CN113620652A - Modified waterproof concrete and preparation method thereof - Google Patents
Modified waterproof concrete and preparation method thereof Download PDFInfo
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- CN113620652A CN113620652A CN202111027525.0A CN202111027525A CN113620652A CN 113620652 A CN113620652 A CN 113620652A CN 202111027525 A CN202111027525 A CN 202111027525A CN 113620652 A CN113620652 A CN 113620652A
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- polyvinyl alcohol
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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
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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
- 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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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention provides modified waterproof concrete which comprises cement, fine aggregate, broken stone, water and a waterproof agent, wherein the waterproof agent is prepared from a high molecular polymer and water, the high molecular polymer is polyvinyl alcohol or a polyvinyl alcohol modified substance, and the polymerization degree of the high molecular polymer is 1500-2000. Compared with the waterproofing agent in the prior art, the invention takes the polyvinyl alcohol or polyvinyl alcohol modifier with certain molecular weight/polymerization degree as the waterproofing agent, can obtain better waterproofing performance improvement effect by adding a small amount of the waterproofing agent in the preparation process of concrete, achieves the ideal waterproofing purpose without reducing the important performance of the waterproofing agent, simplifies the preparation process of the waterproofing agent and ensures that the concrete has good waterproofing performance.
Description
Technical Field
The invention belongs to the technical field of concrete building materials, and particularly relates to modified waterproof concrete and a preparation method thereof.
Background
The raw materials for producing the cement concrete are rich, and the cement concrete is one of the most widely applied building materials. The concrete is in a low tensile strength and low strain resistance state in the early hardening stage, the internal stress generated by shrinkage deformation caused by drying shrinkage, plastic shrinkage, temperature shrinkage, self-shrinkage and the like in the condensation hardening process exceeds the tensile strength of the concrete, and a plurality of cracks are generated on the surface and inside of the concrete after pouring, so that the safety and the durability of a concrete engineering structure are seriously influenced.
In view of the above-mentioned drawbacks of concrete, the person skilled in the art in the development of concrete waterproofers is based mainly on the following considerations: the waterproof agent needs to be easily soluble in water and can chemically react with cement hydration precipitates to generate crystals or gel so as to reduce the volume shrinkage of concrete and improve the crack resistance of the concrete; in the growth process of the gel, the gel fills and blocks the pores in the concrete, and cuts off the communication of capillary tubes in the concrete, so that the internal porosity of the concrete is reduced, and the compactness and impermeability of the concrete are improved.
Based on the above thought, the existing waterproof agent is mainly prepared by compounding various inorganic salts, high polymer materials and a proper amount of organic matters which are rich in cement activity and strengthening components through a certain process. Wherein the high molecular material is selected from water-soluble organosilicon water-soluble resin, sodium methylsilicate and triethoxy silicon, the inorganic salt is selected from silicon powder, fly ash, volcanic ash, silicate, nitrite and sodium chloride, and the organic substance is selected from stearic acid, cross-linking agent, water reducing agent and triethanolamine.
The existing waterproof agent has the defects of complex components, serious influence on hydration and hardening of cement, complex preparation process, containing inorganic salts such as sodium chloride and the like which influence the service life of reinforcing steel bars, containing volatile harmful substances and the like. Therefore, the thinking is innovated, a new thought for performing waterproof treatment on concrete is provided, the structurally modified concrete with simple components is developed, the impermeability of the concrete is improved, and the method has important significance for improving the durability of a concrete structure and the application universality.
Disclosure of Invention
The invention aims to prepare an environment-friendly waterproof agent with excellent performance by using polyvinyl alcohol (PVA) with a certain molecular weight and a modified product thereof as raw materials through proper preparation or certain modification, and the environment-friendly waterproof agent is used for preparing novel waterproof concrete, improving the crack resistance of the concrete and further improving the safety and durability of concrete engineering.
