CN117510180A - Calcium-alcohol complex and preparation method and application thereof - Google Patents
Calcium-alcohol complex and preparation method and application thereof Download PDFInfo
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- CN117510180A CN117510180A CN202311469576.8A CN202311469576A CN117510180A CN 117510180 A CN117510180 A CN 117510180A CN 202311469576 A CN202311469576 A CN 202311469576A CN 117510180 A CN117510180 A CN 117510180A
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- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000010668 complexation reaction Methods 0.000 title description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011575 calcium Substances 0.000 claims abstract description 25
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 19
- 239000000920 calcium hydroxide Substances 0.000 claims description 14
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 14
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 230000002787 reinforcement Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 5
- 230000001012 protector Effects 0.000 claims 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 46
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 23
- 239000011148 porous material Substances 0.000 abstract description 11
- 239000002105 nanoparticle Substances 0.000 abstract description 10
- 239000007787 solid Substances 0.000 abstract description 10
- 230000035699 permeability Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000000536 complexating effect Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000004575 stone Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 30
- 239000000463 material Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 19
- 235000019441 ethanol Nutrition 0.000 description 17
- 230000001681 protective effect Effects 0.000 description 13
- 239000002253 acid Substances 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229920000620 organic polymer Polymers 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 230000003014 reinforcing effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000007546 Brinell hardness test Methods 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000001808 coupling effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- XQFRJNBWHJMXHO-RRKCRQDMSA-N IDUR Chemical compound C1[C@H](O)[C@@H](CO)O[C@H]1N1C(=O)NC(=O)C(I)=C1 XQFRJNBWHJMXHO-RRKCRQDMSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000010429 evolutionary process Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000013102 re-test Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C04B30/00—Compositions for artificial stone, not containing binders
- C04B30/02—Compositions for artificial stone, not containing binders containing fibrous materials
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/72—Repairing or restoring existing buildings or building materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Aftertreatments Of Artificial And Natural Stones (AREA)
Abstract
The invention relates to a calcium-alcohol complex, a preparation method and application thereof, wherein the method comprises the following steps: dissolving a calcium source into an alcohol ligand, mixing and filtering; adding a poor solvent into the filtered solution, heating, and centrifuging to obtain calcium-alcohol complex gel; and (3) standing the calcium-alcohol complex gel to obtain a calcium-alcohol complex solution. Compared with the prior art, the method has the advantages that the complex is formed by complexing alcohol ligands such as ethylene glycol and the like with a calcium source through a solution-gel-solution conversion path, gel is separated out from the complex when the complex is heated, the gel is kept stand for proper time to be converted back into the solution, and finally, the synthesis of the calcium-alcohol complex solution is realized, the cost is low, the operation is simple, the obtained calcium-alcohol complex can enter micro-pores which are difficult to enter into nanoparticles, the protection effect is relatively thorough, the advantages of high solid content, good permeability and the like are achieved, and the method has good application potential in the field of calcium carbonate cultural relics protection.
Description
Technical Field
The invention belongs to the technical field of cultural relic protection materials, and relates to a calcium-alcohol complex, a preparation method and application thereof.
Background
The calcareous cultural relics are a series of substances which mainly consist of calcium carbonate and have cultural value and historical sediments, and mainly comprise grottoes, inscriptions, sculptures and the like. The calcareous cultural relics witnessed the evolutionary process of the world civilization, and the crystals of the human civilization are aggregated. However, most of these rare calcareous cultural relics are exposed to natural environment for a long time after time gift washing, and due to the long-term coupling effect of multiple natural environment factors such as temperature and humidity change, air pollution, soluble salt crystallization, various diseases such as weathering, denudation, cracking, pulverization, nail lifting and herpes appear, so that the rare cultural relics are seriously damaged. It is therefore currently the most urgent task to scientifically protect calcareous relics against and delay their deterioration.
Calcium carbonate cultural relics generally have a loose porous structure due to calcium carbonate loss and microcrack generation during degradation. Constructing a suitable cultural relic protecting material, filling and binding the pores of a calcareous cultural relic to reinforce it is one of the most important ways to prevent further degradation thereof, so that the development of the cultural relic protecting material has been put into great effort in the last decades, and various cultural relic protecting materials mainly including organic polymer protecting materials, silicon-based protecting materials and calcium-based protecting materials have been developed. Organic polymer protective materials mainly comprise polyacrylic resin, epoxy resin, organic fluorine resin, polyurethane and the like, and have been widely paid attention to and applied to due to good permeability and film forming property. However, the organic polymer-based protective material generally has problems of poor durability, irreversibility, and the like. The silicon-based protective material is an oligomer prepared by hydrolysis and polymerization of a series of different siloxane monomers, and has the advantages of good permeability, ageing resistance and the like. However, the silicon-based protective material has the problems of potential glare, easiness in cracking and the like. In addition, the organic polymer protective material and the silicon-based protective material can block pores due to the polymer characteristics; and the components and the basic physical and chemical properties of the materials are different from those of the calcareous cultural relics, so that the problems of protective damage and the like can be caused.
