CN108424023A - A kind of hydrophobic material and its preparation method and application - Google Patents
A kind of hydrophobic material and its preparation method and application Download PDFInfo
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- CN108424023A CN108424023A CN201810353868.8A CN201810353868A CN108424023A CN 108424023 A CN108424023 A CN 108424023A CN 201810353868 A CN201810353868 A CN 201810353868A CN 108424023 A CN108424023 A CN 108424023A
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- hydrophobic material
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- paper mill
- mill sludge
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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
- 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
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/65—Water proofers or repellants
-
- 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
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/27—Water resistance, i.e. waterproof or water-repellent 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)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention provides a kind of preparation method of hydrophobic material, includes the following steps：Fenton paper mill sludge is calcined, Fenton paper mill sludge ash is obtained；The Fenton paper mill sludge ash and stearic acid are subjected to ball milling, obtain hydrophobic material.When hydrophobic material volume prepared by the present invention is up to 4%, compression strength 2.5MPa high compared with blank cement sample；When hydrophobic material volume is up to 16%, the contact angle of water droplet and Behavior of Hardened Cement Paste is 102 °.After the Material claddings such as the hydrophobic material of the present invention and cement, apply to the waterproofing works such as underground station top plate, building cover board, side slope gunite concrete, water-stop curtain, corrosion function of the water translocation to engineering can be reduced, while also providing the technology path of Fenton paper mill sludge ash recycling recycling.
Description
Technical field
The present invention relates to sludge building material technical field more particularly to a kind of hydrophobic material and preparation method thereof and answer
With.
Background technology
The paper mill sludge discharge capacity in China occupies first place in the world, and has 20,000,000 tons or more of discharge capacity every year, mainly by filling out
It buries and is handled with fluid bed high-temperature calcination.Land occupation is filled, land resource is caused to waste；Sludge after calcining is lived with volcanic ash
Property, energy replacing partial cement clinker, this has been confirmed by many researchs, and the scientific research institution of the U.S. and Britain is made in research
Improve the performance of cement-based material for admixture.Since environmental requirement is continuously improved, large-scale paper mill generally requires to use
Fluidized bed processing, resulting calcining amount of sludge rise year by year.This kind of papermaking byproduct is reasonably recycled
It is that current social is badly in need of the difficult problem of environmental protection solved.
Transmission of the water in concrete pore is the main reason for causing its performance to deteriorate.Civil engineering Seepage water needs
Substantial contribution is spent, it sometimes can also schedule delays.The widely used ordinary cement sill of civil engineering has water-wet behavior,
It is mainly handled outer painting water-repellent paint or by way of being laid with waterproof membrane when using under water or under wet environment.In power
Or under alternate load effect, for waterproof layer once impaired, concrete structure can then lose barrier, easily deteriorate.Exploitation is fine and close and anti-
The strong cement-based material of aqueous energy is to solve the problems, such as this effective way, and the research and development of simple and fast additive are particularly important.
Zhang Ru (surfaces of Zhang Ru, Han Qing, Qian Weiwei, Li Si, Hou Tong plum paper mill sludges is modified and its mechanism of action just
The papermaking of step research [J] China, 2014,33 (01):15-19.) et al. propose with the dilution of papermaking wet mud and a variety of modifying agent
Liquid is raw material, its surface can generate hydrophobic grouping after hydro-thermal method, wherein stearic acid modified activation index is high, can be improved and has
The compatibility of machine high polymer.Hong S.Wang(Hong S.Wong,Robert Barakat,Alhilai,et
al.Hydrophobic concrete using waste paper sludge ash[J].Cement and concrete
Research, 2015,70:9-20.) the paper mill sludge ash Yu stearic acid ball milling modification of proposition Newsprint Mill, is added to cement
It is used in material, material mechanical performance is improved, moreover it is possible to improve hydrophobicity.Hole Yun et al. (hole Yun, Li Song, the surfaces Han Jin dragon
Activating agent is modified experimental study [J] New Building Materials that metakaolin influences cement performance, 2015,42 (12):60-
62.) it proposes in the mixture incorporation mortar for obtaining metakaolin and stearic acid ball milling modification, its mobility can be improved, significantly
Improve mortar strength.
Fenton paper mill sludge is to use H2O2And Fe2+Strong oxidizer treated sludge, except comprising conventional paper mill sludge at
Exceptionally, iron content is higher.It is rationally calcined according to document and is expected to improve Fenton paper mill sludge activity, generated with stearic acid ball milling modification
The feasibility of hydrophobic material is stronger.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of hydrophobic material, to simplify the preparation of hydrophobic material
Technical process, meanwhile, the mechanical property and hydrophobicity performance of hydrophobic material are improved, one is provided for the recycling of paper mill sludge
Feasible technology path.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
The present invention provides a kind of preparation methods of hydrophobic material, include the following steps：
Fenton paper mill sludge is calcined, Fenton paper mill sludge ash is obtained；
The Fenton paper mill sludge ash and stearic acid are subjected to ball milling, obtain hydrophobic material.
Preferably, the temperature of the calcining is 800-1000 DEG C, and the time of calcining is 1.5-2.5h.
Preferably, the weight ratio of the stearic acid and Fenton paper mill sludge ash is 1:24-25.
Preferably, the rotating speed of the ball milling is 350-400r/min, and the time of ball milling is 4-6h.
The present invention provides the hydrophobic materials that preparation method described in above-mentioned technical proposal is prepared.
Preferably, the ingredient of the hydrophobic material includes Al2O3, calcium aluminoferrite, calcium silicates, wollastonite and calcium aluminium Huang grow
Stone.
Preferably, the pH value of water solution of the hydrophobic material is 11.0-12.0.
Preferably, the grain size of the hydrophobic material is 75 μm or less.
The present invention provides the hydrophobic materials described in above-mentioned technical proposal in cement base hydrophobic material and concrete
Using.
The present invention provides a kind of preparation methods of hydrophobic material, include the following steps：Fenton paper mill sludge is calcined,
Obtain Fenton paper mill sludge ash；The Fenton paper mill sludge ash and stearic acid are subjected to ball milling, obtain hydrophobic material.The present invention
By mixing stearic acid mechanical mill activation modification Fenton paper mill sludge, on the one hand, paper mill sludge ash active constituent metakaolin,
Al2O3、CaCO3The a large amount of activity hydroxies in surface occur elimination reaction with stearic acid and generate C ≡ C, C-O-C or lipid hydrophobic grouping, together
When reduce surface energy, the Behavior of Hardened Cement Paste of hardening and the interfacial transition zone of aggregate can be evenly distributed in hydration reaction；On the other hand,
Calcine the C formed2A large amount of inert particle physical efficiencys such as F play nucleation in aquation, and the C-S-H gel energy clusters of generation are at this
A little granule surfaces, the intensity of concrete is improved at closely knit interface.
The present invention passes through heat treatment so that Fenton paper mill sludge have in cement applications certain pozzolanic activity and
Micro aggregates filling effect, sludge gray surface forms hydrophobic grouping after stearic acid modified, and water droplet instills hydrophobic material in rolling
Pearl and impermeable, good dispersion improve its mechanics and hate to which agglomeration not occur in Portland cement stirring
Aqueous energy.Data according to the embodiment it is found that the hydrophobic material for preparing of the present invention when cement replacement amount is up to 4%, pressure resistance
Degree is up to 73.08MPa compared with blank cement sample 71.53MPa high 2.5Mpa, contact angle and water absorption rate without substantially changeing；Hydrophobicity material
When expecting volume up to 16%, compression strength 61.43MPa reduces 10.1Mpa water droplets and Behavior of Hardened Cement Paste compared with blank cement sample 71.53Mpa
Contact angle be 102 °, water absorption rate 1.8% reduces 2% than blank cement sample 3.8%.By the present invention hydrophobic material with
After the Material claddings such as cement, the waterproofing works such as underground station top plate, building cover board, side slope gunite concrete, water-stop curtain are applied to,
Corrosion function of the water translocation to engineering can be reduced, while also providing the skill of Fenton paper mill sludge ash recycling recycling
Art route.
Specific implementation mode
The present invention provides a kind of preparation methods of hydrophobic material, include the following steps：
Fenton paper mill sludge is calcined, Fenton paper mill sludge ash is obtained；
The Fenton paper mill sludge ash and stearic acid are subjected to ball milling, obtain hydrophobic material.
The present invention calcines Fenton paper mill sludge, obtains Fenton paper mill sludge ash.In the present invention, the temperature of the calcining
The time of preferably 800-1000 DEG C, more preferably 850-950 DEG C, the calcining is preferably 1.5-2.5h, more preferably 1.8-
2.2h.The present invention keeps the compound containing Fe, Al, Si, Ca in sludge compound anti-by horn shape protrusion block generation melting by calcining
It answers, generates the compound of calcium iron aluminium phase and unbodied SiO2、Al2O3Fine granular grains body significantly increases, and surface is round and smooth,
Good modified effect can be reached under mechanical ball mill with stearic acid, hydrophobicity is made to greatly improve.
After obtaining Fenton paper mill sludge ash, the Fenton paper mill sludge ash and stearic acid are carried out ball milling by the present invention, are obtained
Hydrophobic material.In the present invention, the weight ratio of the stearic acid and Fenton paper mill sludge ash is preferably 1:24-25.In this hair
In bright, the rotating speed of the ball milling is preferably 350-400r/min, and the time of more preferably 360-380r/min, the ball milling are preferred
For 4-6h, more preferably 6h.The present invention does not have the mode of the ball milling special restriction, selects those skilled in the art known
Mode carry out ball milling.
The present invention provides the hydrophobic materials that preparation method described in above-mentioned technical proposal is prepared.In the present invention,
The ingredient of the hydrophobic material preferably includes Al2O3, calcium aluminoferrite, calcium silicates, wollastonite and cacoclasite.Wherein silicon ash
Stone, Al2O3There is a large amount of activity hydroxy on surface, and the hydrophobic group of lipid, such as-C=are can get through stearic acid modified rear surface
O ,-CH can reduce the agglomeration between mixture, and be dispersed in the interfacial transition zone of slurry and aggregate, hinder the migration of moisture
Reach hydrophobic effect with penetrating into；With hydrated cementitious, cacoclasite and calcium aluminoferrite aquation are slow, can make the slurry of hardening
Body structure becomes fine and close, generates preferable gelatinization results, reduces the water absorption rate of Behavior of Hardened Cement Paste.In the present invention, the hydrophobicity material
The pH value of material is preferably 11.0-12.0.In the present invention, the grain size of the hydrophobic material is 75 μm or less.
The present invention provides the hydrophobic materials described in above-mentioned technical proposal in cement base hydrophobic material and concrete
Using.
In the present invention, application process of the hydrophobic material in cement base hydrophobic material includes the following steps：
Hydrophobic material, Portland cement and polypropylene fibre are mixed, mixed material is obtained；
Material stirring to be mixed to polypropylene fibre is uniformly dispersed not conglomeration, adds water to stir evenly to get cement base hydrophobic
Material.
In the present invention, the Portland cement is preferably 42.5 portland cements of PO, the hydrophobic material, water,
The mass ratio of Portland cement is preferably 5-19：7-35：20-100；The polypropylene fibre is preferably long 19mm, long thin
Than 380, tensile strength 358MPa；The mass ratio of the polypropylene fibre and hydrophobic material is preferably 2-3：1000.
In the present invention, application process of the hydrophobic material in concrete includes the following steps：
Hydrophobic material, Portland cement, stone, sand are mixed, dry batch is obtained；
The mixed liquor of polycarboxylate water-reducer and water is mixed with the dry batch, obtains concrete.
In the present invention, the Portland cement is preferably 42.5 portland cements of PO；The stone is preferably grain
Diameter is the cobble of 10-16mm and 16-20mm, and the mass ratio for the cobble that the grain size is 10-16mm and grain size is 16-20mm is preferred
It is 7:3.In the present invention, the sand is preferably river sand, and configuration fineness modulus is 2.8.In the present invention, the polycarboxylic acids subtracts
The water-reducing rate of aqua is preferably 20%.In the present invention, the mass ratio of the water, Portland cement, sand and stone is excellent
It is selected as 14：27-29：47：100.In the present invention, the mass ratio of the hydrophobic material and Portland cement is preferably 1-
9：The mass ratio of 24-100, polycarboxylate water-reducer and hydrophobic material is preferably 7：50-100.
A kind of preparation method of hydrophobic material provided by the invention is described in detail with reference to embodiment, but
It is that they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Fenton paper mill sludge is calcined into 2.5h at 1000 DEG C, obtains Fenton paper mill sludge ash；By Fenton papermaking after cooling
Sludge ash is with stearic acid according to weight ratio 24:1 is uniformly mixed, and then under conditions of rotating speed is 350r/min, carries out ball milling 6h,
Obtain hydrophobic material.After testing, the grain size of the hydrophobic material obtained is 45-75 μm and accounts for 99.87%, and 45 μm or less account for
0.13%.
Embodiment 2
Fenton paper mill sludge is calcined into 2.5h at 800 DEG C, obtains Fenton paper mill sludge ash；It is after cooling that Fenton papermaking is dirty
Plaster is with stearic acid according to weight ratio 25:1 is uniformly mixed, and then under conditions of rotating speed is 380r/min, carries out ball milling 6h, obtains
To hydrophobic material.After testing, the grain size of the hydrophobic material obtained is 45-75 μm and accounts for 89.36%, and 45 μm or less account for
10.64%.
Embodiment 3
Hydrophobic material, Portland cement and polypropylene fibre prepared by embodiment 1 example mixing in mass ratio is equal
It is even, obtain mixed material；Material stirring to be mixed to polypropylene fibre is uniformly dispersed not conglomeration, and water is added to stir evenly to get water
Mud base hydrophobic material；Wherein, hydrophobic material, water, Portland cement three mass ratio be 19：35：100；Polypropylene
The mass ratio of fiber and hydrophobic material is 3：1000.
The cement base hydrophobic material mix is molded to the prism test block of 40mm × 40mm × 160mm, demoulding standard is supported
The actual measurement compression strength protected after 28d is 59.02MPa, and flexural strength 7.59MPa, water absorption rate 1.81%, middle part is wrecked at face
102 ° of the contact angle of water droplet and Behavior of Hardened Cement Paste.
Embodiment 4
Hydrophobic material, Portland cement and polypropylene fibre prepared by embodiment 1 example mixing in mass ratio is equal
It is even, obtain mixed material；Material stirring to be mixed to polypropylene fibre is uniformly dispersed not conglomeration, and water is added to stir evenly to get water
Mud base hydrophobic material；Wherein, hydrophobic material, water, Portland cement three mass ratio be 5：7：20；Polypropylene fibre
Mass ratio with hydrophobic material is 2：1000.
The cement base hydrophobic material mix is molded to the prism test block of 40mm × 40mm × 160mm, demoulding standard is supported
The actual measurement compression strength protected after 28d is 53.75MPa, and flexural strength 6.56MPa, water absorption rate 2.74%, middle part is wrecked at face
116 ° of the contact angle of water droplet and Behavior of Hardened Cement Paste.
Embodiment 5
Hydrophobic material, Portland cement, stone, sand prepared by embodiment 2 mixes, and obtains dry batch；It will
The mixed liquor of polycarboxylate water-reducer and water is mixed with the dry batch, obtains concrete；Wherein, the water, normal silicate water
The mass ratio of mud, sand and stone is 14：27：47：100；The mass ratio of the hydrophobic material and Portland cement is
9：100, the mass ratio of polycarboxylate water-reducer and hydrophobic material is 7：100.
The concrete mixing is molded to the square test block of 100mm × 100mm × 100mm, after demoulding standard curing 28d
Actual measurement compression strength be 43.68MPa, the unit area capillary water absorption height in tensile splitting strength 1.97MPa, 1d is average
Rate of rise is 0.352mm/h.
Embodiment 6
Hydrophobic material, Portland cement, stone, sand prepared by embodiment 2 mixes, and obtains dry batch；It will
The mixed liquor of polycarboxylate water-reducer and water is mixed with the dry batch, obtains concrete；Wherein, the water, normal silicate water
The mass ratio of mud, sand and stone is 14：29：47：100；The mass ratio of the hydrophobic material and Portland cement is
1：24, the mass ratio of polycarboxylate water-reducer and hydrophobic material is 7：50.
The concrete mixing is molded to the square test block of 100mm × 100mm × 100mm, after demoulding standard curing 28d
Actual measurement compression strength be 39.73MPa, the unit area capillary water absorption height in tensile splitting strength 1.87MPa, 1d is average
Rate of rise is 0.416mm/h.
As seen from the above embodiment, the present invention provides a kind of preparation method of hydrophobic material, include the following steps：It will
Fenton paper mill sludge is calcined, and Fenton paper mill sludge ash is obtained；The Fenton paper mill sludge ash and stearic acid are subjected to ball milling, obtained
Hydrophobic material.The present invention passes through heat treatment so that Fenton paper mill sludge has certain volcanic ash in cement applications and lives
Property and micro aggregates filling effect, after stearic acid modified sludge gray surface formed hydrophobic grouping, water droplet instill hydrophobic material
In ball shape and impermeable, good dispersion its mechanics is improved to which agglomeration not occur in Portland cement stirring
And hydrophobicity performance.Data according to the embodiment it is found that when the hydrophobic material volume for preparing of the present invention is up to 4%, compression strength compared with
The high 2.5MPa of blank cement sample；When hydrophobic material volume is up to 16%, the contact angle of water droplet and Behavior of Hardened Cement Paste is 102 °.This is sent out
After the Material claddings such as bright hydrophobic material and cement, applies to underground station top plate, building cover board, side slope gunite concrete, stops
The waterproofing works such as water curtain can reduce corrosion function of the water translocation to engineering, while also provide a Fenton paper mill sludge
The technology path that grey recycling recycles.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of hydrophobic material, includes the following steps：
Fenton paper mill sludge is calcined, Fenton paper mill sludge ash is obtained；
The Fenton paper mill sludge ash and stearic acid are subjected to ball milling, obtain hydrophobic material.
2. preparation method according to claim 1, which is characterized in that the temperature of the calcining is 800-1000 DEG C, calcining
Time be 1.5-2.5h.
3. preparation method according to claim 1, which is characterized in that the weight of the stearic acid and Fenton paper mill sludge ash
Than being 1:24-25.
4. preparation method according to claim 1, which is characterized in that the rotating speed of the ball milling is 350-400r/min, ball
Time consuming is 4-6h.
5. the hydrophobic material that any one of Claims 1 to 4 preparation method is prepared.
6. hydrophobic material according to claim 5, which is characterized in that the ingredient of the hydrophobic material includes Al2O3、
Calcium aluminoferrite, calcium silicates, wollastonite and cacoclasite.
7. hydrophobic material according to claim 6, which is characterized in that the hydrophobic material and water in mass ratio 1：10
Mixing, centrifugation the surveyed pH value of rear solution are 11.0-12.0.
8. hydrophobic material according to claim 7, which is characterized in that the grain size of the hydrophobic material be 75 μm with
Under.
9. application of claim 5~8 any one of them hydrophobic material in cement base hydrophobic material or concrete.
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| CN201810353868.8A CN108424023B (en) | 2018-04-19 | 2018-04-19 | Hydrophobic material and preparation method and application thereof |
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| CN201810353868.8A CN108424023B (en) | 2018-04-19 | 2018-04-19 | Hydrophobic material and preparation method and application thereof |
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| CN111777988A (en) * | 2020-05-29 | 2020-10-16 | 清华苏州环境创新研究院 | Hydrophobic material and preparation method thereof |
| CN115093148A (en) * | 2022-06-27 | 2022-09-23 | 深圳大学 | Hydrophobic regenerated material and preparation method and application thereof |
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| CN115093148A (en) * | 2022-06-27 | 2022-09-23 | 深圳大学 | Hydrophobic regenerated material and preparation method and application thereof |
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| Publication number | Publication date |
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| CN108424023B (en) | 2020-11-10 |
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