In order to achieve the purpose, the invention adopts the following technical scheme:
the modified waterproof concrete comprises the following components in parts by weight: the waterproof agent is prepared from a single high-molecular polymer and water, wherein the single high-molecular polymer is polyvinyl alcohol or a polyvinyl alcohol modifier, and the polymerization degree of the single high-molecular polymer is 1500-2000.
Further, the molecular weight of the polyvinyl alcohol is 66000-88000 g/mol, and the mass ratio of the polyvinyl alcohol to the cement is 0.00015-0.00040: 1.
further, the polyvinyl alcohol modifier is sulfonated polyvinyl alcohol or esterified polyvinyl alcohol.
The preparation method of the modified waterproof concrete comprises the following steps:
(1) dissolving a single high molecular polymer in water at 45-95 ℃, and cooling to obtain the waterproof agent;
(2) mixing and stirring cement, fine aggregate, broken stone, water and a waterproof agent to obtain the modified waterproof concrete.
Further, the single high molecular polymer is polyvinyl alcohol or a polyvinyl alcohol modified product.
Further, the polyvinyl alcohol modifier is sulfonated polyvinyl alcohol or esterified polyvinyl alcohol.
The invention adopts polyvinyl alcohol (PVA) or modified products thereof with a certain molecular weight as the waterproof agent, the specific molecular chain length of the waterproof agent is long, the waterproof agent has abundant cement active groups such as hydroxyl groups, and because of similar compatibility, the PVA and the modified products thereof are easy to be compatible with polar inorganic salts, the tensile strength and the strain resistance of concrete at the initial stage of cement hydration can be improved, and the generation of cracks is reduced.
After the cement-based material is cast and molded, a concave liquid surface is formed in the capillary tube of the surface layer material when water is evaporated due to the hydrophilicity of water and the cement-based material. The vertical component of the surface tension on the concave liquid surface forms tensile stress to the material between the tube walls, and at the moment, the material is in a plastic stage, and the plastic tensile strength of the material is lower. Tensile stress sigma generated if capillary tube on surface of material loses water and shrinkscGreater than the plasticity of the materialTensile strength fpI.e. sigmac>fpThe surface layer of the material is cracked.
When polyvinyl alcohol or its modifier with a certain molecular weight is doped in the cement-based material, the formed high molecular solution reduces the vapor pressure of water and the evaporation rate of water, so that the capillary tension formed by the capillary shrinkage due to dehydration is reduced.
Meanwhile, the long molecular chain of the polyvinyl alcohol or the modified polyvinyl alcohol with a certain molecular weight increases the plastic tensile strength of the material for resisting cracking by virtue of the interface adsorption binding force, the mechanical engaging force and the like between the polyvinyl alcohol or the modified polyvinyl alcohol with a certain molecular weight and a cement base, so that the sigma isc≤fpThe cracking condition of the material is reduced or even eliminated.
The common cement concrete is reported to have lower tensile strength within 4d, which is only about 0.02MPa, and if the crack stress of 0.2MPa is borne by molecular chains of polyvinyl alcohol or a modifier thereof in 0.5 percent of doping amount (mass ratio of the waterproof agent to the cement), the stress borne by the macromolecular chains is about 40MPa, which is much smaller than the strength of main chain chemical bonds (carbon-carbon bonds) of the polyvinyl alcohol or the modifier thereof, which means that the macromolecular chains are long enough to limit the generation and the expansion of plastic shrinkage cracks as long as the adhesion between the macromolecular chains and the cement base is good.
The quantity of active groups such as hydroxyl groups and the like also has influence on the improvement of the tensile strength and the stress resistance of the cement at the initial stage of hydration, if the quantity of the hydroxyl groups is too small, the bonding force between the polyvinyl alcohol and the modifier thereof and the cement base is weak, and when a crack is expanded, the polyvinyl alcohol and the modifier thereof are easy to pull out, so that the crack resistance is limited; too much hydroxyl groups easily cause water absorption of concrete, and the water absorption capacity is too large. In addition, active groups such as hydroxyl groups have a retarding effect on cement, and excessive hydroxyl groups cause serious cement retarding, so that the strength of concrete is reduced.
