CN113087545B - Pure inorganic strengthening-moss removing compound agent for protecting weathered stone cultural relics and preparation method thereof - Google Patents
Pure inorganic strengthening-moss removing compound agent for protecting weathered stone cultural relics and preparation method thereof Download PDFInfo
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 32
- 239000004575 stone Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000002633 protecting effect Effects 0.000 title claims abstract description 13
- 150000001875 compounds Chemical class 0.000 title claims description 26
- 239000008139 complexing agent Substances 0.000 claims abstract description 31
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 claims description 3
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011435 rock Substances 0.000 abstract description 22
- 238000007596 consolidation process Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 239000012744 reinforcing agent Substances 0.000 abstract description 5
- 238000005728 strengthening Methods 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 3
- 230000035699 permeability Effects 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 1
- 241000700670 Bryozoa Species 0.000 description 13
- 230000002787 reinforcement Effects 0.000 description 10
- 230000003014 reinforcing effect Effects 0.000 description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- 239000001963 growth medium Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000002609 medium Substances 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000004763 spore germination Effects 0.000 description 2
- 238000004154 testing of material Methods 0.000 description 2
- 241000195940 Bryophyta Species 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
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- 239000004576 sand Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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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
- 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
- C04B41/5072—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 with oxides or hydroxides not covered by C04B41/5025
- C04B41/5074—Copper oxide or solid solutions thereof
- C04B41/5075—Copper oxide
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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Abstract
The invention discloses a pure inorganic strengthening-moss removing complexing agent for protecting weathered stone cultural relics and a preparation method thereof, wherein the complexing agent consists of the following raw materials in percentage by mass, and nano magnesium oxide MgO5.0-18.0%; MgCl chloride2·6H2O5.0% -19.0%; nano GO @ CuO0.02% -0.10%; deionized water H2O8.0% -24.0%; 50.0 to 80.0 percent of dispersant. The reinforcing-moss removing complexing agent disclosed by the invention is good in permeability, and does not change the original appearance of the cultural relics when permeating into weathered rocks; the mechanical strength of the rock is obviously improved after the strengthening treatment; the moss on the rock surface can be effectively killed, and meanwhile, the moss spores are inactivated; the reinforcing agent in the complexing agent can anchor the moss removing agent in the consolidation product, so that the moss removing agent is prevented from running off when being subjected to rain wash, and the moss removing effect has long-acting property.
Description
Technical Field
The invention belongs to the field of cultural relic protection, and particularly relates to a pure inorganic strengthening-moss removing complexing agent for protecting weathered stone cultural relics and a preparation method thereof.
Background
Weathering degradation of stone cultural relics is often accompanied by simultaneous occurrence of multiple diseases. Taking the sandstone grotto cultural relics in south as an example, the moist and rainy environment not only leads to the erosion of the cementing material in the rock but also promotes the growth of moss. This is because the surface becomes loose and the porosity increases after the rock has weathered, providing space for the growth of moss; the dissolved minerals also provide nutrients for the growth of the moss. The moss is a common plant planted on the surface of the stone cultural relic and is rich in rhizoid, and the rhizoid is attached to the surface of the rock or penetrates into the pores of the rock to play a role in fixing in the growth process. Organic matters secreted in the growth process of the moss and the grown rhizoid form a layer of 'biological organic film' on the surface of the rock to store water and nutrients. When the moss is dried and dead on the sandstone surface, the biofilm on the surface is cracked and curled, and the biofilm can be peeled off from the body together with the consolidated sand, so that the degradation of the rock is accelerated. After the moss is stripped from the rock body, the loose sandstone is exposed to provide places and nutrients for the regrowth of the moss, and a vicious circle is formed. In addition, the moss is attached to the surface of the stone cultural relic to shield the original appearance of the cultural relic, thereby destroying the aesthetic feeling of the cultural relic. Therefore, the damage of the moss to the stone cultural relics is not negligible. Therefore, the prevention of the growth of the moss on the surface of the stone cultural relic has important significance for the long-term preservation of the stone cultural relic.
