CN115925447B - Wettability-pH response modifier and application method thereof - Google Patents
Wettability-pH response modifier and application method thereof Download PDFInfo
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- CN115925447B CN115925447B CN202211716468.1A CN202211716468A CN115925447B CN 115925447 B CN115925447 B CN 115925447B CN 202211716468 A CN202211716468 A CN 202211716468A CN 115925447 B CN115925447 B CN 115925447B
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- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000003607 modifier Substances 0.000 title claims abstract description 31
- 230000004044 response Effects 0.000 title claims abstract description 13
- -1 alkyl dicarboxylic acid Chemical compound 0.000 claims abstract description 107
- 239000004568 cement Substances 0.000 claims abstract description 93
- 239000000463 material Substances 0.000 claims abstract description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 150000004671 saturated fatty acids Chemical class 0.000 claims abstract description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 239000003929 acidic solution Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 28
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 20
- 238000004140 cleaning Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- 239000003469 silicate cement Substances 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 14
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 14
- 229920001971 elastomer Polymers 0.000 claims description 14
- 238000000465 moulding Methods 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 12
- 230000002209 hydrophobic effect Effects 0.000 claims description 12
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 12
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 12
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 claims description 12
- 239000005639 Lauric acid Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 235000021314 Palmitic acid Nutrition 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 6
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 6
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims 4
- 230000008859 change Effects 0.000 abstract description 9
- 238000012423 maintenance Methods 0.000 abstract description 6
- 230000036571 hydration Effects 0.000 abstract description 3
- 238000006703 hydration reaction Methods 0.000 abstract description 3
- 230000009545 invasion Effects 0.000 abstract description 3
- 239000003002 pH adjusting agent Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000003075 superhydrophobic effect Effects 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
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- 230000007935 neutral effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005316 response function Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
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- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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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
Landscapes
- Aftertreatments Of Artificial And Natural Stones (AREA)
Abstract
The invention discloses a wettability-responsive pH modifier, which comprises the following components in parts by weight: 50-70 parts of alkyl dicarboxylic acid, 30-50 parts of saturated fatty acid and 1900-2000 parts of absolute ethyl alcohol, and the modifier can change the hydrophilicity of the cement-based material into hydrophobicity. Two methods of using the wettability-responsive pH modifying agent are also disclosed. The invention is convenient for water entering and cement hydration in the early maintenance process, does not reserve water stains on the horizontal surface of the sample, and can meet the requirements of stain resistance and water invasion resistance in the later service stage; the raw materials are green, environment-friendly, nontoxic and harmless, and the cost is low; the preparation method is simple to operate and has low equipment requirement; the substrate is cement-based material, so that the application of the stimulus response surface is expanded; the wettability pH response surface is rapidly prepared, the prepared hydrophilic-hydrophobic adjustable cement-based material is hydrophilic in early maintenance stage, and the prepared hydrophilic-hydrophobic adjustable cement-based material is converted into hydrophobicity after being treated by an acidic solution in service stage.
Description
Technical Field
The invention relates to a modifier and a use method thereof, in particular to a modifier with wettability responding to pH and a use method thereof.
Background
In natural environment, animals or plants can selectively evolve interface molecules and construct specific chemical structures to obtain functional surfaces with various wettability and variability in order to cope with complex and various external changes. This motivates researchers to develop new materials, such as superhydrophobic surface structures that mimic the superhydrophobic surface structure of plants such as lotus leaves to produce superhydrophobic materials, and that mimic responsive biological interfaces in natural environments to produce responsive polymers and superhydrophobic surfaces that can interact with external stimuli. Smart responsive materials can be prepared using responsive polymers and super-wetted surfaces, and these materials that respond intelligently to stimuli are widely used in a variety of emerging fields.
The current research for preparing the wettability stimulus response surface is mainly focused on substrates such as sponge, fabric, metal, crystal and the like, and related research for realizing the wettability stimulus response function on cement-based substrates is not yet available. In the field of cement-based materials, (super) hydrophobic cement-based materials are mainly obtained by internally blending low surface energy functional components or preparing coatings. However, the existing method can only obtain the surface of the cement-based material with a single (super) hydrophobic function, is unfavorable for water entering and cement hydration in the early maintenance process, is easy to reserve water stains on the horizontal surface of the sample, and cannot meet the requirements of stain resistance and water invasion resistance in the later service stage.
