CN112551943B - Organic silicon slow-release type powder water repellent and preparation method thereof - Google Patents
Organic silicon slow-release type powder water repellent and preparation method thereof Download PDFInfo
- Publication number
- CN112551943B CN112551943B CN202011482783.3A CN202011482783A CN112551943B CN 112551943 B CN112551943 B CN 112551943B CN 202011482783 A CN202011482783 A CN 202011482783A CN 112551943 B CN112551943 B CN 112551943B
- Authority
- CN
- China
- Prior art keywords
- water repellent
- cement
- slow
- zeolite
- release
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention belongs to the technical field of marine construction engineering, and discloses an organic silicon slow-release type powder water repellent and a preparation method thereof. The organic silicon slow-release powder water repellent mainly comprises the following components in percentage by mass: 45-55% of zeolite, 40-50% of organosilane, 3-6% of alcohol sealant and 0.5-3% of surfactant. The invention also discloses a preparation method of the water repellent. The organosilicon release rate of the organosilicon slow-release powder water repellent is controllable, the organosilicon retention rate in 60 minutes is 45-60%, the hydrophobic modification effect on portland cement or composite portland cement is good, and the corrosion resistance of the cement is good, such as: the contact angle of the modified cement paste is 100-125 degrees, and the diffusion coefficient of chloride ions in 28-day age is 0.1-0.3 multiplied by 10 ‑12 m 2 /s。
Description
Technical Field
The invention belongs to the technical field of powder materials, and particularly relates to an organic silicon slow-release type powder water repellent and a preparation method thereof.
Background
With the construction of the landmark ocean engineering with ultra-long design life, the durability of the cement concrete in the severe environment is concerned. Corrosive ions such as chloride ions, sulfate ions, magnesium ions and the like in seawater can cause corrosion of the steel bars, so that the bond stress of the steel bars is reduced, the structure is cracked and fails, and the corrosion resistance of the cement-based material is inevitably improved.
The migration of corrosive ions in seawater into the interior of cement concrete is usually carried out in a liquid phase, so that the improvement of the hydrophobicity of cement concrete is the key to the improvement of the anti-corrosion capability and durability. At present, the hydrophobic modification of cement concrete is mainly realized by methods of surface coating, doping of polymer emulsion or organic silicon powder and the like. The surface coating has limited protection depth (usually less than 500 μm), the surface of the cement paste can completely lose the protection effect after deterioration and cracking under the action of external erosion, and the polymer emulsion can form a polymer film to wrap the cementing material particles, so that the integrity of the cement paste is damaged, and the continuous hydration and the compressive strength development of the cementing material are not facilitated. By utilizing the hydrolysis of organic silicon in an alkaline environment, the combination of silanol groups and hydroxyl groups on the wall of the cement paste and the directional arrangement of hydrophobic functional groups, the hydrophobicity of the cement paste is improved, and the mechanical property of the material is not remarkably reduced, so that the method is a more generally applicable hydrophobic modification mode. However, the existing organic silicon powder water repellent mainly adopts an organic matter cage structure to wrap organic silicon, the powder density is low, and poor dispersion of the organic silicon powder is easy to occur when cement concrete is modified. In addition, the organic silicon is hydrolyzed too fast, the self-polycondensation phenomenon is serious, the uniform distribution of hydrophobic functional groups on the wall of the hole of the cement paste cannot be ensured, and the hydrophobic modification effect is weaker than expected. The design of a hydrophobic functional material with controllable organic silicon release process is a fundamental solution for effectively improving the hydrophobicity of cement concrete.
Disclosure of Invention
The invention provides an organosilicon slow-release powder water repellent and a preparation method thereof, aiming at the problems of uneven dispersion of an organosilicon powder water repellent and over-quick release of organosilicon components. According to the invention, organic silicon is loaded by using the modified inorganic mineral, the loading characteristic of the inorganic mineral to the organic silicon is regulated and controlled by carrying out composite modification on the inorganic mineral, and the distribution uniformity of hydrophobic groups is improved by using the compatibility of the inorganic mineral and a cement concrete system. Specifically, the invention provides a method for preparing an organosilicon slow-release powder water repellent by taking chemically-thermally treated composite modified zeolite as a carrier, carrying out organosilane loading in a vacuum environment, coating and sealing the zeolite by using alcohols and drying.