Reinforcing and moss removing in the protection of stone cultural relics are carried out separately for a long time, and the operation process is complex, time-consuming and labor-consuming. A large number of literature reports indicate that the effect of the moss removing agent is obviously restricted by the environment, rainfall can cause the dissolution and loss of the moss removing agent, and moss appears on the surface of rock again. If the reinforcing agent and the moss removing agent are compounded, the reinforcing agent can anchor the moss removing agent in the solidified product so that the moss removing agent is subjected to rain wash and is prevented from running off, and the drug effect exertion time of the moss removing agent is prolonged. In order to solve the problem of moss growth on the surface of weathered rock, the invention provides a pure inorganic composite protective material with a reinforcing function and a moss removing function.
Disclosure of Invention
Aiming at the problem of the propagation of moss on the surface of weathered stone cultural relics in the nature, the invention provides a pure inorganic strengthening-moss removing compound agent with the strengthening function and the moss removing function. The complexing agent is compounded with the coating removing agent on the basis of ensuring the strengthening performance, simplifies the operation steps and solves the problem of quick failure of the coating removing agent.
The invention is realized by the following technical scheme:
the invention discloses a pure inorganic strengthening-moss removing compound agent for protecting weathered stone cultural relics, which comprises the following raw materials in percentage by mass:
as a further improvement, the dispersant of the invention is ethanol C2H5OH, Ethyl acetate CH3COOC2H5And isopropyl alcohol C3H7Any one of OH.
As a further improvement, the preparation method of the nano GO @ CuO provided by the invention comprises the following steps:
1) placing 0.6-1.5mg/mL nano Graphene Oxide (GO) water dispersion and N, N-dimethylformamide in a round bottom bottle, stirring and heating to 80-95 ℃;
2) injecting 0.1-0.5M copper acetate or copper chloride solution into the system, and stirring at 80-95 ℃;
3) washing the mixture with deionized water, centrifuging and collecting precipitate;
4) the precipitate and H2Sealing O in a polytetrafluoroethylene-lined stainless steel autoclave, carrying out hydrothermal reaction at the temperature of 120 ℃ and 180 ℃ for 8-12 hours, and finally carrying out centrifugation and drying to obtain the nano GO @ CuO.
The invention also discloses a preparation method of the pure inorganic strengthening-moss removing complexing agent for protecting weathered stone cultural relics, which comprises the following steps:
1) mixing nano MgO and nano GO @ CuO according to the mass ratio of 1 (0.003-0.03) for ultrasonic treatment, and then mixing the mixture with H2Sealing O in a polytetrafluoroethylene-lined stainless steel autoclave, and finally centrifuging and drying to obtain a compound of nano magnesium oxide and nano GO @ CuO when carrying out hydrothermal reaction for 4-8 hours;
2) mixing the compound and a dispersing agent according to the mass ratio of 1 (3-10), and then carrying out ultrasonic treatment for 10-20 min to uniformly disperse the nano particles in the dispersing agent to obtain a suspension A;
3) mixing magnesium chloride hexahydrate and deionized water according to the mass ratio of 1 (1.05-1.8) to obtain a solution B;
4) when the reinforcing-moss removing complexing agent is used, the solution B is slowly added into the suspension A according to the mass ratio of the suspension A to the solution B of (1.5-7.0) to 1, and ultrasonic treatment is carried out to obtain the reinforcing-moss removing complexing agent.
The invention has the following beneficial effects:
the reinforcing-moss removing compound agent provided by the invention has the advantages that no obvious color difference is generated after the reinforcing-moss removing compound agent is applied to the surface of weathered stone cultural relics, and the mechanical strength is obviously improved.
The nano GO @ CuO in the strengthening-moss removing complexing agent disclosed by the invention not only can inactivate moss spores contacted with the nano GO @ CuO, prevent the moss spores from germinating on the surface of a rock, but also can kill moss growing on the surface of the rock.
The purpose of step 1 in the preparation of the reinforcing-moss removing complexing agent is to anchor the nano MgO on the graphene oxide by utilizing the excellent adsorption property of the graphene oxide. After the nano MgO participates in the curing reaction, the nano GO @ CuO can be fixed in the nano MgO @ CuO, so that the coating remover cannot flow away with water after being subjected to rain wash, and the service time of the coating remover is prolonged.