Disclosure of Invention
The invention aims to: in order to overcome the defects in the prior art, the invention aims to provide a modifier which reduces adverse effects of hydrophobicity in early curing stages of cement-based materials, is quickly prepared and has wettability responding to pH, and the invention also aims to provide two methods for using the modifier which is convenient and practical and meets the wettability responding to pH and required by stain resistance and water intrusion resistance.
The technical scheme is as follows: the invention relates to a wettability-to-pH response modifier, which comprises the following components in parts by weight: 50-70 parts of alkyl dicarboxylic acid, 30-50 parts of saturated fatty acid and 1900-2000 parts of absolute ethyl alcohol, and the modifier can change the hydrophilicity of the cement-based material into hydrophobicity.
Further, the alkyl dicarboxylic acid is any one of suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid.
Further, the saturated fatty acid is any one of capric acid, lauric acid, myristic acid, palmitic acid, pearlitic acid and stearic acid.
The first method of using the above wettability-responsive pH modifier, namely the impregnation method, comprises the steps of:
Adding saturated fatty acid and alkyl dicarboxylic acid into absolute ethyl alcohol according to the weight portion ratio, and stirring until the saturated fatty acid and the alkyl dicarboxylic acid are completely dissolved to obtain a modifier;
Step two, mixing water and silicate cement, stirring uniformly, pouring the slurry into a rubber mold for molding, removing the mold, and curing in a natural environment;
step three, taking out the product obtained in the step two, cleaning the surface by using deionized water, cleaning by using absolute ethyl alcohol, and drying the cleaned cement-based material;
Immersing the substance obtained in the third step into the modifier prepared in the second step, taking out the treated cement-based material substrate, washing with absolute ethyl alcohol, and drying to obtain the cement-based material.
In the second step, the water cement ratio of water to silicate cement is 0.3-0.4, and the curing time is 7-8 days.
Further, in the third step, the drying temperature is 45-50 ℃ and the drying time is 6-8 h.
Further, in the fourth step, the immersing time is 6-8 hours, the drying temperature is 45-55 ℃, and the drying time is 5-7 hours.
The second method of using the wettability-responsive pH modifier, i.e., the internal blending method, comprises the steps of:
Step one, according to the weight portion ratio, saturated fatty acid and alkyl dicarboxylic acid react with excessive hydrogen oxide salt solution, and saturated fatty acid salt and alkyl dicarboxylic acid salt are obtained after filtration and drying;
controlling the mass percentage of the alkyl dicarboxylic acid salt in the mixed components to be 50-70%, then adding water at 35-45 ℃, and stirring until the alkyl dicarboxylic acid salt is completely dissolved to obtain the additive;
step three, mixing and stirring the additive, water and silicate cement uniformly, pouring the slurry into a rubber mold for molding, removing the mold, and curing in a natural environment;
And fourthly, washing the cement sample with hydrochloric acid or sulfuric acid solution with the pH value of 4-6 after maintenance, and drying at the temperature of 40-50 ℃ to change the cement-based material from hydrophilic to hydrophobic.
In the third step, the water cement ratio of water to silicate cement is 0.3-0.4, and the curing time is 7-8 days.
The preparation principle is as follows: according to the surface characteristics of the cement-based material, such as strong hydrophilicity and rich hydroxyl, the grafting is realized by adopting carboxylate at one end of saturated fatty acid, and the methyl at the other end has lower surface energy so as to realize the hydrophobic function; grafting is achieved by using carboxylate groups at one end of the alkyl dicarboxylic acid, and the carboxylate groups at the other end are deprotonated at high pH values and become more hydrophilic to achieve the response capability to pH values. And the corresponding organic acid salt is prepared by the saturated fatty acid and the alkyl dicarboxylic acid so as to be dissolved in water to realize the internal mixing in the cement-based material. Compared with the impregnation method which utilizes physical adsorption effects such as hydrogen bond formation between the metacarboxylic acid functional group and the cement-based material, the internal doping method has better modification effect durability.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable characteristics:
1. The method is convenient for water entering and cement hydration in the early maintenance process, water stains cannot be reserved on the horizontal surface of the sample, and the requirements of stain resistance and water invasion resistance in the later service stage can be met;
2. The raw materials are green, environment-friendly, nontoxic and harmless, and the cost is low; the preparation method is simple to operate and has low equipment requirement;
3. the substrate is a cement-based material, so that the application of the stimulus response surface in the field of cement-based materials is expanded;
4. The prepared wettability-pH response modifier can be used for rapidly preparing a wettability pH response surface on a cement-based material base, and the prepared hydrophilic-hydrophobic adjustable cement-based material is hydrophilic in an early maintenance stage and is converted into hydrophobicity after being treated by an acidic solution in a service stage.