The purpose of the invention is realized by adopting the following technical scheme:
an organosilicon slow-release powder water repellent mainly comprises the following components in percentage by mass:
the grain diameter of the zeolite is 0.5-15 mu m, and the apparent density is 1.9-2.3 g/cm 3 。
The organosilane is one or more of vinyltrimethoxysilane, dodecyl trimethoxysilane, hexadecyl trimethoxysilane, octadecyl trimethoxysilane, vinyltriethoxysilane, butyl triethoxysilane and octyl triethoxysilane.
The alcohol sealant is one or more of polyvinyl alcohol, polyethylene glycol and polypropylene glycol. The molecular weight of the alcohol sealant is 600-1000.
The surfactant is more than one of alkyl glucoside, fatty glyceride, lecithin and sodium dodecyl benzene sulfonate.
The alkyl glucoside is more than one of dodecyl glucoside, hexadecyl glucoside and octadecyl glucoside; the fatty acid glyceride is more than one of lauric glyceride, caprylic glyceride and glyceryl monostearate.
Before use, the zeolite is treated by acid and calcined at 200-500 ℃.
The acid is nitric acid, and the concentration of the acid is 1-4 mol/L; the acid treatment time is 30-90 min;
the time of calcination treatment is 30-90 min.
The preparation method of the organic silicon slow-release powder water repellent comprises the following steps: treating zeolite with acid, and calcining at 200-500 ℃ to obtain composite modified zeolite; placing the composite modified zeolite in a vacuum environment, adding organosilane, a surfactant and water, and uniformly stirring; keeping the vacuum environment, adding an alcohol sealant, uniformly stirring, filtering and drying to obtain the organic silicon slow-release powder water repellent.
The acid treatment is that nitric acid with the concentration of 1-4 mol/L and zeolite are evenly mixed at the temperature of 25-45 ℃, are filtered after being oscillated for 30-90 minutes, are washed by water until the zeolite washing liquid is neutral, and are dried to constant weight;
the calcination treatment is to preserve the temperature of the zeolite after the acid treatment for 30-90 min at 200-500 ℃ and then naturally cool the zeolite to room temperature; the calcining treatment is to raise the temperature from room temperature to 200-500 ℃ at the heating rate of 10-20 ℃/min;
placing the composite modified zeolite in a vacuum environment, adding organosilane, a surfactant and water, and uniformly stirring, specifically, placing the composite modified zeolite in an environment with the pressure of 0.1-0.3 kPa, maintaining for 10-30 min, adding the organosilane, the surfactant and the water, and stirring for 10-40 min;
the vacuum environment is kept, the alcohol sealant is added and stirred uniformly, namely, the alcohol sealant is added and stirred for 10-40 min in the environment with the pressure of 0.1-0.3 kPa.
The slow release effect of the organosilicon slow release type powder water repellent is as follows: after the organic silicon slow-release powder water repellent is soaked in a liquid phase environment with the pH value of 12-13 for 60 minutes, the retention rate of organic silicon is 45-60 percent.
The modification effect of the organosilicon slow-release powder water repellent of the invention is as follows: when the water repellent is mixed in 5-20%, the contact angle of silicate or composite silicate cement slurry is 100-125 deg., and the chlorine ion diffusion coefficient in 28 days is 0.1-0.3X 10 -12 m 2 /s。
The organic silicon slow-release type powder water repellent is applied to the field of ocean construction engineering with high requirement on erosion resistance.
Compared with the prior art, the invention has the following advantages and effects:
1) The chemical-thermal treatment composite modification of the zeolite improves the pore content and the pore diameter of the zeolite, can ensure the continuous and uniform release of the organosilane while improving the adsorption performance of the organosilane, and reduces the adverse effect of the organosilane on the early hydration of the gelled material;
2) The organic silicon slow-release powder water repellent has a simple preparation method, organic silane is directly loaded in vacuum by utilizing the porous structure of the composite modified zeolite, and the requirement of the conventional silanol surface coating technology on the accurate control of the pH value (8-9) is avoided;
3) The organosilane release process of the organosilicon slow-release powder water repellent is controllable, and the regulation and control of the zeolite pore structure are realized by controlling chemical-heat treatment conditions (nitric acid concentration, heat treatment temperature and treatment time), so that the control of the organosilane slow-release process is realized;
4) The strong alkaline environment formed by the hydration of the cementing material is utilized to promote the hydrolysis of the alcohol sealant on the surface of the organosilicon slow-release powder water repellent and organosilane to form silanol, so that the silanol is bonded with the hydroxyl on the surface of a hydration product to generate hydrophobicity, and the distribution uniformity of hydrophobic improving components is improved;
5) The organic silicon slow-release powder water repellent adopts chemically-thermally treated composite modified zeolite as a dispersion medium, so that the density improvement and performance development of cement paste can be ensured through volcanic ash reaction while the uniform release of organic silane is ensured;
6) The organic silicon slow-release powder water repellent has excellent organic silicon slow-release effect, the retention rate of the organic silicon is 45-60% in 60 minutes, the hydrophobic property modification effect on silicate or composite silicate cement is remarkable, the transition of the pore wall of a cement-based material from hydrophilicity (the wetting angle is less than 50 ℃) to hydrophobicity (the wetting angle is 100-125 ℃) is realized, and the chloride ion diffusion coefficient is reduced to 0.1-0.3 multiplied by 10 within 28 days -12 m 2 And/s is lower than the current standard limit of the marine Portland cement by one order of magnitude.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
The organic silicon slow-release type powder water repellent comprises zeolite, organic silane, an alcohol sealant and a surfactant; the invention adopts chemical-heat treatment composite modified zeolite, and realizes the preparation of the organic silicon slow-release powder water repellent by a vacuum loading and drying mode.
