CN115925447A - Modifier with wettability responding to pH and using method thereof - Google Patents
Modifier with wettability responding to pH and using method thereof Download PDFInfo
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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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- Aftertreatments Of Artificial And Natural Stones (AREA)
Abstract
The invention discloses a modifier for wettability response to pH, which comprises the following substances 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, wherein the modifier can convert the hydrophilicity of the cement-based material into hydrophobicity. The invention also discloses two using methods of the wettability-pH response modifier. The method is convenient for water to enter and cement to hydrate in the early maintenance process, water stains cannot be remained on the horizontal surface of the sample, and the requirements of stain resistance and water intrusion resistance in the later service stage can be met; the raw materials are green and environment-friendly, nontoxic and harmless, and low in cost; the preparation method is simple to operate and low in equipment requirement; the used substrate is a 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 and hydrophobic adjustable cement-based material has hydrophilic characteristics in the early maintenance stage, and is converted into hydrophobic property after being treated by an acid solution in the 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 variable properties in order to respond to complex and various external changes. This has motivated researchers to develop new materials, for example, to mimic the superhydrophobic surface structure of plants such as lotus leaves to make superhydrophobic new materials, to mimic the responsive biological interfaces in the natural environment to make responsive polymers and superhydrophobic surfaces that can interact with external stimuli. The response polymer and the super-wetting surface can be used for preparing intelligent response materials, and the materials capable of intelligently responding to stimuli are widely applied to various emerging fields.
At present, research for preparing wettability stimulus response surfaces mainly focuses on substrates such as sponges, fabrics, metals, crystals and the like, and related exploration for realizing wettability stimulus response functions on cement-based material substrates is lacked. In the field of cement-based materials, (super) hydrophobic cement-based materials are obtained mainly by incorporating low surface energy functional components or preparing coatings. However, the existing method can only obtain the surface of the cement-based material with single (super) hydrophobic function, is not beneficial to water entering and cement hydration in the early curing process, is easy to retain water stains on the horizontal surface of the sample, and cannot meet the requirements of stain resistance and water intrusion resistance in the later service stage.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects in the prior art, the invention aims to provide a modifier which reduces the adverse effect of hydrophobicity in the early curing stage of a cement-based material, is prepared quickly and has wettability response to pH, and the invention also aims to provide two convenient and practical methods for using the modifier which meets the requirements of stain resistance and water intrusion resistance and has wettability response to pH.
The technical scheme is as follows: the modifier for wettability response to pH comprises the following substances 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, wherein the modifier can convert 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, and tridecanedioic acid.
The saturated fatty acid is any one of capric acid, lauric acid, myristic acid, palmitic acid, pearlescent fatty acid and stearic acid.
The first method of using the above-described pH-responsive modifier, namely the impregnation method, comprises the steps of:
step one, adding saturated fatty acid and alkyl dicarboxylic acid into absolute ethyl alcohol according to the weight part ratio, and stirring until the saturated fatty acid and the alkyl dicarboxylic acid are completely dissolved to obtain a modifier;
step two, mixing and stirring water and portland cement uniformly, pouring the slurry into a rubber mold for molding, removing the mold, and maintaining 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;
and step four, immersing the substance obtained in the step three in the modifier prepared in the step two, taking out the treated cement-based material substrate, cleaning with absolute ethyl alcohol, and drying to obtain the cement-based material.
Furthermore, in the second step, the water cement ratio of water to portland 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 immersion time is 6-8 h, the drying temperature is 45-55 ℃, and the drying time is 5-7 h.
The second method of using the above-mentioned wettability-pH-responsive modifier, i.e. the internal doping method, comprises the steps of:
reacting saturated fatty acid and alkyl dicarboxylic acid with excessive hydroxide solution according to the weight part ratio, filtering and drying to obtain saturated fatty acid salt and alkyl dicarboxylic acid salt;
step two, controlling the mass percent of the alkyl dicarboxylate in the mixed components to be 50-70%, then adding 35-45 ℃ water, and stirring until the alkyl dicarboxylate is completely dissolved to obtain an additive;
step three, mixing and stirring the additive, water and portland cement uniformly, pouring the slurry into a rubber mold for molding, removing the mold, and maintaining in a natural environment;
and step four, washing the cement sample by using a hydrochloric acid or sulfuric acid solution with the pH value of 4-6 after maintenance, and drying at 40-50 ℃ to change the hydrophilicity of the cement-based material into hydrophobicity.