Drawings
FIG. 1 is a schematic illustration of the wetting of surface droplets of a modified cement-based material prepared by the dipping method of the present invention;
FIG. 2 is a graph showing the change of the surface contact angle of the modified cement-based material prepared by the impregnation method of the present invention;
FIG. 3 is a graph showing the change of the surface contact angle with the pH value of a solution for preparing a modified cement-based material by the dipping method of the present invention;
FIG. 4 is a graph showing the variation of the surface contact angle with the doping amount of the modified cement-based material prepared by the internal doping method of the present invention;
FIG. 5 is a graph of the surface wettability transition for a modified cement-based material prepared by the in-situ doping method of the present invention.
Detailed Description
Example 1
A method of using a wettability-responsive pH modifying agent, comprising the steps of:
placing 70 parts of saturated fatty acid and 30 parts of alkyl dicarboxylic acid in a container, wherein the alkyl dicarboxylic acid is dodecanedioic acid, the saturated fatty acid is lauric acid, adding 1900 parts of absolute ethyl alcohol, namely controlling the mass percentage of the alkyl dicarboxylic acid in the mixed components (saturated fatty acid and saturated fatty acid) to be 30%, and stirring until the mixed components are completely dissolved in the ethyl alcohol to obtain a modifier with the mass percentage of 5 wt%;
Mixing water and silicate cement according to a water cement ratio of 0.4, uniformly stirring, pouring the slurry into a rubber mold for molding, removing the mold after 1d, and curing for 7d in a natural environment;
Step three, taking out the product obtained in the step two, cleaning the surface by using deionized water, cleaning by using absolute ethyl alcohol, and drying the cleaned cement-based material in a drying oven at 50 ℃ for 6 hours;
Immersing the substance obtained in the third step in the modifier prepared in the second step, immersing for 6 hours, taking out the treated cement-based material substrate, cleaning with absolute ethyl alcohol, and drying in a drying oven at 50 ℃ for 6 hours to obtain the cement-based material.
Example 2
A method of using a wettability-responsive pH modifying agent, comprising the steps of:
firstly, placing 50 parts of saturated fatty acid and 50 parts of alkyl dicarboxylic acid into a container, wherein the alkyl dicarboxylic acid is dodecanedioic acid, the saturated fatty acid is lauric acid, adding 1900 parts of absolute ethyl alcohol, namely controlling the mass percentage of the alkyl dicarboxylic acid in the mixed components (saturated fatty acid and saturated fatty acid) to be 50%, and stirring until the mixed components are completely dissolved in the ethyl alcohol to obtain a modifier with the mass percentage of 5 wt%;
Mixing water and silicate cement according to a water cement ratio of 0.4, uniformly stirring, pouring the slurry into a rubber mold for molding, removing the mold after 1d, and curing for 7d in a natural environment;
Step three, taking out the product obtained in the step two, cleaning the surface by using deionized water, cleaning by using absolute ethyl alcohol, and drying the cleaned cement-based material in a drying oven at 50 ℃ for 6 hours;
Immersing the substance obtained in the third step in the modifier prepared in the second step, immersing for 6 hours, taking out the treated cement-based material substrate, cleaning with absolute ethyl alcohol, and drying in a drying oven at 50 ℃ for 6 hours to obtain the cement-based material.