The reinforcing-moss removing compound agent is a pure inorganic material, and has good weather resistance and long service life.
The invention combines two steps of reinforcing and removing moss into one, simplifies the operation process, solves the problem of quick failure of the moss removing agent, and provides a new material for protecting weathered stone cultural relics with moss growing on the surface.
In conclusion, the reinforcing-moss removing complexing agent disclosed by the invention is good in permeability, and cannot change the original appearance of the cultural relics when permeating into weathered rocks; the mechanical strength of the rock is obviously improved after the strengthening treatment; the moss on the rock surface can be effectively killed, and meanwhile, the moss spores are inactivated; the reinforcing agent in the complexing agent can anchor the moss removing agent in the consolidation product, so that the moss removing agent is prevented from running off when being subjected to rain wash, and the moss removing effect has long-acting property. The reinforcing and coating removing compound agent has a good reinforcing and protecting effect on stone cultural relics weathered by organisms, solves the problems of loose and fragile rocks and quick coating removing agent failure, is a pure inorganic material, has good aging resistance and long service life, and can be widely applied to the protection of weathered stone cultural relics.
Drawings
FIG. 1 is a photograph (500-fold) of bryozoa spores on a medium prepared with a consortium-desmutum complexing agent containing 0.02% nano GO @ CuO;
in FIG. 1, (a) growth of bryozoan spores after 3 days; (b) moss spore growth after 28 days;
FIG. 2 is a photograph (500-fold) of bryozoa spores on a medium prepared with a consortium-desmutum complexing agent containing 0.1% nano GO @ CuO;
in fig. 2, (a) growth of bryozoan spores after 3 days; (b) moss spore growth after 28 days;
FIG. 3 photo (500 times) of bryozoa spores on medium prepared with strengthening-desmutting complexing agent without nano GO @ CuO added;
in fig. 3, (a) growth of bryozoan spores after 3 days; (b) growth of bryophyte spores after 28 days.
Detailed Description
The invention discloses a pure inorganic strengthening-moss removing compound agent for protecting weathered stone cultural relics, which comprises the following raw materials in percentage by mass:
the dispersant is ethanol (C)2H5OH), ethyl acetate (CH)3COOC2H5) And isopropyl alcohol (C)3H7OH) is used.
The preparation method of the nano GO @ CuO comprises the following steps: firstly, 0.6-15 mg/mL of GO water dispersion and 35-40 mL of N, N-dimethylformamide are placed in a round bottom bottle, stirred and heated to 80-95 ℃. Then, 0.1-0.5M copper acetate or copper chloride solution is injected into the system, and the mixture is stirred for 0.5-2.5h at the temperature of 80-95 ℃; . And then, washing the mixture for 2-3 times by using deionized water, and centrifugally collecting precipitates. Finally, the precipitate and H are combined2And sealing O in a polytetrafluoroethylene-lined stainless steel autoclave, carrying out hydrothermal reaction for 8-12 hours at 120-180 ℃, and finally carrying out centrifugation and drying to obtain the nano GO @ CuO.
The preparation method of the strengthening-moss removing complexing agent for protecting weathered stone cultural relics is characterized by comprising the following steps of:
1) mixing nano MgO and nano GO @ CuO according to the mass ratio of 1 (0.003-0.03) for ultrasonic treatment, and then mixing the mixture withH2Sealing O in a polytetrafluoroethylene-lined stainless steel autoclave for hydrothermal reaction for 4-8 hours, and finally centrifuging and drying to obtain a compound of nano magnesium oxide and nano GO @ CuO;
2) mixing the compound and a dispersing agent according to the mass ratio of 1 (3-10), and then carrying out ultrasonic treatment for 10-20 min to uniformly disperse the nano particles in the dispersing agent to obtain a suspension A;
3) mixing magnesium chloride hexahydrate and deionized water according to the mass ratio of 1 (1.05-1.8) to obtain a solution B;
4) when the reinforcing-moss removing complexing agent is used, the solution B is slowly added into the suspension A according to the mass ratio of the suspension A to the solution B of (1.5-7.0) to 1, and ultrasonic treatment is carried out to obtain the reinforcing-moss removing complexing agent.