An organosilicon slow-release powder water repellent is divided into four types according to the types of components, the mass fractions of the components with different types are shown in table 1, the mass fractions of the components can fluctuate within a specified range, and the sum of the mass fractions of the components is required to be 100%.
TABLE 1 component types and mass fractions of organosilicon sustained-release powder water repellent
Example 1
The organosilicon slow-release powder water repellent in the embodiment mainly comprises zeolite, dodecyl trimethoxy silane, polypropylene glycol (molecular weight is 800) and dodecyl glucoside; the technical parameters of the chemical-heat treatment composite modification are as follows: the concentration of nitric acid is 2mol/L, the temperature of nitric acid is 35 ℃, the oscillation time is 60 minutes, the calcination temperature is 250 ℃, and the heat preservation time is 45 minutes; the technical parameters of the vacuum loading of the organosilane are as follows: the pressure intensity of the cavity is 0.1kPa, the pressure intensity is maintained for 15 minutes, the zeolite, the organosilane, the surfactant and the deionized water are stirred together for 20 minutes, and after the alcohol sealant is added, the pressure intensity is maintained at 0.1kPa and the stirring is continued for 20 minutes; the mass contents of the components and the modifying effect of the organosilicon sustained-release powdery water repellent prepared in the embodiment on portland cement are shown in table 2.
TABLE 2 proportion of organosilicon slow-release type powder water repellent and modifying effect on portland cement
Example 2
The organosilicon slow-release powder water repellent in the embodiment mainly comprises zeolite, butyl triethoxysilane, polyethylene glycol (molecular weight is 1000) and octadecyl glucoside; the technical parameters of the chemical-heat treatment composite modification are as follows: the concentration of nitric acid is 3mol/L, the temperature of nitric acid is 40 ℃, the oscillation time is 60 minutes, the calcination temperature is 300 ℃, and the heat preservation time is 60 minutes; the technical parameters of vacuum loading of organosilane are as follows: the pressure of the cavity is 0.1kPa, the pressure maintaining time is 15 minutes, the zeolite, the organosilane, the surfactant and the deionized water are stirred together for 20 minutes, and after the alcohol sealant is added, the stirring is continued for 20 minutes under the pressure maintaining condition of 0.1 kPa; the mass contents of the components and the modifying effect of the organosilicon slow-release powder water repellent prepared in the example on portland cement are shown in table 3.
TABLE 3 proportioning of organosilicon slow-release type powder water repellent and modifying effect on Portland cement
Example 3
The organic silicon slow-release type powder water repellent in the embodiment mainly comprises zeolite, octadecyl trimethoxy silane, polyvinyl alcohol (molecular weight is 800) and lauric glyceride; the chemical-heat treatment composite modification technical parameters are as follows: the concentration of nitric acid is 4mol/L, the temperature of nitric acid is 40 ℃, the oscillation time is 30 minutes, the calcination temperature is 200 ℃, and the heat preservation time is 60 minutes; the technical parameters of the vacuum loading of the organosilane are as follows: the pressure of the cavity is 0.1kPa, the pressure maintaining time is 15 minutes, the zeolite, the organosilane, the surfactant and the deionized water are stirred together for 20 minutes, and after the alcohol sealant is added, the stirring is continued for 20 minutes under the pressure maintaining condition of 0.1 kPa; the mass contents of the components and the modifying effect of the organosilicon sustained-release powder water repellent prepared in this example on portland cement are shown in table 4.