Example 3
A method of using a wettability-responsive pH modifying agent, comprising the steps of:
placing 30 parts of saturated fatty acid and 70 parts of alkyl dicarboxylic acid in a container, wherein the alkyl dicarboxylic acid is dodecanedioic acid, the saturated fatty acid is lauric acid, adding 1900 parts of absolute ethyl alcohol, namely controlling the mass percent of the alkyl dicarboxylic acid in the mixed components (saturated fatty acid and saturated fatty acid) to be 70%, and stirring until the mixed components are completely dissolved in the ethyl alcohol to obtain a modifier with the mass percent of 5 wt%;
Mixing water and silicate cement according to a water cement ratio of 0.4, uniformly stirring, pouring the slurry into a rubber mold for molding, removing the mold after 1d, and curing for 7d in a natural environment;
Step three, taking out the product obtained in the step two, cleaning the surface by using deionized water, cleaning by using absolute ethyl alcohol, and drying the cleaned cement-based material in a drying oven at 50 ℃ for 6 hours;
Immersing the substance obtained in the third step in the modifier prepared in the second step, immersing for 6 hours, taking out the treated cement-based material substrate, cleaning with absolute ethyl alcohol, and drying in a drying oven at 50 ℃ for 6 hours to obtain the cement-based material.
Alkaline liquids with pH=7 and pH=13 are prepared by using sodium hydroxide, and the two liquids are sucked by using a dropper and respectively dripped on the surface of the cement-based material treated by the modifier. The wetting condition of the liquid drops with different pH values on the surface is shown as figure 1, the surface of the modified cement-based material substrate has good hydrophobic characteristic on the liquid drops with pH=7, and a silver mirror phenomenon exists; whereas for ph=13 the droplets are hydrophilic in character and spread out rapidly wetting the surface.
Comparative example 1
The remaining steps of this comparative example are the same as in example 1, except that: in the first step, 100 parts of saturated fatty acid and 0 part of alkyl dicarboxylic acid are adopted, namely, the mass percentage of the alkyl dicarboxylic acid in the mixed components (saturated fatty acid and saturated fatty acid) is controlled to be 0%.
Comparative example 2
The remaining steps of this comparative example are the same as in example 1, except that: in the first step, 0 part of saturated fatty acid and 100 parts of alkyl dicarboxylic acid are adopted, namely, the mass percentage of the alkyl dicarboxylic acid in the mixed components (saturated fatty acid and saturated fatty acid) is controlled to be 100 percent.
Alkaline liquid with ph=13 was prepared using sodium hydroxide, neutral liquid with ph=7 was prepared using deionized water, contact angles of cement-based material surfaces modified with modifiers of different mixing component ratios obtained in examples 1 to 3 and comparative examples 1 to 2 were tested with a viewing screen optical contact angle meter to two pH drops, test drop sizes were 5 μl, three sites were tested per surface, and measurement results are shown in fig. 2. When the alkyl dicarboxylic acid accounts for 0% and 30%, the contact angle difference of the cement-based material substrate to the liquid drops with the pH value of 7 and the liquid drops with the pH value of 13 is not obvious, and the cement-based material substrate is kept at 130-140 degrees and is in a hydrophobic characteristic. When the alkyl dicarboxylic acid accounts for 50% and 70%, the contact angle of the cement-based material substrate surface on the liquid drops with the pH value of 7 and the pH value of 13 is obviously different, the contact angle of the liquid drops with the pH value of 7 is 115-135 degrees, the liquid drops with the pH value of 7 are hydrophobic, and the contact angle of the liquid drops with the pH value of 13 is below 50 degrees, and the liquid drops with the pH value of 7 are hydrophilic. When the alkyl dicarboxylic acid accounts for 100%, the cement-based material substrate has no obvious difference in contact angle between the liquid drops with the pH value of 7 and 13, and the contact angle is kept at about 20 degrees. At a 70% ratio of alkyl dicarboxylic acid, the difference in contact angle between the two droplets is at a maximum of 101 °. When the pH of the solution is < 7, the contact angle is the same as that at ph=7.
Example 4
A method of using a wettability-responsive pH modifying agent, comprising the steps of:
placing 40 parts of saturated fatty acid and 60 parts of alkyl dicarboxylic acid in a container, wherein the alkyl dicarboxylic acid is suberic acid, the saturated fatty acid is capric acid, adding 2000 parts of absolute ethyl alcohol, namely controlling the mass percentage of the alkyl dicarboxylic acid in the mixed components to be 60%, and stirring until the mixed components are completely dissolved in the ethyl alcohol to obtain a modifier with the mass percentage of 4.8 wt%;
Mixing water and silicate cement with a water cement ratio of 0.3, uniformly stirring, pouring the slurry into a rubber mold for molding, removing the mold after 1d, and curing for 8d in a natural environment;
step three, taking out the product obtained in the step two, cleaning the surface by using deionized water, cleaning by using absolute ethyl alcohol, and drying the cleaned cement-based material in a drying oven at 45 ℃ for 8 hours;
Immersing the substance obtained in the third step in the modifier prepared in the second step, immersing for 8 hours, taking out the treated cement-based material substrate, cleaning with absolute ethyl alcohol, and drying in a drying oven at 45 ℃ for 7 hours to obtain the cement-based material.
