CN112175424B - Solution for protecting stone cultural relics, preparation method and application thereof - Google Patents
Solution for protecting stone cultural relics, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a barium hydroxide solution for protecting stone cultural relics, a preparation method and application thereof, and belongs to the field of stone cultural relic protection. Barium salt, organic base, penetrating agent and perfluoro coupling agent are used as solute to be dissolved in mixed solvent of isopropanol and deionized water to obtain barium hydroxide solution. According to the invention, the perfluorinated coupling agent is subjected to hydrophobic and oleophobic treatment on the stone cultural relic, so that the corrosion effect of the stone cultural relic by acid rain is reduced, and the generated crosslinking effect can play a role in reinforcing the weathered stone cultural relic; the barium salt permeating into cracks of the stone cultural relic reacts with carbon dioxide to generate barium carbonate which can play a role in reinforcing and filling gaps; the added penetrant can make barium salt penetrate into the deeper part of the stone cultural relic. The method has the characteristics of safety, high efficiency, simple process, large-scale application potential and the like, and is suitable for the fields of stone cultural relic protection and the like.
Description
Technical Field
The invention belongs to the field of stone cultural relic protection, and particularly relates to a barium hydroxide solution for stone cultural relic protection, and a preparation method and application thereof.
Background
The stone cultural relics are naturally weathered and deteriorated to different degrees due to human factors and natural factors, particularly the weathering of the outdoor stone cultural relics is more serious, the stability of the stone cultural relics can be improved through reinforcement, and the service life of the cultural relics is prolonged. Among them, inorganic reinforcing materials have been widely used before the nineteenth century, and most of the inorganic reinforcing agents are used for forming a barrier layer or a substitute layer by filling stone pores through condensation of salt in a solution or a chemical reaction with stone. The inorganic reinforcing materials commonly used internationally are: lime water, barium hydroxide, alkaline earth silicate, fluorosilicate and the like. For example, the barium hydroxide is used for reinforcing limestone, and barium carbonate solid is generated by the action of barium hydroxide and carbon dioxide in air and filled between pores of limestone to reinforce the stone cultural relics.
The other is polymer, which is very commonly applied in the reinforcement and sealing of stone cultural relics and ancient buildings, and mainly comprises epoxy resin, acrylic resin and organic silicon resin. The epoxy resin contains benzene ring and ether bond, so that it has strong chemical solvent resistance and certain resistance to acid, alkali and organic solvent. Meanwhile, the adhesive contains hydroxyl, ether bond, amino and other polar genes, has high adhesive force to the stone cultural relics, has ideal effect, and can change color after long-term use. Acrylic resin is widely used in the paint industry due to its good chemical stability, heat resistance, weather resistance, etc., but its water resistance is poor, thus limiting its application in the protection of stone cultural relics. Among organic polymers for protecting stone cultural relics, the organic silicon resin has relatively good permeability, hydrophobicity and weather resistance, so that the organic silicon resin not only has a reinforcing effect, but also has waterproof performance, but also needs high-temperature curing, thereby limiting the application occasions of the organic silicon resin.
Disclosure of Invention
The purpose of the invention is as follows: provides a barium hydroxide solution for protecting stone cultural relics, a preparation method and application thereof, which aim to solve the problems involved in the background technology.
The technical scheme is as follows: a barium hydroxide solution for protecting stone cultural relics is prepared by dissolving barium salt, organic alkali, penetrant and perfluoro coupling agent as solute in mixed solvent of isopropanol and deionized water to obtain barium hydroxide solution. Wherein, the components comprise, by mass, 40-60 parts of isopropanol, 40-60 parts of water, 8-15 parts of barium salt, 0.8-1.5 parts of organic base, 0.05-0.5 part of penetrating agent and 0.05-1.5 parts of perfluoro coupling agent.
In a further implementation process, the barium salt is at least one of barium chloride, barium nitrate and barium acetate.
In a further implementation process, the organic base is at least one of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, monomethylamine, monoethylamine, monopropylamine, dimethylamine and diethylamine.
In the further implementation process, the penetrating agent is at least one of fatty alcohol-polyoxyethylene ether, nonylphenol polyoxyethylene ether and polyether modified silicone oil.
