CN103555086A - Earthen ruins return repair protecting agent - Google Patents
Earthen ruins return repair protecting agent Download PDFInfo
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- CN103555086A CN103555086A CN201310521436.0A CN201310521436A CN103555086A CN 103555086 A CN103555086 A CN 103555086A CN 201310521436 A CN201310521436 A CN 201310521436A CN 103555086 A CN103555086 A CN 103555086A
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Abstract
The invention discloses an earthen ruins return repair protecting agent, comprising ZB-F600 bi-component trifluorochloroethylene polymer (FEVE) watery fluororesin, a solvent and an ultraviolet absorbent, wherein the mass ratio of the ZB-F600 bi-component FEVE watery fluororesin to the solvent is 1:3 to 1:7; the ultraviolet absorbent accounts for 0.1-0.2% of mass of the earthen ruins return repair protecting agent; the solvent is a mixed solution of distilled water and absolute ethyl alcohol, of which the mass ratio is 3:7 to 6:4; the ultraviolet absorbent is UV-531, UV-328, or a mixture of UV-531 and UV-238. The earthen ruins return repair protecting agent disclosed by the invention has the performances of water tolerance, acid resistance, alkali resistance, strong adhesive force and strong ageing resistance; the loosen and dropping earthen ruins can be subjected to return repair protection; the returned and repaired earthen ruins is simple and unsophisticated in original appearance, small in color change, and high in mechanical strength; long-term preservation of cultural objects is facilitated.
Description
Technical field
The invention belongs to Techniques of Relics Protection field, be specifically related to the return renovation agent in the native ruins that a kind of restorable reparation becomes flexible, comes off.
Background technology
China's soil ruins area is huge, especially rams native ruins more, and many-sided valuable information such as historical, cultural, artistic, scientific and technological are being carried in these native ruins.Ram native ruins owing to ramming the limitation of material, being subject to manually to ram level and ramming the unequal factor of the inner internal stress of soil layer itself affects, with the passing of the years, these native ruins are because physics, chemistry, biological, the impact of the factor such as artificial, occurred loosening, peel off, cracking, collapse, the diseases such as weathering, as built and ram native ruins for version containing optical gate ruins, mostly ramming soil layer has occurred becoming flexible, come off, there is crack in ground, ruins, passageway, even there is large fracture, oneself is precarious, as protected not in time, to constitute a threat to ruins resistance to overturning.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of water-fast, acidproof, alkaline-resisting, clinging power strong, good permeability, resistance of aging are strong native ruins return restoration and protection agent.
Solving the problems of the technologies described above adopted technical scheme is: the return restoration and protection agent of native ruins is comprised of the two component FEVE water-based fluororesins of ZB-F600, solvent, uv-absorbing agent; the mass ratio of the two component FEVE water-based fluororesins of ZB-F600 and solvent is 1:3～1:7; uv-absorbing agent accounts for 0.1%～0.2% of native ruins return restoration and protection agent quality; described solvent is the mixed solution that the mass ratio of distilled water and dehydrated alcohol is 3:7～6:4, and uv-absorbing agent is the mixture of UV-531, UV-328 or UV-531 and UV-328.
The mixed solution that the mass ratio of the preferred distilled water of solvent of the present invention and dehydrated alcohol is 3:7～4:6, the best is the mixed solution that the mass ratio of distilled water and dehydrated alcohol is 4:6.
Preferred 1:3～the 1:5 of mass ratio of the two component FEVE water-based fluororesins of ZB-F600 of the present invention and solvent, the best is 1:3.
The mixture that the mass ratio of the preferred UV-531 of uv-absorbing agent of the present invention or UV-531 and UV-328 is 1:1; when uv-absorbing agent is UV-531; uv-absorbing agent the best accounts for 0.1% of native ruins return restoration and protection agent quality; when uv-absorbing agent is the mass ratio of UV-531 and the UV-328 mixture that is 1:1, uv-absorbing agent the best accounts for 0.2% of native ruins return restoration and protection agent quality.
The two component FEVE water-based fluororesins of ZB-F600 of the present invention are provided by Zhenbang Fluorine-coating Co., Ltd., Dalian; The chemical name of UV-531 is Octabenzone, and the chemical name of UV-328 is 2-(2H-benzotriazole-2-yl)-4, and 6-di-tert-pentyl phenol, provides by Nanjing Holley bright chemical company limited.
