CN103224408A - Reinforcement material for preservation of cultural relics, and preparation method and application thereof - Google Patents
Reinforcement material for preservation of cultural relics, and preparation method and application thereof Download PDFInfo
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- CN103224408A CN103224408A CN2013101405509A CN201310140550A CN103224408A CN 103224408 A CN103224408 A CN 103224408A CN 2013101405509 A CN2013101405509 A CN 2013101405509A CN 201310140550 A CN201310140550 A CN 201310140550A CN 103224408 A CN103224408 A CN 103224408A
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Abstract
The invention relates to a reinforcement material for preservation of cultural relics, and a preparation method and an application thereof. The reinforcement material for the preservation of the cultural relics is an organic silicon composite material prepared by a sol-gel reaction by using tetraethoxysilane as a matrix, silicon dioxide nanoparticles and terminal-hydroxyl polydimethylsiloxane as terminal-hydroxyl polydimethylsiloxane modifiers, wherein the mass ratio of the tetraethoxysilane to the nanosized silicon dioxide and to the polydimethylsiloxane is 100 : (0-25) : (0-6).
Description
Technical field
The invention belongs to the Techniques of Relics Protection field, relate to a kind of do not ftracture organosilicon protective material and use properties thereof that is used for the historical relic reinforcement protection, be specially adapted to the protection and the reinforcing of stone cultural artifact.
Background technology
Stone cultural artifact is the important component part in the cultural heritage, because its loose porous constructional feature, is easy to be subjected to the disadvantageous effect from environment Zhong Shui, salt, wind effect, and the protecting materials of needing excellent property badly carries out reinforcement protection.In general; require that stone cultural artifact protecting materials viscosity is low, good penetrability, good weatherability; with the historical relic matrix cohesive force, sticking power and consistency preferably should be arranged; certain reversibility is arranged; nontoxic, environmental friendliness; do not change the cultural heritage outward appearance, consider contingent change of properties in its deterioration process, should not produce after material takes place to wear out has the destructive novel substance to historical relic.Silicone based material is with its hypertonicity, good and to the stable advantage of uv irradiating with the stone material consistency; from all kinds of protecting materialss, show one's talent; in the stone cultural artifact protection, obtained extensive studies and application, used the most extensive with tetraethoxy (TEOS) and oligomer thereof in the employed various commercial protective agents.
Yet; because the existence of wicking action etc.; the organosilicon protecting materials very easily ftractures in gelation exsiccant process after being penetrated in the stone material matrix; the cracking fragment can form the secondary capillary network in stone matter matrix; the stone water-intake rate is increased, may quicken the various deteriorations that cause under the water effect.At the problem of organosilicon material brittle cracking, existing in the world multiple research typically has PMC (Particle Modified Consolidant) protective material, introduces metal nanoparticle in organosilicon, reduces wicking action; Introduce elastomeric segments such as polydimethylsiloxane, strengthen flexible.Although they have all obtained significant anti-cracking effect, also there are many defectives.Relatively outstanding and physical constraints the problem used have: the PMC protective material is very big to the influence of stone material matrix appearance color; The introducing of elastomeric segments makes the anti-salt damage ability of stone material reduce, and causes deterioration.
Chinese patent application 201110208130.0 discloses a kind of protecting stone material film nano material and preparation method thereof; material uses the PEO polyoxyethylene to make tensio-active agent in this application; hydrochloric acid or ammoniacal liquor are that Preparation of Catalyst silicon oxide colloid ball is induced self-assembly method (EISA) preparation by solvent evaporates; reach the protection purpose by protecting in stone surface filming envelope; but do not relate to and make protecting materials enter the inner filling pore of stone matter matrix to form the successive gel network structure and reinforce; the new energy of also not mentioned material aspect cracking modification and salt tolerant protection; in addition; the material require of this method preparation uses tensio-active agent; catalyst system therefor is hydrochloric acid or ammoniacal liquor, and historical relic itself is had certain corrosive nature.