The technical solution of the present invention is further illustrated by the following specific examples:
example 1
Preparation of strengthening-moss removing compound agent
Accurately weighing 0.336g nanometer MgO and 0.0015g nanometer GO @ CuO mixed ultrasonic for 20min, and mixing the mixture with 50mLH2O is sealed in a stainless steel autoclave with a polytetrafluoroethylene lining, and the hydrothermal reaction is carried out for 6 hours at 120 ℃. And finally, centrifuging and drying to obtain a mixture of nano magnesium oxide and nano GO @ CuO. The mixture was ultrasonically dispersed for 15min with 4.618g of absolute ethanol to give suspension A. 0.339g of MgCl2·6H2O dissolved in 0.480g H2Obtaining solution B in O; slowly adding the solution B into the suspension A, and performing ultrasonic treatment for 10min to obtain the strengthening-moss removing complexing agent.
Second, testing physical properties of the strengthening-moss removing compound
2g of the reinforcing liquid was sucked up by a rubber head dropper and dropped onto the surface of a standard weathered rock sample (20 mm. times.20 mm) having a compressive strength of 0.88MPa at a rate of 40 drops/min. After the reinforcement, the sample is placed in an environment with the temperature of 25 +/-10 ℃ and the relative humidity of 60 +/-20% for maintenance. The consolidation was repeated three times a day. And finally, the sample is solidified in the natural environment after being reinforced for three times. After one week, the mass, the chromaticity and the strength of the sample after reinforcement were measured with an analytical balance, a colorimeter and a universal material testing machine, respectively. The mass increase rate of the sample after reinforcement is 6.5%, the compressive strength is 11.56MPa, and the color difference before and after reinforcement is 3.74.
Example 2
Preparation of strengthening-moss removing compound agent
Accurately weighing 0.336g nanometer MgO and 0.0075g nanometer GO @ CuO, mixing and ultrasonic treating for 20min, and mixing the mixture with 50mLH2O is sealed in a stainless steel autoclave with a polytetrafluoroethylene lining, and the hydrothermal reaction is carried out for 6 hours at 120 ℃. And finally, centrifuging and drying to obtain a mixture of nano magnesium oxide and nano GO @ CuO. The mixture was ultrasonically dispersed for 15min with 4.618g of absolute ethanol to give suspension A. 0.339g of MgCl2·6H2O dissolved in 0.480g H2Obtaining solution B in O; slowly adding the solution B into the suspension A, and performing ultrasonic treatment for 10min to obtain the strengthening-moss removing complexing agent.
Second, testing physical properties of the strengthening-moss removing compound
2g of the reinforcing liquid was sucked up by a rubber head dropper and dropped onto the surface of a standard weathered rock sample (20 mm. times.20 mm) having a compressive strength of 0.88MPa at a rate of 40 drops/min. After the reinforcement, the sample is placed in an environment with the temperature of 25 +/-10 ℃ and the relative humidity of 60 +/-20% for maintenance. The consolidation was repeated three times a day. And finally, the sample is solidified in the natural environment after being reinforced for three times. After one week, the mass, the chromaticity and the strength of the sample after reinforcement were measured with an analytical balance, a colorimeter and a universal material testing machine, respectively. Through calculation, the mass increase rate of the sample after reinforcement is 6.6%, the compressive strength is 11.38MPa, and the color difference before and after reinforcement is 7.60. The content of the nano GO @ CuO in the complexing agent is improved, the mass increase rate and the compressive strength change of a reinforced sample are not large, the color difference is obviously increased, the use amount of the nano GO @ CuO is not too much, and the retention of the aesthetic value of the cultural relics is not facilitated when the use amount of the nano GO @ CuO exceeds 0.1 percent.
Comparative example 1
The same as example 1 except that nano GO @ CuO was not added, the other steps were the same as example 1. The mass increase rate of the sample after reinforcement is 7.4%, the compressive strength is 11.61MPa, and the color difference before and after reinforcement is 4.86. The test result shows that the addition of the nano GO @ CuO does not damage the reinforcing effect of the reinforcing-moss removing complexing agent, and simultaneously can reduce the color difference of the sample before and after reinforcing.