Furthermore, in the third step, the water cement ratio of water to portland 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 groups, grafting is realized by carboxylate radicals at one end of saturated fatty acids, and the methyl groups at the other end have lower surface energy, so that a hydrophobic function is realized; grafting is realized by using carboxylate radical at one end of alkyl dicarboxylic acid, and the carboxylate radical at the other end can be deprotonated at a high pH value and becomes more hydrophilic so as to realize the response capability to the pH value. And saturated fatty acid and alkyl dicarboxylic acid are prepared into corresponding organic acid salt so as to be dissolved in water to realize internal mixing in the cement-based material. Compared with the impregnation method which utilizes the physical adsorption effects of hydrogen bonds and the like formed between the carboxylic acid function group and the cement-based material, the durability of the modification effect of the internal doping method is better.
Has the advantages that: compared with the prior art, the invention has the following remarkable characteristics:
1. the water entering and cement hydration in the early curing process are facilitated, water stains cannot remain on the horizontal surface of the sample, and the requirements of contamination resistance and water intrusion resistance in the later service stage can be met;
2. the raw materials are green and environment-friendly, nontoxic and harmless, and low in cost; the preparation method is simple to operate and low in equipment requirement;
3. the used substrate is a cement-based material, and the application of the stimulus response surface in the field of cement-based materials is expanded;
4. the prepared modifier with the wettability responding to the pH can quickly prepare a wettability pH response surface on a cement-based material base, the prepared hydrophilic and hydrophobic adjustable cement-based material has hydrophilic characteristics in an early maintenance stage, and the prepared hydrophilic and hydrophobic adjustable cement-based material is converted into hydrophobicity after being treated by an acidic solution in a service stage.
Drawings
FIG. 1 is a graph of the surface droplet wetting potential of a modified cement-based material prepared by the impregnation method of the present invention;
FIG. 2 is a graph showing the change of contact angle of the surface of the modified cement-based material prepared by the dipping method according to the present invention;
FIG. 3 is a graph of surface contact angle as a function of pH of a solution for a modified cementitious material prepared by the dipping method of the present invention;
FIG. 4 is a graph showing the variation of surface contact angle with doping amount in the modified cement-based material prepared by the internal doping method according to the present invention;
FIG. 5 is a graph showing the surface wettability transition of the modified cement-based material prepared by the incorporation method of the present invention.
Detailed Description
Example 1
A method of using a wettability-pH responsive modifier comprising the steps of:
step one, 70 parts of saturated fatty acid and 30 parts of alkyl dicarboxylic acid are placed in a container, wherein the alkyl dicarboxylic acid is dodecanedioic acid, the saturated fatty acid is lauric acid, 1900 parts of absolute ethyl alcohol is added, namely the mass percent of the alkyl dicarboxylic acid in the mixed components (the saturated fatty acid and the saturated fatty acid) is controlled to be 30%, and the mixture is stirred until the mixed components are completely dissolved in the ethyl alcohol, so that the modifier with the mass percent of 5wt% is obtained;
step two, mixing and stirring water and portland cement uniformly according to the water cement ratio of 0.4, pouring the slurry into a rubber mold for molding, removing the mold after 1d, and maintaining for 7d in a natural environment;
step three, taking out the product obtained in the step two, washing the surface by using deionized water, then washing by using absolute ethyl alcohol, and drying the washed cement-based material in a drying oven at 50 ℃ for 6 hours;
and step four, immersing the obtained substance in the step three in the modifier prepared in the step two, performing immersion treatment for 6 hours, taking out the treated cement-based material substrate, cleaning the cement-based material substrate by using absolute ethyl alcohol, and drying the cement-based material substrate in a drying oven at 50 ℃ for 6 hours to obtain the cement-based material.