The alkyl dicarboxylic acid in this embodiment may be replaced with any one of suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, and the saturated fatty acid may be replaced with any one of capric acid, lauric acid, myristic acid, palmitic acid, pearlitic acid, and stearic acid.
Example 5
A method of using a wettability-responsive pH modifying agent, comprising the steps of:
Placing 60 parts of saturated fatty acid and 40 parts of alkyl dicarboxylic acid in a container, wherein the alkyl dicarboxylic acid is tridecanedioic acid, the saturated fatty acid is stearic acid, adding 2000 parts of absolute ethyl alcohol, namely controlling the mass percentage of the alkyl dicarboxylic acid in the mixed components to be 40%, and stirring until the mixed components are completely dissolved in the ethyl alcohol to obtain a modifier with the mass percentage of 5 wt%;
Mixing water and silicate cement with a water cement ratio of 0.3, uniformly stirring, pouring the slurry into a rubber mold for molding, removing the mold after 1d, and curing for 8d in a natural environment;
step three, taking out the product obtained in the step two, cleaning the surface by using deionized water, cleaning by using absolute ethyl alcohol, and drying the cleaned cement-based material in a drying oven at 45 ℃ for 8 hours;
Immersing the substance obtained in the third step in the modifier prepared in the second step, immersing for 8 hours, taking out the treated cement-based material substrate, cleaning with absolute ethyl alcohol, and drying in a drying oven at 55 ℃ for 5 hours to obtain the cement-based material.
Example 6
A cement paste sample was prepared and subjected to dipping treatment by the method of example 1 to obtain a cement-based material having a wettability pH intelligent response function on the surface. Alkaline liquids at ph=8, 9, 10, 11, 12, 13 were formulated with sodium hydroxide, neutral liquids at ph=7 were formulated with deionized water, acidic liquids at ph=3, 5 were formulated with hydrochloric acid, and contact angles of cement-based material surfaces treated with the modifier to drops at different pH values were tested with reference to the method of example 1.
The results are shown in FIG. 3, where the cement-based material substrate surface wettability of the 70% alkyl dicarboxylic acid group has a stimulus response capability to pH. When the pH of the liquid drop is 7 or less, the contact angle is 135 ° or more, the surface exhibits hydrophobicity, when the pH of the liquid drop is more than 7, the contact angle of the surface gradually decreases, and when ph=12, the contact angle is 22 °, and the surface exhibits hydrophilicity. The 0% alkyl dicarboxylic acid group always maintains a contact angle of 130 ° or more and the 100% alkyl dicarboxylic acid group maintains a contact angle of 25 ° or less.
Example 7
A method of using a wettability-responsive pH modifying agent, comprising the steps of:
Step one, reacting saturated fatty acid and alkyl dicarboxylic acid with excessive hydrogen oxide salt solution, filtering and drying to obtain saturated fatty acid salt and alkyl dicarboxylic acid salt;
Weighing saturated fatty acid salt and alkyl dicarboxylic acid salt according to a proportion, placing the saturated fatty acid salt and the alkyl dicarboxylic acid salt in a container, controlling the mass percentage of the alkyl dicarboxylic acid salt in the mixed components to be 50%, adding 35 ℃ water, and stirring until the saturated fatty acid salt and the alkyl dicarboxylic acid salt are completely dissolved to obtain the additive;
step three, mixing and stirring the additive, water and silicate cement uniformly, wherein the water-cement ratio is 0.3, pouring the slurry into a rubber mold for molding, removing the mold after 1d, and curing for 7 days in a natural environment;
And fourthly, flushing the cement sample with HCl solution with pH value of 4 after curing, and drying at 40 ℃, wherein the cement-based material is changed from hydrophilicity to hydrophobicity.