The preparation method of the present invention's soil ruins return restoration and protection agent is: according to the quality proportioning of above-mentioned raw materials; after distilled water and dehydrated alcohol are mixed; add uv-absorbing agent; 50～60 ℃ of heated and stirred 2 hours; add again the two component FEVE water-based fluororesins of ZB-F600; be stirred to and disperse to form homodisperse emulsion completely, be prepared into the return restoration and protection agent of native ruins.
The using method that the ruins return restoration and protection agent of the present invention's soil is carried out return restoration and protection to the native ruins of becoming flexible, ftracture, coming off is:
1, splicing.Splicing generally has 3 kinds of methods: spell from the bottom to top (1); (2) from top to bottom spell; (3) partial splice, integral body is closed up.During splicing, first fragment is conscientiously repeatedly observed and studied, after then examination being spelled, fragment and the splicing position of tram are numbered.
2, infiltrate.First with rubber pipette bulb, blow off as far as possible the dust in crack, then by the ruins return restoration and protection agent of the present invention soil and distilled water in mass ratio for after 1:20 mixes, be sprayed at and splice on position and fragment section, infiltrate.
3, bonding.The ruins return restoration and protection agent of the present invention's soil is dripped on the fragment section being seeped into after infiltration, be then bonded on splicing position.
4, repair.Adopt the ruins return restoration and protection agent of the present invention's soil repeatedly to repair splicing position, to reach and integral body harmonious effect mutually.
That the ruins return restoration and protection agent of the present invention soil has is water-fast, acidproof, alkaline-resisting, clinging power strong, good permeability, performance that resistance of aging is strong, can carry out return restoration and protection to the native ruins of becoming flexible, coming off.Various physical strengths, the mechanical property of the native ruins body after return reparation are all effectively improved, and are more conducive to the permanent preservation of historical relic, and the native ruins original appearance after its return is processed is simple and unsophisticated, and chromatic aberration is little, and mechanical strength is high.The invention process technique is simple, and return repairing effect is remarkable, can be used for the native ruins return restoration and protection that becomes flexible, comes off.
Accompanying drawing explanation
Fig. 1 is the thermogravimetric analysis figure of the native ruins of embodiment 1 return restoration and protection agent film forming.
Fig. 2 is the preprosthetic photo of Hanyangling soil property clay warrior in armour.
Fig. 3 is that Hanyangling soil property clay warrior in armour adopts the photo after the return restoration and protection agent of the native ruins of embodiment 1 is repaired.
The emperor of Tu4Shi Tang city wall rams the photo of the loosening exfoliation of soil layer containing optical gate soil ruins.
The emperor of Tu5Shi Tang city wall rams the loosening exfoliation of soil layer containing optical gate soil ruins and adopts the photo after the return restoration and protection agent of the native ruins of embodiment 1 is repaired.
The emperor of Tu6Shi Tang city wall rams the photo of the loosening exfoliation of soil layer containing optical gate soil ruins.
The emperor of Tu7Shi Tang city wall rams the loosening exfoliation of soil layer containing optical gate soil ruins and adopts the photo after the return restoration and protection agent of the native ruins of embodiment 2 is repaired.
The emperor of Tu8Shi Tang city wall rams the photo of the loosening exfoliation of soil layer containing optical gate soil ruins.
The emperor of Tu9Shi Tang city wall rams the loosening exfoliation of soil layer containing optical gate soil ruins and adopts the photo after the return restoration and protection agent of the native ruins of embodiment 3 is repaired.
Figure 10 is that the emperor of Tang city wall rams the photo of the loosening exfoliation of soil layer containing optical gate soil ruins.
Figure 11 is that the emperor of Tang city wall rams the photo after the loosening exfoliation employing of the soil layer native ruins of embodiment 4 return restoration and protection agent is repaired containing optical gate soil ruins.
Figure 12 is that the emperor of Tang city wall rams the photo of the loosening exfoliation of soil layer containing optical gate soil ruins.
Figure 13 is that the emperor of Tang city wall rams the photo after the loosening exfoliation employing of the soil layer native ruins of embodiment 5 return restoration and protection agent is repaired containing optical gate soil ruins.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in more detail, but the invention is not restricted to these embodiment.