TABLE 4 formulation of slow-release organosilicon powder water repellent and modifying effect on Portland cement
Comparative example 1
Conventional organosilicon water repellent is adopted. The contact angle of the modified Portland cement is 108 degrees, and the diffusion coefficient of chlorine ions is 0.32 multiplied by 10 -12 m 2 /s。
Comparative example 2
Polytetrahydrofuran diol was used as a sealant, and the other conditions were the same as in example 1.
Contact angle of modified portland cement97 ° and a chlorine ion diffusion coefficient of 0.87 × 10 -12 m 2 The silicone retention was 17% at 60 min/s.
Comparative example 3
The zeolite was not subjected to the chemical-thermal treatment, and the other conditions were the same as in example 1.
The contact angle of the modified portland cement is 92 degrees, and the diffusion coefficient of chloride ions is 1.06 multiplied by 10 -12 m 2 The silicone retention was 32% at 60 min/s.
Comparative example 4
The amount of zeolite used in the water repellent was 70% and organosilane was 24%, and the other conditions were the same as in example 1.
The contact angle of the modified portland cement is 96 degrees, and the diffusion coefficient of chloride ions is 0.97 multiplied by 10 -12 m 2 The silicone retention was 10% at 60 min/s.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (5)
1. An organosilicon slow-release powder water repellent is characterized in that: the paint mainly comprises the following components in percentage by mass:
zeolite 45 to 55%
40 to 50% of organosilane
3 to 6 percent of alcohol sealant
And 0.5 to 3 percent of surfactant;
the particle size of the zeolite is 0.5 to 15 mu m;
the organosilane is one or more of vinyl trimethoxy silane, dodecyl trimethoxy silane, hexadecyl trimethoxy silane, octadecyl trimethoxy silane, vinyl triethoxy silane, butyl triethoxy silane and octyl triethoxy silane;
the alcohol sealant is one or more of polyvinyl alcohol, polyethylene glycol and polypropylene glycol; the molecular weight of the alcohol sealant is 600 to 1000;
the surfactant is one or more of alkyl glucoside, fatty glyceride, lecithin and sodium dodecyl benzene sulfonate;
the alkyl glucoside is more than one of dodecyl glucoside, hexadecyl glucoside and octadecyl glucoside; the fatty acid glyceride is more than one of lauric acid glyceride, caprylic acid glyceride and glycerin monostearate;
the preparation method of the organic silicon slow-release powder water repellent comprises the following steps: uniformly mixing nitric acid with the concentration of 1-4 mol/L and zeolite at the temperature of 25-45 ℃, oscillating for 30-90 minutes, filtering, washing with water until the zeolite washing liquid is neutral, and drying to constant weight to obtain acid-treated zeolite; raising the temperature of the zeolite after acid treatment from room temperature to 200-500 ℃ at a heating rate of 10-20 ℃/min, keeping the temperature for 30-90min, and then naturally cooling to room temperature to obtain the composite modified zeolite; placing the composite modified zeolite in an environment with the pressure of 0.1-0.3 kPa, maintaining for 10-30min, then adding organosilane, a surfactant and water, and stirring for 10-40min; and (3) adding an alcohol sealant into the environment with the pressure of 0.1-0.3kPa, stirring for 10-40min, filtering, and drying to obtain the organic silicon slow-release powder water repellent.
2. The application of the organosilicon slow-release powder water repellent as claimed in claim 1, wherein: the organic silicon slow-release type powder water repellent is used for preparing cement concrete, improving the water repellency of the cement, improving the anti-erosion capacity of the cement and improving the organic silicon slow-release effect.
3. Use according to claim 2, characterized in that: the cement concrete is used for ocean building engineering, improves the hydrophobicity of cement, and improves the chloride ion corrosion resistance of cement.
4. A cement concrete characterized in that: comprising a cement-based material and an organosilicon slow-release powder hydrophober as defined in claim 1.