In this example, the alkyl dicarboxylic acid is any one of suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and tridecanedioic acid, and the saturated fatty acid is any one of capric acid, lauric acid, myristic acid, palmitic acid, pearlescent acid, and stearic acid.
Example 8
A method of using a wettability-responsive pH modifying agent, comprising the steps of:
Step one, reacting saturated fatty acid and alkyl dicarboxylic acid with excessive hydrogen oxide salt solution, filtering and drying to obtain saturated fatty acid salt and alkyl dicarboxylic acid salt;
Weighing saturated fatty acid salt and alkyl dicarboxylic acid salt according to a proportion, placing the saturated fatty acid salt and the alkyl dicarboxylic acid salt in a container, controlling the mass percentage of the alkyl dicarboxylic acid salt in the mixed components to be 70%, adding water at 45 ℃, and stirring until the mixture is completely dissolved to obtain an additive;
Step three, mixing and stirring the additive, water and silicate cement uniformly, wherein the water-cement ratio is 0.4, pouring the slurry into a rubber mold for molding, removing the mold after 1d, and curing for 8 days in a natural environment;
And fourthly, flushing the cement sample with sulfuric acid solution with the pH value of 5 after curing, and drying at 45 ℃ to change the cement-based material from hydrophilic to hydrophobic.
In this example, the alkyl dicarboxylic acid is any one of suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and tridecanedioic acid, and the saturated fatty acid is any one of capric acid, lauric acid, myristic acid, palmitic acid, pearlescent acid, and stearic acid.
Example 9
A method of using a wettability-responsive pH modifying agent, comprising the steps of:
Step one, reacting saturated fatty acid and alkyl dicarboxylic acid with excessive hydrogen oxide salt solution, filtering and drying to obtain saturated fatty acid salt and alkyl dicarboxylic acid salt;
Weighing saturated fatty acid salt and alkyl dicarboxylic acid salt according to a proportion, placing the saturated fatty acid salt and the alkyl dicarboxylic acid salt in a container, controlling the mass percentage of the alkyl dicarboxylic acid salt in the mixed components to be 60%, adding water at 40 ℃, and stirring until the saturated fatty acid salt and the alkyl dicarboxylic acid salt are completely dissolved to obtain the additive;
step three, mixing and stirring the additive, water and silicate cement uniformly, wherein the water-cement ratio is 0.3, pouring the slurry into a rubber mold for molding, removing the mold after 1d, and curing for 7 days in a natural environment;
And fourthly, washing the cement sample with hydrochloric acid solution with the pH value of 6 after curing, and drying at 45 ℃ to change the cement-based material from hydrophilic to hydrophobic.
In this example, the alkyl dicarboxylic acid is any one of suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and tridecanedioic acid, and the saturated fatty acid is any one of capric acid, lauric acid, myristic acid, palmitic acid, pearlescent acid, and stearic acid.
Example 10
A method of using a wettability-responsive pH modifying agent, comprising the steps of:
Step one, reacting saturated fatty acid and alkyl dicarboxylic acid with excessive hydrogen oxide salt solution, filtering and drying to obtain saturated fatty acid salt and alkyl dicarboxylic acid salt;
Weighing saturated fatty acid salt and alkyl dicarboxylic acid salt in proportion, placing the saturated fatty acid salt and the alkyl dicarboxylic acid salt in a container, controlling the mass percentage of the alkyl dicarboxylic acid salt in the mixed components to be 0%, 70% and 100%, adding water at 40 ℃, and stirring until the saturated fatty acid salt and the alkyl dicarboxylic acid salt are completely dissolved to obtain the additive;
and thirdly, mixing and stirring the additive, water and silicate cement uniformly, wherein the water-cement ratio is 0.4, and the mixed components account for 0%, 0.5%, 1.0%, 1.5% and 2.0% of the dosage of the cementing material. Pouring the slurry into a rubber mold for molding, removing the mold after 1d, and curing for 7 days in a natural environment;
And fourthly, washing the cement sample with hydrochloric acid solution with the pH value of 6 after curing, and drying at 45 ℃ to change the cement-based material from hydrophilic to hydrophobic.