Summary of the invention
Therefore, the object of the present invention is to provide a kind of novel nano silicon-dioxide-hydroxyl-terminated injecting two methyl siloxane-tetraethoxy ternary complex protection material and preparation method thereof, to meet stone cultural artifact protection requirement.
At this; on the one hand; the invention provides a kind of historical relic's protection reinforcement material; described historical relic's protection material is to be base material with the tetraethoxy; with Nano particles of silicon dioxide and hydroxyl-terminated injecting two methyl siloxane is the organosilicon matrix material that properties-correcting agent makes by solgel reaction, and the mass ratio of wherein said tetraethoxy, nano silicon oxide and polydimethyl silica is 100:(0～25): (0～6).
Of the present invention is the protection solution of main component with the tetraethoxy; this viscosity of material is low; easily be penetrated in the porous stone cultural artifact, act on the stone material and environment steam reactive polymeric, the colloidal silicon of generation deposits in the rock pore structure; perhaps with hydrophilic stone material in hydroxyl reaction; generate stable Si-O-Si key, play the effect of original cementing matter in the sandstone, strengthen reactive force between mineral particle; thereby obviously strengthen the intensity of former deterioration stone material, play good reinforcement protection effect.Select nanoparticle and elastomeric segments simultaneously tetraethoxy to be carried out modification, reached anti-rimose purpose, and obtained good weathering resistance.The network of silica that tetraethoxy generates in the trielement composite material mainly provides the performance of reinforcing; Nanoparticle can improve organosilicon rimose problem, improves the anti-salt aged problem of historical relic, remedies the infringement of elastomerics PDMS to the salt tolerant aging resistance; Elastomerics PDMS then further improves organosilicon rimose problem, improves the change of the aberration that nanoparticle brings simultaneously.By three's synergy, obtain the material of over-all properties optimum.
On the other hand, the invention provides a kind of method for preparing above-mentioned historical relic's protection reinforcement material, comprise that the Virahol colloidal sol, catalyzer and the water that mix tetraethoxy, nano silicon oxide are to carry out one-step hydrolysis just, the mass ratio of wherein said tetraethoxy and nano silicon oxide is 100:(0～25), the mol ratio of described tetraethoxy and water is (0.1～10): 1; And add the polydimethylsiloxane stirring at room and made described historical relic's protection reinforcement material in 2～10 hours, the mass ratio of wherein said tetraethoxy and polydimethylsiloxane is 100:(0～6).
Method of the present invention uses Nano particles of silicon dioxide, terminal hydroxy group modified dimethyl polysiloxane (PDMS) and tetraethoxy to carry out solgel reaction jointly, can prepare do not ftracture, the processing method of the compound historical relic's protection material of ternary of superior performance.This material is added a small amount of Nano particles of silicon dioxide and elastic PDMS, is used sol-gel process to make by tetraethoxy, is good fluidity, translucent liquid.
Preferably, the mass percentage concentration of nano silicon oxide is 0.5～5% in the Virahol colloidal sol of described nano silicon oxide.
Preferably, the particle diameter of described Nano particles of silicon dioxide is 5～50nm, more preferably 10～20nm.
Preferably, the molecular weight of described hydroxyl-terminated injecting two methyl siloxane is 400-5000, and the hydroxyl massfraction is 4～6%, and viscosity is 5-500cp.
Preferably, described catalyzer is a dibutyl tin laurate, and the mass ratio of described tetraethoxy and catalyzer is 100:(1～5).Catalyst system therefor is a neutral catalyst, adopts acidity or basic catalyst agent compared to existing technology, more meets the requirement of historical relic's protection material.
Preferably, described one-step hydrolysis just stirs down at 40-70 ℃ and carried out in 4-8 hour.
Another aspect; the invention provides a kind of application of above-mentioned historical relic's protection reinforcement material; comprise: adopt dipping, spraying or the method for brushing is applied to historical relic with described protecting materials and carries out osmotic treated, and will place the air normal temperature and pressure through the historical relic of osmotic treated or place in the climatic chamber and solidify.
Preferably, described historical relic is a stone cultural artifact.
