CN106517945A - Graphene/ferric ferrous oxide composite powder modified wave-absorbing cement - Google Patents
Graphene/ferric ferrous oxide composite powder modified wave-absorbing cement Download PDFInfo
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- CN106517945A CN106517945A CN201610990060.1A CN201610990060A CN106517945A CN 106517945 A CN106517945 A CN 106517945A CN 201610990060 A CN201610990060 A CN 201610990060A CN 106517945 A CN106517945 A CN 106517945A
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- graphene
- ferroso
- cement
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- ferric oxide
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1018—Coating or impregnating with organic materials
- C04B20/1029—Macromolecular compounds
- C04B20/1033—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0042—Powdery mixtures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
- C04B2111/00258—Electromagnetic wave absorbing or shielding materials
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
Graphene/ferric ferrous oxide composite powder modified wave-absorbing cement is disclosed. The wave-absorbing cement includes graphene/ferric ferrous oxide composite powder, expanded polystyrene and Portland cement. In the wave-absorbing cement, the filling rate of the expanded polystyrene is 40-70 vol%, the particle size of the expanded polystyrene is 2-6 mm, and the volume content of the graphene/ferric ferrous oxide composite powder is 2-5%. The graphene/ferric ferrous oxide composite powder and the expanded polystyrene are doped in the cement, and absorption in the whole frequency range in a microwave frequency range of 8-18 GHz reaches -14.2 dB or above, and therefore the wave-absorbing property of the cement is enhanced.
Description
Technical field
The present invention relates to new material technology field, more particularly to a kind of Graphene/ferroso-ferric oxide powder modified
Inhale ripple cement.
Background technology
Cement material is various composites for including Multimetal oxide, itself has certain absorbing property,
But cement material to the absorption of electromagnetic wave mainly by subscale electromagnetic consumable, absorbing property is than relatively low.In cement matrix
After adding traditional wave absorbing agent, although the absorbing property of cement material can be improved, greatly reduce and space wave impedance
Matching degree, therefore absorbing property raising degree is little.If wave transparent particle is added in cement matrix, although electromagnetic wave transparent material
Adding reduces the content of wave absorbing agent, but can be obviously improved the impedance matching of cement composite material, while wave transparent particle Jing
After cement mixing, its surface can be wrapped by one layer of cement layer, also can produce scattering and reflex to incident electromagnetic wave.When saturating
When the number of ripple particle is enough, the decay to incident electromagnetic wave is played by the multiple reflections and Multiple Scattering between each particle
The important effect of root.Simultaneously during the Multiple Scattering of electromagnetic wave, cement matrix itself also can produce certain to electromagnetic wave
It is lost, therefore the addition of wave transparent particle is expected to greatly improve the absorbing property of cement composite material.
Expanded polystyrene (EPS) (Expanded polystyrene, EPS) is a kind lightweight, includes the bubble of little continuous pore
The series of advantages such as foam, water suction firm low, acid and alkali-resistance low with density, good heat preservation performance, in industrial or agricultural, transportation and building
It has been used widely in the fields such as industry.But it is applied to absorbing material field, there is not yet report.
The content of the invention
It is an object of the invention to a kind of suction ripple cement of Graphene/ferroso-ferric oxide powder modified is proposed, can
So that the absorbing property of conventional cement is greatly improved.
In the first invention of the present invention, using the expanded polystyrene (EPS) that adulterates in cement, the suction of portland cement is improved
Ripple performance, although which is that frequency range can reach good wave-absorbing effect at certain, but which is in the microwave frequency band of 8-18GHz, very
Difficult full frequency band reaches the absorption of -10dB, therefore the present invention is improved to which, so that its full frequency band possesses higher absorption.
It is that, up to this purpose, the present invention is employed the following technical solutions：
A kind of suction ripple cement of Graphene/ferroso-ferric oxide powder modified, including Graphene/ferroso-ferric oxide is compound
Powder, expanded polystyrene (EPS) and portland cement, in the suction ripple cement of the Graphene/ferroso-ferric oxide powder modified,
The filling rate of expanded polystyrene (EPS) is 40-70vol%, and the particle diameter of expanded polystyrene (EPS) is 2-6mm, Graphene/tetra- oxidation
The volume content of three-iron composite granule be 2-5%, Graphene：Ferroso-ferric oxide mass ratio is 2：1-1：2.
