CN104163656B - A kind of method reinforcing carbonate rock stone cultural artifact - Google Patents
A kind of method reinforcing carbonate rock stone cultural artifact Download PDFInfo
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- CN104163656B CN104163656B CN201410333753.4A CN201410333753A CN104163656B CN 104163656 B CN104163656 B CN 104163656B CN 201410333753 A CN201410333753 A CN 201410333753A CN 104163656 B CN104163656 B CN 104163656B
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Abstract
A kind of method reinforcing carbonate rock stone cultural artifact, comprises the following steps: rock surface is cleaned up by (1) with deionized water；(2) with tartaric acid and ammonia furnishing pH=3.8 ~ 4.4, tartaric acid concentration is 0.15 ~ 0.20mol L‑1Tartaric acid ammonia solution, process rock surface；(3) then stone surface is processed with modified tetraethyl orthosilicate colloidal sol；(4) under room temperature aging more than 7 days.The invention have the advantage that due to teos hydrolysis generation be silicon dioxide, therefore good with the compatibility of stone material base, do not change by the protection outward appearance of stone cultural artifact, color and feel；Hydrophobic, the comprcssive strength of stone material, acidproof, resistance to soiling is made to be improved.
Description
Technical field
The present invention relates to the reinforcement means of loose calcium carbonate rock, the top layer being mainly used in calcium carbonate stone cultural artifact inferior reinforces.
Background technology
China has a large amount of precious historical relic and historic site, and wherein outdoors stone cultural relics occupies consequence, as Six Dynasties's stone inscription, the Giant Stone Buddha at Leshan Mountain, Yungang Grottoes, the Dunhuang Caves, the Longmen Grottoes, south ring hall rock cave, Dazu Rock Carvings etc..These historical relics are important history resource and tourist resources.Outdoors stone cultural relics is broadly divided into silicates and carbonate by rock composition.Silicates rock includes granite, glutenite etc..Granite is hard, durable, stability is high, and such as Yungang Grottoes, its major part chisels on Anhydrite quartzy sandstone, and its main component is SiO2, next to that Al2O3；Glutenite main component is also SiO2, but SiO in this rocks2The overwhelming majority is the superfine quartz particles of sedimentary facies, and intergrain bond thing is easily destroyed, and hardness is the highest, easy-weathering, such as the Giant Stone Buddha at Leshan Mountain (soft siltstone), Mo kao grotto at Dunhuang etc.；Carbonate rock rocks includes limestone (CaCO3Be main) and dolomite (have the MgCO of certain content3) etc., its stability is between granite and glutenite, as Six Dynasties's stone inscription, south ring hall rock cave, the Longmen Grottoes etc..Six Dynasties's stone inscription belongs to carbonate rock, represent early Medieval China Central-South side in period art of stone carving top level, it is the gem of art that can compare favourably with ancient Egypt, Babylon, India, Greece, Rome, the Renaissance time equivalence works, worldwide there is impact.Due to chemical action (aerosol, SO in acid rain, air2、NOXAnd organic pollution), physical action (freeze thawing, salt action), the bio secretion being attached to stone cultural artifact goes out the corrosiveness of acid, causes the destruction of the carbonate stone cultural artifacts such as Six Dynasties's stone inscription.In order to prevent chemistry, physics and biological agent to the corrosion of stone cultural artifact and deterioration, or in order to reinforce frangible, fracture, the stone material of slump, generally it is coated with last layer protective material at stone surface.Currently used protective material widely is alkoxy silane, such as tetraethyl orthosilicate.The siloxane polymer generated when this kind of protective material processes rock can produce bridging action between particles of inorganic material, by the hydrolysis of alkoxyl, is bound up with siloxane chain and makes weakness, loose sandstone be reinforced and strengthen between adjacent particle.The product of alkoxy silane reaction is similar with the sandstone containing silicon compound, has the good compatibility, affinity with sandstone, thus has well protection to sandstone.The protection of carbonate rock; owing to alkoxy silane lacks affinity with carbonate rock; chemical bond can not be formed between rock and polymer and protection to carbonate rock is not ideal enough, thus limit alkoxy silane and be applied to the reinforcing of carbonate rock.Tetraethyl orthosilicate is the Typical Representative of alkoxy silane, has the steam effect that viscosity is low, can penetrate in the hole and environment of stone material and forms the advantages such as the stable gel with siliconoxygen bond.But tetraethyl orthosilicate is in stone material hole dry run, owing to there is gas-liquid flexure plane inside gel, capillary force is different, causes Gel Tear to produce crack, thus especially can not reinforce deterioration stone material effectively to stone material.