Embodiment 1
Take that to prepare the two component FEVE water-based fluororesin 100g of native ruins return restoration and protection agent ZB-F600 used be example, its raw material is composed as follows:
Its preparation method is: according to the quality proportioning of above-mentioned raw materials; after distilled water and dehydrated alcohol are mixed; add UV-328 and UV-531; 50～60 ℃ of heated and stirred 2 hours; add again the two component FEVE water-based fluororesins of ZB-F600; be stirred to and disperse to form homodisperse emulsion completely, be prepared into the return restoration and protection agent of native ruins.
Embodiment 2
Take that to prepare the two component FEVE water-based fluororesin 100g of native ruins return restoration and protection agent ZB-F600 used be example, its raw material is composed as follows:
Its preparation method is identical with embodiment 1.
Embodiment 3
Take that to prepare the two component FEVE water-based fluororesin 100g of native ruins return restoration and protection agent ZB-F600 used be example, its raw material is composed as follows:
Its preparation method is identical with embodiment 1.
Embodiment 4
Take that to prepare the two component FEVE water-based fluororesin 100g of native ruins return restoration and protection agent ZB-F600 used be example, its raw material is composed as follows:
Its preparation method is identical with embodiment 1.
Embodiment 5
Take that to prepare the two component FEVE water-based fluororesin 100g of native ruins return restoration and protection agent ZB-F600 used be example, its raw material is composed as follows:
Its preparation method is identical with embodiment 1.
Embodiment 6
Take that to prepare the two component FEVE water-based fluororesin 100g of native ruins return restoration and protection agent ZB-F600 used be example, its raw material is composed as follows:
Its preparation method is identical with embodiment 1.
Embodiment 7
Take that to prepare the two component FEVE water-based fluororesin 100g of native ruins return restoration and protection agent ZB-F600 used be example, its raw material is composed as follows:
Its preparation method is identical with embodiment 1.
In order to determine optimum material proportion of the present invention, a large amount of laboratory study tests has been carried out in invention, and various laboratories situation is as follows:
Laboratory apparatus: SNB-AI intelligence Brookfield viscometer, Shanghai Nirun Intelligent Technology Co., Ltd.; The popular pH meter of SartoriusPB-10, Sai Duolisi scientific instrument (Beijing) company limited provides; The xeothermic weatherometer of BHO-401A, Shanghai Yi Heng Science and Technology Ltd. produces; X-RiteVS-450 spectrophotometer, U.S. X. Rite Inc. produces; Germany Binder growth cabinet KBF series hydrothermal aging instrument, Louis, Hong Kong business corporation produces; Ultraviolet light and aging proofing box, the auspicious scientific and technological Instrument Ltd. of Shang Hai Jing produces; Q1000DSC+LNCS+FACSQ600SDT Thermo System, U.S. TA company provides; QT-1136PC computer servo system universal testing machine ，Gao Tai detecting instrument company limited provides.
1, determine solvent composition
The mixed solution that the mass ratio of distilled water and dehydrated alcohol of take is respectively 1:9,2:8,3:7,4:6,5:5,6:4 is solvent, the two component FEVE water-based fluororesins of ZB-F600 and solvent are distinguished in mass ratio for 1:9,2:8,3:7,4:6,5:5,6:4 mix, be mixed with emulsion, carry out performance test, test result is as follows:
(1) viscosity test
Adopt SNB-AI intelligence Brookfield viscometer, the emulsion being mixed with is carried out to viscosity test, test condition is room temperature (25 ℃), and test result is in Table 1, and in table, data are the mean value of three groups of tests of parallel survey.
Table 1 emulsion viscosity (mPa.s)
(2) Mechanics Performance Testing
By emulsion film forming on the slide glass that scribbles vacuum silicone grease of test 1 preparation, consumption is 4mL/ slide glass (specification 25mm * 75mm).After to be filmed being dried, the thickness of film forming and mechanical property are tested, test result is in Table 2 and 3.
Table 2 film forming thickness (mm)
The mechanical property of table 3 film forming (N)
From table 1～3, when the mass ratio of distilled water and dehydrated alcohol is 1:9～6:4, the two component FEVE water-based fluororesins of ZB-F600 are with solvent quality during than 3:7～6:4, and the mechanical property of the viscosity of emulsion, film forming thickness and film forming is all better.
(3) stability of emulsion test
By 1 standing for some time of the emulsion being mixed with of test, observe its stability.Test-results shows, when the mass ratio of distilled water and dehydrated alcohol is 1:9, the emulsion property of preparation is all unstable, and emulsion has faint yellow precipitation to generate after 1 day in sealing and standing, and precipitation capacity increases along with the increase of the two component FEVE water-based fluororesin concentration of ZB-F600.When the mass ratio of distilled water and dehydrated alcohol is 3:7, sealing and standing has precipitation to generate after two months, when the mass ratio of distilled water and dehydrated alcohol is 4:6, sealing and standing does not have precipitation half a year yet and generates, but it is too large that distilled water ratio accounts for the ratio of solvent, drip and to ooze soil sample and can make soil sample surface have and mud phenomenon.
Comprehensive test (1)～(3) result, it is 3:7～6:4 that the present invention selects the mass ratio of distilled water and dehydrated alcohol, the mass ratio of optimal selection distilled water and dehydrated alcohol is 4:6.
2, determine the proportioning of the two component FEVE water-based fluororesins of ZB-F600 and solvent
The mixed solution that the mass ratio of distilled water and dehydrated alcohol of take is 4:6 is solvent, by the two component FEVE water-based fluororesins of ZB-F600 and solvent, be that 1:1,1:2,1:3,1:5,1:7 mix in mass ratio, be mixed with emulsion, drip and ooze soil sample (80g/ soil sample and 100g/ soil sample), test its perviousness, test-results is in Table 4.
Table 4 droplet oozes soil sample infiltration result
From table 4, when the mass ratio of the two component FEVE water-based fluororesins of ZB-F600 and solvent is 1:1～1:2, dripping after oozing soil sample changes larger to soil sample surface topography, when the mass ratio of the two component FEVE water-based fluororesins of ZB-F600 and solvent is 1:3～1:7, perviousness is better, drip and ooze after soil sample, soil sample surface is without conjunctiva.Therefore, it is 1:3～1:7 that the present invention selects the mass ratio of the two component FEVE water-based fluororesins of ZB-F600 and solvent, and the best is 1:3.
3, uv-absorbing agent screening
The mixed solution that the mass ratio of distilled water and dehydrated alcohol of take is 4:6 is solvent, according to the mass ratio of the two component FEVE water-based fluororesins of ZB-F600 and solvent, is 1:3, adds different uv-absorbing agents, is mixed with 100g emulsion.After to be filmed, sample is put into ultraviolet light and aging proofing box, ultraviolet lamp power is 60W, vertical irradiation distance is 5cm, ultraviolet ageing certain hour (every test in 12 hours once), taking-up until with extraneous balance after, measure its mass loss (△ m) and colour-change (DE*), test result is in Table 5 and 6.
Table 5 ultraviolet ageing changes rule (g) to the quality of film
The color change rule of table 6 ultraviolet ageing to film
From table 5 and 6, when UV-531 and UV-328 compound use, under ultraviolet radiation, the mass loss of film forming and aberration change are all better than using separately UV-531 or UV-328.Therefore optimal selection of the present invention is usingd mixture that the mass ratio of UV-531 and UV-328 is 1:1 as uv-absorbing agent, uv-absorbing agent accounts for 0.2% of native ruins return restoration and protection agent quality.
In order to determine beneficial effect of the present invention, contriver has carried out various performance tests to the native ruins return restoration and protection agent of embodiment 1 preparation, and concrete test case is as follows:
1, mechanical property rule over time
By native ruins return restoration and protection agent film forming on the slide glass that scribbles vacuum silicone grease of embodiment 1, consumption is 4mL/ slide glass (specification 25mm * 75mm).After to be filmed being dried, under identical same condition, keep different time, respectively at doing tensile test under room temperature (25 ℃), test result is the mean values of 10 groups of tests of parallel survey in Table the following test data of 7().
The mechanical property change with time of table 7 film forming
Note: in table, freezing and thawing test is to be a circulation at 40～-40 ℃, 40 ℃ and-40 ℃ respectively keep 12 hours; During xeothermic weathering test, film is peeled rapidly and returns to indoor temperature measurement again from xeothermic ageing oven takes out.