In order to make the molecular chain of polyvinyl alcohol or its modified product possess the capability of raising tensile strength and stress resistance in the early stage of cement hydration, the polyvinyl alcohol or its modified product must possess molecular chain with a certain length and a certain quantity of active groups of hydroxyl group, etc.
If the molecular chain is too short, namely the molecular weight is too small, when a tiny crack just starts to appear, the short molecular chain is bridged between the cracks, certain constraint force is exerted on the beginning of the crack, after the crack is expanded to a certain degree, the molecular chain is too short, the molecular chain is not high in bonding force with a cement-based material, the molecular chain is easy to pull out, the crack resistance is limited, and therefore the polymerization degree of the polyvinyl alcohol and the polyvinyl alcohol modifier is required to be more than or equal to 1500.
Along with the increase of molecular chains, namely molecular weight, the polymerization degree of the polyvinyl alcohol or the modified product thereof is increased, the chain growth may aggravate the mutual winding among chains, the solubility is reduced, the uniform dispersion in concrete is not facilitated, the improvement of the tensile strength and the stress resistance of the cement at the initial stage of hydration is further hindered, and the mechanical property of the concrete is reduced, so the polymerization degree of the polyvinyl alcohol and the modified product thereof is not more than 2000.
In short, the polymerization degree of the polyvinyl alcohol and the modified polyvinyl alcohol is controlled to be between 1500 and 2000, for example, the molecular weight of the polyvinyl alcohol is generally controlled to be between 66000 and 88000.
When the P/C (polymer mass/cement mass) is less than 0.015%, the polyvinyl alcohol or polyvinyl alcohol modifier plays an insignificant role in improving the waterproof effect of concrete due to too low concentration. When the traditional concrete modifier is used for improving the waterproofness of concrete, a large amount of additive (usually P/C is higher than 0.05%) is usually required to be doped, so that an organic-inorganic composite film matrix can be formed in a hydration process, cement hydration products in the concrete are mutually interpenetrated with the concrete to form a spatial network microstructure, a larger amount of modifier is required to be doped to form a wrapping effect of a composite film to achieve the purpose of improving the waterproofness of the concrete, however, the complexity of components and the large amount of additive increase the difficulty in controlling and adjusting cement quality indexes, the concrete setting time is prolonged and the consistency is increased, the hydration of the cement is delayed, the hydration of the cement is incomplete, cement particles are agglomerated and polymerized, other performances of the concrete are deteriorated, and the modification cost is increased.
Therefore, the dosage of the polyvinyl alcohol or the modifier thereof in the concrete needs to be controlled, the intertwining among the polymer chain segments can be reduced, the film forming is not needed, and the waterproofness of the concrete can be effectively improved on the premise of not changing other performances of the concrete.
The invention takes polyvinyl alcohol or polyvinyl alcohol modifier with certain molecular weight/polymerization degree as the waterproof agent, and in the preparation process of concrete, the better waterproof performance improvement effect can be obtained by controlling the mixing amount of the polyvinyl alcohol or polyvinyl alcohol modifier, and the invention meets the requirements of first-class products of concrete waterproof agents. The waterproof agent can reach ideal waterproof performance without lowering its important performance, and has simple preparation process and excellent waterproof performance.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
The first scheme is as follows: as polyvinyl alcohol (PVA): and (3) dissolving polyvinyl alcohol in hot water at 65-90 ℃ in a mass ratio of 3-8: 97-92, and cooling to obtain the waterproof agent.
Polyvinyl alcohol (PVA) includes grades 0578, 0588, 1588, 1599, 1778, 1788, 1792, 1799, 2099, etc.