Summary of the invention
The present invention proposes the fissureless preparation method of tetraethyl orthosilicate, and can apply to the carbonate stone cultural artifacts such as Six Dynasties's stone inscription.
For reaching above-mentioned purpose; the present invention takes following measure: first with deionized water by clean for the surface clean of rock to be reinforced; then with tartaric acid ammonia solution pretreatment; stone cultural artifact is processed again with modified tetraethyl orthosilicate colloidal sol; the microfissure making loose rock is filled; silicon dioxide on Surface mulch, thus makes loose calcium carbonate rock be reinforced and protect.
The present invention is achieved by the following technical solutions.
A kind of method reinforcing carbonate rock stone cultural artifact, comprises the following steps.
(1) with deionized water, rock surface is cleaned up.
(2) with tartaric acid and ammonia furnishing pH=3.8 ~ 4.4, tartaric acid concentration is 0.15 ~ 0.20mol L-1Tartaric acid ammonia solution, process rock surface, make rock surface generate Calcium d-tartrate transition layer, so that functional hydroxy group on rock surface band.
(3) generating the reinforcement protection layer with silicon dioxide as main component in then processing stone surface, loose rock hole with modified tetraethyl orthosilicate colloidal sol, these protective layers are connected by hydroxyl with calcium carbonate.
(4) under room temperature aging more than 7 days.
The preparation method of the modified tetraethyl orthosilicate colloidal sol described in step (3): first under room temperature, tetraethyl orthosilicate and ethanol are mixed, stir 10 minutes, add deionized water, the most ultrasonic 10 minutes, adding hydroxyl the most with vigorous stirring is the polydimethylsiloxane of end group, is finally stirred vigorously lower addition surfactant 1-Aminooctane, control tetraethyl orthosilicate during dropping: ethanol: water: polydimethylsiloxane: 1-Aminooctane mol ratio is 1:16:10:0.04:0.002；Described hydroxyl be the polydimethylsiloxane molecular weight of end group be Mn ≈ 550.
In the preparation method of the modified tetraethyl orthosilicate colloidal sol described in step of the present invention (3), described ethanol can be substituted by isopropanol or acetone.Described surfactant 1-Aminooctane, can be substituted by dibutyl tin laurate.
Tetraethyl orthosilicate colloidal sol described in step of the present invention (3) processes the operation of stone surface can use the methods such as brushing, spray.
Advantages of the present invention: due to teos hydrolysis generation is silicon dioxide, therefore good with the compatibility of stone material base, does not change by the protection outward appearance of stone cultural artifact, color and feel；Hydrophobic, the comprcssive strength of stone material, acidproof, resistance to soiling is made to be improved.
Accompanying drawing explanation
Fig. 1 is pH value of the present invention curve chart over time.
Fig. 2 is Ca of the present invention2+Concentration curve chart over time.
Fig. 3 Antacid effectiveness evaluating apparatus schematic diagram.
Detailed description of the invention
Below in conjunction with embodiment, invention is elaborated.
Embodiment 1.
(1) with deionized water, rock surface is cleaned up；
(2) with tartaric acid and ammonia furnishing pH=3.8, tartaric acid concentration is 0.15mol L-1Tartaric acid ammonia solution, process rock surface, make rock surface generate Calcium d-tartrate transition layer, so that functional hydroxy group on rock surface band；
(3) generating the reinforcement protection layer with silicon dioxide as main component in then processing stone surface, loose rock hole with modified tetraethyl orthosilicate colloidal sol, these protective layers are connected by hydroxyl with calcium carbonate；
(4) under room temperature aging 30 days.
Prepared by the modified tetraethyl orthosilicate colloidal sol described in step (3): under room temperature, first tetraethyl orthosilicate and ethanol are mixed, stir 10 minutes, add deionized water, under the conditions of being stirred for ultrasonic 10 minutes, then being stirred vigorously lower addition hydroxyl is the polydimethylsiloxane of end group, is finally stirred vigorously lower addition surfactant 1-Aminooctane, control tetraethyl orthosilicate during dropping: ethanol: water: polydimethylsiloxane: 1-Aminooctane mol ratio is 1:16:10:0.04:0.002；Described hydroxyl be the polydimethylsiloxane molecular weight of end group be Mn ≈ 550.
Acid resistance, the stone material processed with modified tetraethyl orthosilicate colloidal sol, under the sulfuric acid solution leaching of pH=4.0, pH and Ca determined2+It is respectively less than untreated stone material, with commercial materials stone protector material depot Sol (Coesol) quite (Fig. 1).
Antacid effectiveness evaluation methodology.