In a further embodiment, the perfluoro coupling agent is at least one of tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane.
In further embodiments, the perfluorinated coupling agent has the structural formula:
Wherein R is a fluoroalkyl chain with a carbon chain length of 6-10, and is selected from one of nonafluorohexyl, undecafluoroheptyl, tridecafluorooctyl, pentadecafluorononyl and heptadecafluorodecyl; x is any integer of 1-7; y is any integer of 1 to 3.
The invention also provides a preparation method of the barium hydroxide solution for protecting the stone cultural relics, which comprises the following steps: adding barium salt into a solvent consisting of isopropanol and deionized water, stirring for 0.5-3 h, adding an organic base and a penetrating agent, adjusting the pH to be more than 7, adding a perfluoro coupling agent, and stirring for 0.5-3 h to obtain a barium hydroxide solution.
The invention also provides an application of the barium hydroxide solution for protecting the stone cultural relics in reinforcing and sealing the stone cultural relics, and the using method comprises the following steps: cleaning the sandstone stone block with a wool brush, then uniformly brushing the barium hydroxide solution on the surface of the sandstone stone block, standing for 16-24 hours to enable the sandstone stone block to fully absorb the material, then brushing the barium hydroxide solution for the second time, and standing for 2-3 days.
Has the advantages that: the invention relates to a barium hydroxide solution for protecting stone cultural relics, a preparation method and application thereof, and applies a hydrophobic and oleophobic technology to the field of cultural relic protection from the theory of cultural relic protection. The method has the advantages that the perfluorinated coupling agent is introduced to carry out hydrophobic and oleophobic treatment on the stone cultural relic, so that the corrosion effect of the stone cultural relic by acid rain is reduced, and the generated crosslinking effect can play a role in reinforcing the weathered stone cultural relic; the barium salt permeating into cracks of the stone cultural relic reacts with carbon dioxide to generate barium carbonate which can play a role in reinforcing and filling gaps; the added penetrant can make barium salt penetrate into the deeper part of the stone cultural relic. The method has the characteristics of safety, high efficiency, simple process, large-scale application potential and the like, and is suitable for the fields of stone cultural relic protection and the like.
Compared with the prior art, the method has the following advantages: 1. good compatibility: the protective material is a common mineral material, is close to the rock in property, and cannot change the components of the original cultural relics; 2. the solution used in the treatment process is transparent and can penetrate to a certain depth of the rock, and a hard shell is not formed on the surface like other inorganic protective materials or organic materials; 3. the generated mineralized film is barium carbonate, the glossiness of the original rock surface is not influenced, and the appearance, color and hand feeling of the protected stone cultural relic are not changed; 4. the barium carbonate mineralized substance and the perfluorinated coupling agent are filled and adhered to the rock microcracks in a certain microstructure, so that the strength and the water immersion resistance of loose rock are enhanced, the barium carbonate mineralized substance is gradually filled into rock micropores and covers the surface layer, does not chemically react with a protected substrate material, is firstly damaged when being corroded by the outside, and can play double roles of reinforcement and protection; 5. barium carbonate is a relatively stable inorganic compound, and has no aging and yellowing problems like an organic polymer protective film; 6. the perfluorinated coupling agent is covered on the surface of the loose rock, so that the corrosion of the stone cultural relics by rainwater and organic substances is reduced, and the water resistance and the stain resistance of the stone cultural relics are improved; 7. the added penetrant can make barium salt penetrate into the deeper part of the stone cultural relic.
Drawings
FIG. 1a is a photograph showing the appearance of a barium hydroxide solution of example 4 of the present invention after storage at 50 ℃ for 12 hours; FIG. 1b is a photograph showing the appearance of the barium hydroxide solution of example 1 of the present invention after storage at 50 ℃ for 12 hours.
Detailed Description
Waste water, waste gas and waste residue generated by the development of modern industry generate serious environmental pollution, and the aging and deterioration of the stone cultural relics are accelerated. The serious damage to the stone cultural relics is acid rain formed by dissolving acid harmful gases such as sulfur dioxide, nitrogen oxides and the like in the atmosphere in rain fog and humid air, for example, the long-term action of sulfur dioxide can change very hard limestone mainly containing barium carbonate into powdery gypsum, and the corrosion mechanism can be expressed by the following chemical reaction equation:
2CaCO3+ 2SO2+ O2+ 2H2O = 2CaSO4 ·2H2O + 2CO2
in natural environment, the stone cultural relics are gradually weathered and deteriorated, and the speed of the stone cultural relics is directly related to the quality of the stone raw materials. The quality of the stone cultural relic raw material is closely related to factors such as the type of the stone cultural relic, the type of the cementing material, the porosity and the like. The stone cultural relics are divided into sand (conglomerate) rock, limestone rock, granite and the like. Granite is hard, durable and has the highest stability, but the stone cultural relics belonging to the stone cultural relic structure are very few, and most of the caverns are sand (gravel) rock structures and are easy to differentiate. There is also a certain amount of cement inside the stone relic, the stone relic of the mud cement is most easily differentiated. This is because the clay cement contains a large amount of clay such as montmorillonite which has a layered structure with voids between the layers of the structural units and can absorb a large amount of water. After water absorption, the unit cell expands strongly, and after water loss, the unit cell contracts. When the environmental climate changes, the stone cultural relics expand and contract repeatedly, and the differentiation of the stone cultural relics is accelerated.
The stone is a porous substance, and the chemical weathering and the physical weathering of the stone cultural relic with larger porosity are more obvious, especially the stone cave temple (or the opencast stone cultural relic). Since the mountain (or ground) is closely connected to it, the capillaries absorb a large amount of groundwater and soluble salts present inside the stone pores. Along with the repeated change of the environmental temperature and humidity, soluble salts are dissolved and recrystallized to periodically change, and the crisp powder is deteriorated by extrusion force generated by crystallization. The cultural relic protection work is to achieve the purpose of prolonging the preservation time of the cultural relic by researching the cultural relic materials and the protection materials.
The stone cultural relics are naturally weathered and deteriorated to different degrees due to human factors and natural factors, particularly the weathering of the outdoor stone cultural relics is more serious, the stability of the stone cultural relics can be improved through reinforcement, and the service life of the cultural relics is prolonged. When the protective material is selected, the construction condition and the influence on the surrounding environment must be considered, and the ecological protection principle is met.
Inorganic reinforcing materials have been widely used before the nineteenth century, and most of the inorganic reinforcing agents use salts in a solution to coagulate in stone pores or to chemically react with stone to plug the stone pores to form a barrier layer or a substitute layer. The inorganic reinforcing materials commonly used internationally are: lime water, barium hydroxide, alkaline earth silicate, fluorosilicate and the like. For example, the barium hydroxide is used for reinforcing limestone, and barium carbonate solid is generated and filled between pores of limestone to reinforce the stone cultural relics by utilizing the action of the barium hydroxide and carbon dioxide in air:
Ba(OH)2 + CO2 = BaCO3
in addition, barium hydroxide reacts with sulfate in the rock or sulfur dioxide in the air and rainwater to generate barium sulfate, and barium sulfate solids are generated to fill in the pores of the limestone to reinforce the stone cultural relics.
2Ba(OH)2 + 2SO2 + O2 + 2H2O = 2BaSO4 +4H2O
Organic reinforcing agents have been used for the protection of stone cultural relics and ancient buildings for over forty years and are divided into two categories: one is a micromolecular compound, such as tetraethoxysilane and the like, which is used for reinforcing sandstone, brick and tile and clay cultural relics and protecting the stone cultural relics. It is realized according to the reaction of ethoxy and hydroxyl in the stone cultural relic:
-OH (in stone cultural relics) + C2H5O2Si2(OC2 H5 )3 = -O2Si2(OC2H5 )3 + C2H5OH
For the weak, loose and seriously weathered stone cultural relics, the molecular structure of inorganic particles contains hydroxyl, and the similar reaction can occur, so that the functions of adhesion and reinforcement are achieved. At the same time, two, three or four molecules of tetraethoxysilane may polymerize into dimers, trimers or tetramers. That is, the polymer contains a silica skeleton, which can produce a reinforcing and strengthening effect, but the coating layer of tetraethoxysilane having a large brittleness is easily peeled off.