Compared with organic polymer protective materials and silicon-based protective materials, the calcium-based protective materials have the characteristics of durability and compatibility with calcium carbonate cultural relics, and are ideal materials for protecting the calcium carbonate cultural relics. Calcium hydroxide is the most studied calcium-based protective material at present, and mainly comprises two types of lime water and nano calcium hydroxide stable dispersion liquid. Lime water, namely calcium hydroxide aqueous solution, can enter larger pores in loose and porous cultural relics and react with carbon dioxide in the pores to generate calcium carbonate, so that the loose and porous calcium carbonate cultural relics are filled and bonded. However, the solubility of calcium hydroxide in water is poor, which results in lower solid content of lime water, and the effect of single protection is limited; and a large amount of water is brought to the cultural relics after being used for a plurality of times, so that the problems of water damage, salt damage and the like are caused. Compared with lime water, the nano calcium hydroxide stable dispersion liquid has higher solid content, so that the nano calcium hydroxide stable dispersion liquid is widely studied and used in the field of cultural relic protection. However, nano-scale particles cannot enter micro-pores in the internal structure of the cultural relics, which can only be accessed by a solution, and the solid content of nano-calcium hydroxide is limited compared with that of organic polymer-based protective materials and silicon-based protective materials, so that the nano-calcium hydroxide still needs to be reinforced for many times. In addition, the degraded calcareous relics generally have complex and uneven porous structures, and calcium hydroxide nanoparticles easily block small holes on the walls of large holes, so that the inside of the large holes is prevented from being reinforced. The development of new calcareous cultural relic protection materials to solve the above-mentioned problems is therefore a current urgent need and a great challenge.
Patent CN114133208A discloses a stone cultural relic reinforcing and protecting material, a preparation method and application thereof, which consists of an alcohol solvent and amorphous nano calcium carbonate dispersed in the alcohol solvent; the cultural relic reinforcing and protecting material is utilized to carry out reinforcing and protecting on a cultural relic matrix through spontaneous conversion from amorphous nano calcium carbonate to crystalline calcium carbonate; materials in solution or powder form can be prepared by dispersing, reacting, separating or drying. Although the amorphous nano calcium carbonate dissolved in the alcohol solution is used for effectively protecting the rock, the nano calcium carbonate is actually dispersed in the alcohol solvent in the form of nano particles, and due to the limitation of the size of the nano particles, tiny gaps and cracks which cannot be accessed by the nano particles in the porous structure of the rock cannot be effectively protected; secondly, the alcohol solvent selected in the patent has a low boiling point, and amorphous calcium carbonate is easy to permeate back to the surface to form a calcium carbonate layer when the solvent volatilizes, so that the appearance of a protected object is adversely affected; finally, the amorphous nano calcium carbonate dispersion in the patent has low content of the active substance calcium element.
Disclosure of Invention
The invention aims to overcome at least one defect in the prior art and provide a calcium-alcohol complex, a preparation method and application thereof, wherein the calcium-alcohol complex can enter micro-pores which are difficult to enter by nano particles, has a relatively thorough protection effect, has the advantages of high solid content, good permeability and the like, and has good application potential in the field of calcium carbonate cultural relics protection.
The aim of the invention can be achieved by the following technical scheme:
one of the technical schemes of the invention is to provide a preparation method of a calcium-alcohol complex, which comprises the following steps:
(1) Dissolving a calcium source into an alcohol ligand, and filtering after the calcium source is completely dissolved and mixed;
(2) Adding a poor solvent into the filtered solution to form a mixed solution, separating out gel from the mixed solution under the influence of the poor solvent when heating, and centrifuging to obtain calcium-alcohol complex gel;
(3) And (3) standing the calcium-alcohol complex gel until the gel is converted into a colorless transparent solution, so as to obtain the calcium-alcohol complex solution.
Further, in the step (1), the alcohol ligand is ethylene glycol, and the calcium source is one or more selected from calcium, calcium oxide and calcium hydroxide.
Further, the mass/volume ratio of the calcium source to the alcohol ligand in step (1) is (0.2-1 g) (5-20 mL).