5. The cement concrete according to claim 4, wherein: the mixing amount of the organic silicon slow-release type powder water repellent is 5 to 20 percent of the mass of the cement-based material;
the cement-based material is portland cement or composite portland cement.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011482783.3A CN112551943B (en) | 2020-12-16 | 2020-12-16 | Organic silicon slow-release type powder water repellent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011482783.3A CN112551943B (en) | 2020-12-16 | 2020-12-16 | Organic silicon slow-release type powder water repellent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112551943A CN112551943A (en) | 2021-03-26 |
| CN112551943B true CN112551943B (en) | 2022-12-13 |
Family
ID=75063983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011482783.3A Active CN112551943B (en) | 2020-12-16 | 2020-12-16 | Organic silicon slow-release type powder water repellent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112551943B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685093B (en) * | 2022-04-27 | 2023-06-27 | 长沙标朗住工科技有限公司 | Wall repairing paste and preparation method and application thereof |
| CN115385603B (en) * | 2022-08-26 | 2023-05-30 | 山东竣鸿环保科技有限公司 | Concrete mineral blended aggregate and preparation process and application thereof |
| CN115504726B (en) * | 2022-09-20 | 2023-09-08 | 安徽理工大学 | Preparation method of slow-release hydrophobic microcapsule and hydrophobic concrete |
| CN116514434A (en) * | 2023-05-06 | 2023-08-01 | 济南大学 | Whiskering inhibitor, preparation process thereof and application thereof in aluminosilicate cementing material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102226072A (en) * | 2011-05-06 | 2011-10-26 | 同济大学 | Preparation method of organic silicon microcapsule powder waterproof agent |
| CN111253115A (en) * | 2018-12-03 | 2020-06-09 | 怀化雁荡山新型墙体材料有限公司 | Waterproof durable light wall material and preparation method thereof |
-
2020
- 2020-12-16 CN CN202011482783.3A patent/CN112551943B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102226072A (en) * | 2011-05-06 | 2011-10-26 | 同济大学 | Preparation method of organic silicon microcapsule powder waterproof agent |
| CN111253115A (en) * | 2018-12-03 | 2020-06-09 | 怀化雁荡山新型墙体材料有限公司 | Waterproof durable light wall material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《酸处理对斜发沸石结构影响的研究》;许静等;《燃料化学学报》;20180831;第46卷(第8期);第1000-1008页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112551943A (en) | 2021-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112551943B (en) | Organic silicon slow-release type powder water repellent and preparation method thereof | |
| KR101577463B1 (en) | Mixture containing organosilicon compound and use thereof | |
| JP7195011B2 (en) | Superhydrophobic coating and its preparation method and application, Superhydrophobic foamed concrete and its preparation method | |
| CN112624662B (en) | High-dispersion organic-inorganic composite powder water repellent and preparation method thereof | |
| CN112919849B (en) | Organic-inorganic composite hydrophobic functional material and preparation method thereof | |
| CN103755304B (en) | Capillary crystalline waterproofing agent and preparation method thereof | |
| CN111848059B (en) | Water-control moisture-proof mortar for basement | |
| CN109679498B (en) | Nano-alumina modified silane waterproofing agent and preparation method and application thereof | |
| CN112266638A (en) | Water repellent based on inorganic silicate and preparation method and application thereof | |
| CN114656190A (en) | Fatty acid concrete hydrophobic pore suppository and preparation method thereof | |
| CN112194396B (en) | Slow-release hydrophobing agent for cement-based material, hydrophobic cement and preparation method thereof | |
| CN111875320B (en) | Super-hydrophobic microcapsule polymer cement-based anticorrosive paint and preparation method and application thereof | |
| CN113979701B (en) | Cement-based waterproof coating, raw material composition thereof, and preparation method and application thereof | |
| CN111732445A (en) | Preparation method of durable composite waterproof material for concrete | |
| CN115746661A (en) | Preparation method of self-repairing hydrophobic antibacterial anticorrosive coating | |
| CN114956867B (en) | Modified hexagonal boron nitride-silane composite emulsion, preparation method and application thereof, and concrete surface protection method | |
| CN112624688B (en) | Low-wetting and high-durability composite portland cement and preparation method thereof | |
| CN113185858B (en) | Vinyl silane modified graphene oxide composite material and preparation method and application thereof | |
| CN116042048A (en) | Ion stimulus response self-repairing coating based on synergistic effect of corrosion inhibitors and preparation method thereof | |
| CN114656285A (en) | Silane permeable material | |
| KR100502278B1 (en) | Coating compositions that manufactured by organic-inorganic crosslinked polymer for the protection of concrete structure and its manufacture method | |
| KR100547389B1 (en) | Organic-inorganic cross-linked composite polymer coating composition and manufacturing method for strengthening interfacial adhesion of new and old concrete | |
| CN107555836B (en) | Cement mortar waterproof additive and preparation process thereof | |
| CN109020619A (en) | A kind of corrosion-resistant waterproof material suitable for concrete | |
| CN115504726B (en) | Preparation method of slow-release hydrophobic microcapsule and hydrophobic concrete |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |