CN111747716A - Modified high-strength durable natural hydraulic lime slurry and preparation method thereof - Google Patents
Modified high-strength durable natural hydraulic lime slurry and preparation method thereof Download PDFInfo
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- CN111747716A CN111747716A CN202010609638.0A CN202010609638A CN111747716A CN 111747716 A CN111747716 A CN 111747716A CN 202010609638 A CN202010609638 A CN 202010609638A CN 111747716 A CN111747716 A CN 111747716A
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- hydraulic lime
- modified high
- strength durable
- slurry
- durable natural
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/10—Lime cements or magnesium oxide cements
- C04B28/12—Hydraulic lime
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
- C04B24/122—Hydroxy amines
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Abstract
A modified high-strength durable natural hydraulic lime slurry and a preparation method thereof comprise the following components: hydraulic lime: 93.6 to 99.9 percent; triethanolamine: 0.1% -7.4%; the balance of water; the preparation method comprises the following steps of 1, weighing a certain amount of hydraulic lime according to a proportion, slowly stirring for 2-3 min while gradually adding water, then dropwise adding a proper amount of triethanolamine, slowly stirring for 1-3 min, then quickly stirring for 30-90 s, pausing for 1-2 min, scraping off mortar on the inner wall of a stirrer, and then continuously stirring to uniformly disperse the mortar; obtaining modified high-strength durable natural hydraulic lime slurry; and 2) pouring the modified high-strength durable natural hydraulic lime slurry obtained in the step 1) into a 40 x 40 mm mold, scraping off redundant slurry, drying a sample placed in the mold for 24 hours in an atmospheric environment, demolding, and placing the sample into a constant-temperature constant-humidity curing box with the temperature of 20 ℃ and the relative humidity of 60-70% for curing. The modification aims to improve the service life, the mechanical property, the fluidity and the setting time of the ancient cultural relics in the ancient building cultural relics restoration.
Description
Technical Field
The invention belongs to the technical field of modified materials, and particularly relates to modified high-strength durable natural hydraulic lime slurry and a preparation method thereof, which are applied to building construction and cultural relic protection.
Background
Lime, as a traditional binding material, has a long history and is widely applied to the field of building and cultural relic protection. However, the traditional lime material has limited application range in the protection and repair of ancient architecture cultural relics due to the defects of low early strength, slow setting time, poor durability and the like. With the continuous development of scientific technology, hydraulic lime (NHL 2, wherein the calcium-silicon ratio is about 2) is developed and gradually replaces the traditional air hardening lime, the hydraulic ingredient is increased on the basis of retaining the air hardening ingredient of the lime body, and meanwhile, the hydraulic lime has good compatibility with ancient building materials, and the hydraulic lime has attracted extensive attention in the field of cultural relic protection.
As is known to all, immovable cultural relics (such as ancient buildings, stone cultural relics, earthen sites and the like) are influenced by external natural factors such as temperature difference, sunlight, wind erosion, acid rain, freeze thawing and the like for a long time, so that diseases such as surface layer weathering, salting out, cracks and even shedding are easy to occur, the stability of the cultural relics is reduced, and the service life is shortened. The natural hydraulic lime as a hydraulic inorganic cementing material has the advantages of high mechanical strength, high curing speed, good water resistance and corrosion resistance and the like, can be used in a dry environment, can adapt to a humid environment or underwater engineering, and can meet the condition that the cultural relic environment is changeable. However, in the practical application process, the requirements of further modification and optimization in the aspects of strength, coagulation time, volume stability, freeze-thaw cycle resistance and the like are found.
In recent years, the modification of natural hydraulic lime has received much attention from researchers. In 2017, M.Marbarbero-Barrera (Barbero-Barrera, M.M., N.Flores mediaa, and C.Guardia-Martini. infiluence of the addition of water graphite powder on the physical and pharmaceuticalrostructural performance of hydraulic lime pastes[J]Construction and meeting Materials, 2017, 149: 599-. Subsequently, Kai Luo in 2019 (Luo, K., et al. Effect of nano-SiO)2on early hydration of natural hydrauliclime[J]Construction and Building Materials, 2019, 216: 119-2The early hydration performance of the hydraulic lime is modified and researched, and the hydration process of the hydraulic lime is improved by controlling the volcanic ash reaction, so that the mechanical property of the hydraulic lime is improved. Adding nanometer SiO when the age is 28 days2The strength of the sample can reach 3.6 MPa.