Example 3
First, mixing preparation of strengthening-moss removing complexing agent and plant culture medium
Accurately weighing 0.336g nanometer MgO and 0.0015g nanometer GO @ CuO mixed ultrasonic for 20min, and mixing the mixture with 50mLH2O is sealed in a stainless steel autoclave with a polytetrafluoroethylene lining, and the hydrothermal reaction is carried out for 6 hours at 120 ℃. And finally, centrifuging and drying to obtain a mixture of nano magnesium oxide and nano GO @ CuO. 0.339g of MgCl2·6H2O dissolved in 0.480gH2Obtaining solution B in O; slowly adding the solution B into the mixture, and performing ultrasonic treatment for 10min to obtain undiluted strengthening-moss removing compound agent. The complexing agent and the plant culture medium are uniformly mixed according to the volume ratio of 1:10, and poured into a culture dish. The moss spore suspension is inoculated on the culture medium after the culture medium is cooled. Finally, the dishes were placed in a climatic incubator (temperature 24 ℃, humidity 85%).
Second, moss spore germination experiment
After a period of time, the growth of the bryozoans spores was observed under a microscope (500-fold) with extra depth of field. FIG. 1(a) is the microscopic morphology of bryozoans after 3 days of culture. (b) Is the micro-morphology after 28 days of culture. Inactivation of bryozoans spores inoculated on the medium was observed after 28 days. The experiment shows that the strengthening-moss removing complexing agent can extinguish fire and stop moss spores from germinating.
Example 4
Preparation of strengthening-moss removing compound agent
Accurately weigh 0.336g of nano MgO and 0.015g of nano GO @ CuO mixed ultrasonic for 20min, then mix the mixture with 50mLH2O is sealed in a stainless steel autoclave with a polytetrafluoroethylene lining, and the hydrothermal reaction is carried out for 6 hours at 120 ℃. And finally, centrifuging and drying to obtain a mixture of nano magnesium oxide and nano GO @ CuO. 0.339g of MgCl2·6H2O dissolved in 0.480gH2Obtaining solution B in O; slowly adding the solution B into the mixture, and performing ultrasonic treatment for 10min to obtain undiluted strengthening-moss removing compound agent. Combining a complexing agent withThe plant culture medium is uniformly mixed according to the volume ratio of 1:10 and poured into a culture dish. The moss spore suspension is inoculated on the culture medium after the culture medium is cooled. Finally, the dishes were placed in a climatic incubator (temperature 24 ℃, humidity 85%).
Second, moss spore germination experiment
After a period of time, the growth of the bryozoans spores was observed under a microscope (500-fold) with extra depth of field. FIG. 2(a) is the microscopic morphology of bryozoans after 3 days of culture. (b) Is the micro-morphology after 28 days of culture. Inactivation of bryozoans spores inoculated on the medium was observed after 28 days. The experiment shows that the strengthening-moss removing complexing agent can extinguish fire of moss spores and prevent the moss spores from germinating.
Comparative example 2
The same as example 3, except that nano GO @ CuO was not added, the other steps were the same as example 3. FIG. 3(a) is the microscopic morphology of bryozoans after 3 days of culture. (b) Is the micro-morphology after 28 days of culture. After 28 days, the moss spores inoculated on the culture medium are observed to be green and still keep activity, which indicates that the nano GO @ CuO can effectively kill the moss spores to inactivate the moss spores in the complexing agent, and the moss spores cannot be inactivated only by the reinforcing agent.
Example 5
The preparation of the strengthening-moss removing compound agent is the same as that of example 1. 2g of the reinforcing liquid is sucked by a rubber head dropper and is dripped on a weathered rock sample with moss growing on the surface at the speed of 40 drops/min. The consolidation was repeated three times a day. Discoloration of the moss was observed after 5 days and complete withered and yellow death after 12 days, indicating that the reinforcement-moss complex was able to kill the moss on the rock surface.