Beneficial effect of the present invention:
1) protective material does not ftracture under physical environment;
2) good with the stone material consistency;
3) salt tolerant evil superior performance;
4) little to the stone material appearance effects;
5) consolidation effect is obvious;
6) obviously improve the stone material hydrophobicity performance.
7) preparation and using method are simple to operation.
Description of drawings
Fig. 1 is through the SEM photo of the historical relic of reinforcement protecting material reinforcing of the present invention;
The pictorial diagram of Fig. 2 before and after the dried salt circulation of historical relic that reinforcement protecting material of the present invention is reinforced.
Embodiment
Further specify the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that the following embodiment of accompanying drawing only is used to illustrate the present invention, and unrestricted the present invention.
Novel indehiscent organosilicon historical relic's protection material of the present invention, main ingredient is tetraethoxy, Nano particles of silicon dioxide, hydroxyl-terminated injecting two methyl siloxane.Adopt sol-gel technology, preparation is not ftractureed, the compound historical relic's protection material of ternary of superior performance is at first to having added tetraethoxy prehydrolysis under catalyzer and certain temperature of silicon dioxde isopropanol solution, adds other components again.
Preparation method of the present invention and using method comprise the steps:
(1) protecting materials preparation: the Virahol colloidal sol, catalyzer and the water that add nano silicon oxide in an amount of tetraethoxy carry out one-step hydrolysis just, add polydimethylsiloxane again, normal temperature magnetic agitation 2-10 hour.
(2) reinforcement process: adopt the method for dipping, spraying, brushing etc. that protecting materials is applied to stone cultural artifact, but look the practical situation multi-pass operations.The stone material sample of having constructed placed the air normal temperature and pressure or place in the climatic chamber solidify.
At first Nano particles of silicon dioxide is adopted the method for ultra-sonic dispersion, be made into uniform sol with Virahol, the Nano particles of silicon dioxide size can be the 5-50 nano level, preferred 10-20nm, and wherein the nano-silicon massfraction in the Virahol colloidal sol of Nano particles of silicon dioxide is 0.5～5%.
The Virahol colloidal sol and the tetraethoxy that mix the Nano particles of silicon dioxide of above-mentioned preparation, both consumptions can be 100:(0～25 according to the mass ratio of tetraethoxy and nano silicon oxide) determine, about ultra-sonic dispersion 10 minutes, add entry and catalyzer and carry out one-step hydrolysis just.The present invention controls organosilyl hydrolytie polycondensation process by the consumption of control water, and the mol ratio of water and tetraethoxy can be 0.1:1-10:1.The preferred neutral catalyst of catalyst system therefor of the present invention can not produce acid and alkali corrosion to stone cultural artifact, dibutyl tin laurate (DBTL) for example, and catalyst consumption can be the 1-5% of tetraethoxy quality.Just one-step hydrolysis can carry out in stirring under 40-70 ℃ in 4-8 hour, and stirring can be adopted magnetic agitation.
Add then, for example drip hydroxyl-terminated injecting two methyl siloxane, stirred under the room temperature 2～10 hours, can obtain good fluidity, translucent uniform protecting materials system.The molecular weight of used hydroxyl-terminated injecting two methyl siloxane is 400-5000, and the hydroxyl massfraction is 4～6%, and viscosity is 5-500cp.The consumption of hydroxyl-terminated injecting two methyl siloxane can be the 0-6% of tetraethoxy quality
Above-mentioned each amounts of components of the present invention is through determining that in whole protecting agent system, the mass ratio of tetraethoxy, nano silicon oxide and polydimethyl silica is 100:(0～25 after the experiment repeatedly): (0～6).
The protecting materials of above-mentioned preparation can be applicable to historical relic, when particularly stone cultural artifact is reinforced, for example adopts the method for dipping, spraying, brushing etc. to carry out penetration operation, but looks the practical situation multi-pass operations.The stone material sample of having constructed placed the air normal temperature and pressure or place in the climatic chamber solidify.