2, mechanical property variation with temperature rule
After to be filmed being dried, keep same time (2h) under differing temps, in the lower test of room temperature (25 ℃) mechanical property, test result is in Table 8.
The mechanical property of table 8 film forming varies with temperature rule
| Intensity (N) | 0 |
20 |
40 |
60 |
80 |
100℃ | 120℃ |
| 2h | 0.2842 | 0.2928 | 0.3395 | 0.3609 | 0.7061 | 1.4483 | 3.4008 |
3, atmospheric exposure test
Select respectively the 0.1mol/L NaOH aqueous solution, 1mol/L ammonia soln, 1mol/L aqueous hydrochloric acid, 1mol/L aqueous sulfuric acid, 1mol/L aqueous nitric acid carries out atmospheric exposure test, and test-results is in Table 9.
Table 9 atmospheric exposure test result
| Intensity (N) | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| NaOH | 0.7385 | 1..5884 | 2.9960 | 4.0964 | 4.6915 | 6.6174 | 7.2401 |
| NH 3·H 2O | 0.7384 | 0.8238 | 1.2100 | 2.2661 | 2.5587 | 2.6133 | 4.1016 |
| HCl | 0.2900 | 0.3076 | 0.3205 | 0.3328 | 0.3459 | 0.3475 | 0.4414 |
| HNO3 | 0.4394 | 0.4901 | 0.5297 | 0.5523 | 0.6005 | 0.6394 | 0.7018 |
| H2SO4 | 0.3060 | 0.3266 | 0.3327 | 0.3508 | 0.3626 | 0.3695 | 0.3698 |
From table 7～9; this soil ruins return restoration and protection agent is under various different experimental conditions; over time; its mechanical property not only can well keep; and have an increase to a certain degree; illustrate that this soil ruins return restoration and protection agent has excellent mechanical property, the native ruins that reparation is become flexible, come off for return, improving its mechanical strength has positive effect.
4, thermostability experiment
The film 2.5mg that the return restoration and protection agent of the native ruins of embodiment 1 is become puts into Q1000DSC+LNCS+FACSQ600SDT Thermo System tester, carries out the measurement of decomposition temperature, and its test result is shown in Fig. 1.From figure, can clearly find out, at 280 ℃ of left and right films, start to decompose, 400 ℃ are decomposed completely, illustrate that the ruins return restoration and protection agent of the present invention's soil has good thermotolerance.
For further proof beneficial effect of the present invention, the native ruins return restoration and protection agent that contriver adopts embodiment 1 is to the Hanyangling soil property clay warrior in armour restoration and protection of replying to the topic, and test-results is shown in Fig. 2～3.As seen from the figure, its original appearance of soil property clay warrior in armour after this soil ruins return restoration and protection agent reparation obtains complete reproduction.And at annual tracing observation subsequently, soil property clay warrior in armour does not change, intact, there is not any pathology in repair place again.Illustrate that this soil ruins return restoration and protection agent has good repairing effect.
The native ruins return restoration and protection Ji Dui emperor of the Tang city wall that adopts embodiment 1～5 rams the loosening exfoliation of the soil layer restoration and protection of replying to the topic containing optical gate soil ruins, and test-results is shown in Fig. 4～13.As seen from the figure; the emperor of Tang city wall after this soil ruins return restoration and protection agent reparation comes off and locates the existing effect reparation in crack containing the native ruins of optical gate its cracking of rammer soil layer; better reproduce native ruins original appearance; and at annual tracing observation subsequently; there is not cracking obscission in repair place, the cracking disease that comes off is effectively administered again.
Claims (9)
1. a native ruins return restoration and protection agent; it is characterized in that: it is comprised of the two component FEVE water-based fluororesins of ZB-F600, solvent, uv-absorbing agent; the mass ratio of the two component FEVE water-based fluororesins of ZB-F600 and solvent is 1:3～1:7; uv-absorbing agent accounts for 0.1%～0.2% of native ruins return restoration and protection agent quality; described solvent is the mixed solution that the mass ratio of distilled water and dehydrated alcohol is 3:7～6:4, and uv-absorbing agent is the mixture of UV-531, UV-328 or UV-531 and UV-328.