Example 2
A method of using a wettability-pH responsive modifier comprising the steps of:
placing 50 parts of saturated fatty acid and 50 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 (the saturated fatty acid and the 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 percent of 5 wt%;
step two, mixing and stirring water and portland cement uniformly according to the water cement ratio of 0.4, pouring the slurry into a rubber mold for molding, removing the mold after 1d, and maintaining for 7d in a natural environment;
step three, taking out the product obtained in the step two, washing the surface by using deionized water, then washing by using absolute ethyl alcohol, and drying the washed cement-based material in a drying oven at 50 ℃ for 6 hours;
and step four, immersing the obtained substance in the step three in the modifier prepared in the step two, performing immersion treatment for 6 hours, taking out the treated cement-based material substrate, cleaning the cement-based material substrate by using absolute ethyl alcohol, and drying the cement-based material substrate in a drying oven at 50 ℃ for 6 hours to obtain the cement-based material.
Example 3
A method of using a wettability-pH responsive modifier comprising the steps of:
step one, 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 (the saturated fatty acid and the 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%;
step two, mixing and stirring water and portland cement uniformly according to the water cement ratio of 0.4, pouring the slurry into a rubber mold for molding, removing the mold after 1d, and maintaining for 7d in a natural environment;
step three, taking out the product obtained in the step two, washing the surface by using deionized water, then washing by using absolute ethyl alcohol, and drying the washed cement-based material in a drying oven at 50 ℃ for 6 hours;
and step four, immersing the obtained substance in the step three in the modifier prepared in the step two, performing immersion treatment for 6 hours, taking out the treated cement-based material substrate, cleaning the cement-based material substrate by using absolute ethyl alcohol, and drying the cement-based material substrate in a drying oven at 50 ℃ for 6 hours to obtain the cement-based material.
Preparing alkaline liquid with pH =7 and pH =13 by using sodium hydroxide, sucking the two liquids by using a dropper, and respectively dropwise adding the liquids to the surface of the cement-based material treated by the modifier. The wetting conditions of the liquid drops with different pH values on the surface are shown in figure 1, the modified cement-based material substrate surface has good hydrophobic characteristics for the liquid drops with pH =7, and a 'silver mirror phenomenon' exists; while hydrophilic to the pH =13 droplet, the droplet spreads rapidly wetting out on the surface.
Comparative example 1
The remaining steps of this comparative example are the same as 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 percent 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 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 percent of the alkyl dicarboxylic acid in the mixed components (saturated fatty acid and saturated fatty acid) is controlled to be 100%.
An alkaline liquid with pH =13 was prepared by using sodium hydroxide, deionized water was used as a neutral liquid with pH =7, contact angles of the surfaces of the modifier-modified cement-based materials obtained in examples 1 to 3 and comparative examples 1 to 2 were measured with a view screen optical contact angle measuring instrument for droplets with two pH values, the sizes of the droplets were measured to be 5 μ L, and three sites were measured on each surface, and the measurement results are shown in FIG. 2. When the proportion of the alkyl dicarboxylic acid is 0% and 30%, the difference of contact angles of the cement-based material substrate to liquid drops with pH =7 and pH =13 is not obvious, and the contact angles are kept between 130 DEG and 140 DEG, and the cement-based material substrate has a hydrophobic characteristic. When the percentage of the alkyl dicarboxylic acid is 50% and 70%, the contact angles of the surface of the cement-based material substrate to the liquid drops with pH =7 and pH =13 are obviously different, the contact angle to the liquid drops with pH =7 is 115-135 degrees and is of a hydrophobic character, and the contact angle to the liquid drops with pH =13 is below 50 degrees and is of a hydrophilic character. When the alkyl dicarboxylic acid accounts for 100%, the contact angles of the cement-based material substrate to the liquid drops with the pH =7 and the pH =13 are not obviously different, and are kept to be about 20 degrees. When the alkyl dicarboxylic acid accounts for 70%, the difference of the contact angles of the two liquid drops is the largest, and the difference is 101 degrees. When the pH of the solution was < 7, the contact angle was the same as at pH = 7.