Remove by the reinforcement material of inventing on microscopic examination, surface hydrophobicity test, water-intake rate and porosity detection, ventilation property detection, intensity test, outward appearance chromatism test and the salt tolerant evil test shows have the organosilicon material good penetrability, and the good general characteristic of stone material consistency, compare with present existing modified organic silicon material, also have tangible advantage.1) reinforcement material does not ftracture after acting on stone matter matrix, and capillary pressure reduces and the existence of elastomeric segments has effectively improved organosilyl shortcoming; 2) protecting materials that applies is less to the historical relic appearance effects, has solved the shortcoming that the PMC strengthening agent causes big aberration substantially; 3) salt tolerant evil superior performance may be that the existence of nanoparticle has hindered the soluble salt transport process; 4) consolidation effect is obvious, and the silica silicon skeleton that the teos hydrolysis polycondensation forms has played the reinforcement protection effect; 5) the stone material hydrophobicity performance improves, and the outer pending methyl group that polydimethylsiloxane provides has played hydrophobic effect at stone surface.
Microscopic examination: SEM(S-4800; Hitachi) observe the historical relic sample, referring to Fig. 1, it illustrates the SEM photo of the historical relic of reinforcing through reinforcement protecting material of the present invention; therefrom as seen, protected cultural artifact surface generated continuously, densification, flawless, nanoparticle cluster visible microstructure.
Surface hydrophobicity test: use Static Contact angle measuring instrument (JC2000C goes up marine morning), record and reinforce sample, and blank stone material is almost completely hydrophilic, illustrates that hydrophobic nature greatly improves to 100-120 ° of the contact angle average out to of deionized water.
Water-intake rate and porosity detect: use ceramic water-intake rate determinator (Hunan, Hunan section) to test; the stone material water-intake rate of handling without protecting materials is 11.97%; porosity is 24.18%, and water-intake rate slightly is reduced to 10-10.5% after protective material of the present invention is reinforced, and porosity is 21-21.5%.This is relevant with above-mentioned hydrophobic nature raising, and explanation protection processing does not change the stone material microstructure to a great extent.
Ventilation property detects: the anti-water vapour by Deutsche Industry Norm 52615 test stone materials sees through ability, the anti-steam permeable coefficient of blank stone material is 1.356, the anti-steam permeable coefficient of reinforcing sample is 1.77-1.79, ventilation property decreases but reduces seldom, can keep the original ventilation property of historical relic preferably.
Intensity test: to bulk sample carry out mechanical test (5592 material universal testing machines, Instron), the blank sample average intensity value is 12.8MPa, reinforcing the sample average intensity level is 14.2-15.5MPa, fastening strength is moderate.
The outward appearance chromatism test: same point color value (CM2600d spectrophotometer, Konica) before and after the record protecting stone material is handled, recording its aberration Δ E is 3～13, can be satisfied with the value of chromatism requirement (Δ E＜5) that historical relic's protection allows when more excellent condition.
Salt tolerant evil test: will reinforcing sample, to be soaked in concentration be in 16% the metabisulfite solution 7 hours, and taking-up places 60 ℃ of baking ovens (DHG-9075A, Shanghai one perseverance), kept 15 hours, and be a circulation.Sample appearance is complete substantially after 5 circulations, and mass loss is less than 13%.Referring to Fig. 2, it illustrates the pictorial diagram before and after the dried salt circulation of historical relic that reinforcement protecting material of the present invention is reinforced, therefrom as seen after 5 dried wet salts circulations sample appearance complete substantially.
Further exemplify embodiment below to describe the present invention in detail.Should understand equally; following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The temperature that following example is concrete, time, charging capacity etc. also only are examples in the OK range, promptly, those skilled in the art can do by the explanation of this paper and select in the suitable scope, and not really want to be defined in the hereinafter concrete numerical value of example.
Embodiment 1
Nano particles of silicon dioxide (nano-SiO with 5g particle diameter 15nm
2) be made into even colloidal sol with the 95g Virahol, get this colloidal sol of 40g and mix ultra-sonic dispersion 10 minutes with 9g tetraethoxy (TEOS).Drip the DBTL of 3g water, 0.09g, stir 4h, drip 0.45g hydroxyl-terminated injecting two methyl siloxane (PDMS) and continue to stir 1h, obtain translucent homogeneous solution at 40 ℃ of lower magnetic forces.The TEOS, nano silicon oxide, the PDMS mass ratio that add are 100:22.2:5; The add-on of water is 3g, and water silicon is 4:1 than (mol ratio of tetraethoxy and water).