Example 6
The other steps are the same as in example 5. And after the moss on the surface of the sample is completely dead, placing the sample in a natural environment, and allowing the sample to be subjected to rain water. After three months, the moss on the surface of the sample is observed not to revive again, which indicates that the moss removing effect of the compound agent has long-acting property.
The foregoing is illustrative of only a few specific embodiments of the invention. It is obvious that the present invention is not limited to the above embodiments, but many variations are possible, and all variations that can be derived or suggested by a person skilled in the art from the disclosure of the present invention should be considered as the protection scope of the present invention.
Claims (2)
1. The pure inorganic strengthening-moss removing compound agent for protecting weathered stone cultural relics is characterized by comprising the following raw materials in percentage by mass:
the preparation method of the pure inorganic strengthening-moss removing complexing agent for protecting weathered stone cultural relics comprises the following steps:
1) mixing nano MgO and nano GO @ CuO according to the mass ratio of 1 (0.003-0.03) for ultrasonic treatment, and then mixing the mixture with H2Sealing O in a polytetrafluoroethylene-lined stainless steel autoclave for hydrothermal reaction for 4-8 hours, and finally centrifuging and drying to obtain a compound of nano magnesium oxide and nano GO @ CuO;
2) mixing the compound and a dispersing agent according to the mass ratio of 1 (3-10), and then carrying out ultrasonic treatment for 10-20 min to uniformly disperse the nano particles in the dispersing agent to obtain a suspension A;
3) mixing magnesium chloride hexahydrate and deionized water according to the mass ratio of 1 (1.05-1.8) to obtain a solution B;
4) when in use, the solution B is slowly added into the suspension A according to the mass ratio of the suspension A to the solution B of (1.5-7.0) to 1 and ultrasonic treatment is carried out to obtain the strengthening-moss removing complexing agent;
the preparation method of the nano GO @ CuO comprises the following steps:
firstly, placing 0.6-15 mg/mL nano Graphene Oxide (GO) water dispersion and N, N-dimethylformamide in a round bottom bottle, stirring and heating to 80-95 ℃;
then, 0.1-0.5M copper acetate or copper chloride solution is injected into the system, and the mixture is stirred for 0.5-2.5h at the temperature of 80-95 ℃;
then, washing the mixture for 2-3 times by using deionized water, and centrifugally collecting precipitates;
finally, the precipitate and H are combined2And sealing O in a polytetrafluoroethylene-lined stainless steel autoclave, carrying out hydrothermal reaction for 8-12 hours at 120-180 ℃, and finally carrying out centrifugation and drying to obtain the nano GO @ CuO.
2. The pure inorganic strengthening-moss removing compound agent for protecting weathered stone cultural relics as claimed in claim 1, wherein the dispersant is ethanol C2H5OH, Ethyl acetate CH3COOC2H5And isopropyl alcohol C3H7Any one of OH.
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| CN108434509A (en) * | 2018-03-15 | 2018-08-24 | 广西中医药大学 | Chinese medicine antibacterial paper diaper detachably containing graphene oxide-copper silver nanoparticle compound |
| CN109573997A (en) * | 2018-11-07 | 2019-04-05 | 江苏城乡建设职业学院 | A kind of preparation method of graphene oxide-loaded vulcanization carbon/carbon-copper composite material |
| CN110510985A (en) * | 2019-06-04 | 2019-11-29 | 浙江大学 | A kind of pure inorganic magnesium-based reinforcement material of osmosis type and preparation method and reinforcement means for the reinforcing of sandstones stone cultural artifact |
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| CN108434509A (en) * | 2018-03-15 | 2018-08-24 | 广西中医药大学 | Chinese medicine antibacterial paper diaper detachably containing graphene oxide-copper silver nanoparticle compound |
| CN109573997A (en) * | 2018-11-07 | 2019-04-05 | 江苏城乡建设职业学院 | A kind of preparation method of graphene oxide-loaded vulcanization carbon/carbon-copper composite material |
| CN110510985A (en) * | 2019-06-04 | 2019-11-29 | 浙江大学 | A kind of pure inorganic magnesium-based reinforcement material of osmosis type and preparation method and reinforcement means for the reinforcing of sandstones stone cultural artifact |
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