Example 4
A method of using a wettability-pH responsive modifier comprising the steps of:
placing 40 parts of saturated fatty acid and 60 parts of alkyl dicarboxylic acid in a container, 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 fraction of 4.8 wt%;
step two, mixing and stirring water and portland cement uniformly according to the water cement ratio of 0.3, pouring the slurry into a rubber mold for molding, removing the mold after 1d, and maintaining for 8d in a natural environment;
step three, taking out the product obtained in the step two, washing the surface by using deionized water, then washing by using absolute ethyl alcohol, and drying the washed cement-based material in a drying oven for 8 hours at the temperature of 45 ℃;
and step four, immersing the substance obtained in the step three in the modifier prepared in the step two, performing immersion treatment for 8 hours, taking out the treated cement-based material substrate, cleaning the cement-based material substrate by using absolute ethyl alcohol, and drying the cement-based material substrate for 7 hours at the temperature of 45 ℃ in a drying oven to obtain the cement-based material.
In this embodiment, the alkyl dicarboxylic acid may be replaced with any one of suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and 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-pH responsive modifier comprising the steps of:
placing 60 parts of saturated fatty acid and 40 parts of alkyl dicarboxylic acid in a container, adding 2000 parts of absolute ethyl alcohol, namely controlling the mass percent 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 percent of 5 wt%;
step two, mixing and stirring water and portland cement uniformly according to the water cement ratio of 0.3, pouring the slurry into a rubber mold for molding, removing the mold after 1d, and maintaining for 8d in a natural environment;
step three, taking out the product obtained in the step two, washing the surface by using deionized water, then washing by using absolute ethyl alcohol, and drying the washed cement-based material in a drying oven for 8 hours at the temperature of 45 ℃;
and step four, immersing the obtained substance in the step three in the modifier prepared in the step two, performing immersion treatment for 8 hours, taking out the treated cement-based material substrate, cleaning the cement-based material substrate by using absolute ethyl alcohol, and drying the cement-based material substrate in a drying oven at 55 ℃ for 5 hours to obtain the cement-based material.
Example 6
A cement paste sample is prepared and subjected to impregnation treatment by referring to the method of example 1, and a cement-based material with a wettability pH intelligent response function on the surface is obtained. Basic liquids with pH =8, 9, 10, 11, 12, 13 were formulated using sodium hydroxide, neutral liquids with pH =7 using deionized water, acidic liquids with pH =3, 5 were formulated using hydrochloric acid, and the surfaces of cement-based materials treated with the modifier were tested for contact angles of droplets at different pH values with reference to the method of example 1.
The results of the measurements are shown in fig. 3, and the wettability of the surface of the cement-based material substrate with 70% of alkyl dicarboxylic acid group has the stimulation response capability to the pH value. When the droplet pH is 7 or less, the contact angle is 135 ° or more, the surface exhibits hydrophobicity, when the droplet pH is more than 7, the surface contact angle gradually decreases, and when pH =12, the contact angle is 22 °, the surface exhibits hydrophilicity. The contact angle of 0% alkyl dicarboxylic acid group is always maintained at 130 ° or more, and the contact angle of 100% alkyl dicarboxylic acid group is maintained at 25 ° or less.
Example 7
A method of using a wettability-pH responsive modifier comprising the steps of:
reacting saturated fatty acid and alkyl dicarboxylic acid with excessive hydroxide solution, filtering and drying to obtain saturated fatty acid salt and alkyl dicarboxylic acid salt;
step two, 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 percent of the alkyl dicarboxylic acid salt in the mixed components to be 50%, then adding 35 ℃ water, and stirring until the saturated fatty acid salt and the alkyl dicarboxylic acid salt are completely dissolved to obtain an additive;
step three, mixing and stirring the additive, water and portland cement uniformly, pouring the slurry into a rubber mold for molding, removing the mold after 1d, and maintaining for 7 days in a natural environment, wherein the water-cement ratio is 0.3;
and step four, after maintenance, washing the cement sample by using an HCl solution with the pH value of 4, and drying at 40 ℃ to change the hydrophilicity of the cement-based material into hydrophobicity.
In this embodiment, 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, pearlitic acid, and stearic acid.
Example 8
A method of using a wettability-pH responsive modifier comprising the steps of:
reacting saturated fatty acid and alkyl dicarboxylic acid with excessive hydroxide solution, filtering and drying to obtain saturated fatty acid salt and alkyl dicarboxylic acid salt;
step two, 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 percent of the alkyl dicarboxylic acid salt in the mixed components to be 70%, then adding water at 45 ℃, and stirring until the saturated fatty acid salt and the alkyl dicarboxylic acid salt are completely dissolved to obtain an additive;
step three, mixing and stirring the additive, water and portland cement uniformly, pouring the slurry into a rubber mold for molding, removing the mold after 1d, and maintaining for 8 days in a natural environment, wherein the water-cement ratio is 0.4;
and step four, washing the cement sample by using a sulfuric acid solution with the pH value of 5 after maintenance, and drying at 45 ℃ to change the hydrophilicity of the cement-based material into hydrophobicity.
In the present embodiment, 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, pearlitic acid, and stearic acid.
Example 9
A method of using a wettability-pH responsive modifier comprising the steps of:
reacting saturated fatty acid and alkyl dicarboxylic acid with excessive hydroxide solution, filtering and drying to obtain saturated fatty acid salt and alkyl dicarboxylic acid salt;
weighing saturated fatty acid salt and alkyl dicarboxylate in proportion, placing the saturated fatty acid salt and the alkyl dicarboxylate in a container, controlling the mass percentage of the alkyl dicarboxylate in the mixed components to be 60%, adding water at 40 ℃, and stirring until the saturated fatty acid salt and the alkyl dicarboxylate are completely dissolved to obtain an additive;
step three, mixing and stirring the additive, water and portland cement uniformly, pouring the slurry into a rubber mold for molding, removing the mold after 1d, and maintaining for 7 days in a natural environment, wherein the water-cement ratio is 0.3;
and step four, washing the cement sample by using a hydrochloric acid solution with the pH value of 6 after maintenance, and drying at 45 ℃ to change the hydrophilicity of the cement-based material into hydrophobicity.
In this embodiment, 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, pearlitic acid, and stearic acid.
Example 10
A method of using a wettability-pH responsive modifier comprising the steps of:
reacting saturated fatty acid and alkyl dicarboxylic acid with excessive hydroxide solution, filtering and drying to obtain saturated fatty acid salt and alkyl dicarboxylic acid salt;
weighing saturated fatty acid salt and alkyl dicarboxylate in proportion, placing the saturated fatty acid salt and the alkyl dicarboxylate in a container, controlling the mass percent of the alkyl dicarboxylate 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 dicarboxylate are completely dissolved to obtain an additive;
step three, mixing and stirring the additive, water and portland 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 maintaining for 7 days in a natural environment;
and step four, washing the cement sample by using a hydrochloric acid solution with the pH value of 6 after maintenance, and drying at 45 ℃ to change the hydrophilicity of the cement-based material into hydrophobicity.
And (3) testing the contact angle of the clean water on the surface of the cement-based material obtained in the step three of different mixing component distribution ratios by using a screen optical contact angle measuring instrument, wherein the size of the test liquid drop is 5 mu L, each surface is tested at three points, and the measurement result is shown in figure 4. It can be seen that when the ratio of the alkyl dicarboxylate in the mixed components is 0%, the contact angle increases with the increase of the amount of the admixture, and finally reaches 120 ° or more; when the proportion of the alkyl dicarboxylate in the mixed components is 70%, the contact angle is gradually reduced after gently increasing, and the contact angle is maintained below 50 DEG, so that the mixed components are hydrophilic; when the ratio of the alkyl dicarboxylate in the mixed components is 100%, the contact angle decreases rapidly after a slight increase, and at higher contents, the contact angle cannot be measured due to strong hydrophilicity.
Example 11
A method of using a wettability-pH responsive modifier comprising the steps of:
reacting saturated fatty acid and alkyl dicarboxylic acid with excessive hydroxide solution, filtering and drying to obtain saturated fatty acid salt and alkyl dicarboxylic acid salt;
weighing saturated fatty acid salt and alkyl dicarboxylate in proportion, placing the saturated fatty acid salt and the alkyl dicarboxylate in a container, controlling the mass percentage of the alkyl dicarboxylate in the mixed components to be 70%, adding water at 40 ℃, and stirring until the saturated fatty acid salt and the alkyl dicarboxylate are completely dissolved to obtain an additive;
step three, mixing and stirring the additive, water and portland 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 maintaining for 7 days in a natural environment;
and step four, washing the cement sample by using a hydrochloric acid solution with the pH value of 5 after maintenance, and drying at 40 ℃ to change the cement-based material from hydrophilicity to hydrophobicity.
The contact angle of the surface of the cement-based material before and after the treatment of the clear water is tested by using a view screen optical contact angle measuring instrument, the size of the test liquid drop is 5 mu L, three points are tested on each surface, and the measurement result is shown in figure 5. When the ratio of the alkyl dicarboxylate in the mixed components is 70%, the cement-based material before treatment has hydrophilic characteristics, and the contact angle is kept below 40 ℃; the contact angle of the treated cement-based material is increased, and when the mixed components account for 2.0 percent of the dosage of the cementing material, the contact angle is changed from 30 degrees to 120 degrees.
Claims (10)
1. The modifier for wettability response to pH is characterized by comprising the following substances in parts by weight: 30-70 parts of alkyl dicarboxylic acid, 30-70 parts of saturated fatty acid and 1900-2000 parts of absolute ethyl alcohol, wherein the modifier can convert the hydrophilicity of the cement-based material into the hydrophobicity.
2. A wettability-responsive modifier as claimed in claim 1, wherein: the alkyl dicarboxylic acid is any one of suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and tridecanedioic acid.
3. A wettability modifier for pH response according to claim 1, wherein: the saturated fatty acid is any one of capric acid, lauric acid, myristic acid, palmitic acid, pearlescent fatty acid and stearic acid.
4. A method of using a wettability-pH-responsive modifier according to any one of claims 1 to 3, characterized by the steps of:
step one, adding saturated fatty acid and alkyl dicarboxylic acid into absolute ethyl alcohol according to the weight part ratio, and stirring until the saturated fatty acid and the alkyl dicarboxylic acid are completely dissolved to obtain a modifier;
step two, mixing and stirring water and portland cement uniformly, pouring the slurry into a rubber mold for molding, removing the mold, and maintaining 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;
and step four, immersing the substance obtained in the step three in the modifier prepared in the step one, taking out the treated cement-based material substrate, cleaning with absolute ethyl alcohol, and drying to obtain the cement-based material.
5. The method of claim 4 for using a wettability-responsive modifier, characterized in that: in the second step, the water cement ratio of water to portland cement is 0.3-0.4, and the curing time is 7-8 days.
6. The method of claim 4 for using a wettability-responsive modifier, characterized in that: in the third step, the drying temperature is 45-50 ℃, and the drying time is 6-8 h.
7. The method of claim 4 for using a wettability-responsive modifier, characterized in that: in the fourth step, the immersion time is 6-8 h, the drying temperature is 45-55 ℃, and the drying time is 5-7 h.
8. The method of claim 4, wherein said modifying agent is selected from the group consisting of: in the fourth step, the drying temperature is 45-55 ℃, and the drying time is 5-7 h.
9. A method of using a wettability-pH-responsive modifier according to any one of claims 1 to 3, comprising the steps of:
reacting saturated fatty acid and alkyl dicarboxylic acid with excessive hydroxide solution according to the weight part ratio, filtering and drying to obtain saturated fatty acid salt and alkyl dicarboxylic acid salt;
step two, controlling the mass percent of the alkyl dicarboxylate in the mixed components to be 50-70%, then adding 35-45 ℃ water, and stirring until the alkyl dicarboxylate is completely dissolved to obtain an additive;
step three, mixing and stirring the additive, water and portland cement uniformly, pouring the slurry into a rubber mold for molding, removing the mold, and maintaining in a natural environment;
and step four, washing the cement sample by using a hydrochloric acid or sulfuric acid solution with the pH value of 4-6 after maintenance, and drying at 40-50 ℃ to change the hydrophilicity of the cement-based material into hydrophobicity.
10. The method of claim 4, wherein said modifying agent is selected from the group consisting of: in the third step, the water cement ratio of water to portland cement is 0.3-0.4, and the curing time is 7-8 days.
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