CN113336486A - Cement-based composite material with damping function - Google Patents
Cement-based composite material with damping function Download PDFInfo
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- CN113336486A CN113336486A CN202110616582.6A CN202110616582A CN113336486A CN 113336486 A CN113336486 A CN 113336486A CN 202110616582 A CN202110616582 A CN 202110616582A CN 113336486 A CN113336486 A CN 113336486A
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- silicon powder
- cement
- composite material
- waterborne polyurethane
- based composite
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- 239000002131 composite material Substances 0.000 title claims abstract description 111
- 239000004568 cement Substances 0.000 title claims abstract description 93
- 238000013016 damping Methods 0.000 title claims abstract description 51
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 128
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- 239000010703 silicon Substances 0.000 claims abstract description 43
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- 239000002904 solvent Substances 0.000 claims abstract description 5
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- 239000002245 particle Substances 0.000 claims description 24
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
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- 230000035484 reaction time Effects 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- 229940093430 polyethylene glycol 1500 Drugs 0.000 claims description 5
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- DYFFAVRFJWYYQO-UHFFFAOYSA-N n-methyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(C)C1=CC=CC=C1 DYFFAVRFJWYYQO-UHFFFAOYSA-N 0.000 claims description 4
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical group CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 3
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- 238000005303 weighing Methods 0.000 claims description 3
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- 229910052786 argon Inorganic materials 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 239000004567 concrete Substances 0.000 description 5
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- C—CHEMISTRY; METALLURGY
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- 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
-
- 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
- C04B20/02—Treatment
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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
- 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
- C04B20/02—Treatment
- C04B20/023—Chemical treatment
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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
- 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
- C04B20/1037—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/3234—Polyamines cycloaliphatic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The invention provides a cement-based composite material with a damping function and a preparation method thereof. The preparation method specifically comprises the following steps: firstly, carrying out surface activation on the silicon powder by adopting plasma, and then carrying out silanization reaction to obtain the surface-modified silicon powder. Then adding a proper amount of dihydroxy polyether, hydrophilic chain extender and diamine chain extender into a solvent, dissolving, adding the prepared silicon powder, and uniformly dispersing. Then adding diisocyanate solution and catalyst, reacting for 6-10 hours at 80-110 ℃, and filtering to obtain the silicon powder-waterborne polyurethane composite filler. Adding the silicon powder-waterborne polyurethane composite filler into the cement powder, and uniformly stirring; and adding water according to the water-cement ratio, fully stirring, pouring into a mould, demoulding and maintaining to obtain the cement-based composite material with the damping function. The cement-based composite material effectively solves the influence of low-frequency vibration on the environment, fills the gap in the prior art, and has important practical application value.
Description
Technical Field
The invention belongs to the field of materials, relates to a cement-based damping composite material and a preparation method thereof, and particularly relates to a composite damping material prepared by adding a core-shell structured filler to a cement-based material and a preparation method thereof.
Background
China is a big country of cement industry, and the cement industry is one of the pillars of the main basic raw material industry of China, and has a great position in the sustainable development of national economy. With the development of science and technology and the enhancement of environmental protection consciousness of people, the sustainable development of the cement industry is more and more emphasized. Along with the development of the Chinese transportation rail, the running speed of the train is continuously improved, the power effect generated by the train load is more and more obvious, the rail plate structure is extremely easy to influence, the safety performance of the rail plate structure can be greatly reduced, a plurality of potential safety hazards appear, and the running stability of the rail plate structure is influenced. Meanwhile, according to the development trend of transportation tracks, besides subways, more and more railway lines pass through or are close to vibration and noise sensitive points of urban districts, residential districts, hospitals, schools and cultural relics protection according to units and the like, and vibration and noise generated by train operation can seriously affect life and work of people along the railway lines. Therefore, it is a technical problem to improve the vibration and energy absorption performance of the composite material.
The cement-based composite material is a composite material with damping performance improved by adding inorganic fibers, fillers, polymers and the like into a cement-based material. Compared with the common cement-based material, the cement-based damping composite material has higher impact resistance and shock resistance, fundamentally improves the defects of high noise and high vibration of the concrete pavement, increases the pavement flexibility and brings new vitality to the concrete pavement. In the existing literature on damping materials, indexes such as damping ratio, loss factor and the like are generally adopted, and different damping frequencies are not analyzed. In practical applications, however, low frequency vibrations propagate the most; therefore, the low-frequency vibration which is most harmful to the environment and difficult to eliminate is below 200 Hz, especially below 50 Hz, and no targeted solution exists at present.
At present, relevant researches are carried out to add silanized silicon powder into concrete, so that the damping performance of concrete materials and structures is improved, and the self shock resistance of the concrete structure is enhanced. But the study does not address the problem of low frequency vibrations.
Disclosure of Invention
Aiming at the problems of the existing cement-based composite material, the invention provides a cement-based composite material with a damping function and a preparation method thereof. The cement-based composite material effectively solves the influence of low-frequency vibration on the environment, fills the gap in the prior art, and has important practical application value.
The technical scheme of the invention is as follows: the cement-based composite material with the damping function is prepared by adopting the following method:
(1) preparing surface-modified silicon powder: and activating the surface of the silicon powder by adopting plasma, and then performing silanization reaction on a proper amount of the surface-activated silicon powder to obtain the surface-modified silicon powder. Through silanization modification, canIntroducing large silicon powder on the surface Amount of terminal amino groupAnd the preparation of the silicon powder/waterborne polyurethane composite filler is facilitated.
The specific steps of carrying out surface activation on the silicon powder are as follows: putting the silicon powder into a culture dish, and preferably just spreading the silicon powder on the bottom of the surface dish; controlling the vacuum degree to be 10Pa, and introducing cleaning gas for the plasma with the pressure of 100 Pa; and applying high-frequency voltage to break down the gas, ionizing the gas through glow discharge to generate plasma, completely covering the silicon powder with the plasma, and treating for a certain time to obtain the surface-activated silicon powder. Wherein the particle size of the silicon powder is 200-800 meshes, and the cleaning gas is oxygen, hydrogen, argon or nitrogen; the time for activating the surface is 30s-5 min.
The silanization reaction comprises the following specific steps: weighing a proper amount of surface-activated silicon powder, slowly adding the silicon powder into a silane coupling agent methanol solution under the condition of stirring, stirring at room temperature to perform a silanization reaction, filtering, washing and drying in vacuum to obtain the surface-modified silicon powder. Wherein the silane coupling agent is a silane coupling agent with amino and hydroxyl functional groups on the surface; the concentration of the silane coupling agent methanol solution is 0.5-5%; the silanization reaction time is 2-8 hours.
(2) Preparing the silicon powder-waterborne polyurethane composite filler: and (2) adding a proper amount of dihydroxy polyether, a hydrophilic chain extender and a diamine chain extender into a solvent, stirring and dissolving, adding the surface-modified silicon powder obtained in the step (1), and stirring to uniformly disperse the silicon powder. Then adding a diisocyanate solution and a catalyst, reacting for 6-10 hours at the temperature of 80-110 ℃, washing and filtering to obtain powdery solid silicon powder coated by the waterborne polyurethane elastomer, namely the silicon powder-waterborne polyurethane composite filler. The surface-modified silicon powder prepared in the step (1),introducing a large amount of terminal amino groups on the surface of the silicon powder(ii) a Because the reactivity of the amino group and the isocyanate is far greater than that of the hydroxyl group, when the amino group and the isocyanate react with the diisocyanate group, the surface modified silicon powder is firstly bonded with one isocyanate functional group of the diisocyanate groupSilanized silicon powder with great amount of urea bonds formed on its surface(ii) a And the other isocyanate functional group in the diisocyanate continuously reacts with components such as dihydroxy polyether and the like, so that a core-shell structure with the surface of the silicon powder coated with the waterborne polyurethane coating is formed.
The step (2) also comprises the treatment of the silicon powder-waterborne polyurethane composite filler, which specifically comprises the following steps: dispersing powdery silicon powder-waterborne polyurethane composite filler intoStirring the mixture in 0.1mol/L NaOH solution until no agglomerated solid particles exist, continuing stirring the mixture for 20 to 30min, and then filtering, washing and drying the mixture to obtain the treated silicon powder-waterborne polyurethane composite filler. By the above treatment with Na+By substitution of H in carboxyl groups+The agglomeration of the silicon powder-aqueous polyurethane composite filler caused by the existence of a large number of hydrogen bonds is avoided. Therefore, the silicon powder-waterborne polyurethane composite filler realizes the full dispersion in the cement paste, and ensures the optimization of the damping effect. Wherein, the dihydroxy polyether is one or more of polyethylene glycol 600, polyethylene glycol 1000 and polyethylene glycol 1500; the hydrophilic chain extender is 2, 2-dimethylolpropionic acid or 2, 2-dimethylolbutyric acid; the diamine chain extender is diethyl toluene diamine or N, N' -dialkyl methyl diphenylamine; the diisocyanate is diphenylmethane diisocyanate, toluene diisocyanate or hexamethylene diisocyanate.
(3) Preparing a cement-based composite material: adding the silicon powder-waterborne polyurethane composite filler obtained in the step (2) into cement powder according to the proportion of 0.2-1.0wt% of the cement powder, and uniformly stirring; and adding water according to the proportion of 0.4-0.5: 1, fully stirring, pouring into a mould, demoulding and maintaining to obtain the cement-based composite material with the damping function. In the silicon powder-aqueous polyurethane composite filler with the core-shell structure prepared in the step (2), aqueous polyurethane molecules are grafted on the surface of the silicon powder, and the end group of the silicon powder is modified into sodium salt; after the sodium salt-containing composite filler is added into a cement-based material, the filler can be uniformly dispersed in cement paste by utilizing the hydrophilicity of the sodium salt, and the carboxyl formed after the ionization of the sodium salt and cement are subjected to hydration reaction, so that the two are compounded in a chemical bonding mode. After the reaction is complete and the curing is carried out, a microcosmic constraint damping structure is formed among the silica powder, the waterborne polyurethane and the cement paste, the silica powder and the cement paste can be displaced mutually under the vibration condition, and the waterborne polyurethane is sheared and deformed, so that the vibration energy is converted into heat energy to play a role in energy consumption. Meanwhile, the silicon powder can also play a role in energy consumption through self vibration, namely the energy of the vibration is converted into the kinetic energy of the silicon powder. By changing the particle size of the silicon powder, the molecular structure of the waterborne polyurethane, the thickness of the coating of the waterborne polyurethane and other factors, the damping frequency range of the material can be adjusted to adapt to different use requirements.
Preferably, the silane coupling agent is KH-540, KH-550, KH-551, KH-620, KH-791, KH-792, KH-901 or KH-902.
The cement-based damping composite material prepared by the method contains silicon powder coated by the waterborne polyurethane elastomer. The content of the silica powder coated by the aqueous polyurethane elastomer in the cement-based composite material is 0.2-1.0 wt%.
The invention has the beneficial effects that:
1. the cement-based composite material with the damping function provided by the invention realizes vibration reduction of low-frequency vibration below 200 Hz, achieves remarkable results, solves the influence of the low-frequency vibration on the environment, fills the blank of the prior art, and has important practical application value.
2. According to the cement-based composite material with the damping function, the adopted filler is silicon powder coated by the waterborne polyurethane elastomer with the core-shell structure, and a dual energy consumption mechanism is realized through the vibration of the silicon powder and the elastic deformation of the waterborne polyurethane coating, so that the damping performance of the composite material is improved.
3. The cement-based composite material with the damping function solves the problem of filler agglomeration by further processing the silicon powder-waterborne polyurethane composite filler, and further improves the damping performance.
Drawings
FIG. 1 is a scanning electron microscope image of the silica powder-waterborne polyurethane composite filler prepared in example 1 described herein;
FIG. 2 is a scanning electron microscope image of the cement-based damping composite prepared in example 1 described herein;
FIG. 3 is an 1/3 octave spectrum of a cement-based damping composite prepared according to example 1 described herein. Wherein FIG. 3a is an 1/3 octave spectrum at 0-50 Hz, and FIG. b is a partial magnified view of FIG. 3a at 0-10 Hz.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
1. activation and silanization of the surface of the silicon powder:
the method adopts plasma to carry out surface activation on silicon powder, and comprises the following specific operation steps: putting a certain amount of silicon powder in a culture dish, and preferably just spreading the silicon powder on the bottom of a surface dish; the vacuum degree was controlled to 10Pa, and a cleaning gas for plasma was introduced at a pressure of 100Pa to maintain the pressure of the cleaning gas at 100 Pa. And applying high-frequency voltage to break down the gas, ionizing the gas through glow discharge to generate plasma, completely covering the silicon powder with the plasma, and treating for a certain time to obtain the surface-activated silicon powder. Wherein the particle size of the silicon powder is 200 meshes, and the cleaning gas is nitrogen; the time for the surface activation was 60 s.
The silanization reaction comprises the following specific steps: weighing a proper amount of silicon powder with activated surfaces, slowly adding the silicon powder into a silane coupling agent methanol solution under the condition of stirring, and stirring and reacting for 2 hours at room temperature to complete the silanization reaction. And filtering, washing and vacuum drying to obtain the surface-modified silicon powder. Wherein, the silane coupling agent KH-550; the concentration of the silane coupling agent methanol solution is 5%.
2. Preparing the silicon powder-waterborne polyurethane composite filler:
(1) 0.09mol of polyethylene glycol 600, 0.06mol of polyethylene glycol 1000 and 0.012mol of N, N' -dialkyl methyl diphenylamine are added into 200ml of acetone solvent, stirred and dissolved, then added with surface-modified silicon powder and stirred to be uniformly dispersed. Then 0.025mol of toluene diisocyanate solution and 2 drops of dibutyltin dilaurate catalyst are added into the mixture to react for 8 hours at the temperature of 80 ℃, and after washing and filtering, the obtained powdery solid is silicon powder coated by the waterborne polyurethane elastomer, namely the silicon powder-waterborne polyurethane composite filler. .
(2) And (2) dispersing the silicon powder-waterborne polyurethane composite filler obtained in the step (1) into 0.1mol/L NaOH solution, stirring until agglomerated solid particles do not exist, continuing stirring for 20min, and then filtering, washing and drying to obtain the treated silicon powder-waterborne polyurethane composite filler. And characterizing the silicon powder-waterborne polyurethane composite filler treated by NaOH by adopting SEM.
3. Preparation of cement-based composite materials
Adding the silica powder-waterborne polyurethane composite filler into the cement powder according to the proportion of 0.2 wt%, 0.4 wt%, 0.6 wt%, 0.8 wt% and 1.0wt% of the cement powder, and uniformly stirring; and adding water according to the water-cement ratio of 0.4:1, fully stirring, pouring into a mold, demolding and maintaining to obtain the cement-based composite material with the damping function.
Example 2: in contrast to the embodiment 1, the process of the invention,
1. activation and silanization of silicon powder surface
The cleaning gas adopted for activating the surfaces of the inorganic particles by adopting the plasma is oxygen, the activation time is 3min, and the particle size of the inorganic particles is 500 meshes. The silanization reaction time is 6 hours, the adopted silane coupling agent is KH-620, and the concentration of the silane coupling agent-methanol solution is 0.75 percent.
2. Preparing the silicon powder-waterborne polyurethane composite filler:
(1) 0.015mol of polyethylene glycol 600 and 0.012mol of diethyl toluenediamine are added into 200ml of acetone, stirred and dissolved, and then added with surface-modified silicon powder, stirred and dispersed evenly. Then 0.025mol of diphenylmethane diisocyanate solution and 2 drops of dibutyltin dilaurate catalyst are added into the mixture, the mixture reacts for 6 hours at the temperature of 80 ℃, and after washing and filtering, the obtained powdery solid is silicon powder coated by the waterborne polyurethane elastomer, namely the silicon powder-waterborne polyurethane composite filler.
(2) And (2) dispersing the silicon powder-waterborne polyurethane composite filler obtained in the step (1) into 0.1mol/L NaOH solution, stirring until agglomerated solid particles do not exist, continuing stirring for 25min, and then filtering, washing and drying to obtain the treated silicon powder-waterborne polyurethane composite filler.
3. Preparation of cement-based composite materials
Adding the silica powder-waterborne polyurethane composite filler into cement powder according to the proportion of 0.2 wt%, 0.4 wt%, 0.6 wt%, 0.8 wt% and 1.0wt% of the cement powder, and uniformly stirring; and adding water according to the water-cement ratio of 0.45:1, fully stirring, pouring into a mold, demolding and maintaining to obtain the cement-based composite material with the damping function.
Example 3: in contrast to the embodiment 1, the process of the invention,
1. activation and silanization of silicon powder surface
The cleaning gas adopted for activating the surfaces of the inorganic particles by adopting the plasma is hydrogen, the activation time is 5min, and the particle size of the inorganic particles is 800 meshes. The silanization reaction time is 8 hours, the adopted silane coupling agent is KH-792, and the concentration of the silane coupling agent-methanol solution is 0.5%.
2. Preparing the silicon powder-waterborne polyurethane composite filler:
(1) 0.013mol of polyethylene glycol 600, 0.012mol of polyethylene glycol 1500 and 0.012mol of 2, 2-dimethylolbutyric acid are added into 200ml of acetone solvent, stirred and dissolved, then added with the surface modified silicon powder, and stirred to be uniformly dispersed. Then 0.025mol of hexamethylene diisocyanate solution and 2 drops of dibutyltin dilaurate catalyst are added into the mixture to react for 8 hours at the temperature of 110 ℃, and after washing and filtering, the obtained powdery solid is silicon powder coated by the waterborne polyurethane elastomer, namely the silicon powder-waterborne polyurethane composite filler.
(2) And (2) dispersing the silicon powder-waterborne polyurethane composite filler obtained in the step (1) into 0.1mol/L NaOH solution, stirring until agglomerated solid particles do not exist, continuing stirring for 30min, and then filtering, washing and drying to obtain the treated silicon powder-waterborne polyurethane composite filler.
3. Preparation of cement-based composite materials
Adding the silica powder-waterborne polyurethane composite filler into cement powder according to the proportion of 0.2 wt%, 0.4 wt%, 0.6 wt%, 0.8 wt% and 1.0wt% of the cement powder, and uniformly stirring; and adding water according to the water-cement ratio of 0.5:1, fully stirring, pouring into a mold, demolding and maintaining to obtain the cement-based composite material with the damping function.
Example 4: in contrast to the embodiment 1, the process of the invention,
1. activation and silanization of silicon powder surface
The cleaning gas adopted for activating the surfaces of the inorganic particles by adopting the plasma is hydrogen, the activation time is 1min, and the particle size of the inorganic particles is 600 meshes. The silanization reaction time is 8 hours, the adopted silane coupling agent is KH-620, and the concentration of the silane coupling agent-methanol solution is 0.5 percent.
2. Preparing the silicon powder-waterborne polyurethane composite filler:
(1) 0.075mol of polyethylene glycol 600, 0.075mol of polyethylene glycol 1500 and 0.012mol of 2, 2-dimethylolbutyric acid are added into 200mL of acetone, stirred and dissolved, then added with surface-modified silicon powder, and stirred to be uniformly dispersed. Then 0.025mol of hexamethylene diisocyanate solution and 2 drops of dibutyltin dilaurate catalyst are added into the mixture to react for 10 hours at the temperature of 95 ℃, and after washing and filtering, the obtained powdery solid is silicon powder coated by the waterborne polyurethane elastomer, namely the silicon powder-waterborne polyurethane composite filler.
(2) And (2) dispersing the silicon powder-waterborne polyurethane composite filler obtained in the step (1) into 0.1mol/L NaOH solution, stirring until agglomerated solid particles do not exist, continuing stirring for 25min, and then filtering, washing and drying to obtain the treated silicon powder-waterborne polyurethane composite filler.
3. Preparation of cement-based composite materials
Adding the silica powder-waterborne polyurethane composite filler into cement powder according to the proportion of 0.2 wt%, 0.4 wt%, 0.6 wt%, 0.8 wt% and 1.0wt% of the cement powder, and uniformly stirring; and adding water according to the water-cement ratio of 0.45:1, fully stirring, pouring into a mold, demolding and maintaining to obtain the cement-based composite material with the damping function.
Example 5: in contrast to the embodiment 1, the process of the invention,
1. activation and silanization of silicon powder surface
The cleaning gas adopted for activating the surfaces of the inorganic particles by adopting the plasma is hydrogen, the activation time is 30s, and the particle size of the inorganic particles is 600 meshes. The silanization reaction time is 8 hours, the adopted silane coupling agent is KH-551, and the concentration of the silane coupling agent-methanol solution is 0.75 percent.
2. Preparing the silicon powder-waterborne polyurethane composite filler:
(1) 0.025mol of polyethylene glycol 1500 and 0.012mol of N, N' -dialkyl methyl diphenylamine are added into 200mL of acetone, stirred and dissolved, and then added with surface-modified silicon powder and stirred to be uniformly dispersed. Then 0.025mol of diphenylmethane diisocyanate solution and 2 drops of dibutyltin dilaurate catalyst are added into the mixture, the mixture reacts for 10 hours at the temperature of 95 ℃, and after washing and filtering, the obtained powdery solid is silicon powder coated by the waterborne polyurethane elastomer, namely the silicon powder-waterborne polyurethane composite filler.
(2) And (2) dispersing the silicon powder-waterborne polyurethane composite filler obtained in the step (1) into 0.1mol/L NaOH solution, stirring until agglomerated solid particles do not exist, continuing stirring for 30min, and then filtering, washing and drying to obtain the treated silicon powder-waterborne polyurethane composite filler.
3. Preparation of cement-based composite materials
Adding the silicon powder-waterborne polyurethane composite filler into cement powder according to the proportion of 0.2 wt%, 0.4 wt%, 0.6 wt%, 0.8 wt% and 1 wt% of the cement powder, and uniformly stirring; and adding water according to the water-cement ratio of 0.45:1, fully stirring, pouring into a mold, demolding and maintaining to obtain the cement-based composite material with the damping function.
Example 6: SEM representation of silicon powder-waterborne polyurethane composite filler and cement-based composite material
The applicant respectively performs SEM characterization on the silicon powder-water-based polyurethane composite fillers prepared in examples 1 to 5, and finds that the SEM images of the composite fillers are similar. The following description will be made by taking example 1 as an example.
As shown in fig. 1, fig. 1a shows silicon powder without surface treatment, and fig. 1b shows silicon powder particles coated with the aqueous polyurethane coating prepared in example 1, i.e., a silicon powder-aqueous polyurethane composite filler. As can be seen from fig. 1a, the surface of the untreated silicon powder is rough; while the silicon powder particles coated by the aqueous polyurethane coating in fig. 1b have smooth surfaces, and the aqueous polyurethane coating can be uniformly coated on the silicon powder surface. FIG. 1c shows that the silicon powder particles coated with the aqueous polyurethane coating without being treated with NaOH solution are significantly agglomerated due to hydrogen bonds formed by a large amount of carboxyl groups on the surface of the silicon powder particles. While figure 1d shows that the particles treated with NaOH solution have been completely dispersed, indicating that the treated particles solve the problem of hydrogen bond agglomeration.
Meanwhile, the cross sections of the cement-based composite materials prepared in examples 1 to 5 after cutting, grinding and polishing are characterized by adopting SEM, and SEM images of the composite fillers are similar. Next, a cement-based composite material (FIG. 2) having a composite filler content of 1.0wt% in example 1 will be described. Wherein, fig. 2a is undoped cement paste, and fig. 2b is image of the cement paste doped with silica powder damping filler coated by aqueous polyurethane coating. As can be seen from fig. 2b, the filler particles can be uniformly dispersed in the cement paste without agglomeration. This is because the filler was treated with NaOH solution. FIG. 2c is an enlarged view of a portion of the damping particles in the cement slurry. As can be clearly seen from fig. 2c, a uniform, dense and continuous waterborne polyurethane coating exists on the surface of the silica powder, and both sides of the coating are tightly connected with the silica powder and the cement paste respectively, which is due to the fact that the two interfaces are connected by chemical bonds. The constrained damping structure can be formed only if the interfaces on the two sides of the coating are completely and tightly connected, so that the maximum energy consumption is generated when shock is received. FIG. 2d is the cathodoluminescence image of FIG. 2c, wherein the luminescent color of the marker polymer is red. It can be seen that the red light emitting part is the outline of the polymer coating, with the outside being the cement paste and the contents being the silica fume particles.
Example 7: detection of vibration damping performance of cement-based composite material
The applicant respectively tests the damping performance of the cement-based composite materials prepared in the examples 1 to 5, and the test results are similar. The following description will be made by taking example 1 as an example.
FIG. 3 is an 1/3 octave spectrum of cement-based composites of varying damping filler content prepared in example 1. As can be seen from FIG. 3, in the frequency range of 0-50 Hz, at the dosage of 0.2% -1%, the amplitude is reduced from 65-90dB to 57-86dB and the vibration amplitude is reduced by 5-12% along with the increase of the dosage. When the mixing amount reaches 1%, the damping effect is particularly remarkable, and the maximum damping amplitude can reach 10.34 dB. According to the vibration reduction level of the current urban subway, the primary vibration reduction effect is 5-10dB, and the intermediate vibration reduction effect is 10-15 dB. Therefore, the cement-based composite material developed by the invention can optimally reach the medium-level vibration reduction level.
In summary, the cement-based composite material realizes vibration reduction of low-frequency vibration below 50 Hz, achieves remarkable results, solves the problem of influence of the low-frequency vibration on the environment, fills the blank of the prior art, and has important practical application value. The cement-based composite material adopts silicon powder coated by the waterborne polyurethane elastomer with the core-shell structure as a filler, and realizes a dual energy consumption mechanism through the vibration of the silicon powder and the elastic deformation of the waterborne polyurethane coating, so that the damping performance of the composite material is improved.
Claims (10)
1. The cement-based composite material with the damping function is characterized in that: the preparation method comprises the following steps:
(1) preparing surface-modified silicon powder: activating the surface of the silicon powder by adopting plasma, and then performing silanization reaction on a proper amount of the surface-activated silicon powder to obtain surface-modified silicon powder;
(2) preparing the silicon powder-waterborne polyurethane composite filler: adding a proper amount of dihydroxy polyether, a hydrophilic chain extender and a diamine chain extender into a solvent, stirring and dissolving, adding the surface-modified silicon powder obtained in the step (1), and stirring to uniformly disperse the silicon powder; adding a diisocyanate solution and a catalyst, reacting for 6-10 hours at the temperature of 80-110 ℃, washing, filtering to obtain powdery solid silicon powder coated by the waterborne polyurethane elastomer, namely the silicon powder-waterborne polyurethane composite filler;
(3) preparing a cement-based composite material: adding the silicon powder-waterborne polyurethane composite filler obtained in the step (2) into cement powder according to the proportion of 0.2-1.0wt% of the cement powder, and uniformly stirring; and adding water according to the proportion of 0.4-0.5: 1, fully stirring, pouring into a mould, demoulding and maintaining to obtain the cement-based composite material with the damping function.
2. The cement-based composite material with damping function as claimed in claim 1, wherein: the step (2) also comprises the treatment of the silicon powder-waterborne polyurethane composite filler, which specifically comprises the following steps: dispersing the powdery silicon powder-waterborne polyurethane composite filler into 0.1mol/L NaOH solution, stirring until no agglomerated solid particles exist, continuing stirring for 20-30min, and then filtering, washing and drying to obtain the treated silicon powder-waterborne polyurethane composite filler.
3. The cement-based composite material with damping function as claimed in claim 2, wherein: the dihydroxy polyether in the step (2) is one or more of polyethylene glycol 600, polyethylene glycol 1000 and polyethylene glycol 1500; the hydrophilic chain extender is 2, 2-dimethylolpropionic acid or 2, 2-dimethylolbutyric acid; the diamine chain extender is diethyl toluene diamine or N, N' -dialkyl methyl diphenylamine; the diisocyanate is diphenylmethane diisocyanate, toluene diisocyanate or hexamethylene diisocyanate.
4. The cement-based composite material with damping function as claimed in claim 2, wherein: the specific steps of carrying out surface activation on the silicon powder in the step (1) are as follows: putting the silicon powder into a culture dish, and preferably just spreading the silicon powder on the bottom of the surface dish; controlling the vacuum degree to be 10Pa, introducing cleaning gas for plasma with the pressure of 100Pa, applying high-frequency voltage to enable the plasma to completely cover the silicon powder, and treating for a certain time to obtain the silicon powder with activated surface.
5. The cement-based composite material with damping function as claimed in claim 4, wherein: the particle size of the silicon powder is 200-800 meshes, and the cleaning gas is oxygen, hydrogen, argon or nitrogen; the time for activating the surface is 30s-5 min.
6. The cement-based composite material with damping function as claimed in claim 2, wherein: the silanization reaction of the step (1) comprises the following specific steps: weighing a proper amount of surface-activated silicon powder, slowly adding the silicon powder into a silane coupling agent methanol solution under the condition of stirring, stirring at room temperature to perform a silanization reaction, filtering, washing and drying in vacuum to obtain the surface-modified silicon powder.
7. The cement-based composite material with damping function as claimed in claim 6, wherein: the silane coupling agent is a silane coupling agent with amino and hydroxyl functional groups on the surface; the concentration of the silane coupling agent methanol solution is 0.5-5%; the silanization reaction time is 2-8 hours.
8. The cement-based composite material with damping function as claimed in claim 7, wherein: the silane coupling agent is KH-540, KH-550, KH-551, KH-620, KH-791, KH-792, KH-901 or KH-902.
9. A cement-based damping composite prepared by the method of any one of claims 1 to 8, wherein: the cement-based composite material contains silicon powder coated by the waterborne polyurethane elastomer.
10. The cement-based damping composite as claimed in claim 9, wherein: the content of the silica powder coated by the waterborne polyurethane elastomer is 0.2-1.0wt% of the weight of the cement powder.
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