreated fabric are returned
The result of elasticity, anti-flammability and mechanical property is as follows:
As seen from the above table, the flexibility of the modified flame-retardant textile of graphene aerogel prepared by the present invention is good, has excellent
Different flame retardant property, and mechanical property also significantly improves.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (10)
1. a kind of preparation method for the flame-retardant textile that the graphene aerogel based on microvesicle templated sol gel method is modified, feature
It is, comprising the following steps:
(1) alkyl polyglycoside and lauryl sodium sulfate are added in deionized water, are uniformly dispersed, it is molten obtains foam precursor
Liquid；
(2) it will be added in DL-cysteine in graphene oxide solution, pre-add thermal agitation obtains the graphene oxide of prereduction
The hydrosol；
(3) the graphene oxide hydrosol of the foam precursor solution of step (1) preparation and the prereduction of step (2) preparation is mixed
It closes, fabric is placed in one, high speed shear forms stable foam in fabric surface, takes out fabric, is rapidly frozen, foam film
It splits, the graphene oxide liquid crystal porous material of partial reduction is prepared；
(4) the graphene oxide liquid crystal porous material by the partial reduction of step (3) preparation thaws at room temperature, heating reduction,
It is freeze-dried again, obtains the modified flame-retardant textile of graphene aerogel.
2. a kind of fire-retardant the knitting of graphene aerogel modification based on microvesicle templated sol gel method according to claim 1
The preparation method of object, it is characterised in that: in the step (1), the content of alkyl polyglycoside is 0.3- in foam precursor solution
0.4%, the content of lauryl sodium sulfate is 0.1-0.15%.
3. a kind of fire-retardant the knitting of graphene aerogel modification based on microvesicle templated sol gel method according to claim 1
The preparation method of object, it is characterised in that: in the step (2), the temperature of pre-add thermal agitation is 50-60 DEG C, and stirring rate is
600-2500r/min, time 15-30min.
4. a kind of fire-retardant the knitting of graphene aerogel modification based on microvesicle templated sol gel method according to claim 1
The preparation method of object, it is characterised in that: in the step (2), the amount ratio of graphene oxide and DL-cysteine is 1:5-8,
The content of graphene oxide is 1-2.5mg/mL.
5. a kind of fire-retardant the knitting of graphene aerogel modification based on microvesicle templated sol gel method according to claim 1
The preparation method of object, it is characterised in that: in the step (3), the revolving speed of high speed shear is 15000-20000r/min, and the time is
30-60min。
6. a kind of fire-retardant the knitting of graphene aerogel modification based on microvesicle templated sol gel method according to claim 1
The preparation method of object, it is characterised in that: in the step (3), the height of foam is 80-100 μm, density is 500-850/
cm2。
7. a kind of fire-retardant the knitting of graphene aerogel modification based on microvesicle templated sol gel method according to claim 1
The preparation method of object, it is characterised in that: in the step (3), the temperature of fast freezing is -10~-20 DEG C, time 2-4h.
8. a kind of fire-retardant the knitting of graphene aerogel modification based on microvesicle templated sol gel method according to claim 1
The preparation method of object, it is characterised in that: in the step (3), the size of the graphene oxide liquid crystal porous material of partial reduction
For 80-100cm, with a thickness of 8-15mm, aperture is 84-110 μm, and the wall thickness of porous material is 3-10 μm.
9. a kind of fire-retardant the knitting of graphene aerogel modification based on microvesicle templated sol gel method according to claim 1
The preparation method of object, it is characterised in that: in the step (4), the temperature of heating reduction is 70-80 DEG C, time 1-2h.
10. a kind of fire-retardant knitting of the graphene aerogel modification based on microvesicle templated sol gel method described in claim 1-9
Object.
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| CN110528268A (en) * | 2019-08-19 | 2019-12-03 | 成都良品家饰工程有限公司 | A kind of nanometer of light purification fabric and its manufacturing method |
| CN113184832A (en) * | 2021-03-09 | 2021-07-30 | 中国科学院兰州化学物理研究所 | Flexible three-dimensional graphene aerogel, preparation method and application thereof, flexible three-dimensional graphene-based piezoresistive sensor and application thereof |
| CN115652639A (en) * | 2022-10-13 | 2023-01-31 | 河北钢铁集团矿业有限公司 | High-performance composite industrial gas film for building film material and preparation method thereof |
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| CN115652639A (en) * | 2022-10-13 | 2023-01-31 | 河北钢铁集团矿业有限公司 | High-performance composite industrial gas film for building film material and preparation method thereof |
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