CN109734076A - A kind of preparation method of large area high intensity super-elasticity grapheme foam material - Google Patents
A kind of preparation method of large area high intensity super-elasticity grapheme foam material Download PDFInfo
- Publication number
- CN109734076A CN109734076A CN201811621418.9A CN201811621418A CN109734076A CN 109734076 A CN109734076 A CN 109734076A CN 201811621418 A CN201811621418 A CN 201811621418A CN 109734076 A CN109734076 A CN 109734076A
- Authority
- CN
- China
- Prior art keywords
- elasticity
- foam material
- graphene
- high intensity
- grapheme foam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a kind of preparation methods of large area high intensity super-elasticity grapheme foam material, belong to three-dimensional grapheme technical field of material.The graphene oxide solution reduction of foaming is first generated into graphene hydrogel block, and carry out freezing icing and thawing processing, it is tiled under hygrometric state again and one layer and carries out transverse direction and longitudinal compression, obtain one layer of large-area graphene hydrogel, tiling graphene hydrogel block can also be repeated on large-area graphene hydrogel and compressed, the large-area graphene hydrogel of MULTILAYER COMPOSITE is obtained, last natural air drying obtains large area high intensity super-elasticity grapheme foam material.The method of the invention is simple to operation, and scalability is strong, and the area of prepared grapheme foam material can reach 1m2More than, density 30mg/cm3~90mg/cm3, limited compression rebound strain reach 95% or more and ultimate compression strength reach 20MPa or more.
Description
Technical field
The present invention relates to a kind of preparation methods of super-elasticity grapheme foam material, belong to three-dimensional grapheme material preparation skill
Art field.
Background technique
Grapheme foam is that have as made of highly conductive, high thermal conductivity, high flexible two-dimensional graphene nanomaterial assembly
Macroscopical light material of three-dimensional porous structure, in energy storage and conversion, environmental improvement, energy-saving and emission-reduction, mechanics sensing, electromagnetism
The fields such as shielding, light flame-retardant have huge application prospect.Super-elasticity grapheme foam material (answer by limited compression rebound at present
Becoming larger in 90%) the shortcomings that, to be that density of material is extremely low (be less than 10mg/cm3) and ultimate compression strength it is smaller (be less than 2MPa).
This is because when prior art preparation large area super-elasticity grapheme foam material, due to graphene oxide confusion liquid crystalline phase and
Non-uniform heat transfer causes structure extremely uneven and elasticity of compression variation, such as 104925787 B of Chinese invention patent CN
With 106006615 B of CN.And Freeze Drying Technique is commonly used in preparation process, it is time-consuming compared with constant pressure and dry method
Energy consumption is not suitable for large scale preparation, such as 106809822 B of patent of invention CN.
Summary of the invention
For asking for the super-elasticity grapheme foam material for having both large area, high density and high intensity cannot be prepared at present
Topic, the present invention provides a kind of preparation method of large area high intensity super-elasticity grapheme foam material, prepared by this method
The area of grapheme foam material can reach 1m2More than, density 30mg/cm3~90mg/cm3, limited compression rebound strain
Reach 95% or more, ultimate compression strength reaches 20MPa or more.
The purpose of the present invention is what is be achieved through the following technical solutions.
A kind of preparation method of large area high intensity super-elasticity grapheme foam material, the described method comprises the following steps:
(1) reducing agent and surfactant is added into the graphene oxide water solution that concentration is 6mg/mL~20mg/mL,
Then mixed solution foaming is made by stirring and (the miscible solution volume after foaming is hair to foam volume multiple 1.5~2.5
1.5~2.5 times of mixed liquor volume before bubble), and the mixed solution after foaming is poured into mold, then 80 DEG C or less into
Row reduction reaction obtains graphene hydrogel block；
(2) first by graphene hydrogel block, freezing freezes completely at -20 DEG C~-10 DEG C, then carries out at 70 DEG C or less
It thaws and melts completely, obtain the graphene hydrogel block of ice crystal double teeming；
(3) the graphene hydrogel block by two pieces or more ice crystal double teemings closely tiles one layer under hygrometric state, then to stone
The length or/and width direction of black alkene hydrogel block carry out small scale transverse compression, make adjoining graphite alkene hydrogel block it
Between contact close, and longitudinal large scale compression is carried out to the thickness direction of graphene hydrogel block, regulates and controls its internal three-dimensional
Structure obtains large-area graphene hydrogel；
Wherein, transverse compression ratio (decrement of length or width and the ratio of the length or width before compression) is 5%
~20%, longitudinal compression ratio (decrement of thickness and the ratio of the thickness before compression) is 80%~90%；According to prepared
The size of super-elasticity grapheme foam material determine the area that tiles under hygrometric state of graphene hydrogel of ice crystal double teeming
Size；
(4) the large-area graphene hydrogel natural air drying for preparing step (3), obtains large area high intensity super-elasticity stone
Black alkene foamed material.
Further, the graphene hydrogel of two pieces or more ice crystal double teemings is big prepared by step (3) under hygrometric state
It closely tiles on area graphite alkene hydrogel one layer, the operation according still further to step (3) carries out transverse compression and longitudinal compression respectively,
Obtain two layers of compound large-area graphene hydrogel；And so on, the large-area graphene hydrogel of MULTILAYER COMPOSITE is prepared, then
By the large-area graphene hydrogel natural air drying of MULTILAYER COMPOSITE, large area high intensity super-elasticity grapheme foam material is obtained.
Wherein, the compound layer of large-area graphene hydrogel is determined according to the thickness size of prepared super-elasticity grapheme foam material
Number.
Further, in step (1), the reduction reaction 8h~for 24 hours preferably at 60 DEG C~80 DEG C.
Further, in step (1), reducing agent be vitamin C, hydrazine hydrate, hydroiodic acid, ethylenediamine or sodium borohydride,
Additive amount is the 10%~250% of graphene oxide quality；Surfactant is anionic surfactant, amphoteric ion surface
One or more of activating agent and nonionic surfactant, preferably sodium dodecyl sulfate, alkyl glycosides or coconut oleoyl amine third
Base glycine betaine, additive amount are the 50%~150% of graphene oxide quality.
Further, in step (1), graphene hydrogel block is preferably shaped to cuboid or square.
Further, longitudinal compression ratio preferably 85%~90%.
The utility model has the advantages that
The structure and density that not only can change grapheme foam material in such a way that hygrometric state compresses, significantly improve graphite
The ultimate compression strength and conductivity of alkene foamed material, and three-dimensional macro assembling can be carried out to the grapheme foam material,
Large area preparation is realized in outer dimension.Using the grapheme foam material of the method for the invention preparation, its internal presents is oriented
The double-arch structure of arrangement, arcading spacing are 5 μm~30 μm, and density reaches 30mg/cm3~90mg/cm3, area is up to 1m2And with
On, limited compression rebound strain reaches 95% or more, and ultimate compression strength reaches 20MPa or more, conductivity reach 100S/m with
On.The method of the invention is simple to operation, and scalability is strong, large area can prepare in situ under atmospheric atmosphere.
Detailed description of the invention
Fig. 1 is that cross-sectional scanning electron of the super-elasticity grapheme foam material of the preparation of embodiment 1 under low magnification is aobvious
Micro mirror picture.
Fig. 2 is that cross-sectional scanning electron of the super-elasticity grapheme foam material of the preparation of embodiment 1 under high-amplification-factor is aobvious
Micro mirror picture.
Fig. 3 is the compression verification load-deformation curve of super-elasticity grapheme foam material prepared by embodiment 1.
Specific embodiment
The present invention is further elaborated with reference to the accompanying drawings and detailed description, wherein the method is as without especially
Explanation is conventional method, and the raw material can be gotten from open business unless otherwise instructed.
In following embodiment:
Stainless steel mould: the size of its internal cavity is 12cm × 8cm × 6cm (length × width × height)；
The calculating of density: the specific size of prepared super-elasticity grapheme foam material is measured using ruler and is calculated
Its volume (V) then weighs and obtains its quality (M), finally calculates density (ρ=M/V)；
The calculating of conductivity: the resistance of prepared super-elasticity grapheme foam material is measured using electrochemical workstation
(R), according to its sectional area (S) and length (L), conductivity (σ=L/R*S) is finally calculated；
SEM characterization: using JSM-7500F model cold field emission scanning electron microscope.
Compressive stress strain curve test: being tested using Shimadzu Corporation AGS-X model electronic universal tester,
In, compression speed 10mm/min, the size of sample is 5mm × 6mm × 6mm (length × width × height).
Embodiment 1
(1) 2.4g dimension is first added in the graphene oxide water solution for being 12mg/mL equipped with 100mL concentration in the beaker of 500mL
Raw element C, stirring are completely dissolved vitamin C, add 2.4mL mass fraction as 50% alkyl glycosides solution, then with
The revolving speed Quick mechanical of 2500r/min stirs 5min, and making the foam volume multiple of mixed solution is about 2.0, and the mixing is molten
Liquid pours into stainless steel mould, then the reduction reaction 12h at 70 DEG C, obtains graphene hydrogel block；
(2) graphene hydrogel is first freezed at -10 DEG C 12h, then carries out complete thawing of thawing at 20 DEG C, obtain ice
The graphene hydrogel block of brilliant double teeming；
(3) it by graphene hydrogel block under hygrometric state, is closely tiled one layer, is put down on substrate in a manner of floor tile
The area of paving is about 0.5m2；Then the length and width direction of graphene hydrogel block are carried out respectively using plate small
Ratio transverse compression makes to be in close contact between adjoining graphite alkene hydrogel block, and transverse compression ratio is about 10%, then to graphite
Thickness (or height) direction of alkene hydrogel block carries out longitudinal large scale compression, and longitudinal compression ratio is about 90%, obtains one
Layer large-area graphene hydrogel；
(4) using step (3) preparation large-area graphene hydrogel as substrate, repeatedly step (3), obtain two layers it is compound
Large-area graphene hydrogel；Again using two layers of compound large-area graphene hydrogel as substrate, repeats step (3), obtain three
The compound large-area graphene hydrogel of layer；
(5) three layers of compound large-area graphene hydrogel natural air drying for preparing step (4), it is high-strength to obtain large area
Spend super-elasticity grapheme foam material.
By testing it is found that the density of super-elasticity grapheme foam material prepared by the present embodiment is about 60mg/cm3,
Conductivity is up to 378S/m；The double-arch structure aligned is presented in its internal microstructure, and arcading spacing is 5 μm~30 μm and (connects
Encircle spacing finger-type into the maximum distance between the upper layer and lower layer graphene of arcading), as depicted in figs. 1 and 2；Limited compression rebound is answered
Change reaches 97%, and ultimate compression strength is up to 47MPa, as shown in Figure 3.
Embodiment 2
(1) 2.6g dimension is first added in the graphene oxide water solution for being 16mg/mL equipped with 80mL concentration in the beaker of 500mL
Raw element C, stirring are completely dissolved vitamin C, add 2.6mL mass fraction as 50% alkyl glycosides solution, then with
The revolving speed Quick mechanical of 2500r/min stirs 5min, and making the foam volume multiple of mixed solution is about 2.5, and the mixing is molten
Liquid pours into stainless steel mould, then the reduction reaction 12h at 70 DEG C, obtains graphene hydrogel block；
To graphene hydrogel block prepared by the present embodiment according to step (2)~(5) in embodiment 1 at
Reason, correspondingly, large area high intensity super-elasticity grapheme foam material.
By testing it is found that the density of super-elasticity grapheme foam material manufactured in the present embodiment is about 64mg/cm3, electricity
Conductance is up to 391S/m, and limited compression rebound strain reaches 97%, and ultimate compression strength is up to 51MPa, internal microstructure
The double-arch structure aligned is presented, arcading spacing is 5 μm~30 μm.
Embodiment 3
(1) 2.9g dimension is first added in the graphene oxide water solution for being 8mg/mL equipped with 120mL concentration in the beaker of 500mL
Raw element C, stirring are completely dissolved vitamin C, add 2mL mass fraction as 50% alkyl glycosides solution, then with
The revolving speed Quick mechanical of 2500r/min stirs 5min, and making the foam volume multiple of mixed solution is about 1.5, and the mixing is molten
Liquid pours into stainless steel mould, then the reduction reaction 12h at 70 DEG C, obtains graphene hydrogel block；
Graphene hydrogel prepared by the present embodiment is handled according to step (2)~(5) in embodiment 1, phase
Ying Di, large area high intensity super-elasticity grapheme foam material.
By testing it is found that the density of super-elasticity grapheme foam material manufactured in the present embodiment is about 57mg/cm3, electricity
Conductance reaches 97% up to 334S/m, limited compression rebound strain, and ultimate compression strength is up to 40MPa, internal microstructure
The double-arch structure aligned is presented, arcading spacing is 5 μm~30 μm.
Embodiment 4
On the basis of embodiment 1, will in 1 step of embodiment (2) at -10 DEG C freeze 12h be substituted for it is cold at -15 DEG C
Freeze 10h, other Step By Conditions are same as Example 1, correspondingly, obtain large area high intensity super-elasticity grapheme foam material
Material.
By testing it is found that the density of super-elasticity grapheme foam material manufactured in the present embodiment is about 60mg/cm3, electricity
Conductance reaches 97% up to 358S/m, limited compression rebound strain, and ultimate compression strength is up to 54MPa, internal microstructure
The double-arch structure aligned is presented, arcading spacing is 5 μm~30 μm.
Embodiment 5
On the basis of embodiment 1, area graphene hydrogel block in 1 step of embodiment (3) to be tiled is by 0.5m2
It is substituted for 1.5m2, while transverse compression ratio by 10% be substituted for 15% and longitudinal compression ratio be substituted for by 90%
85%, other Step By Conditions are same as Example 1, correspondingly, obtain large area high intensity super-elasticity grapheme foam material.
By testing it is found that the density of super-elasticity grapheme foam material manufactured in the present embodiment is about 42mg/cm3, electricity
Conductance is up to 215S/m, and limited compression strain reaches 97%, and ultimate compression strength reaches 33MPa, and internal microstructure is presented
The double-arch structure aligned, arcading spacing are 5 μm~30 μm.
Embodiment 6
On the basis of embodiment 1, the three layers of compound large-area graphene water-setting that will be prepared in 1 step of embodiment (4)
Glue is substituted for five layers of compound large-area graphene hydrogel, other Step By Conditions are same as Example 1, correspondingly, obtain
Large area high intensity super-elasticity grapheme foam material.
By testing it is found that the density of super-elasticity grapheme foam material manufactured in the present embodiment is about 60mg/cm3, electricity
Conductance reaches 97% up to 368S/m, limited compression rebound strain, and ultimate compression strength is up to 45MPa, internal microstructure
The double-arch structure aligned is presented, arcading spacing is 5 μm~30 μm.
In conclusion the above is merely preferred embodiments of the present invention, being not intended to limit the scope of the present invention.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (7)
1. a kind of preparation method of large area high intensity super-elasticity grapheme foam material, it is characterised in that: the method includes
Following steps:
(1) reducing agent and surfactant is added into the graphene oxide water solution that concentration is 6mg/mL~20mg/mL, then
Make mixed solution foaming and foam volume multiple 1.5~2.5 by stirring, and the mixed solution after foaming is poured into mold
In, then in 80 DEG C or less progress reduction reactions, obtain graphene hydrogel block；
(2) first by graphene hydrogel block, freezing freezes completely at -20 DEG C~-10 DEG C, then thaws at 70 DEG C or less
Melt completely, obtains the graphene hydrogel block of ice crystal double teeming；
(3) the graphene hydrogel block by two pieces or more ice crystal double teemings closely tiles one layer under hygrometric state, then to graphene
The length or/and width direction of hydrogel block carry out small scale transverse compression, and transverse compression ratio is 5%~20%, and right
The thickness direction of graphene hydrogel block carries out longitudinal large scale compression, and longitudinal compression ratio is 80%~90%, obtains big
Area graphite alkene hydrogel；
(4) the large-area graphene hydrogel natural air drying for preparing step (3), obtains large area high intensity super-elasticity graphene
Foamed material.
2. a kind of preparation method of large area high intensity super-elasticity grapheme foam material according to claim 1, special
Sign is: the method also includes following steps:
By the graphene hydrogel of two pieces or more ice crystal double teemings under hygrometric state the large-area graphene water-setting prepared by step (3)
Closely tile on glue one layer, the operation according still further to step (3) carries out transverse compression and longitudinal compression respectively, obtain two layers it is compound
Large-area graphene hydrogel；And so on, prepare the large-area graphene hydrogel of MULTILAYER COMPOSITE, then by the big of MULTILAYER COMPOSITE
Area graphite alkene hydrogel natural air drying obtains large area high intensity super-elasticity grapheme foam material.
3. a kind of preparation method of large area high intensity super-elasticity grapheme foam material according to claim 1 or 2,
It is characterized in that: in step (1), the reduction reaction 8h~for 24 hours at 60 DEG C~80 DEG C.
4. a kind of preparation method of large area high intensity super-elasticity grapheme foam material according to claim 1 or 2,
Be characterized in that: in step (1), reducing agent is vitamin C, hydrazine hydrate, hydroiodic acid, ethylenediamine or sodium borohydride, and additive amount is
The 10%~250% of graphene oxide quality.
5. a kind of preparation method of large area high intensity super-elasticity grapheme foam material according to claim 1 or 2,
Be characterized in that: surfactant is lauryl sodium sulfate, alkyl glycosides or Cocoamidopropyl betaine, and additive amount is oxygen
The 50%~150% of graphite alkene quality.
6. a kind of preparation method of large area high intensity super-elasticity grapheme foam material according to claim 1 or 2,
Be characterized in that: in step (1), the shape of graphene hydrogel block is cuboid or square.
7. a kind of preparation method of large area high intensity super-elasticity grapheme foam material according to claim 1 or 2,
Be characterized in that: in step (3), longitudinal compression ratio is 85%~90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811621418.9A CN109734076B (en) | 2018-12-28 | 2018-12-28 | Preparation method of large-area high-strength super-elastic graphene foam material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811621418.9A CN109734076B (en) | 2018-12-28 | 2018-12-28 | Preparation method of large-area high-strength super-elastic graphene foam material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109734076A true CN109734076A (en) | 2019-05-10 |
| CN109734076B CN109734076B (en) | 2020-08-07 |
Family
ID=66361714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811621418.9A Active CN109734076B (en) | 2018-12-28 | 2018-12-28 | Preparation method of large-area high-strength super-elastic graphene foam material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109734076B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110316725A (en) * | 2019-07-23 | 2019-10-11 | 浙江大学 | A kind of high-density high-strength graphene frame material and preparation method thereof |
| CN113120884A (en) * | 2021-04-16 | 2021-07-16 | 北京理工大学 | Graphene aerogel with sound absorption and audio recognition functions and application thereof |
| CN115893388A (en) * | 2023-02-10 | 2023-04-04 | 青岛科技大学 | High-modulus and high-elasticity graphene foam material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224229A (en) * | 2013-04-15 | 2013-07-31 | 中国科学院宁波材料技术与工程研究所 | Method for rapid preparation of graphene powder by freezing filtration |
| CN104925787A (en) * | 2015-03-19 | 2015-09-23 | 青岛科技大学 | Method for preparing graphene aerogel through constant pressure drying |
| CN105645404A (en) * | 2016-03-28 | 2016-06-08 | 浙江大学 | Honeycomb-structured graphene aerogel ball and production method thereof |
| CN106517160A (en) * | 2016-11-22 | 2017-03-22 | 青岛科技大学 | Method for preparing isotropic superelastic graphene aerogel |
-
2018
- 2018-12-28 CN CN201811621418.9A patent/CN109734076B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224229A (en) * | 2013-04-15 | 2013-07-31 | 中国科学院宁波材料技术与工程研究所 | Method for rapid preparation of graphene powder by freezing filtration |
| CN104925787A (en) * | 2015-03-19 | 2015-09-23 | 青岛科技大学 | Method for preparing graphene aerogel through constant pressure drying |
| CN105645404A (en) * | 2016-03-28 | 2016-06-08 | 浙江大学 | Honeycomb-structured graphene aerogel ball and production method thereof |
| CN106517160A (en) * | 2016-11-22 | 2017-03-22 | 青岛科技大学 | Method for preparing isotropic superelastic graphene aerogel |
Non-Patent Citations (1)
| Title |
|---|
| HONGSHENG YANG ET AL.: "Reconstruction of Inherent Graphene Oxide Liquid Crystals for Large-Scale Fabrication of Structure-Intact Graphene Aerogel Bulk toward Practical Applications", 《ACS NANO》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110316725A (en) * | 2019-07-23 | 2019-10-11 | 浙江大学 | A kind of high-density high-strength graphene frame material and preparation method thereof |
| CN113120884A (en) * | 2021-04-16 | 2021-07-16 | 北京理工大学 | Graphene aerogel with sound absorption and audio recognition functions and application thereof |
| CN115893388A (en) * | 2023-02-10 | 2023-04-04 | 青岛科技大学 | High-modulus and high-elasticity graphene foam material and preparation method and application thereof |
| CN115893388B (en) * | 2023-02-10 | 2024-06-11 | 青岛科技大学 | High-modulus and high-elasticity graphene foam material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109734076B (en) | 2020-08-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109734076A (en) | A kind of preparation method of large area high intensity super-elasticity grapheme foam material | |
| Rui et al. | Comparative study on the effect of steel and polyoxymethylene fibers on the characteristics of Ultra-High Performance Concrete (UHPC) | |
| Wang et al. | A self-healing cementitious composite with mineral admixtures and built-in carbonate | |
| US20210323879A1 (en) | Nano-modified material for cavity wall with insulation for prefabricated building, and preparation method and use thereof | |
| Yuanliang et al. | Properties of foamed concrete with Ca (OH) 2 as foam stabilizer | |
| Li et al. | Effect of pore shape on the thermal conductivity of partially saturated cement-based porous composites | |
| Zeng et al. | Investigation on air-voids structure and compressive strength of concrete at low atmospheric pressure | |
| CN108654579B (en) | Preparation method of sodium alginate/typha orientalis/graphene oxide composite aerogel | |
| CN109553366A (en) | A kind of modified cement-based composite material and preparation method of graphene | |
| Shon et al. | Freezing and thawing resistance of cellular concrete containing binary and ternary cementitious mixtures | |
| CN109232013B (en) | Preparation method of large-size graphene foam board | |
| CN110294636B (en) | Light heat-insulating nickel metallurgy waste residue foamed ceramic and preparation method thereof | |
| CN112250390B (en) | Nano-fiber curing agent for disintegrating carbonaceous mudstone and preparation and use methods thereof | |
| KR101782845B1 (en) | High thermal insulating and light-weight aerated concrete mix using hydrophilic nano aerogel powder and preparing method of light-weight aerated concrete | |
| CN109205609B (en) | Method for preparing three-dimensional graphene oxide foam material by naturally airing solution | |
| Bagheri et al. | Role of non-reactive powder in strength enhancement of foamed concrete | |
| Wang et al. | Microstructure and properties of cement foams prepared by magnesium oxychloride cement | |
| Qu et al. | Preparation of ultralight glass foams via vacuum-assisted foaming | |
| CN115010514A (en) | High-impermeability low-heat-conductivity inorganic lightweight foam concrete and preparation method thereof | |
| Bi et al. | Properties and characterization of high-performance steam-cured cement-based materials modified by phase change materials | |
| Li et al. | Waterproof ultra-high toughness cementitious composites containing nano reservoir silts | |
| CN109020416B (en) | High-performance graphene concrete and preparation method thereof | |
| Gökçe et al. | Ultra-low density foam concrete production using electrolyzed water | |
| CN108623231A (en) | A kind of lightweight aggregate concrete and preparation method thereof | |
| CN104609820B (en) | Nano silicon heat-barrier material that glass fibre orientation strengthens and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |