Preparation method and application of cement-based compact and hydrophobic integrated material
By acclimating Bacillus coli and Bacillus pasteurellii to improve their alkali tolerance and through the synergistic effect of Bacillus subtilis biofilm, calcium carbonate precipitate and micro-protrusion structure are formed on the surface of cement-based materials, solving the problem of hydrophobic and dense integration of cement-based materials and improving their durability and corrosion resistance.
Patent Information
- Application Number
- CN202511123034.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-12
- Publication Date
- 2025-11-07
AI Technical Summary
Existing technologies cannot achieve a hydrophobic and dense integrated surface layer on cement-based materials, and cannot effectively inhibit the transmission and corrosion of corrosive media such as moisture and ions, thus affecting the durability of concrete infrastructure.
Alkali tolerance was acclimated by Bacillus coli and Bacillus pasteurellii, and combined with Bacillus subtilis biofilm. By controlling the sequential resuscitation of microorganisms, calcium carbonate precipitate and micro-protrusion structure were formed on the surface of cement-based materials, achieving hydrophobic and dense effects.
It significantly improves the hydrophobicity and density of cement-based materials, inhibits the erosion of corrosive media, and has the advantages of simple operation, environmental friendliness, lightweight, wear resistance, and rapid effect.
Smart Images
Figure CN120905080A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application relates to a preparation method of a repair material and application thereof, in particular to a preparation method of a cement-based dense and hydrophobic integrated material and application thereof. BACKGROUND
[0002] Concrete durability degradation is a key bottleneck problem restricting the service life of concrete infrastructure, and the transmission corrosion of erosion media such as water and ions is the main way leading to durability degradation.
[0003] In some existing methods, there is a research on repairing concrete cracks by using microbial mineralization, but in addition to repair, the hydrophobic dense integration of the surface layer of the cement-based material cannot be achieved by the subsequent recovery of various microorganisms. SUMMARY
[0004] The purpose of the present application is to provide a preparation method of a cement-based dense and hydrophobic integrated material, and the obtained cement-based dense and hydrophobic integrated material can not only repair the cement-based material, but also make the cement-based material realize hydrophobicity and densification, so as to greatly inhibit the erosion of erosion media.
[0005] The second purpose of the present application is to provide the application of the cement-based dense and hydrophobic integrated material obtained by the above method.
[0006] Technical scheme: The preparation method of the cement-based dense and hydrophobic integrated material provided by the present application comprises the following steps:
[0007] (1) Bacillus cohnii and Bacillus pasteurii are inoculated into culture solution for expansion culture, and then subjected to alkali resistance domestication; after domestication, the bacterial strains are obtained by centrifugation, and then dispersed in the corresponding culture solution to obtain domesticated Bacillus cohnii bacterial solution and Bacillus pasteurii bacterial solution;
[0008] (2) A nitrogen source, a yeast extract, a calcium source and a sugar source are mixed with the Bacillus cohnii culture solution and the Bacillus pasteurii culture solution to obtain a microbial repair nutrient solution;
[0009] (3) Bacillus subtilis is inoculated into culture solution for expansion culture, and a Bacillus subtilis biofilm is formed during the culture process to obtain a Bacillus subtilis bacterial solution; the Bacillus subtilis bacterial solution is irradiated under UV-C ultraviolet light to make the Bacillus subtilis lose the ability to reproduce while retaining the Bacillus subtilis biofilm, and an inactivated Bacillus subtilis bacterial solution is obtained;
[0010] (4) adding the Bacillus subtilis inactivated bacteria solution obtained in step (3) and the two kinds of bacteria solutions obtained in step (1) into the microbial repair nutrient solution obtained in step (2) for culture, so that the Bacillus subtilis biofilm is coated on the surface of the Bacillus cohnii and the Bacillus pasteurii, and a cement-based dense and hydrophobic integrated material is obtained.
[0011] In step (1), glycerol is added into the obtained two kinds of bacteria solutions in an equal volume of the bacteria solutions for preservation.
[0012] In step (2), the components of the Bacillus cohnii culture solution include beef extract 3.0±0.1 g, peptone 10.0±0.1 g, sodium chloride 5.0±0.1 g, and distilled water 1000±1 g, and the pH of the culture solution is 7.0 and sterilized at 121° for 15 min; the components of the Bacillus pasteurii culture solution include beef extract 3.0±0.1 g, peptone 5.0±0.1 g, urea 20±0.1 g, and distilled water 1000±1 g, and the pH of the culture solution is 7.3 and sterilized at 121° for 15 min.
[0013] In step (3), the culture solution is a Bacillus subtilis culture solution, and the components of the culture solution include beef powder 3.0±0.1 g, peptone 10.0±0.1 g, sodium chloride 5.0±0.1 g, and distilled water 1000±1 g, and the pH of the culture solution is 7.3 and sterilized at 121° for 15 min.
[0014] The mass ratio of the nitrogen source, the yeast extract, the calcium source, the sugar source, the Bacillus subtilis inactivated bacteria solution, the Bacillus cohnii culture solution, and the Bacillus pasteurii culture solution is (4-6):(0.8-1.2):(3-5):(2-4):(8-12):(14-16):(14-16); the nitrogen source is preferably urea, and the sugar source is preferably glucose.
[0015] In step (4), the mass ratio of the microbial repair nutrient solution to the total mass of the two kinds of bacteria solutions obtained in step (1) is 18:1-22:1.
[0016] The cement-based dense and hydrophobic integrated material obtained by the above method is used to repair the concrete, and the cement-based test piece to be repaired is soaked in the cement-based dense and hydrophobic integrated material obtained by the above method, or the cement-based dense and hydrophobic integrated material obtained by the above method is sprayed on the cement-based test piece to be repaired.
[0017] The wear-resistant super-hydrophobic material is sprayed on the cement-based test piece to be repaired; preferably, the model of the wear-resistant super-hydrophobic material is wear-resistant super-hydrophobic XN-204.
[0018] Invention principle: The invention utilizes the mineralization effect of two different Bacillus in succession to realize the pore densification and surface hydrophobic effect of porous cement-based materials. The synergistic mechanism of the two Bacillus is as follows: Bacillus cohnii and Bacillus pasteurii are respectively subjected to alkali resistance domestication, and Bacillus subtilis biofilm is used to improve the stress resistance of the two mineralization strains. The strength of the alkali resistance is used to control the resuscitation of the two microorganisms in succession, so as to achieve the effect of densification first and then improvement of hydrophobic effect. Among them, the alkali resistance of Bacillus cohnii is stronger, and on the surface of cement (alkaline), Bacillus cohnii resuscitates first, produces carbon dioxide through aerobic respiration, and combines with Ca 2+ Under the alkaline environment, calcium carbonate precipitate is produced to block the pores. At the same time, with the production of precipitate, OH - When the pH decreases to a certain extent, the pore blocking of Bacillus cohnii is completed, and Bacillus pasteurii resuscitates to consume urea to continue to produce calcium carbonate, forming a micro-convex structure on the surface of cement to improve the hydrophobic effect.
[0019] Beneficial effects: Compared with the prior art, the present invention has the following remarkable effects:
[0020] (1) The present invention effectively realizes the organic combination of multiple microorganisms by the alkali resistance strength of Bacillus cohnii and Bacillus pasteurii, and introduces Bacillus subtilis biofilm to increase the protection of microorganisms, greatly improve the mineralization efficiency, and improve the surface hydrophobic densification effect of cement-based materials, thereby greatly inhibiting the erosion of erosion medium.(2) The cement-based densification and hydrophobic integrated material using the present invention has the advantages of simple operation, environmental friendliness, light weight, wear resistance, quick effect, etc., and can be used to repair the damaged surface of concrete to realize the surface hydrophobic densification integrated gain. BRIEF DESCRIPTION OF DRAWINGS
[0021] Figure 1 The pore blocking effect of different microbial repair liquids of example 1 and comparative examples 1-4;
[0022] Figure 2 The hydrophobic effect of different microbial repair liquids of example 1 and comparative examples 1-4;
[0023] Figure 3 The enhancement effect of microbial repair liquids of example 1 and comparative examples 1-4 in various environments. DETAILED DESCRIPTION
[0024] The present invention will be further described below.
[0025] Example 1
[0026] A preparation method of a concrete surface hydrophobic densification integrated material, comprising the following steps:
[0027] (A1) Bacillus cohnii and Bacillus pasteurii freeze-dried powder were activated by dissolving in standard culture solution with pH = 7 respectively, and incubated in constant temperature water bath at 30℃ for 1 day, then inoculated in the corresponding newly prepared standard culture solution for secondary activation. The components of Bacillus cohnii standard culture solution include: beef extract 3.0 g, peptone 10.0 g, sodium chloride 5.0 g, distilled water 1000 g; the culture solution pH = 7.0, 121° sterilization for 15 min. The components of Bacillus pasteurii standard culture solution include: beef extract 3.0 g, peptone 5.0 g, urea 20 g, distilled water 1000 g; the culture solution pH = 7.0, 121° sterilization for 15 min, pH = 7.3, 121° sterilization for 15 min.
[0028] (A2) 3.0 g beef extract, 10.0 g peptone, 5.0 g NaCl, 20 g urea were put into a beaker, 1.0 L distilled water was added and stirred uniformly, then it was divided into 7 parts, and the pH was adjusted to 7, 8.5, 9.5, 9.5, 10, 10.5, 11 with 1 mol / L sodium hydroxide solution in turn, and sterilized in a high-pressure steam sterilization pot at 120℃ for 20 min to obtain sterile culture solution, which was cooled to room temperature for standby use.
[0029] (A3) The Bacillus cohnii and Bacillus pasteurii strains activated twice in step (1) were gradient acclimated with the sterile culture solution of step (A2), and the specific process was as follows:
[0030] The activated Bacillus cohnii was inoculated into the culture solution with pH = 9.5, incubated in constant temperature water bath at 30℃ for 1 day, then inoculated into the culture solution with pH = 10.5, and incubated for 1 day, then inoculated into the culture solution with pH = 11 for acclimation, and the strain was taken out after acclimation was completed;
[0031] The activated Bacillus pasteurii was inoculated into the culture solution with pH = 8.5, incubated in constant temperature water bath at 30℃ for 1 day, then inoculated into the culture solution with pH = 9.5, and incubated for 1 day, then inoculated into the culture solution with pH = 10 for acclimation, and the strain was taken out after acclimation was completed;
[0032] The two strains acclimated were centrifuged to obtain bacterial slurry, which was diluted to OD600 value of 0.8 with the corresponding culture solution prepared above, and an equal amount of glycerol was added for cold storage, to obtain Bacillus cohnii and Bacillus pasteurii bacterial liquid after acclimation.
[0033] (A4) The Bacillus subtilis freeze-dried powder is dissolved in a standard culture solution with pH = 7 to activate, and is cultured in a constant temperature water bath at 30℃ for 1 day, then is inoculated into a newly prepared Bacillus subtilis standard culture solution to perform secondary activation, and then the Bacillus subtilis strain after secondary activation is inoculated into a newly prepared Bacillus subtilis standard culture solution to culture, and the Bacillus subtilis gradually forms a Bacillus subtilis biofilm when cultured and proliferated in the standard culture solution. The obtained Bacillus subtilis bacterial solution is irradiated under ultraviolet light with a wavelength of 254 nm, and the irradiation dose is 30 mJ / cm 2 The ultraviolet irradiation kills the Bacillus subtilis without damaging the biofilm, and an inactivated Bacillus subtilis bacterial solution is obtained.
[0034] The Bacillus subtilis standard culture solution comprises beef powder 3.0 g, peptone 10.0 g, sodium chloride 5.0 g, and distilled water 1000 g. The culture solution has pH = 7.3 and is sterilized at 121° for 15 min.
[0035] (A5) 100 g of urea, 20 g of yeast extract, 80 g of calcium lactate, 60 g of glucose, 300 g of Clostridium standard culture solution, and 300 g of Bacillus pasteurii standard culture solution are mixed in a beaker to obtain a microbial repair nutrient solution.
[0036] (A6) 1 mL of the Clostridium bacterial solution and 1 mL of the Bacillus pasteurii bacterial solution after domestication in step (3) are added to the microbial repair nutrient solution in an ultrasonic environment, and are ultrasonically stirred to make the Bacillus subtilis biofilm coat the surfaces of the Clostridium and the Bacillus pasteurii, thereby obtaining a cement-based dense and hydrophobic integrated material.
[0037] The above-prepared cement-based dense and hydrophobic integrated material is applied to repair a cement-based material in the following specific process:
[0038] (B1) First, a cement paste test piece with a size of 20 mm and a water-binder ratio of 0.5 is prepared, and is taken out after curing for 7 days and is dried at 80℃ for 1 day.
[0039] (B2) The cement-based dense and hydrophobic integrated material obtained after ultrasonic stirring in step (A6) is placed in the dried cement paste test piece, and the ultrasonic stirring is stopped after 2 min.
[0040] (B3) The test piece after stopping the ultrasonic stirring is continuously soaked in the microbial repair nutrient solution obtained in step (A5), and is taken out after soaking and repairing for 7 days, is rinsed with running water for 1 min, and is dried at 80℃ for 1 day.
[0041] (B4) Wear-resistant super-hydrophobic XN-204 was diluted with an equal amount of butyl acetate to obtain an XN-204 butyl acetate solution, and the dried test piece was soaked in the XN-204 butyl acetate solution for 10 min, and then taken out and dried at 120°C for 30 min.
[0042] Example 2
[0043] Different from Example 1, the mass ratio of urea, yeast extract, calcium lactate, glucose, Bacillus subtilis inactivated bacteria solution, Bacillus cohnii culture solution, and Bacillus pasteurii culture solution was 4:0.8:3:2:8:14:14.
[0044] Example 3
[0045] Different from Example 1, the mass ratio of urea, yeast extract, calcium lactate, glucose, Bacillus subtilis inactivated bacteria solution, Bacillus cohnii culture solution, and Bacillus pasteurii culture solution was 6:1.2:5:4:12:16:16.
[0046] Example 4
[0047] Different from Example 1, the mass ratio of the microbial repair nutrient solution to the total mass of the two obtained bacterial solutions was 18:1.
[0048] Example 5
[0049] Different from Example 1, the mass ratio of the microbial repair nutrient solution to the total mass of the two obtained bacterial solutions was 22:1.
[0050] Comparative Example 1
[0051] Without adding Bacillus pasteurii and Bacillus subtilis, the other conditions were the same as in Example 1.
[0052] Comparative Example 2
[0053] Without adding Bacillus cohnii and Bacillus subtilis, the other conditions were the same as in Example 1.
[0054] Comparative Example 3
[0055] Without adding Bacillus subtilis, the other conditions were the same as in Example 1.
[0056] Comparative Example 4
[0057] Without adding Bacillus cohnii, Bacillus pasteurii, and Bacillus subtilis, the other conditions were the same as in Example 1.
[0058] From Figure 1It can be seen that the alkali-tolerant Bacillus cohnii and Bacillus pasteurii have a repairing effect on the pores of the cement-based test piece. Among them, the repairing effect of Bacillus cohnii is stronger than that of Bacillus pasteurii, because Bacillus cohnii is more suitable for an alkaline environment and can produce more precipitates; at the same time, it can be seen from the test data of Comparative Examples 1 and 2 that under the synergistic effect of the two kinds of Bacillus, the repairing effect on the pores will be obviously improved, and it can be seen from the test data of Comparative Examples 1, 2 and 3 that under the assistance of Bacillus subtilis biofilm, the repairing effect is further improved, and compared with pure Bacillus cohnii, the water absorption rate is reduced by 65.7% under the synergistic repair.
[0059] From Figure 2 It can be seen that the un-repaired pores will attract small water droplets, causing the water droplets at the bottom to spread around, resulting in a decrease in the contact angle. The repair liquid can not only block the pores on the surface of the cement-based material to reduce the occurrence of capillary phenomenon, but also can create nano-particle protrusions on the surface of the cement-based material to form an air layer between the water droplets and the surface of the test piece, thereby providing hydrophobic effect from two aspects and greatly improving the hydrophobic performance of the test piece. Among them, Bacillus cohnii has a more significant pore blocking effect, and Bacillus pasteurii has a better ability to create nano-particle protrusions, and the combination of the two can achieve super-hydrophobicity of the cement-based test piece.
[0060] From Figure 3 It can be seen that the decrease in water absorption rate means the decrease in porosity, so the compressive strength will increase. Bacillus cohnii is stronger than Bacillus pasteurii in terms of pore blocking effect, so the compressive strength of the test piece repaired by Bacillus cohnii will be higher.
Claims
1. A method for preparing a cement-based material with integrated density and hydrophobicity, characterized in that, Comprise the following steps: (1) Bacillus cohnii and Bacillus pasteurii are inoculated into culture solution respectively for expansion culture, and then subjected to alkali tolerance domestication. After domestication, the strains are taken out, centrifuged to obtain bacterial slurry, and then dispersed in corresponding new culture solution respectively to obtain domesticated Bacillus cohnii and Bacillus pasteurii culture solution; (2) The nitrogen source, yeast extract, calcium source and sugar source are mixed with the Bacillus cohnii culture solution and the Bacillus pasteurii culture solution to obtain a microbial repair nutrient solution; (3) Bacillus subtilis is inoculated into Bacillus subtilis culture solution for expansion culture, and a Bacillus subtilis biofilm is formed during the culture process to obtain a Bacillus subtilis culture solution. The Bacillus subtilis culture solution is irradiated under UV-C ultraviolet light to make the Bacillus subtilis lose the ability to reproduce while retaining the Bacillus subtilis biofilm, thereby obtaining an inactivated Bacillus subtilis culture solution; (4) The inactivated Bacillus subtilis culture solution obtained in step (3) and the two culture solutions obtained in step (1) are added to the microbial repair nutrient solution obtained in step (2) for culture, so that the Bacillus subtilis biofilm is coated on the surface of Bacillus cohnii and Bacillus pasteurii to obtain a cement-based dense and hydrophobic integrated material.
2. The method for preparing the cement-based dense hydrophobic integrated material according to claim 1, characterized in that, In step (4), the mass ratio of the microbial repair nutrient solution to the total mass of the two culture solutions obtained in step (1) is 18:1-22:
1.
3. The method for preparing the cement-based dense hydrophobic integrated material according to claim 1, characterized in that, The mass ratio of the nitrogen source, yeast extract, calcium source, sugar source, inactivated Bacillus subtilis culture solution, Bacillus cohnii culture solution and Bacillus pasteurii culture solution is (4-6):(0.8-1.2):(3-5):(2-4):(8-12):(14-16):(14-16).
4. The method for preparing the cement-based dense hydrophobic integrated material according to claim 1, characterized in that, In step (3), the dose of the ultraviolet irradiation is 10-50 mJ / cm 2 .
5. The method for preparing the cement-based dense hydrophobic integrated material according to claim 1, characterized in that, In step (2), the components of the Bacillus cohnii culture solution include: beef extract 3.0±0.1 g, protein peptone 10.0±0.1 g, sodium chloride 5.0±0.1 g, and distilled water 1000±1 g; the components of the Bacillus pasteurii culture solution include: beef extract 3.0±0.1 g, protein peptone 5.0±0.1 g, urea 20±0.1 g, and distilled water 1000±1 g.
6. The method for preparing the cement-based dense hydrophobic integrated material according to claim 1, characterized in that, In step (3), the culture solution is Bacillus subtilis culture solution, and the components thereof include: beef powder 3.0±0.1 g, protein peptone 10.0±0.1 g, sodium chloride 5.0±0.1 g, and distilled water 1000±1 g.
7. The method for preparing the cement-based dense hydrophobic integrated material according to claim 1, characterized in that, In step (1), an equal volume of glycerol is added to each of the obtained two culture solutions for preservation.
8. Use of the cement-based dense and hydrophobic integrated material obtained by the method of claim 1 in repairing cement-based materials.
9. Use according to claim 8, characterized in that, The cement-based test piece to be repaired is soaked in the cement-based dense and hydrophobic integrated material obtained by the method of claim 1, or the cement-based dense and hydrophobic integrated material obtained by the method of claim 1 is sprayed on the cement-based test piece to be repaired.
10. The use of claim 8, wherein The wear-resistant super-hydrophobic material is sprayed on the cement-based test piece to be repaired.