Although the work of modifying natural hydraulic lime has been continuously carried out, it still has disadvantages in compressive strength, setting time, fluidity, and the like. And the Triethanolamine (TEA) has good dispersibility on inorganic particles, can reduce agglomeration, shorten setting time and improve the fluidity and mechanical property of slurry. Triethanolamine is widely used in cement modification and other aspects as a reinforcing agent and a water reducing agent. The influence of triethanolamine on the performance of cement is researched by Xiao jie Yang (Yang, X., et al, Effect of triethanolamine hydrochloride on the performance of cement [ J ]. constraint and materials 2019, 200: 218-225.) the research finds that the triethanolamine can shorten the setting time of cement, improve the early strength and has obvious modification Effect. However, the modification of the triethanolamine on the natural hydraulic lime body is not reported, and how to modify the hydraulic lime and reduce the cost to the maximum extent and achieve ideal service strength and durability is the key point of the invention and is also the key point of future research in the field of ancient cultural relic restoration and protection.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the modified high-strength durable natural hydraulic lime slurry and the preparation method thereof, and the hydraulic lime slurry is modified by adding the triethanolamine small molecular material, so that the service life, the mechanical property, the fluidity, the setting time and the like of the hydraulic lime slurry in ancient building cultural relic restoration are improved. The slurry has the advantages of simple modification preparation method, low cost, obvious effect, safety and environmental protection.
In order to achieve the purpose, the invention adopts the technical scheme that:
the modified high-strength durable natural hydraulic lime slurry comprises the following components in parts by mass:
hydraulic lime: 93.6 to 99.9 percent;
triethanolamine: 0.1% -7.4%;
the balance of water.
The ratio of the water to the hydraulic lime is 0.5-0.7.
A preparation method of modified high-strength durable natural hydraulic lime slurry comprises the following steps:
and 2) pouring the modified high-strength durable natural hydraulic lime slurry obtained in the step 1) into a 40 x 40 mm mold, scraping off redundant slurry, drying a sample placed in the mold for 24 hours in an atmospheric environment, demolding, placing the sample into a constant-temperature and constant-humidity curing box with the temperature of 20 ℃ and the relative humidity of 60-70% for curing, and performing performance tests such as microstructure characterization, volume density, compressive strength and the like after the curing age is over.
The invention has the beneficial effects that:
the modified natural hydraulic lime mortar prepared by the invention has the advantages that the price of the modified substance triethanolamine is low, the source is wide, and the obvious modification effect can be achieved by adding a small amount of the triethanolamine. In the hybrid structure, the triethanolamine has good dispersibility and hydration performance, and generates a synergistic effect with gas/hydraulic components of hydraulic lime, so that the slurry has higher strength, shorter setting time and excellent fluidity. In addition, the invention has the advantages of simple preparation process, low cost of modified substances, stable process, strong repeatability, no corrosion to cultural relics and good application prospect in the fields of buildings and cultural relic protection.
Drawings
FIG. 1 is a volume density plot of NHL2 for different TEA loadings according to the present invention.
FIG. 2 is a graph of compressive strength of NHL2 for different amounts of TEA of the present invention
FIG. 3 is a graph of the set time for NHL2 with different TEA loadings according to the present invention.
FIG. 4 is a 5000-fold magnified micro-topography effect plot of various 28 d-old TEA-NHL2 samples according to an example of the present invention.
FIG. 5 is a 10000-fold SEM control spectrum of a TEA-NHL2 sample aged 28d according to example of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
Examples
Grouping triethanolamine with parameters of 0%, 0.3%, 0.6%, 1%, 3%, and 5%, wherein 0% is control group.
The modified high-strength durable natural hydraulic lime slurry comprises the following components in parts by mass: hydraulic lime: 93.6 to 99.9 percent; triethanolamine: 0.1% -7.4%; the balance of water. The five materials are prepared according to the following steps:
and 2) pouring the modified high-strength durable natural hydraulic lime slurry obtained in the step 1) into a 40 x 40 mm mold, scraping off redundant slurry, drying a sample placed in the mold for 24 hours in an atmospheric environment, demolding, and placing the sample into a constant-temperature constant-humidity curing box with the temperature of 20 ℃ and the relative humidity of 60-70% for curing.
Five groups of experimental samples of N0, N1, N2, N3, N4 and N5 are obtained, and the performance tests of microstructure characterization, volume density, compressive strength and the like are carried out after the curing age is over.
In summary, the following steps:
the volume density of NHL2 for different TEA loadings is shown in fig. 1, where it can be seen that NHL2 is the most dense in group N3. The volume density is maximum, and the compactness is good.
The compressive strength of NHL2 with different TEA contents is shown in FIG. 2, and it can be seen that the compressive strength of NHL2 is the greatest in group N3. The strength of the modified hydraulic lime is improved within a certain range compared with that of a blank sample, and can reach 84 percent at most.
The coagulation time of NHL2 with different TEA loadings is shown in fig. 3, from which it can be seen that the coagulation time is fastest for group N3.
As shown in fig. 4, where fig. 4a is a blank sample of N0, fig. 4b is N2, fig. 4c is N3, and fig. 4d is N4, the morphology of TEA-free hydraulic lime is much different from the morphology after incorporation. The cured 28d hydraulic lime slurry becomes finer with the increase of the TEA content, has compact structure, small porosity and higher homogenization degree. Group N3, the hydraulic lime sample with 1% TEA was most pronounced (FIG. 4 c). However, when the amount is more than 1%, the hydraulic lime sample has large-scale voids and cavities, the density decreases, and the particle size increases (see fig. 4 d). The change in microstructure can further have a significant effect on mechanical properties.
As can be seen from fig. 5, SEM pictures of blank N0 and optimal sample N3, the sample with TEA incorporated produced more acicular and network-like material than the blank, exhibiting a developed network structure.
The five groups of data show that when the age is 28 days, the compressive strength of the hydraulic lime paste added with triethanolamine can reach 4-4.6 MPa, the compressive strength of the hydraulic lime paste with the age of 56 days can reach 5.4-6.9 MPa, and the compressive strengths of different ages are respectively improved by 60% -84% and 23% -57% compared with that of a blank sample.
Claims (3)
1. The modified high-strength durable natural hydraulic lime slurry is characterized by comprising the following components in parts by mass:
hydraulic lime: 93.6 to 99.9 percent;
triethanolamine: 0.1% -7.4%;
the balance of water.
2. The modified high-strength durable natural hydraulic lime mud of claim 1, wherein the ratio of water to hydraulic lime is 0.5-0.7.
3. A preparation method of modified high-strength durable natural hydraulic lime slurry is characterized by comprising the following steps:
step 1, weighing a certain amount of hydraulic lime according to a proportion, slowly stirring for 2-3 min while gradually adding water, then dropwise adding a proper amount of triethanolamine, slowly stirring for 1-3 min, then quickly stirring for 30-90 s, pausing for 1-2 min, scraping off mortar on the inner wall of a stirrer, and then continuously stirring to uniformly disperse the mortar; obtaining modified high-strength durable natural hydraulic lime slurry;
and 2) pouring the modified high-strength durable natural hydraulic lime slurry obtained in the step 1) into a 40 x 40 mm mold, scraping off redundant slurry, drying a sample placed in the mold for 24 hours in an atmospheric environment, demolding, placing the sample into a constant-temperature and constant-humidity curing box with the temperature of 20 ℃ and the relative humidity of 60-70% for curing, and performing performance tests such as microstructure characterization, setting time, volume density, compressive strength and the like after the curing age is over.
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| CN202010609638.0A CN111747716A (en) | 2020-06-30 | 2020-06-30 | Modified high-strength durable natural hydraulic lime slurry and preparation method thereof |
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| CN202010609638.0A CN111747716A (en) | 2020-06-30 | 2020-06-30 | Modified high-strength durable natural hydraulic lime slurry and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829201A (en) * | 2015-04-21 | 2015-08-12 | 东南大学 | Protection brick and stone ancient building repair lime bonding material |
| CN105272094A (en) * | 2015-10-01 | 2016-01-27 | 北京国文琰文化遗产保护中心有限公司 | Modified hydraulic lime based material and preparation method thereof |
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- 2020-06-30 CN CN202010609638.0A patent/CN111747716A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829201A (en) * | 2015-04-21 | 2015-08-12 | 东南大学 | Protection brick and stone ancient building repair lime bonding material |
| CN105272094A (en) * | 2015-10-01 | 2016-01-27 | 北京国文琰文化遗产保护中心有限公司 | Modified hydraulic lime based material and preparation method thereof |
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Application publication date: 20201009 |