The contact angle of clear water on the surface of the cement-based material obtained in the step three of different mixing component ratios is tested by using a vision screen optical contact angle measuring instrument, the size of a test liquid drop is 5 mu L, three sites are tested on each surface, and the measurement result is shown in figure 4. It can be seen that when the ratio of alkyl dicarboxylic acid salt in the mixed component is 0%, the contact angle increases with increasing doping amount, and finally reaches 120 ° or more; when the ratio of the alkyl dicarboxylic acid salt in the mixed components is 70%, the contact angle shows a tendency of slightly decreasing after rising gently, and keeps below 50 degrees, and the hydrophilicity is shown; the contact angle was not measured due to strong hydrophilicity when the alkyl dicarboxylic acid salt was found to have a 100% ratio in the mixed components, and the contact angle was rapidly decreased after a slight increase, and the contact angle was found to be the same at a higher doping amount.
Example 11
A method of using a wettability-responsive pH modifying agent, comprising the steps of:
Step one, reacting saturated fatty acid and alkyl dicarboxylic acid with excessive hydrogen oxide salt solution, filtering and drying to obtain saturated fatty acid salt and alkyl dicarboxylic acid salt;
Weighing saturated fatty acid salt and alkyl dicarboxylic acid salt according to a proportion, placing the saturated fatty acid salt and the alkyl dicarboxylic acid salt in a container, controlling the mass percentage of the alkyl dicarboxylic acid salt in the mixed components to be 70%, adding water at 40 ℃, and stirring until the saturated fatty acid salt and the alkyl dicarboxylic acid salt are completely dissolved to obtain the additive;
and thirdly, mixing and stirring the additive, water and silicate cement uniformly, wherein the water-cement ratio is 0.4, and the mixed components account for 0%, 0.5%, 1.0%, 1.5% and 2.0% of the dosage of the cementing material. Pouring the slurry into a rubber mold for molding, removing the mold after 1d, and curing for 7 days in a natural environment;
And fourthly, washing the cement sample with hydrochloric acid solution with the pH value of 5 after curing, and drying at 40 ℃ to change the cement-based material from hydrophilic to hydrophobic.
The contact angle of clear water on the surface of the cement-based material before and after the treatment was measured with a vision screen optical contact angle measuring instrument, the size of the measuring droplet was 5. Mu.L, and three sites were measured on each surface, and the measurement results are shown in FIG. 5. When the ratio of the alkyl dicarboxylic acid salt in the mixed components is 70%, the cement-based material before treatment is hydrophilic, and the contact angle is kept below 40 ℃; the contact angle of the cement-based material after treatment is increased, and when the mixed component accounts for 2.0% of the consumption of the cementing material, the contact angle is changed from 30 degrees to 120 degrees.
Claims (9)
1. A method of using a wettability-responsive pH modifying agent, comprising the steps of:
adding saturated fatty acid and alkyl dicarboxylic acid into absolute ethyl alcohol according to the weight portion ratio, and stirring until the saturated fatty acid and the alkyl dicarboxylic acid are completely dissolved to obtain a modifier with the mass fraction of 5 wt%;
Step two, mixing water and silicate cement, stirring uniformly, pouring the slurry into a rubber mold for molding, removing the mold, and curing in a natural environment;
step three, taking out the product obtained in the step two, cleaning the surface by using deionized water, cleaning by using absolute ethyl alcohol, and drying the cleaned cement-based material;
Immersing the substance obtained in the third step into the modifier prepared in the first step, taking out the treated cement-based material substrate, washing with absolute ethyl alcohol, and drying to obtain a cement-based material;
The wettability-to-pH response modifier comprises the following components in parts by weight: 30-70 parts of alkyl dicarboxylic acid, 30-70 parts of saturated fatty acid and 1900 parts of absolute ethyl alcohol, wherein the modifier can convert the cement-based material from hydrophilicity to hydrophobicity;
The alkyl dicarboxylic acid is dodecanedioic acid;
the saturated fatty acid is lauric acid;
The cement-based material is hydrophilic in the early curing stage and is converted into hydrophobicity after being treated by an acidic solution in the service stage.
2. The method of using a wettability-responsive pH modifying agent of claim 1, wherein: the mass percentage of the alkyl dicarboxylic acid in the saturated fatty acid and alkyl dicarboxylic acid mixed component is 50% or 70%.
3. The method of using a wettability-responsive pH modifying agent of claim 1, wherein: in the second step, the water cement ratio of water to silicate cement is 0.3-0.4, and the curing time is 7-8 days.