Use near the verrucano Giant Buddha Temple, Shaanxi, be cut into 2*2*2cm bulk, two kinds of specifications of 4*4*1cm sheet, the ethanol ultrasonic cleaning, dry naturally.With above-mentioned protective material dip treating, taking-up is positioned over climatic chamber, and (SETH-Z-022R ESPEC) solidified one month.
Microscopic examination: SEM(S-4800, Hitachi) observe the stone material sample, show that sandstone surface has generated continuous densification, flawless, nanoparticle cluster visible microstructure.
Surface hydrophobicity test: use Static Contact angle measuring instrument (JC2000C goes up marine morning), record and reinforce contact angle average out to 128.8 degree of sample, and blank stone material is almost completely hydrophilic, illustrates that hydrophobic nature greatly improves to deionized water.
Water-intake rate and porosity detect: use ceramic water-intake rate determinator (Hunan, Hunan section) to test; the stone material water-intake rate of handling without protecting materials is 11.97%; porosity is 24.18%, and water-intake rate slightly is reduced to 10.32% after protective material of the present invention is reinforced, and porosity is 21.43%.Relevant with above-mentioned hydrophobic nature raising, and explanation protection processing does not change the stone material microstructure to a great extent.
Ventilation property detects: the anti-water vapour by Deutsche Industry Norm 52615 test stone materials sees through ability, and the anti-steam permeable coefficient of blank stone material is 1.356, and the anti-steam permeable coefficient of reinforcing sample is 1.781, and ventilation property decreases but reduces few.
Intensity test: to bulk sample carry out mechanical test (5592 material universal testing machines, Instron), the blank sample average intensity value is 12.8MPa, reinforcing the sample average intensity level is 14.2MPa, fastening strength is moderate.
The outward appearance chromatism test: same point color value (CM2600d spectrophotometer, Konica) before and after the record protecting stone material is handled, recording its aberration Δ E is 6.8.The value of chromatism scope (Δ E＜5) that a little higher than historical relic's protection allows.
Salt tolerant evil test: will reinforcing sample, to be soaked in concentration be in 16% the metabisulfite solution 7 hours, and taking-up places 60 ℃ of baking ovens (DHG-9075A, Shanghai one perseverance), kept 15 hours, and be a circulation.Sample appearance is complete substantially after 5 circulations, and mass loss is less than 13%.
Experimental example 2
The basic embodiment 1 that repeats, just the consumption of Nano particles of silicon dioxide is 10% of a tetraethoxy in the component.The microscopic examination sample surfaces does not ftracture continuously, and nanocluster as seen; Value of chromatism Δ E is 6.12, and slight colour-change shows as a little whiting; In the salt tolerant evil circulation sample appearance change little, 5 dried wet salts circulation back mass losses about 16%.
Experimental example 3
The basic embodiment 1 that repeats, just the consumption of Nano particles of silicon dioxide is 5% of a tetraethoxy in the component.The microscopic examination sample surfaces does not ftracture continuously, and nanocluster as seen; Value of chromatism Δ E is 5.47, and colour-change is faint; In the salt tolerant evil circulation sample appearance change little, 5 dried wet salts circulation back mass losses about 18%.
Experimental example 4
The basic embodiment 1 that repeats, just the consumption of hydroxyl-terminated injecting two methyl siloxane is 3% of a tetraethoxy in the component.The microscopic examination sample surfaces does not ftracture continuously, and nanocluster as seen.Value of chromatism Δ E is about 8.8, and colour-change is bigger.In the salt tolerant evil circulation sample appearance change less, 5 dried wet salts circulation back mass losses about 11%.