Further, in the step (1), the mixing temperature is room temperature and the mixing time is 3-5h.
Further, in the step (2), the poor solvent is ethanol.
Further, the volume/mass ratio of the poor solvent to the calcium source in the step (2) is (5-40 mL): 0.2-1 g.
Further, the heating temperature in the step (2) is 90-120 ℃ and the time is 10-30min.
As a preferable technical scheme, the centrifugal speed in the step (2) is 8000-10000rpm, and the time is 1-3min.
Further, the standing temperature in the step (3) is 0-40 ℃ and the time is 1-3h.
One of the technical schemes of the invention is to provide the calcium-alcohol complex prepared by the method, and the complex is in a solution state.
One of the technical schemes of the invention is to provide an application of the calcium-alcohol complex, wherein the complex is used as a reinforcing and protecting agent for protecting calcareous cultural relics.
The working principle of the invention comprises the following aspects:
(1) Complexing alcohol ligand glycol molecules with a calcium source at high temperature to form a complex, and gelling under the induction of poor solvent ethanol;
(2) The complex gel obtained by centrifugation can be converted back into a solution form again after standing for a proper time under a proper temperature condition, and the calcium-alcohol complex solution can enter micro pores which are difficult to enter into nanoparticles, so that the protection effect is relatively thorough;
(3) The calcium-alcohol complex can react with carbon dioxide in the air at the position of the hole to be repaired to generate a three-dimensional calcium carbonate continuous network in situ, has the advantages of high solid content, good permeability and the like, and has good application potential in the field of the protection of calcareous cultural relics.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, through a solution-gel-solution conversion path, alcohol ligand ethylene glycol is complexed with a calcium source to form a complex, gel is separated out from the complex when the complex is heated, and the gel is kept stand for proper time under proper temperature conditions to be converted back into the solution again, so that the synthesis of the calcium-alcohol complex solution is finally realized, the cost is low, the operation is simple, the obtained calcium-alcohol complex can enter micro pores which are difficult to enter into nanoparticles, the protection effect is relatively thorough, the advantages of high solid content, good permeability and the like are achieved, and the method has good application potential in the field of calcium carbonate cultural relics protection;
(2) The calcium-alcohol complex exists stably in a true solution form in a very wide temperature range, has better permeability, has higher effective substances (the solid content of calcium element is higher than 7 percent at most), and can enter micro-pores in cultural relics, wherein nano particles are difficult to enter;
(3) The calcium-alcohol complex and carbon dioxide in the air react in situ at the position of the hole to be repaired to generate a three-dimensional calcium carbonate continuous network with filling and bonding functions, so that damaged calcium carbonate cultural relics are reinforced, and the mechanical property and the weather resistance of the cultural relics are improved;
(4) The solvent of the calcium-alcohol complex solution is high-boiling-point alcohol, so that a calcium carbonate layer is not formed on the surface of the solution by reverse osmosis, and the appearance of a protected object is not adversely affected.
Drawings
FIG. 1 is a photograph of a gel of a calcium-alcohol complex of example 1 of the present invention;
FIG. 2 is a photograph of a calcium-alcohol complex solution in example 1 of the present invention;
FIG. 3 is a graph showing the results of thermogravimetric tests of a calcium-alcohol complex solution according to example 1 of the present invention;
FIG. 4 is a scanning electron microscope image of a simulated cultural relic sample according to comparative example 2 of the invention;
FIG. 5 is a transmission electron microscope image of a simulated cultural relic sample reinforced with a calcium-alcohol complex according to example 1 of the present invention;
FIG. 6 is a graph showing the color difference test results of the simulated cultural relics according to the embodiment 1 and the comparative example 2;
FIG. 7 is a graph showing the results of compressive strength tests of the simulated cultural relics in example 1 and comparative example;
fig. 8 is a graph showing the results of the brinell hardness test of the simulated cultural relic samples in example 1 and comparative example.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
The equipment used in the following examples is representative of conventional equipment in the art unless otherwise specified; unless otherwise indicated, all reagents used are commercially available or prepared by methods conventional in the art, and all of the following examples, not specifically described, are accomplished by means of conventional experimentation in the art.
The invention provides a preparation method of a calcium-alcohol complex, which comprises the following specific steps:
(1) Dissolving a calcium source into an alcohol ligand, wherein the alcohol ligand is glycol, the calcium source is one or more of calcium, calcium oxide and calcium hydroxide, the mass/volume ratio of the calcium source to the alcohol ligand is (0.2-1 g) (5-20 mL), dissolving and mixing the calcium source at room temperature for 3-5h till the calcium source is complete, and filtering;
(2) Adding a poor solvent into the filtered solution to form a mixed solution, wherein the poor solvent is ethanol, the volume/mass ratio of the poor solvent to a calcium source is (5-40 mL) (0.2-1 g), heating the mixed solution at 90-120 ℃ for 10-30min, separating out gel under the influence of the poor solvent, and centrifuging the mixed solution at 8000-10000rpm for 1-3min to obtain calcium-alcohol complex gel;
(3) And (3) standing the calcium-alcohol complex gel at 0-40 ℃ for 1-3 hours until the gel is converted into a colorless transparent solution, so as to obtain the calcium-alcohol complex solution.
The calcium-alcohol complex prepared by the method is in a solution state.
The calcium-alcohol complex is used as a reinforcing and protecting agent for protecting calcareous cultural relics.
Example 1:
a preparation method of a calcium-alcohol complex comprises the following specific steps:
(1) Preparing a calcium hydroxide solution with the concentration of 30mg/mL by taking 600mg of calcium hydroxide as a solute and 20mL of ethylene glycol as a solvent, dissolving and mixing for 4 hours at the room temperature of calcium hydroxide until the mixture is complete, and filtering;
(2) Stirring 20mL of calcium hydroxide solution as a filtering result uniformly, adding absolute ethyl alcohol with the volume twice that of the calcium hydroxide solution, fully mixing, heating the solution at 110 ℃ for 15min, separating out gel under the influence of the absolute ethyl alcohol, centrifuging at 7000rpm for 3min, and pouring out supernatant to obtain calcium-alcohol complex gel, as shown in figure 1;
(3) The calcium-alcohol complex gel as a result of centrifugation was left standing at 25℃for 65 minutes, and was completely converted into a colorless transparent solution, to obtain a calcium-alcohol complex solution, as shown in FIG. 2.
The calcium-alcohol complex prepared by the method is in a solution state, and the residual substance after thermal retest is that the solid content of calcium oxide is more than 10 percent, and the solid content after conversion into calcium element is more than 7 percent, as shown in figure 3.
The simulated cultural relic sample for protection is obtained by cutting a Leshan natural stone block into square stone blocks with 2cm side length and no cracks on the surface, wherein the stone blocks are not defected in whole, and no holes are visible on the surface.
In order to simulate the effect of the cultural relics corroded in the natural world, an acid corrosion method is adopted to simulate damage caused by coupling action of various factors of the cultural relics in the natural environment, and the acid corrosion simulation method comprises the following steps:
placing the stone block in 0.1mol/L hydrochloric acid for 2 hours under the pressure of-0.1 MPa, enabling the hydrochloric acid to enter the stone block for uniform erosion, soaking the stone block in hydrochloric acid with the same concentration for 24 hours at room temperature, and cleaning and drying the stone block by deionized water after soaking.
The calcium-alcohol complex performs permeation reinforcement protection on the simulated cultural relics, and specifically comprises the following steps:
immersing the stone block subjected to acid corrosion treatment in a calcium-alcohol complex solution for 2+/-0.5 h under the pressure of-0.1 MPa until bubbles are not generated on the surface of the stone block, enabling the calcium-alcohol complex solution to fully enter a porous structure in the stone block, cleaning and wiping the surface of the stone block by deionized water, and then protecting the stone block, wherein the protection temperature is 25 ℃, the protection humidity is 60%, and the protection time is 120h.
Comparative example 1:
untreated stone blocks.
Comparative example 2:
stone not protected by calcium-alcohol complex after acid attack.
As shown in fig. 4, the unprotected stone sample in comparative example 2 had an irregular sheet-like surface structure.
As shown in fig. 5, the pores and cracks existing in the stone sample are filled with the calcium-alcohol complex solution of the present embodiment, and the calcium-alcohol complex reacts with carbon dioxide in the air to generate a three-dimensional continuous network of calcium carbonate with filling and binding functions.
And carrying out color difference testing on the stone blocks which are not treated and are corroded by acid and are reinforced, and measuring the color difference by a CR-400 color difference analyzer, wherein DeltaL, deltaa and Deltab are differences of brightness L and chromaticity indexes a and b before and after the stone blocks are reinforced. The color difference value is denoted by Δe, which is the integrated color difference. And (3) selecting nine measuring points on the smooth surface of the stone for color difference test, and taking an average value of color difference results.
As shown in fig. 6, the surface color change of the stone sample reinforced with the calcium-alcohol complex of this example was within an acceptable range.
And testing the mechanical property and the weather resistance of the stone block which is not treated and is corroded by acid and reinforced. The test properties included the hardness in the Rich and compressive strength. The brinell hardness is measured by an HT-2000A pen-type brinell hardness tester, the brinell hardness test is carried out by selecting three measuring points on the flat surface of a stone, the measuring result is the average value of the results of the three measuring points, and all stones are placed on the same substrate during the brinell hardness test. Compressive strength was measured by an E44 electronic universal tester, and three different types of stone (untreated, acid attack treatment, reinforcement treatment) were each averaged.
As shown in FIG. 7, the peak load of the stone sample reinforced with the calcium-alcohol complex of this example reached 25.4MPa, which is 11.8MPa higher than the average peak load of the acid-etched sample of comparative example 2, and was close to 27.8MPa of the average peak load of the untreated sample of comparative example 1.
As shown in fig. 8, the hardness of the stone block sample reinforced by the calcium-alcohol complex of this example reached 132HL, which is also higher than the average hardness of the acid-etched sample of comparative example 2, which is 108HL, and was close to the average hardness of the untreated sample of comparative example 1, which is 156HL.
Example 2:
a calcium-alcohol complex and a preparation method and application thereof are basically the same as those in example 1, except that in step (1), a calcium oxide solution with a concentration of 35mg/mL is prepared by using 700mg of calcium oxide as a solute and 20mL of ethylene glycol as a solvent, and the heating time in step (2) is 20min.
The peak load of the stone sample reinforced by the calcium-alcohol complex of the embodiment reaches 23.4MPa, which is 11.8MPa higher than the average peak load of the acid corrosion sample in the comparative example 2 and is close to 27.8MPa of the average peak load of the untreated sample in the comparative example 1.
The hardness of the stone sample reinforced by the calcium-alcohol complex of the embodiment reaches 134HL, which is also higher than the average hardness of the acid corrosion sample of the comparative example 2, namely 108HL, and is close to the average hardness of the untreated sample of the comparative example 1, namely 156HL.
Example 3:
a calcium-alcohol complex and a preparation method and application thereof are basically the same as those in example 1, except that in step (1), 200mg of calcium oxide is used as a solute and 10mL of ethylene glycol is used as a solvent to prepare a calcium oxide solution with a concentration of 20mg/mL, and in step (2), the heating time is 20min.
The peak load of the stone sample reinforced by the calcium-alcohol complex of the embodiment reaches 24.8MPa, which is 11.8MPa higher than the average peak load of the acid corrosion sample in the comparative example 2 and is close to 27.8MPa of the average peak load of the untreated sample in the comparative example 1.
The hardness of the stone sample reinforced by the calcium-alcohol complex of the embodiment reaches 150HL, which is also higher than the average hardness of the acid corrosion sample of the comparative example 2, namely 108HL, and is close to the average hardness of the untreated sample of the comparative example 1, namely 156HL.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. A method for preparing a calcium-alcohol complex, comprising the steps of:
(1) Dissolving a calcium source into an alcohol ligand, mixing and filtering;
(2) Adding a poor solvent into the filtered solution, heating, and centrifuging to obtain calcium-alcohol complex gel;
(3) And (3) standing the calcium-alcohol complex gel to obtain a calcium-alcohol complex solution.
2. The method for preparing a calcium-alcohol complex according to claim 1, wherein the alcohol ligand in the step (1) is ethylene glycol, and the calcium source is one or more selected from the group consisting of calcium, calcium oxide and calcium hydroxide.
3. The method for producing a calcium-alcohol complex according to claim 1, wherein the mass/volume ratio of the calcium source to the alcohol ligand in the step (1) is (0.2-1 g) (5-20 mL).
4. The method for preparing a calcium-alcohol complex according to claim 1, wherein the mixing temperature in the step (1) is room temperature for 3 to 5 hours.
5. The method for producing a calcium-alcohol complex according to claim 1, wherein the poor solvent in the step (2) is ethanol.
6. The method for producing a calcium-alcohol complex according to claim 1, wherein the ratio of the poor solvent to the calcium source in the step (2) is (5-40 mL) (0.2-1 g).
7. The method for producing a calcium-alcohol complex according to claim 1, wherein the heating temperature in step (2) is 90 to 120 ℃ for 10 to 30 minutes.
8. The method for producing a calcium-alcohol complex according to claim 1, wherein the standing temperature in step (3) is 0 to 40 ℃ for 1 to 3 hours.
9. A calcium-alcohol complex prepared by the method of any one of claims 1 to 8, wherein the complex is in solution.
10. Use of a calcium-alcohol complex according to claim 9 as reinforcement protector for the protection of calcareous relics.
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