4. The method of using a wettability-responsive pH modifying agent of claim 1, wherein: in the third step, the drying temperature is 45-50 ℃ and the drying time is 6-8 hours.
5. The method of using a wettability-responsive pH modifying agent of claim 1, wherein: in the fourth step, the immersing time is 6-8 hours, the drying temperature is 45-55 ℃, and the drying time is 5-7 hours.
6. The method of using a wettability-responsive pH modifying agent of claim 1, wherein: in the fourth step, the drying temperature is 45-55 ℃, and the drying time is 5-7 hours.
7. A method of using a wettability-responsive pH modifying agent, comprising the steps of:
Step one, according to the weight portion ratio, saturated fatty acid and alkyl dicarboxylic acid react with excessive hydrogen oxide salt solution, and saturated fatty acid salt and alkyl dicarboxylic acid salt are obtained after filtration and drying;
Controlling the mass percentage of the alkyl dicarboxylic acid salt in the mixed components to be 50% -70%, then adding 35-45 ℃ water, and stirring until the alkyl dicarboxylic acid salt is completely dissolved to obtain an additive;
step three, mixing and stirring the additive, water and silicate cement uniformly, pouring the slurry into a rubber mold for molding, removing the mold, and curing in a natural environment;
Washing the cement sample with hydrochloric acid or sulfuric acid solution with the pH value of 4-6 after curing, and drying at 40-50 ℃, wherein the cement-based material is changed from hydrophilic to hydrophobic;
The wettability-to-pH response modifier comprises the following components in parts by weight: 30-70 parts of alkyl dicarboxylic acid, 30-70 parts of saturated fatty acid and 1900 parts of absolute ethyl alcohol, wherein the modifier can convert the cement-based material from hydrophilicity to hydrophobicity;
The alkyl dicarboxylic acid is any one of suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and tridecanedioic acid;
The saturated fatty acid is any one of capric acid, lauric acid, myristic acid, palmitic acid, pearlitic acid and stearic acid;
The cement-based material is hydrophilic in the early curing stage and is converted into hydrophobicity after being treated by an acidic solution in the service stage.
8. The method of using a wettability-responsive pH modifying agent of claim 7, wherein: in the third step, the water cement ratio of water to silicate cement is 0.3-0.4, and the curing time is 7-8 days.
9. The method of using a wettability-responsive pH modifying agent of claim 7, wherein: the mass percentage of the alkyl dicarboxylic acid salt in the saturated fatty acid and alkyl dicarboxylic acid mixed component is 70%.
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| CN106187314A (en) * | 2016-07-30 | 2016-12-07 | 王法军 | A kind of processing method of silicate cement mud product super hydrophobic surface |
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| GB0024638D0 (en) * | 2000-10-07 | 2000-11-22 | Dow Corning | Cementitious materials |
| TWI424976B (en) * | 2006-09-06 | 2014-02-01 | Kao Corp | Liquid rheology modifier |
| US9475975B2 (en) * | 2011-02-28 | 2016-10-25 | Kemira Oyj | Defoaming compositions and processes for cementing applications |
| WO2014107181A1 (en) * | 2013-01-07 | 2014-07-10 | The Uab Research Foundation | Multilayer hydrogels with ph-responsive swelling and surface wettability |
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| WO2018198679A1 (en) * | 2017-04-28 | 2018-11-01 | 東レ株式会社 | Semipermeable composite membrane and method for producing same |
| CN108752540B (en) * | 2018-05-29 | 2020-05-26 | 江苏苏博特新材料股份有限公司 | Amphiphilic multifunctional hybrid nano particle, and preparation method and application thereof |
| CN111548095A (en) * | 2020-06-02 | 2020-08-18 | 江苏理工学院 | Method for modifying super-hydrophobicity of surface of portland cement hardened slurry |
| KR102464540B1 (en) * | 2021-12-28 | 2022-11-09 | 김준형 | pH-responsive Cement Admixture Capable of Self-recovery of Cement Composite |
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| CN1553884A (en) * | 2001-07-26 | 2004-12-08 | ���Ǿ������м��幫˾ | Hydraulic binder with enhanced aging properties |
| CN106187314A (en) * | 2016-07-30 | 2016-12-07 | 王法军 | A kind of processing method of silicate cement mud product super hydrophobic surface |
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