Preferably, the expanded polystyrene (EPS) is modified through surface, and method of modifying is as follows：
(1) EPS surfaces are cleaned with inorganic solvent, is made EPS particle surface slightly solubles；
(2) high polymer binder PVA dilute with waters, pour the EPS particles and coupling agent for cleaning into after stirring；
(3) dipping obtains the modified expanded polystyrene (EPS) in the surface after drying.
The Graphene/ferroso-ferric oxide powder preparation method is as follows：
(1), under condition of ice bath, under mechanical agitation, crystalline graphite powder is added in 98% concentrated sulfuric acid, add and account for
The sodium nitrate of graphite powder 50-80wt%, and to account for and react 30-120min under the potassium permanganate of 2-4 times of weight of graphite powder, ice bath；
(2) 30-40 DEG C of constant temperature 4-5h is heated to, deionized water and hydrogen peroxide is added, 1-3h is stirred, 5% concentration is added
HCl centrifuge washings are until sulfate radical-free ion, obtains graphene oxide after being dried；
(3) described graphene oxide is distributed in ethanol solution, ultrasonic disperse obtains graphene oxide colloid
Solution；
(4) the graphene oxide colloidal solution is heated to into 65-75 DEG C, stirring is lower to add mass concentration to be 70-85%
Hydrazine hydrate, reaction 0.5-2 hours after, according to Graphene:Ferroso-ferric oxide mass ratio is 2:1～1:2 ratio, adds four oxygen
Change three iron powders, be well mixed；
(5) centrifugation wash, vacuum drying obtains Graphene/ferroso-ferric oxide powder.
It is as EPS surfaces are hydrophobicity, poor with inorganic silicic acid salt cement compatibility, and EPS grain densities are especially little,
Easily float during with cement mixing and stirring, affect the uniformity of cement slurry, in order to strengthen EPS particles and cement slurry
Compatibility, need to pre-process EPS surfaces.Traditional method is to apply a layer binder in EPS particle surfaces, existing
Technology typically adopts epoxy latex or polyethylene propionate, and which can make EPS particle tables in the mixed process of EPS particles
Face is in a kind of tacky state, after cement slurry is added, can form one layer of cementitious coating in EPS particle surfaces, contribute to
Bonding between EPS particles and between EPS particles and cement matrix, but this method substantially increases EPS cementitious composite materials
The cost of manufacture of material.
Present invention employs a kind of brand-new handling process.First EPS surfaces are cleaned with inorganic solvent, EPS is made
Particle surface slightly soluble.With high polymer binder PVA dilute with waters, the EPS particles and coupling agent for cleaning after stirring, is poured into.
As the dissolving of EPS particle surfaces causes its surface roughness to increase, substantially increase the specific surface area of EPS particles, with
When binding agent mixes, the contact interface area between EPS particles and binding agent is just considerably increased, improve between the two is viscous
Knot performance.
Portland cement is to the decay of electromagnetic wave mainly by the metal oxide and some ore deposits in cement composition
The dielectric loss and magnetic loss of thing material, absorbing property is than relatively low, and cement sample is dense, so as to cause the defeated of material
Enter wave impedance not matching that with free space wave impedance, the wave transparent performance of material is poor.EPS particle dielectric constants than relatively low,
Can be used as a kind of good electromagnetic wave transparent material.After it is added in portland cement, the pore of cement-base composite material can be adjusted
Rate and electromagnetic parameter, substantially increase the matching degree of composite impedance and space wave impedance.And at EPS particle Jing surfaces
After reason, with the compatibility of cement slurry preferably, after being sufficiently mixed with cement, its surface will be wrapped by one layer of cement layer, can be with
Scattered portion electromagnetic wave, therefore EPS filling concretes composite can be equivalent to a kind of closed pore absorbent structure.Work as incident electromagnetic wave
During into composite inner, multiple reflections and scattering will occur between each particle, so as to improve material on incident electricity
The loss and absorption of magnetic wave.
After adding EPS particles in cement, the absorbing property of sample is all improved.During addition 40vol%EPS, reflection is damaged
Consumption reaches -7～-10dB, and the absorbing property of sample increases with the increase of frequency, when frequency reaches 17.7GHz, sample
Reflection loss reached -10.02dB；After EPS filling rates reach 60vol%, absorbing property continues with the increase of frequency
Increase, after frequency is more than 12GHZ, the absorbing property of sample is better than -10dB, when frequency reaches 18GHz, inhales crossing property
- 15.27dB can be reached, a width of 6.2GHz of band better than -10dB, when EPS loadings continue to increase to 70%, material is absorbed
Suction is draped over one's shoulders performance and is declined on the contrary.
The absorbing property of material is the synthesis of material wave transparent performance and drain performance, and material will have good wave absorbtion
Can, it is necessary to assure the wave transparent performance of material reaches certain requirement.After EPS particles are added in cement matrix, material is improved
Wave transparent performance, decayed into the electromagnetic wave inside sample in FPS particle surface Jing multiple reflections and scattering process, so as to
The absorbing property of cement material is improve, is combined when part Graphene/ferroso-ferric oxide is added in EPS filling concrete composites
After powder, the transmission coefficient of composite reduces, reflectance factor increase, but the electricity damage of Graphene/ferroso-ferric oxide composite granule
Consumption but increased incoming electromagnetic by the decay in material internal, so the absorbing property of material can obtain part raising.
Gradually increase with the increase of Graphene/ferroso-ferric oxide composite granule content within the specific limits, that is, absorb system
Number has the process of an increase first.With the further increase of Graphene/ferroso-ferric oxide composite granule content, composite
Electric conductivity improve so that the wave transparent performance of material is further reduced, electromagnetic wave specimen surface reflex strengthen, from
And cause the absorbing property of composite to reduce.
Therefore above-mentioned consideration is based on, in the present invention, Graphene/volume of the ferroso-ferric oxide composite granule in cement is contained
Amount is set as 2-5%.
The present invention is doped and added to Graphene/ferroso-ferric oxide composite granule and expanded polystyrene (EPS) in cement, in 8-
In the microwave frequency band of 18GHz, full frequency band reaches the absorption of more than -14.2dB so that the absorbing property of cement strengthens.
Specific embodiment
Technical scheme is further illustrated below by specific embodiment.
Embodiment 1
A kind of suction ripple cement of Graphene/ferroso-ferric oxide powder modified, including Graphene/ferroso-ferric oxide is compound
Powder, expanded polystyrene (EPS) and portland cement, in the suction ripple cement of the Graphene/ferroso-ferric oxide powder modified,
The filling rate of expanded polystyrene (EPS) is 40vol%, and the particle diameter of expanded polystyrene (EPS) is 2mm, and Graphene/ferroso-ferric oxide is multiple
The volume content for closing powder is 2%.
Embodiment 2
A kind of suction ripple cement of Graphene/ferroso-ferric oxide powder modified, including Graphene/ferroso-ferric oxide is compound
Powder, expanded polystyrene (EPS) and portland cement, in the suction ripple cement of the Graphene/ferroso-ferric oxide powder modified,
The filling rate of expanded polystyrene (EPS) is 70vol%, and the particle diameter of expanded polystyrene (EPS) is 6mm, and Graphene/ferroso-ferric oxide is multiple
The volume content for closing powder is 5%.
Embodiment 3
A kind of suction ripple cement of Graphene/ferroso-ferric oxide powder modified, including Graphene/ferroso-ferric oxide is compound
Powder, expanded polystyrene (EPS) and portland cement, in the suction ripple cement of the Graphene/ferroso-ferric oxide powder modified,
The filling rate of expanded polystyrene (EPS) is 50vol%, and the particle diameter of expanded polystyrene (EPS) is 4mm, and Graphene/ferroso-ferric oxide is multiple
The volume content for closing powder is 3%.
In embodiment of the present invention 1-3, Graphene/ferroso-ferric oxide composite granule and foaming polyphenyl second in cement, are doped and added to
Alkene, in the microwave frequency band of 8-18GHz, full frequency band reaches the absorption of more than -14.2dB so that the absorbing property of cement strengthens.
Claims (3)
1. a kind of suction ripple cement of Graphene/ferroso-ferric oxide powder modified, including Graphene/ferroso-ferric oxide composite powder
Body, expanded polystyrene (EPS) and portland cement, in the suction ripple cement of the Graphene/ferroso-ferric oxide powder modified, send out
The filling rate of foamed polystyrene is 40-70vol%, and the particle diameter of expanded polystyrene (EPS) is 2-6mm, Graphene/tetra- oxidation three
The volume content of iron composite powder body be 2-5%, Graphene：Ferroso-ferric oxide mass ratio is 2:1-1:2.
2. the suction ripple cement of Graphene as claimed in claim 1/ferroso-ferric oxide powder modified, it is characterised in that institute
State expanded polystyrene (EPS) modified through surface, method of modifying is as follows：
(1) EPS surfaces are cleaned with inorganic solvent, is made EPS particle surface slightly solubles；
(2) high polymer binder PVA dilute with waters, pour the EPS particles and coupling agent for cleaning into after stirring；
(3) dipping obtains the modified expanded polystyrene (EPS) in the surface after drying.
3. the suction ripple cement of Graphene as claimed in claim 1 or 2/ferroso-ferric oxide powder modified, the Graphene/
Ferroso-ferric oxide powder preparation method is as follows：
(1), under condition of ice bath, under mechanical agitation, crystalline graphite powder is added in 98% concentrated sulfuric acid, add and account for graphite
The sodium nitrate of powder 50-80wt%, and to account for and react 30-120min under the potassium permanganate of 2-4 times of weight of graphite powder, ice bath；
(2) be heated to 30-40 DEG C of constant temperature 4-5h, add deionized water and hydrogen peroxide, stir 1-3h, add the HCl of 5% concentration from
Heart washing is until sulfate radical-free ion, obtains graphene oxide after being dried；
(3) described graphene oxide is distributed in ethanol solution, ultrasonic disperse obtains graphene oxide colloidal solution；
(4) the graphene oxide colloidal solution is heated to into 65-75 DEG C, stirring is lower to add mass concentration for the water of 70-85%
Hydrazine is closed, after reaction 0.5-2 hours, according to Graphene:Ferroso-ferric oxide mass ratio is 2:1～1:2 ratio, adds four oxidations three
Iron powder, is well mixed；
(5) centrifugation wash, vacuum drying obtains Graphene/ferroso-ferric oxide powder.
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Cited By (8)
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| CN107311555A (en) * | 2017-05-15 | 2017-11-03 | 盐城工学院 | A kind of cement-based absorption material for filling graphene oxide and preparation method thereof |
| CN108409228A (en) * | 2018-02-14 | 2018-08-17 | 盐城工学院 | A kind of single layer cement base wave-absorber and preparation method thereof for mixing nano wave-absorption agent again |
| WO2019052336A1 (en) * | 2017-09-12 | 2019-03-21 | 中晶环境科技股份有限公司 | Thermally insulated article and preparation method therefor |
| CN109626893A (en) * | 2019-01-29 | 2019-04-16 | 济南大学 | Cement ceiling board and its semidry method preparation process with electro-magnetic screen function |
| CN109851298A (en) * | 2019-01-24 | 2019-06-07 | 济南大学 | Electromagnetically shielding cement plate and its semidry method preparation process |
| CN112876185A (en) * | 2021-02-08 | 2021-06-01 | 大连理工大学 | Red mud/steel slag-based wave-absorbing cementing material and preparation method thereof |
| CN112979255A (en) * | 2021-02-08 | 2021-06-18 | 大连理工大学 | NiFe-LDH slag-based composite wave-absorbing cementing material and preparation method thereof |
| CN113277784A (en) * | 2020-07-14 | 2021-08-20 | 李焕醒 | Pumice concrete with electromagnetic wave absorption function |
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| WO2019052336A1 (en) * | 2017-09-12 | 2019-03-21 | 中晶环境科技股份有限公司 | Thermally insulated article and preparation method therefor |
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| CN109851298A (en) * | 2019-01-24 | 2019-06-07 | 济南大学 | Electromagnetically shielding cement plate and its semidry method preparation process |
| CN109851298B (en) * | 2019-01-24 | 2021-07-30 | 济南大学 | Electromagnetic shielding cement board and semi-dry method preparation process thereof |
| CN109626893A (en) * | 2019-01-29 | 2019-04-16 | 济南大学 | Cement ceiling board and its semidry method preparation process with electro-magnetic screen function |
| CN109626893B (en) * | 2019-01-29 | 2021-05-25 | 济南大学 | Cement ceiling board with electromagnetic shielding function and semi-dry method preparation process thereof |
| CN113277784A (en) * | 2020-07-14 | 2021-08-20 | 李焕醒 | Pumice concrete with electromagnetic wave absorption function |
| CN112876185A (en) * | 2021-02-08 | 2021-06-01 | 大连理工大学 | Red mud/steel slag-based wave-absorbing cementing material and preparation method thereof |
| CN112979255A (en) * | 2021-02-08 | 2021-06-18 | 大连理工大学 | NiFe-LDH slag-based composite wave-absorbing cementing material and preparation method thereof |
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