The other is polymer, which is very commonly applied in the reinforcement and sealing of stone cultural relics and ancient buildings, and mainly comprises epoxy resin, acrylic resin and organic silicon resin. The epoxy resin contains benzene ring and ether bond, so that it has strong chemical solvent resistance and certain resistance to acid, alkali and organic solvent. Meanwhile, the adhesive contains hydroxyl, ether bond, amino and other polar genes, has high adhesive force to the stone cultural relics, has ideal effect, and can change color after long-term use. Acrylic resin is widely used in the paint industry due to its good chemical stability, heat resistance, weather resistance, etc., but its water resistance is poor, thus limiting its application in the protection of stone cultural relics. Among organic polymers for protecting stone cultural relics, the organic silicon resin has relatively good permeability, hydrophobicity and weather resistance, so that the organic silicon resin not only has a reinforcing effect, but also has waterproof performance, but also needs high-temperature curing, thereby limiting the application occasions of the organic silicon resin.
Aiming at the defects or the improvement requirements of the prior art, the invention provides a stone cultural relic protection material and a preparation method thereof, and aims to provide a novel stone cultural relic protection material and solve the problem of durable protection of stone cultural relics. The perfluoro-coupling agent adopted by the invention has excellent weather resistance, permeability, hydrophobicity and oleophobicity, can reduce the erosion of water, oil and other dirt to cultural relics, and greatly reduces the damage of acid rain, acid mist and organic matters to the outdoor stone cultural relics. The invention discloses a barium hydroxide solution for protecting stone cultural relics and a preparation method thereof. The invention applies the hydrophobic and oleophobic technology to the field of cultural relic protection based on the cultural relic protection theory. The method has the advantages that the perfluorinated coupling agent is introduced to carry out hydrophobic and oleophobic treatment on the stone cultural relic, so that the corrosion effect of the stone cultural relic by acid rain is reduced, and the generated crosslinking effect can play a role in reinforcing the weathered stone cultural relic; the barium salt permeating into cracks of the stone cultural relic reacts with carbon dioxide to generate barium carbonate which can play a role in reinforcing and filling gaps; the added penetrant can make barium salt penetrate into the deeper part of the stone cultural relic. The method has the characteristics of safety, high efficiency, simple process, large-scale application potential and the like, and is suitable for the fields of stone cultural relic protection and the like.
The purpose of the invention is realized by the following technical scheme: after the barium salt is dissolved in the solvent, the organic base and the penetrating agent are added, and the pH is adjusted to be more than 7. Then adding a perfluoro coupling agent and stirring to obtain a barium hydroxide solution. Wherein the perfluoro-coupling agent is one or more of tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane; the barium salt is one or two of barium chloride, barium nitrate and barium acetate; the organic base is one or more of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, monomethylamine, monoethylamine, monopropylamine, dimethylamine and diethylamine; the solvent is a mixture of water and isopropanol. The penetrating agent is one or more of fatty alcohol-polyoxyethylene ether, nonylphenol polyoxyethylene ether and polyether modified silicone oil.