Experimental provision (Fig. 3) is made up of 5 parts such as magnetically-actuated circulating pump, effusion meter, reservoir, liquid storage beaker and leaching pipes.In experimentation, acid solution realizes circulation by a circulating pump, continues leaching stone sample, leaching time 8h.The flow-control of solution is 6mL min-1, the processing of stone that is leached grows up 50 mm, wide 50 mm, thick 10 mm, and stone material is straight at 45, and stone material is from Dou Cun stone pit, Nanjing, and it is mainly composed of calcium carbonate (content is 97%), and submember is the oxide of silicon, aluminum and ferrum.
In order to intuitively characterize consolidation effect, 10g(80 mesh is selected to sieve) stone material powder mix with 2mL water, compacting under 20MPa in diameter 3.2cm mould, and in one week of placement naturally under room temperature, gained sample is as the dummy sample of loose rock.The modified tetraethyl orthosilicate colloidal sol of 2mL is slowly permeated on dummy sample surface, naturally fastening strength is measured after placing one month under room temperature, recording comprcssive strength and increase to 126.2MPa from 77.4MPa, improve about 163% before unguyed, recording case hardness increases to 84HD(table 1 from 60HD).
Embodiment 2.
(1) with deionized water, rock surface is cleaned up.
(2) with tartaric acid and ammonia furnishing pH=4.0, tartaric acid concentration is 0.17mol L-1Tartaric acid ammonia solution, process rock surface, make rock surface generate Calcium d-tartrate transition layer, so that functional hydroxy group on rock surface band.
(3) generating the reinforcement protection layer with silicon dioxide as main component in then processing stone surface, loose rock hole with modified tetraethyl orthosilicate colloidal sol, these protective layers are connected by hydroxyl with calcium carbonate.
(4) under room temperature aging 30 days.
Prepared by the modified tetraethyl orthosilicate colloidal sol described in step (3): first tetraethyl orthosilicate and isopropanol are mixed, stir 10 minutes, add deionized water, under the conditions of being stirred for ultrasonic 10 minutes, then being stirred vigorously lower addition hydroxyl is the polydimethylsiloxane of end group, finally it is stirred vigorously lower addition surfactant 1-Aminooctane, control tetraethyl orthosilicate during dropping: isopropanol: water: polydimethylsiloxane: 1-Aminooctane mol ratio is 1:16:10:0.04:0.002；Described hydroxyl be the polydimethylsiloxane molecular weight of end group be Mn ≈ 550.
Result records the comprcssive strength of penetration reinforcement dummy sample and case hardness all has decline (table 1) in various degree than embodiment 1.
Embodiment 3.
(1) with deionized water, rock surface is cleaned up.
(2) with tartaric acid and ammonia furnishing pH=4.0, tartaric acid concentration is 0.17mol L-1Tartaric acid ammonia solution, process rock surface, make rock surface generate Calcium d-tartrate transition layer, so that functional hydroxy group on rock surface band.
(3) generating the reinforcement protection layer with silicon dioxide as main component in then processing stone surface, loose rock hole with modified tetraethyl orthosilicate colloidal sol, these protective layers are connected by hydroxyl with calcium carbonate.
(4) under room temperature aging 30 days.
Prepared by the modified tetraethyl orthosilicate colloidal sol described in step (3): first tetraethyl orthosilicate and acetone are mixed, stir 10 minutes, add deionized water, under the conditions of being stirred for ultrasonic 10 minutes, then being stirred vigorously lower addition hydroxyl is the polydimethylsiloxane of end group, finally it is stirred vigorously lower addition surfactant 1-Aminooctane, control tetraethyl orthosilicate during dropping: acetone: polydimethylsiloxane: 1-Aminooctane mol ratio is 1:16:10:0.04:0.002；Described hydroxyl be the polydimethylsiloxane molecular weight of end group be Mn ≈ 550.
Result records the comprcssive strength of penetration reinforcement dummy sample and case hardness all has decline (table 1) in various degree than embodiment 1.
Embodiment 4.
(1) with deionized water, rock surface is cleaned up.
(2) with tartaric acid and ammonia furnishing pH=4.2, tartaric acid concentration is 0.18mol L-1Tartaric acid ammonia solution, process rock surface, make rock surface generate Calcium d-tartrate transition layer, so that functional hydroxy group on rock surface band.
(3) generating the reinforcement protection layer with silicon dioxide as main component in then processing stone surface, loose rock hole with modified tetraethyl orthosilicate colloidal sol, these protective layers are connected by hydroxyl with calcium carbonate.
(4) under room temperature aging 7 days.