2. native ruins return restoration and protection agent according to claim 1, is characterized in that: described solvent is the mixed solution that the mass ratio of distilled water and dehydrated alcohol is 3:7～4:6.
3. native ruins return restoration and protection agent according to claim 1, is characterized in that: described solvent is the mixed solution that the mass ratio of distilled water and dehydrated alcohol is 4:6.
4. according to the native ruins return restoration and protection agent described in claim 2 or 3, it is characterized in that: the mass ratio of the two component FEVE water-based fluororesins of described ZB-F600 and solvent is 1:3～1:5.
5. according to the native ruins return restoration and protection agent described in claim 2 or 3, it is characterized in that: the mass ratio of the two component FEVE water-based fluororesins of described ZB-F600 and solvent is 1:3.
6. native ruins return restoration and protection agent according to claim 4, is characterized in that: described uv-absorbing agent is UV-531, and uv-absorbing agent accounts for 0.1% of native ruins return restoration and protection agent quality.
7. native ruins return restoration and protection agent according to claim 5, is characterized in that: described uv-absorbing agent is UV-531, and uv-absorbing agent accounts for 0.1% of native ruins return restoration and protection agent quality.
8. native ruins return restoration and protection agent according to claim 4, is characterized in that: described uv-absorbing agent is the mixture that the mass ratio of UV-531 and UV-328 is 1:1, uv-absorbing agent accounts for 0.2% of native ruins return restoration and protection agent quality.
9. native ruins return restoration and protection agent according to claim 5, is characterized in that: described uv-absorbing agent is the mixture that the mass ratio of UV-531 and UV-328 is 1:1, uv-absorbing agent accounts for 0.2% of native ruins return restoration and protection agent quality.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104893583A (en) * | 2015-05-22 | 2015-09-09 | 苏州市贝克生物科技有限公司 | Cultural relic surface acid/alkali-corrosion-resistant coating and preparation method thereof |
| CN105604341A (en) * | 2015-12-31 | 2016-05-25 | 陕西师范大学 | High sand content earth relic solidification method |
| CN105602307A (en) * | 2016-03-02 | 2016-05-25 | 沈阳化工大学 | Waterproof transparent coating for protecting cultural relic |
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| CN101608082A (en) * | 2009-07-30 | 2009-12-23 | 陕西师范大学 | The compound envelope that is used for the ancient architecture colour painting is protected agent |
| CN102850816A (en) * | 2011-06-27 | 2013-01-02 | 上海杰事杰新材料(集团)股份有限公司 | Thermoplastic resin composite material and preparation method and application thereof |
| CN103102750A (en) * | 2013-02-04 | 2013-05-15 | 陕西师范大学 | Application of ZB-F600 two-component FEVE water-based fluororesin in repair of silk and paper cultural relic writings and drawings |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101608082A (en) * | 2009-07-30 | 2009-12-23 | 陕西师范大学 | The compound envelope that is used for the ancient architecture colour painting is protected agent |
| CN102850816A (en) * | 2011-06-27 | 2013-01-02 | 上海杰事杰新材料(集团)股份有限公司 | Thermoplastic resin composite material and preparation method and application thereof |
| CN103102750A (en) * | 2013-02-04 | 2013-05-15 | 陕西师范大学 | Application of ZB-F600 two-component FEVE water-based fluororesin in repair of silk and paper cultural relic writings and drawings |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104893583A (en) * | 2015-05-22 | 2015-09-09 | 苏州市贝克生物科技有限公司 | Cultural relic surface acid/alkali-corrosion-resistant coating and preparation method thereof |
| CN105604341A (en) * | 2015-12-31 | 2016-05-25 | 陕西师范大学 | High sand content earth relic solidification method |
| CN105604341B (en) * | 2015-12-31 | 2017-07-11 | 陕西师范大学 | A kind of high sand content earthen ruins reinforcement means |
| CN105602307A (en) * | 2016-03-02 | 2016-05-25 | 沈阳化工大学 | Waterproof transparent coating for protecting cultural relic |
| CN105602307B (en) * | 2016-03-02 | 2018-01-26 | 沈阳化工大学 | A kind of water-fast clear coat of historical relic's protection |
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| CN103555086B (en) | 2016-04-06 |
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