The specific principle is as follows:
Ba2+(i.e., barium salt) + 2OH- = Ba(OH)2
Ba(OH)2 + CO2 = BaCO3
In the presence of rain water, unreacted barium hydroxide is dissolved by water. The hydrophobic membrane formed by the perfluoro-coupling agent is covered on the surface of the unreacted barium hydroxide, so that the barium hydroxide cannot contact water and cannot be dissolved, and the stone cultural relic is better protected. Perfluoro coupling agents (tridecafluorooctyltriethoxysilane, tridecafluorooctyltrimethoxysilane, heptadecafluorodecyltriethoxysilane and heptadecafluorodecyltrimethoxysilane) which are based on the reaction of ethoxy groups with hydroxyl groups in stone relics:
-OH+(C2H5O)3Si(CH2)2C6F13 = -O(C2H5O)2Si(CH2)2 C6F13 + C2H5OH
-OH+ (CH3O)3Si(CH2)2 C6F13 = -O(CH3O)2Si(CH2)2 C6F13 + C2H5OH
-OH + (C2H5O)3Si(CH2)2 C8F17 = -O(C2H5O)2Si(CH2)2 C8F17 + C2H5OH
-OH + (CH3O)3Si(CH2)2 C8F17 = -O(CH3O)2Si(CH2)2 C8F17 + C2H5OH
when in use, firstly, the brush is dipped with a cleaning agent (such as water or alcohol) or not to be dipped with the cleaning agent to clean the surface of the stone cultural relic; then dipping the stone cultural relics into the barium hydroxide solution for infusion and permeation treatment. The perfluorinated coupling agent in the barium hydroxide solution has hydrophilic groups pointing to the stone cultural relics and lipophilic groups facing outwards, so that the stone cultural relics have hydrophobic and oleophobic effects. After barium-containing substances in the barium hydroxide solution penetrate into cracks of the stone cultural relics, the barium-containing substances react with carbon dioxide to generate barium carbonate, the barium carbonate can move to orderly nucleate and directionally grow knots, and barium carbonate mineralizers are generated on the surfaces and in micro-cracks of the barium-containing stone cultural relics, so that the stone cultural relics are reinforced. The added penetrant can make barium salt penetrate into the deeper part of the stone cultural relic. With the continuous and repeated permeation reaction of the perfluoro-coupling agent and the barium-containing substance, mineralized substances are continuously accumulated and grown, so that micro gaps of the loose stone cultural relics are filled. The operation of the invention can use brushing, spraying, soaking and other methods.
The barium hydroxide solution in the invention contains a silane coupling agent and a penetrating agent, wherein the perfluoro coupling agent (tridecafluorooctyltriethoxysilane, tridecafluorooctyltrimethoxysilane, heptadecafluorodecyltriethoxysilane and heptadecafluorodecyltrimethoxysilane) has larger polarity of functional groups, thus influencing the stability of barium salt, causing flocculation in the storage process and needing to be prepared. The present invention therefore further investigated the effect of different types of perfluorinated coupling and penetrants on the stability of barium salts.
Because the influence of the conventional silane coupling agent on the stability of the barium salt is relatively small, based on different influences of different functional groups on the stability of the barium salt, a comparison experiment shows that the 3-glycidyl ether oxypropyl trimethoxy silane can improve the stability of a barium hydroxide solution; therefore, the applicant improves the existing perfluoro coupling agent, reduces the polarity of the perfluoro coupling agent by introducing 3-glycidyloxypropyl and two groups with different polarities (fluoroalkyl and 3-glycidyloxypropyl), improves the stability of the barium hydroxide solution and prolongs the storage time.
In the further implementation process, the novel perfluoro coupling agent with a plurality of active centers and a plurality of types of functional group structures is provided, so that on one hand, the overall polarity of the perfluoro coupling agent is reduced, the stability of the barium hydroxide solution is improved, and the storage time is prolonged. On the other hand, the oil stain repellent has an amphoteric effect, the hydrophilic group points to the stone cultural relic, and the lipophilic group faces outwards, so that the stone cultural relic has hydrophobic and oleophobic effects. The structural formula is as follows:
Wherein R is a fluoroalkyl chain with a carbon chain length of 6-10, and is selected from one of nonafluorohexyl, undecafluoroheptyl, tridecafluorooctyl, pentadecafluorononyl and heptadecafluorodecyl; x is any integer of 1-7; y is any integer of 1 to 3.
The invention will now be further described with reference to the following examples, which are intended to be illustrative of the invention and are not to be construed as limiting the invention.
Example 1
Preparing a barium hydroxide solution: adding 5g of barium chloride and 5g of barium nitrate into a solution of 50g of isopropanol and 50g of deionized water, stirring for 2 hours, adding 0.7g of monoethanolamine, 0.5g of diethanolamine and 0.2g of fatty alcohol-polyoxyethylene ether, adjusting the pH to 10, sequentially adding 0.1g of tridecafluorooctyltriethoxysilane and 0.15g of heptadecafluorodecyltrimethoxysilane, and stirring for half an hour to obtain a barium hydroxide solution.
Example 2
Preparing a barium hydroxide solution: adding 10g of barium chloride into a solution of 40g of isopropanol and 60g of deionized water, stirring for 2 hours, adding 1g of diethylamine, 0.1g of triethanolamine, 0.1g of nonylphenol polyoxyethylene ether and 0.1g of polyether modified silicone oil, adjusting the pH to 7-8, adding 0.3g of tridecafluorooctyl trimethoxy silicon, and stirring for half an hour to obtain a barium hydroxide solution.