Experimental example 5
The basic embodiment 1 that repeats, just the consumption of hydroxyl-terminated injecting two methyl siloxane is 1% of a tetraethoxy in the component.The microscopic examination sample surfaces does not ftracture continuously, and nanocluster as seen; Value of chromatism Δ E is about 12.6, and colour-change is bigger; In the salt tolerant evil circulation sample appearance change less, 5 dried wet salts circulation back mass losses about 9%.
Experimental example 6
Substantially repeat embodiment 1, just water silicon ratio is 0.1:1, the protecting materials that obtain flawless, hydrophobic, good permeability equally, have certain fastening strength, the variation of outward appearance aberration is little, salt resistant character is good.
Experimental example 7
Substantially repeat embodiment 1, just water silicon ratio is 10:1, the protecting materials that obtain flawless, hydrophobic, good permeability equally, have certain fastening strength, the variation of outward appearance aberration is little, salt resistant character is good.
Experimental example 8
The basic embodiment 1 that repeats, only being to use particle diameter is the Nano particles of silicon dioxide of 5nm, the protecting materials that obtain flawless, hydrophobic, good permeability equally, have certain fastening strength, the variation of outward appearance aberration is little, salt resistant character is good.
Experimental example 9
The basic embodiment 1 that repeats, only being to use particle diameter is the Nano particles of silicon dioxide of 50nm, the protecting materials that obtain flawless, hydrophobic, good permeability equally, have certain fastening strength, the variation of outward appearance aberration is little, salt resistant character is good.
Experimental example 10
The basic embodiment 1 that repeats, just stone quality sample treatment process is spraying, the protection effect with embodiment 1.
Experimental example 11
The basic embodiment 1 that repeats, just stone quality sample treatment process is for brushing, the protection effect with embodiment 1.
Industrial applicability
Ordinary methods such as historical relic reinforcement material of the present invention and stone material consistency are good, good fluidity, employing infiltration, coating are used for historical relic's protection; gel at normal temperatures and pressures; play the effect of good reinforcement protection; consolidation effect is obvious; can obviously improve the stone material hydrophobicity performance, and have superior salt tolerant evil performance, and reinforce little the historical relic appearance effects; be expected to be widely used in historical relic, especially the reinforcement protection of stone cultural artifact.
Claims (10)
1. historical relic's protection reinforcement material; it is characterized in that; described historical relic's protection material is to be base material with the tetraethoxy; with Nano particles of silicon dioxide and hydroxyl-terminated injecting two methyl siloxane is the organosilicon matrix material that properties-correcting agent makes by solgel reaction, and the mass ratio of wherein said tetraethoxy, nano silicon oxide and polydimethylsiloxane is 100:(0～25): (0～6).
2. a method for preparing the described historical relic's protection reinforcement material of claim 1 is characterized in that, comprising:
The Virahol colloidal sol, catalyzer and the water that mix tetraethoxy, nano silicon oxide are to carry out one-step hydrolysis just, the mass ratio of wherein said tetraethoxy and nano silicon oxide is 100:(0～25), the mol ratio of described tetraethoxy and water is (0.1～10): 1; Add the polydimethylsiloxane stirring at room and made described historical relic's protection reinforcement material in 2～10 hours, the mass ratio of wherein said tetraethoxy and polydimethylsiloxane is 100:(0～6).
3. method according to claim 2 is characterized in that, the mass percentage concentration of nano silicon oxide is 0.5～5% in the Virahol colloidal sol of described nano silicon oxide.
4. according to claim 2 or 3 described methods, it is characterized in that the particle diameter of described Nano particles of silicon dioxide is 5～50nm.
5. method according to claim 4 is characterized in that, the particle diameter of described Nano particles of silicon dioxide is 10～20nm.
6. according to each described method in the claim 2 to 5, it is characterized in that the molecular weight of described hydroxyl-terminated injecting two methyl siloxane is 400～5000, the hydroxyl massfraction is 4～6%, and viscosity is 5～500cp.
7. according to each described method in the claim 2 to 6, it is characterized in that described catalyzer is a dibutyl tin laurate, the mass ratio of described tetraethoxy and catalyzer is 100:(1～5).