Prepared by the modified tetraethyl orthosilicate colloidal sol described in step (3): first tetraethyl orthosilicate and ethanol are mixed, stir 10 minutes, add deionized water, under the conditions of being stirred for ultrasonic 10 minutes, then being stirred vigorously lower addition hydroxyl is the polydimethylsiloxane of end group, finally it is stirred vigorously lower addition dibutyl tin laurate, control tetraethyl orthosilicate during dropping: ethanol: water: polydimethylsiloxane: dibutyl tin laurate mol ratio is 1:16:10:0.04:0.002；Described hydroxyl be the polydimethylsiloxane molecular weight of end group be Mn ≈ 550.
Result records the comprcssive strength of penetration reinforcement dummy sample and case hardness all has decline (table 1) in various degree than embodiment 1.
Table 1 stone material be modified tetraethyl orthosilicate colloidal sol process after comprcssive strength and the change of hardness
Claims (3)
1. the method reinforcing carbonate rock stone cultural artifact, is characterized in that comprising the following steps:
(1) with deionized water, rock surface is cleaned up；
(2) with tartaric acid and ammonia furnishing pH=3.8 ~ 4.4, tartaric acid concentration is 0.15 ~ 0.20mol L-1Tartaric acid ammonia solution, process rock surface；
(3) then stone surface is processed with modified tetraethyl orthosilicate colloidal sol；
(4) under room temperature aging more than 7 days；
The preparation method of the modified tetraethyl orthosilicate colloidal sol described in step (3): first under room temperature, tetraethyl orthosilicate and ethanol are mixed, stir 10 minutes, add deionized water, the most ultrasonic 10 minutes, adding hydroxyl the most with vigorous stirring is the polydimethylsiloxane of end group, is finally stirred vigorously lower addition surfactant 1-Aminooctane, control tetraethyl orthosilicate during dropping: ethanol: water: polydimethylsiloxane: 1-Aminooctane mol ratio is 1:16:10:0.04:0.002；Described hydroxyl be the polydimethylsiloxane molecular weight of end group be Mn ≈ 550.
The method of reinforcing carbonate rock stone cultural artifact the most according to claim 1, is characterized in that, in the preparation method of the modified tetraethyl orthosilicate colloidal sol described in step (3), described ethanol is substituted by isopropanol or acetone；Described surfactant 1-Aminooctane is substituted by dibutyl tin laurate.
The method of reinforcing carbonate rock stone cultural artifact the most according to claim 1, is characterized in that the tetraethyl orthosilicate colloidal sol described in step (3) processes operating with of stone surface and brushes or spraying method.
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| CN105016657B (en) * | 2015-07-14 | 2017-02-01 | 东莞环球经典新型材料有限公司 | Stain-resistant artificial stone plate and preparation method thereof |
| CN108084872B (en) * | 2017-12-01 | 2020-06-05 | 华南协同创新研究院 | Weathered rock cultural relic reinforcing agent and preparation method thereof |
| CN111620716B (en) * | 2020-04-28 | 2022-10-11 | 江苏新视界先进功能纤维创新中心有限公司 | Preparation method and protection method of ancient building outer wall protection coating |
| CN111499408A (en) * | 2020-04-29 | 2020-08-07 | 同济大学 | Solidified compact carbonate material, solidification method and detection method thereof |
| CN112209741B (en) * | 2020-10-09 | 2022-07-05 | 西北工业大学 | Reinforcing and protecting method for open-air brick stone cultural relics based on nano composite material |
| CN114958252B (en) * | 2022-06-17 | 2023-04-14 | 西安交通大学 | Calcium carbonate oligomer-reinforced siloxane-modified polyvinyl alcohol solution for sandstone relic protection, and method and application thereof |
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| CN103224408A (en) * | 2013-04-22 | 2013-07-31 | 中国科学院上海硅酸盐研究所 | Reinforcement material for preservation of cultural relics, and preparation method and application thereof |
| CN103570280A (en) * | 2013-01-11 | 2014-02-12 | 中国科学院上海硅酸盐研究所 | Preparation method and reinforcement method of crispy powder ceramic culture relic reinforcement material |
| CN103601835A (en) * | 2013-01-11 | 2014-02-26 | 中国科学院上海硅酸盐研究所 | Reinforcing and protecting material for weathered ceramic cultural relics, preparation method and reinforcing method thereof |
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| CN103570280A (en) * | 2013-01-11 | 2014-02-12 | 中国科学院上海硅酸盐研究所 | Preparation method and reinforcement method of crispy powder ceramic culture relic reinforcement material |
| CN103601835A (en) * | 2013-01-11 | 2014-02-26 | 中国科学院上海硅酸盐研究所 | Reinforcing and protecting material for weathered ceramic cultural relics, preparation method and reinforcing method thereof |
| CN103224408A (en) * | 2013-04-22 | 2013-07-31 | 中国科学院上海硅酸盐研究所 | Reinforcement material for preservation of cultural relics, and preparation method and application thereof |
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