Example 3
Preparing a barium hydroxide solution: adding 6g of barium nitrate and 5g of barium acetate into a solution of 60g of isopropanol and 40g of deionized water, stirring for 1h, adding 0.8g of diethylamine, 0.1g of diisopropanolamine and 0.1g of polyether modified silicone oil, adjusting the pH to 7-8, adding 0.2g of heptadecafluorodecyltriethoxysilane, and stirring for 20 min to obtain a barium hydroxide solution.
Example 4
Preparation of novel perfluoro coupling agent: 1.0mol of 3-glycidoxypropyltrimethoxysilane and 2mol of tridecafluorooctyltrimethoxysilane are put into a three-neck flask provided with a condensation reflux device and a thermometer, and are uniformly mixed under the protection of nitrogen, 89ml of isopropanol is slowly dripped at room temperature, the condensation controlled reaction temperature is kept at about 25 ℃, after the dripping is finished, the three-neck flask is continuously stirred for 0.25h, heated to a low boiling state, the condensation reflux reaction is kept for 4h, and then the solvent is removed by fractional distillation to obtain a colorless and transparent solution.
Preparing a barium hydroxide solution: adding 5g of barium chloride and 5g of barium nitrate into a solution of 50g of isopropanol and 50g of deionized water, stirring for 2 hours, adding 0.7g of monoethanolamine, 0.5g of diethanolamine and 0.2g of fatty alcohol-polyoxyethylene ether, adjusting the pH to 10, sequentially adding 0.35g of the novel perfluoro coupling agent, and stirring for half an hour to obtain a barium hydroxide solution.
Example 5
Preparation of novel perfluoro coupling agent: 1.0mol of 3-glycidoxypropyltriethoxysilane and 2mol of heptadecafluorodecyltriethoxysilane are put into a three-neck flask provided with a condensation reflux device and a thermometer, and after uniform mixing under the protection of nitrogen, 89ml of isopropanol is slowly dripped at room temperature, the condensation is kept to control the reaction temperature to be about 25 ℃, after dripping is finished, the three-neck flask is continuously stirred for 0.25h, heated to a low boiling state, the condensation reflux reaction is kept for 5h, and then the solvent is removed by fractional distillation to obtain a colorless and transparent solution.
Preparing a barium hydroxide solution: adding 5g of barium chloride and 5g of barium nitrate into a solution of 50g of isopropanol and 50g of deionized water, stirring for 2 hours, adding 0.7g of monoethanolamine, 0.5g of diethanolamine and 0.2g of fatty alcohol-polyoxyethylene ether, adjusting the pH to 10, sequentially adding 0.39g of the novel perfluoro coupling agent, and stirring for half an hour to obtain a barium hydroxide solution.
Comparative example 1
Preparing a barium hydroxide solution: adding 6g of barium nitrate and 5g of barium acetate into a solution of 60g of isopropanol and 40g of deionized water, stirring for 1h, adding 0.8g of diethylamine, 0.1g of diisopropanolamine and 0.1g of polyether modified silicone oil, adjusting the pH to 7-8, and stirring for 20 minutes to obtain a barium hydroxide solution.
Comparative example 2
Preparing a barium hydroxide solution: adding 6g of barium nitrate and 5g of barium acetate into a solution of 60g of isopropanol and 40g of deionized water, stirring for 1h, adding 0.8g of diethylamine and 0.1g of diisopropanolamine, adjusting the pH to 7-8, and stirring for 20 minutes to obtain a barium hydroxide solution.
Example of detection
Selecting fresh sandstone stones with the specification of 10cm multiplied by 10 cm. Cleaning the sandstone stone block with a wool brush, then uniformly coating the surface of the sandstone stone block with a barium hydroxide solution, standing for 24 hours to enable the sandstone stone block to fully absorb the material, then coating the sandstone stone block with the barium hydroxide solution for the second time, and standing for 2 days. And (5) detecting all the sample blocks after coating. Detecting items: the water content of the surface layer of the red sandstone, the free water permeability of the surface, the width of a scratch, the ultrasonic wave speed and the chroma. The surface water permeability is determined according to DIN 52617. The scratch width is referred to GB/T9279-1988. The reference standard of the ultrasonic wave speed is JB/T10326-. The reference standard for color is ISO 7724-2-1984. Referring to FIG. 1, the appearance of the barium hydroxide solution of examples 1 and 4 was shown after storing at 50 ℃ for 12 hours. See table 1 for specific sandstone block performance parameters.
Description of the drawings: in table 1, the blank is a sandstone block without any surface treatment and the test method is as follows: the test method in example 1 was the same.
Through the comparison and the discovery after the evaluation of the detection data before and after the surface layer of the sandstone block is reinforced: the use of the barium hydroxide solution obviously reduces the surface water content and the surface free water permeability of the rock, obviously improves the surface strength and compactness, has better hydrophobic property and small color difference value change, and achieves the protection effect. Referring additionally to FIG. 1, it can be seen that the novel perfluorinated coupling agent synthesized by the present invention has better stability to barium hydroxide.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
Claims (6)
1. The solution for protecting the stone cultural relics is characterized by comprising the following components in parts by mass: 40-60 parts of isopropanol, 40-60 parts of water, 8-15 parts of barium salt, 0.8-1.5 parts of organic base, 0.05-0.5 part of penetrating agent and 0.05-1.5 parts of perfluoro coupling agent;
the structural formula of the perfluoro coupling agent is as follows:
Wherein R is a fluoroalkyl chain with a carbon chain length of 6-10; x is any integer of 1-7; y is any integer of 1-3;
the preparation of the solution comprises the following steps: adding barium salt into a solvent consisting of isopropanol and deionized water, stirring for 0.5-3 h, adding an organic base and a penetrating agent, adjusting the pH to be more than 7, adding a perfluoro coupling agent, and stirring for 0.5-3 h to obtain the solution.
2. The solution for protecting a stone cultural relic, according to the claim 1, wherein R is selected from one of nonafluorohexanyl, undecafluoroheptanyl, tridecafluorooctanyl, pentadecafluorononanyl and heptadecafluorodecanyl.
3. The solution for protecting a stone relic according to claim 1, characterized in that the barium salt is at least one of barium chloride, barium nitrate and barium acetate.
4. A stone relic protection solution according to claim 1, characterized in that the organic base is at least one of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, monomethylamine, monoethylamine, monopropylamine, dimethylamine, diethylamine.
5. The solution for protecting stone relics of claim 1, wherein the penetrating agent is at least one of fatty alcohol-polyoxyethylene ether, nonylphenol polyoxyethylene ether and polyether modified silicone oil.
6. The use of the solution for protecting stone cultural relics, which is based on any one of claims 1 to 5, for reinforcing and sealing stone cultural relics, and is characterized in that the use method comprises the following steps: cleaning the sandstone stone block with a wool brush, uniformly brushing the solution on the surface of the sandstone stone block, standing for 16-24 hours to enable the sandstone stone block to fully absorb the material, brushing the solution for the second time, and standing for 2-3 days.
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|---|---|---|---|---|
| WO2001087801A2 (en) * | 2000-05-15 | 2001-11-22 | E.I. Dupont De Nemours And Company | A method for protection of stone with substantially amorphous fluoropolymers |
| CN101100395A (en) * | 2007-06-19 | 2008-01-09 | 东莞拓扑实业有限公司 | Nano stone protectant and preparation method thereof |
| CN109233478A (en) * | 2018-07-27 | 2019-01-18 | 东莞环球经典新型材料有限公司 | A kind of fluorine-containing organic silicon stone protective agent and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001087801A2 (en) * | 2000-05-15 | 2001-11-22 | E.I. Dupont De Nemours And Company | A method for protection of stone with substantially amorphous fluoropolymers |
| CN101100395A (en) * | 2007-06-19 | 2008-01-09 | 东莞拓扑实业有限公司 | Nano stone protectant and preparation method thereof |
| CN109233478A (en) * | 2018-07-27 | 2019-01-18 | 东莞环球经典新型材料有限公司 | A kind of fluorine-containing organic silicon stone protective agent and preparation method thereof |
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