8. according to each described method in the claim 2 to 7, it is characterized in that described one-step hydrolysis just stirs down at 40～70 ℃ and carried out in 4～8 hours.
9. the application of the described historical relic's protection reinforcement material of claim 1; it is characterized in that; comprise: adopt dipping, spraying or the method for brushing is applied to historical relic with described protecting materials and carries out osmotic treated, and will place the air normal temperature and pressure through the historical relic of osmotic treated or place in the climatic chamber and solidify.
10. application according to claim 9 is characterized in that, described historical relic is a stone cultural artifact.
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| CN103739307A (en) * | 2013-12-13 | 2014-04-23 | 四川大学 | Sandstone stone cultural relic protection material, preparation method and application method |
| CN103964737A (en) * | 2014-04-25 | 2014-08-06 | 纳谷新材料(杭州)有限公司 | Nano-silicon-modified double-component wear-resistant penetration hardener and preparation method thereof |
| CN104163656A (en) * | 2014-07-15 | 2014-11-26 | 南昌大学 | Method for reinforcing carbonate rock stone historical relics |
| CN109577091A (en) * | 2018-12-08 | 2019-04-05 | 郑州大学 | A kind of paper relics reinforcing liquid |
| CN111499408A (en) * | 2020-04-29 | 2020-08-07 | 同济大学 | Solidified compact carbonate material, solidification method and detection method thereof |
| CN111620716A (en) * | 2020-04-28 | 2020-09-04 | 嘉兴海欣生态科技有限公司 | Preparation method and protection method of ancient building outer wall protection coating |
| CN112209741A (en) * | 2020-10-09 | 2021-01-12 | 西北工业大学 | Reinforcing and protecting method for open-air brick stone cultural relics based on nano composite material |
| CN114790119A (en) * | 2022-04-01 | 2022-07-26 | 哈尔滨工程大学 | Low-water-absorption organic/inorganic composite silicon-based coating on concrete surface and preparation method thereof |
| CN115637104A (en) * | 2022-11-04 | 2023-01-24 | 山东大学 | Preparation method and application of tetraethoxysilane-siloxane-surfactant hybrid material |
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| CN103739307A (en) * | 2013-12-13 | 2014-04-23 | 四川大学 | Sandstone stone cultural relic protection material, preparation method and application method |
| CN103739307B (en) * | 2013-12-13 | 2015-08-05 | 四川大学 | A kind of sandstones stone cultural artifact protecting materials and methods for making and using same |
| CN103964737A (en) * | 2014-04-25 | 2014-08-06 | 纳谷新材料(杭州)有限公司 | Nano-silicon-modified double-component wear-resistant penetration hardener and preparation method thereof |
| CN103964737B (en) * | 2014-04-25 | 2016-01-20 | 纳谷新材料(杭州)有限公司 | Wear-resisting infiltration stiffening agent of nano-silicon modified double components and preparation method thereof |
| CN104163656A (en) * | 2014-07-15 | 2014-11-26 | 南昌大学 | Method for reinforcing carbonate rock stone historical relics |
| CN104163656B (en) * | 2014-07-15 | 2016-09-28 | 南昌大学 | A kind of method reinforcing carbonate rock stone cultural artifact |
| CN109577091A (en) * | 2018-12-08 | 2019-04-05 | 郑州大学 | A kind of paper relics reinforcing liquid |
| CN111620716A (en) * | 2020-04-28 | 2020-09-04 | 嘉兴海欣生态科技有限公司 | Preparation method and protection method of ancient building outer wall protection coating |
| 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 |
| CN112209741A (en) * | 2020-10-09 | 2021-01-12 | 西北工业大学 | Reinforcing and protecting method for open-air brick stone cultural relics based on nano composite material |
| CN114790119A (en) * | 2022-04-01 | 2022-07-26 | 哈尔滨工程大学 | Low-water-absorption organic/inorganic composite silicon-based coating on concrete surface and preparation method thereof |
| CN115637104A (en) * | 2022-11-04 | 2023-01-24 | 山东大学 | Preparation method and application of tetraethoxysilane-siloxane-surfactant hybrid material |
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