Scheme 1 waterproof agent ratio
Reference sample concrete ratio
Base ratio (kg/m)3): 330kg of cement, 750kg of fine aggregate, 464kg of gravel (5 mm-10 mm), 696kg of gravel (10 mm-20 mm), 3.30kg of water reducing agent and 175kg of water.
The concrete is prepared by adopting the water-proofing agents in the embodiments in the table 1 according to the following concrete sample proportions:
sample ratio (kg/m)3): 330kg of cement, 750kg of fine aggregate, 464kg of gravel (5 mm-10 mm), 696kg of gravel (10 mm-20 mm), 1.65kg of waterproofing agent and 175kg of water.
Table 2 scheme one concrete ratio
The concrete may be prepared by any method known to those skilled in the art, and is not particularly limited.
And (3) sample performance characterization:
the concrete data of the concrete prepared by adopting the water-proofing agent of the example 1 are shown in a table 3 by taking GB8076-2008 concrete admixture and JC/T474-2008 mortar and concrete water-proofing agent as detection bases and JC/T474-2008 mortar and concrete water-proofing agent as judgment bases and entrusting national metal product quality supervision and inspection center/Zhengzhou metal product research institute Limited company material laboratories to perform detection according to first-class products.
Table 3 example a sample characterization data
Table 3 shows that the performance indexes of the concrete doped with the waterproof agent can meet the requirements of first-class products of the concrete waterproof agent. The waterproof agent can slow down the initial setting time to a certain extent, the bleeding rate ratio is 11%, the compressive strength is improved to 105%, and the shrinkage ratio is 99%, which shows that the waterproof agent has less influence on the hydration process of cement in concrete, can ensure the strength of the concrete, has the penetration height ratio of 28%, and meets the requirement that the penetration height ratio of first-class products is less than 30%.
Examples 2-9 the concrete prepared according to the formulation ratio was characterized in the above characterization manner, and all performance indexes were in accordance with the requirements of the first class of concrete waterproofing agents.
In addition, the performance indexes of the concrete prepared according to the P/C ratio of less than 0.015 percent are not obviously improved. When the P/C exceeds 0.040%, the concrete is deteriorated in the indexes such as setting time and water absorption.
In other embodiments, sulfonated polyvinyl alcohol and esterified polyvinyl alcohol are prepared by sulfonation and esterification of the polyvinyl alcohol with the same grade, and the carboxylic acid selected for esterification is fatty acid, aromatic acid or polycarboxylic acid. And preparing the waterproof agent by sulfonated polyvinyl alcohol and esterified polyvinyl alcohol according to the second scheme and the third scheme respectively.
Scheme II: according to the formula of sulfonated polyvinyl alcohol: and (3) dissolving sulfonated polyvinyl alcohol in hot water at the temperature of 55-95 ℃ according to the mass ratio of water to water of 3-8: 97-92, and cooling to obtain the waterproof agent.
The third scheme is as follows: according to the following weight percentage of esterified polyvinyl alcohol: and (3) dissolving the esterified polyvinyl alcohol in hot water at the temperature of 45-85 ℃ according to the mass ratio of water to water of 3-8: 97-92, and cooling to obtain the waterproof agent.
Reference sample concrete ratio
Base ratio (kg/m)3): 330kg of cement, 750kg of fine aggregate, 464kg of gravel (5 mm-10 mm), 696kg of gravel (10 mm-20 mm), 3.30kg of water reducing agent and 175kg of water.
Preparing concrete according to the sample concrete proportion of the waterproof agent obtained according to the second scheme and the third scheme:
sample ratio (kg/m)3): 330kg of cement, 750kg of fine aggregate, 464kg of gravel (5 mm-10 mm), 696kg of gravel (10 mm-20 mm), 1.65kg of waterproofing agent and 175kg of water.
And the prepared sample concrete is characterized, and all performance indexes can meet the requirements of first-class products of concrete waterproofing agents.
A new concrete waterproof idea is provided according to the characteristics of cement hydration in concrete and the reasons for concrete cracks. According to the new concrete water-proofing idea it is proposed to use polyvinyl alcohol or polyvinyl alcohol modified material as raw material to prepare water-proofing agent. The waterproof agent is simple to prepare, environment-friendly and convenient to use. The water-proofing agent meets the requirements of first-class concrete water-proofing agent through the detection of a material laboratory of Zhengzhou Metal products institute Limited of China center for quality supervision and inspection of metal products/Zhongzhou group.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. The modified waterproof concrete comprises the following components in parts by weight: the waterproof agent is characterized by also comprising a waterproof agent, wherein the waterproof agent is prepared from a single high-molecular polymer and water, the single high-molecular polymer is polyvinyl alcohol or a polyvinyl alcohol modifier, and the polymerization degree of the single high-molecular polymer is 1500-2000.
2. The modified waterproof concrete of claim 1, wherein the molecular weight of the polyvinyl alcohol is 66000-88000 g/mol, and the mass ratio of the polyvinyl alcohol to the cement is 0.00015-0.00040: 1.
3. the modified waterproof concrete of claim 1, wherein the polyvinyl alcohol modification is sulfonated polyvinyl alcohol or esterified polyvinyl alcohol.
4. A preparation method of the modified waterproof concrete according to claims 1 to 3, characterized by comprising the following steps:
(1) dissolving the single high molecular polymer in water at 45-95 ℃, and cooling to obtain the waterproof agent;
(2) and mixing and stirring the cement, the fine aggregate, the broken stone, the water and the waterproof agent to obtain the modified waterproof concrete.
5. The method for preparing modified waterproof concrete according to claim 4, wherein the single high molecular polymer is polyvinyl alcohol or a polyvinyl alcohol modification.
6. The method for preparing modified waterproof concrete according to claim 5, wherein the polyvinyl alcohol modifier is sulfonated polyvinyl alcohol or esterified polyvinyl alcohol.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006219321A (en) * | 2005-02-09 | 2006-08-24 | Denki Kagaku Kogyo Kk | Cement admixture and cement composition using the same |
| CN1962528A (en) * | 2005-11-08 | 2007-05-16 | 芮志平 | Repairing material for cement concrete structure |
| CN101500958A (en) * | 2006-08-01 | 2009-08-05 | 电气化学工业株式会社 | Cement admixture and cement composition making use of the same |
| CN102757196A (en) * | 2012-07-25 | 2012-10-31 | 天津市南开区房地产管理局 | Waterproof cement additive and cement containing same |
| CN106830842A (en) * | 2017-03-02 | 2017-06-13 | 江世妹 | A kind of cement base perfusion mortar |
| WO2018167425A1 (en) * | 2017-03-15 | 2018-09-20 | Institut Français Des Sciences Et Technologies Des Transports, De L'amenagement Et Des Reseaux | Curing agent for a cementitious formulation |
-
2021
- 2021-09-02 CN CN202111027525.0A patent/CN113620652B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006219321A (en) * | 2005-02-09 | 2006-08-24 | Denki Kagaku Kogyo Kk | Cement admixture and cement composition using the same |
| CN1962528A (en) * | 2005-11-08 | 2007-05-16 | 芮志平 | Repairing material for cement concrete structure |
| CN101500958A (en) * | 2006-08-01 | 2009-08-05 | 电气化学工业株式会社 | Cement admixture and cement composition making use of the same |
| CN102757196A (en) * | 2012-07-25 | 2012-10-31 | 天津市南开区房地产管理局 | Waterproof cement additive and cement containing same |
| CN106830842A (en) * | 2017-03-02 | 2017-06-13 | 江世妹 | A kind of cement base perfusion mortar |
| WO2018167425A1 (en) * | 2017-03-15 | 2018-09-20 | Institut Français Des Sciences Et Technologies Des Transports, De L'amenagement Et Des Reseaux | Curing agent for a cementitious formulation |
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