CN108249850B - A method of impervious hydrophobic cement is prepared using oleic acid modified coal ash - Google Patents

A method of impervious hydrophobic cement is prepared using oleic acid modified coal ash Download PDF

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CN108249850B
CN108249850B CN201810044932.4A CN201810044932A CN108249850B CN 108249850 B CN108249850 B CN 108249850B CN 201810044932 A CN201810044932 A CN 201810044932A CN 108249850 B CN108249850 B CN 108249850B
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oleic acid
cement
flyash
coal ash
modified coal
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CN108249850A (en
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刘鹏
王发洲
冯传法
高衣宁
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Wuhan University of Technology WUT
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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
    • C04B20/02—Treatment
    • C04B20/023—Chemical treatment
    • 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
    • C04B20/026—Comminuting, e.g. by grinding or breaking; Defibrillating fibres other than asbestos
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Abstract

The present invention relates to a kind of methods for preparing impervious hydrophobic cement using oleic acid modified coal ash, flyash is modified itself and cement and water mixed-forming again using oleic acid by dry milling processes, the surface group of the c-terminus of oleic acid molecular and flyash connects in the process, and hydrophobic effect is played at the alkyl end of oleic acid molecular.The present invention solve the problems, such as ordinary cement product be subject to water infiltration and erosion damage and influence use, there is many advantages, such as preparation method is simple, the period is short, mild condition, at low cost, water proof anti-seepage significant effect.

Description

A method of impervious hydrophobic cement is prepared using oleic acid modified coal ash
Technical field
The present invention relates to cement material technical fields, and in particular to it is a kind of using oleic acid modified coal ash prepare it is impervious hydrophobic The method of cement.
Background technique
The infiltration and erosion of water are to influence a key factor of its service life in cement, concrete.This is because Contain a large amount of porous structures in cement and concrete, capillary effect, erosion and the infiltration (freeze thawing) of water cause pole to building Big physical and chemical degradation, so that the function of building structure is affected, it is typical such as road surface, bridge and house.In addition, chlorine Ion and sulfate ion can penetrate into cement and inside concrete with dampening, and steel bar corrosion, structure is caused to expand Split and durability shorten etc. serious consequences.Therefore develop impervious waterproof cement seem very necessary with it is urgent.
Since flyash can produce gelling system and can significantly improve the machinability of concrete, can substitute Part of cement, this is also relatively common in cement industry, but the cement products for adulterating flyash still remains the above problem.Cause This, it is necessary to be modified with organic matter before flyash doping.If directly mixed organic matter in cement system, will not obtain Dispersion well can not play due effect, and modified organic matter used also must careful selection.Oleic acid is as a kind of common Organic matter, one end of molecule are carboxyl, can generate bridging with the silicone hydroxyl of flyash, the other end is alkyl, can be played Hydrophobic effect, to generate the effect of water proof anti-seepage.
Summary of the invention
It is an object of the invention to overcome the problems, such as that impermeability existing for existing cement material, waterproofness are poor, one kind is provided The method for preparing impervious hydrophobic cement using oleic acid modified coal ash.This method is divided using the silicone hydroxyl and oleic acid of fine coal gray surface Carboxyl in son reacts, and the surface of carboxyl one end of oleic acid molecular and flyash is chained up, oleic acid molecular it is another End moieties can generate hydrophobic effect, and hydrophobic effect can be generated by adding it in cement, play the effect of water proof anti-seepage Fruit.To achieve the above object, the technical solution adopted in the present invention is as follows:
The method for preparing impervious hydrophobic cement using oleic acid modified coal ash, comprising the following steps: first by flyash with Oleic acid mixing dry grinding, the two react to obtain the modified flyash of oleic acid；Then the modified flyash of oleic acid is mixed with cement It closes, is stirred after adding water with friction speed, finally pour into mold and conserve to obtain the final product.
Further, mass ratio when flyash is mixed with oleic acid is 10-24:1.
Further, agate ball, the body of agate ball and flyash are also added into flyash and oleic acid mixing dry milled process Product is than being 4-5:1.Agate ball, which is added, can increase the uniformity coefficient that material mixes in dry milled process.
Further, flyash-oleic acid mixture is contained with container when dry grinding, then put it into ball mill, ball milling Machine revolving speed is 200-300 revs/min, and the dry grinding time is 6-8h.
Further, the flyash, cement of oleic acid modification, the mass ratio of water three are 1:7-15:2-5.
Further, the modified flyash of oleic acid and cement mixing and after adding water, first mix slowly a period of time, then quickly Stirring a period of time, it is then allowed to stand a period of time, finally quickly stirs a period of time again.This slow-to-fast-stops-fast stirring side Formula can improve bleed and the anti-permeability performance of cement.
Further, the time for mixing slowly or quickly stirring each time is respectively 30s, 30s, quiescent time 60s.
Further, curing condition are as follows: temperature: 20 ± 2 DEG C, humidity: 95 ± 5%, the time: 28d.
Further, the cement is ordinary portland cement.
The present invention is reacted by the silicone hydroxyl of carboxyl and fine coal gray surface in oleic acid molecular, so that oleic acid molecular The surface of c-terminus and flyash is chained up, and the alkyl end of oleic acid molecular provides hydrophobic function, is entrained in common silicic acid The water absorption rate that cement products can be substantially reduced in salt cement, improves service life.
Compared with prior art, the invention has the following advantages: oleic acid molecular is passed through chemical bond linkage to powder by (1) Hydrophobic effect is played at the surface of coal ash, the alkyl end of oleic acid, and 1-7d water absorption rate is down to 0.013mm/d after adding it in cement1 /2, water proof anti-seepage significant effect (2) preparation method is simple, and the period is short, mild condition, is not necessarily to Special complex equipment, cost is relatively low.
Specific embodiment
To make those of ordinary skill in the art fully understand technical solution of the present invention and beneficial effect, below in conjunction with specific Embodiment is further described.
Embodiment 1
Step 1: 475 grams of flyash and 25 grams of oleic acid are fitted into rubber container, and agate ball is packed into as grinding medium Matter.The volume ratio of agate ball and sample is 5:1.
Step 2: rubber container is placed on ball mill, flyash and oleic acid is set to react by dry milling processes.Ball milling Machine revolving speed is 300 rpms, continuous rotation ball milling 8 hours.
Step 3: collecting the flyash sample after ball milling, the modified flyash sample of 35 grams of oleic acid and 350 grams are weighed Portland cement, stirring mix them thoroughly.123 grams of water is added into above-mentioned aggregate sample, first mixes slowly 30 seconds, then Quickly stirring 30 seconds are then allowed to stand 60 seconds, finally quickly stir 30 seconds again.
Step 4: above-mentioned slurry is poured into mold, conserve 28 days, demoulds under 20 ± 2 DEG C and 95 ± 5% relative humidity Final products are obtained afterwards.
Step 5: final products take 10 interface measurement Static water contact angles, referring to People's Republic of China's light industry row Industry standard test water absorption rate.Measuring Static water contact angles is 85 °, 1-6 hours water absorption rate 0.043mm/d1/2, 1-7 days water absorption rates 0.013mm/d1/2。
Embodiment 2
Step 1: 475 grams of flyash and 20 grams of oleic acid are fitted into rubber container, and agate ball is packed into as grinding medium Matter.The volume ratio of agate ball and sample is 5:1.
Step 2: rubber container is placed on ball mill, flyash and oleic acid is set to react by dry milling processes.Ball milling Machine revolving speed is 300 rpms, continuous rotation ball milling 8 hours.
Step 3: collecting the flyash sample after ball milling, the modified flyash sample of 35 grams of oleic acid and 350 grams are weighed Portland cement, stirring mix them thoroughly.123 grams of water is added into above-mentioned aggregate sample, first mixes slowly 30 seconds, then Quickly stirring 30 seconds are then allowed to stand 60 seconds, finally quickly stir 30 seconds again.
Step 4: above-mentioned slurry is poured into mold, conserve 28 days, demoulds under 20 ± 2 DEG C and 95 ± 5% relative humidity Final products are obtained afterwards.
Step 5: final products take 10 interface measurement Static water contact angles, referring to People's Republic of China's light industry row Industry standard test water absorption rate.Measuring Static water contact angles is 45 °, 1-6 hours water absorption rate 0.087mm/d1/2, 1-7 days water absorption rates 0.045mm/d1/2。
Embodiment 3
Step 1: 475 grams of flyash and 30 grams of oleic acid are fitted into rubber container, and agate ball is packed into as grinding medium Matter.The volume ratio of agate ball and sample is 5:1.
Step 2: rubber container is placed on ball mill, flyash and oleic acid is set to react by dry milling processes.Ball milling Machine revolving speed is 300 rpms, continuous rotation ball milling 8 hours.
Step 3: collecting the flyash sample after ball milling, the modified flyash sample of 35 grams of oleic acid and 350 grams are weighed Portland cement, stirring mix them thoroughly.123 grams of water is added into above-mentioned aggregate sample, first mixes slowly 30 seconds, then Quickly stirring 30 seconds are then allowed to stand 60 seconds, finally quickly stir 30 seconds again.
Step 4: above-mentioned slurry is poured into mold, conserve 28 days, demoulds under 20 ± 2 DEG C and 95 ± 5% relative humidity Final products are obtained afterwards.
Step 5: final products take 10 interface measurement Static water contact angles, referring to People's Republic of China's light industry row Industry standard test water absorption rate.Measuring Static water contact angles is 65 °, 1-6 hours water absorption rate 0.065mm/d1/2, 1-7 days water absorption rates 0.036mm/d1/2。
Embodiment 4
Step 1: 475 grams of flyash and 25 grams of oleic acid are fitted into rubber container, and agate ball is packed into as grinding medium Matter.The volume ratio of agate ball and sample is 5:1.
Step 2: rubber container is placed on ball mill, flyash and oleic acid is set to react by dry milling processes.Ball milling Machine revolving speed is 300 rpms, continuous rotation ball milling 8 hours.
Step 3: collecting the flyash sample after ball milling, the modified flyash sample of 25 grams of oleic acid and 350 grams are weighed Portland cement, stirring mix them thoroughly.123 grams of water is added into above-mentioned aggregate sample, first mixes slowly 30 seconds, then Quickly stirring 30 seconds are then allowed to stand 60 seconds, finally quickly stir 30 seconds again.
Step 4: above-mentioned slurry is poured into mold, conserve 28 days, demoulds under 20 ± 2 DEG C and 95 ± 5% relative humidity Final products are obtained afterwards.
Step 5: final products take 10 interface measurement Static water contact angles, referring to People's Republic of China's light industry row Industry standard test water absorption rate.Measuring Static water contact angles is 75 °, 1-6 hours water absorption rate 0.056mm/d1/2, 1-7 days water absorption rates 0.021mm/d1/2。
Embodiment 5
Step 1: 475 grams of flyash and 45 grams of oleic acid are fitted into rubber container, and agate ball is packed into as grinding medium Matter.The volume ratio of agate ball and sample is 5:1.
Step 2: rubber container is placed on ball mill, flyash and oleic acid is set to react by dry milling processes.Ball milling Machine revolving speed is 300 rpms, continuous rotation ball milling 8 hours.
Step 3: collecting the flyash sample after ball milling, the modified flyash sample of 45 grams of oleic acid and 350 grams are weighed Portland cement, stirring mix them thoroughly.123 grams of water is added into above-mentioned aggregate sample, first mixes slowly 30 seconds, then Quickly stirring 30 seconds are then allowed to stand 60 seconds, finally quickly stir 30 seconds again.
Step 4: above-mentioned slurry is poured into mold, conserve 28 days, demoulds under 20 ± 2 DEG C and 95 ± 5% relative humidity Final products are obtained afterwards.
Step 5: final products take 10 interface measurement Static water contact angles, referring to People's Republic of China's light industry row Industry standard test water absorption rate.Measuring Static water contact angles is 74 °, 1-6 hours water absorption rate 0.056mm/d1/2, 1-7 days water absorption rates 0.020mm/d1/2。
Comparative example 1
Step 1: weighing 350 grams of Portland cements, 123 grams of water are added, first mix slowly 30 seconds, then quickly stirring It 30 seconds, is then allowed to stand 60 seconds, finally quickly stirs 30 seconds again.
Step 2: above-mentioned slurry is poured into mold, conserve 28 days, demoulds under 20 ± 2 DEG C and 95 ± 5% relative humidity Final products are obtained afterwards.
Step 3: final products take 10 interface measurement Static water contact angles, referring to People's Republic of China's light industry row Industry standard test water absorption rate.Measuring Static water contact angles is 0 °, 1-6 hours water absorption rate 0.120mm/d1/2, 1-7 days water absorption rates 0.085mm/d1/2。
After 35g is added with the unmodified flyash of batch in 1 first step of comparative example, other operations are constant, gained sample Water absorption rate is significantly larger than the water absorption rate that same amount oleic acid modified coal ash sample is added.

Claims (8)

1. a kind of method for preparing impervious hydrophobic cement using oleic acid modified coal ash, which comprises the following steps: first Flyash is first mixed into dry grinding with oleic acid, the two reacts to obtain the modified flyash of oleic acid；Then the powder that oleic acid is modified Coal ash and cement mixing are stirred with friction speed after adding water, finally pour into mold and conserve to obtain the final product；Wherein flyash and oleic acid are mixed Mass ratio when conjunction is 10-24:1, the modified flyash of oleic acid, cement, water three mass ratio be 1:7-15:2-5.
2. a kind of method for preparing impervious hydrophobic cement using oleic acid modified coal ash according to claim 1, feature It is: is also added into agate ball in flyash and oleic acid mixing dry milled process, the volume ratio of agate ball and flyash is 4-5:1.
3. a kind of method for preparing impervious hydrophobic cement using oleic acid modified coal ash according to claim 1, feature It is: contains flyash-oleic acid mixture with rubber container when dry grinding, then put it into ball mill, drum's speed of rotation is 200-300 revs/min, the dry grinding time is 6-8h.
4. a kind of method for preparing impervious hydrophobic cement using oleic acid modified coal ash according to claim 1, feature Be: the modified flyash of oleic acid and cement mixing and after adding water first mix slowly a period of time, then quickly one section of stirring when Between, it is then allowed to stand a period of time, finally quickly stirs a period of time again.
5. a kind of method for preparing impervious hydrophobic cement using oleic acid modified coal ash according to claim 4, feature The time for being: mixing slowly each time or quickly stir is respectively 30s, 30s, quiescent time 60s.
6. a kind of method for preparing impervious hydrophobic cement using oleic acid modified coal ash according to claim 1, feature Be: curing condition is 20 ± 2 DEG C of temperature, humidity 95 ± 5%, time 28d.
7. a kind of method for preparing impervious hydrophobic cement using oleic acid modified coal ash according to claim 1, feature Be: the cement is ordinary portland cement.
8. the impervious hydrophobic cement that any one of the claim 1-7 preparation method obtains.
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Publication number Priority date Publication date Assignee Title
CN109650807B (en) * 2018-12-27 2022-01-04 武汉理工大学 High-strength cement concrete prepared from modified fly ash and polymer and preparation method thereof
CN112194396B (en) * 2020-09-21 2022-03-08 东南大学 Slow-release hydrophobing agent for cement-based material, hydrophobic cement and preparation method thereof
CN114854304A (en) * 2022-05-27 2022-08-05 扬州工业职业技术学院 Super-hydrophobic coating with environmental protection and antifouling performance

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CN104671825A (en) * 2015-02-16 2015-06-03 盐城工学院 Nickel slag autoclaved aerated concrete block and preparation method thereof
CN105175003A (en) * 2015-09-14 2015-12-23 河南兴安新型建筑材料有限公司 Non-lime fly ash autoclaved aerated concrete and preparation method thereof

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