CN102121111B - Method for removing calcified soil rust from ancient mural painting and cultural relic colored drawing - Google Patents
Method for removing calcified soil rust from ancient mural painting and cultural relic colored drawing Download PDFInfo
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- CN102121111B CN102121111B CN2010106011800A CN201010601180A CN102121111B CN 102121111 B CN102121111 B CN 102121111B CN 2010106011800 A CN2010106011800 A CN 2010106011800A CN 201010601180 A CN201010601180 A CN 201010601180A CN 102121111 B CN102121111 B CN 102121111B
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- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims 2
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- 238000010992 reflux Methods 0.000 claims 1
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- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
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Abstract
一种古代壁画和文物彩绘上钙化土锈去除方法，由配制钙化土锈去除剂、配制中和溶液、涂擦钙化土锈去除剂、涂擦中和溶液步骤组成。本发明经过大量的实验、现场试验，实验结果证明，采用本发明方法和钙化土锈去除剂以及中和溶液，可有效地去除古代壁画和文物彩绘上的钙化土锈，且不影响古代壁画和文物彩绘的图案和色彩，对壁画颜料层、地仗层没有损伤。本发明可用于对古代壁画和文物彩绘的修复。A method for removing calcified soil rust on ancient murals and colorful paintings of cultural relics comprises the steps of preparing a calcified soil rust remover, preparing a neutralizing solution, rubbing the calcified soil rust remover, and rubbing the neutralizing solution. The present invention has gone through a large number of experiments and field tests, and the experimental results prove that the calcified soil rust on ancient murals and cultural relics can be effectively removed by adopting the method of the present invention, calcified soil rust remover and neutralizing solution, without affecting ancient murals and The patterns and colors of the painted cultural relics will not damage the mural paint layer and ground layer. The invention can be used for repairing ancient murals and colorful paintings of cultural relics.
Description
Technical field
The invention belongs to the Techniques of Relics Protection field, be specifically related to remove the removal method of calcification soil rust on ancient wall, the historical relic colored drawing.
Background technology
On the thousands of width of cloth Tang tomb mural painting that Shaanxi last century 50 to the nineties is unearthed most bondings serious soil rust, particularly visitor make figure, maid of honour figure, in wait upon figure, drive hawk play dog figure, the figure of the horse Drung nationality, bird appreciation catch national treasure levels such as cicada figure, row halberd figure, its original appearance of grade one cultural relics of the state is almost hidden pollution totally by the soil rust.Spring and autumn to be all to be bonded with serious calcification soil rust on all kinds of rare cultural relics of reducing to enormous amount such as bright clear all kinds of colored drawing potteries, pottery horse, Zhu's book, black book Earthen Bottle, inscription on the memorial tablet within a tomb, makes its most colors, figure, the literal original appearance is covered and pollute, and is beyond recognition.
The serious covering of calcification soil rust polluted ancient wall, the paint-coated artistic original appearance of historical relic and historical information, and more serious is that its pigment, sizing material layer have been caused heavy corrosion with ground battle layer.Free ca, mg ion in the soil rust permeate among pigment, sizing material layer, form deposition knot first with carbon dioxide in air, the very easy onychoptosis that rises that causes mural painting coloured drawing pigment, sizing material layer.Free calcium, mg ion permeate among ground battle layer, form deposition knot first, the knot first hollowing of battle layer with carbon dioxide in air with causing.As time goes on, the type self-destroyed knot first corrosion phenomenon of its pigment, sizing material layer and ground battle layer can be on the rise.
For calcification soil rust; Forefathers once carried out removal with oxalic acid, acetic acid, Sodium hexametaphosphate 99, EDTA, and certain effect is also arranged, and all there is certain injury the back to it in pigment, sizing material layer and the ground battle layer but above-mentioned materials infiltrates; Like the dissolved corrosion of acetic acid, the complexing corrosion of EDTA etc.
Summary of the invention
Technical problem to be solved by this invention is to overcome the shortcoming of above-mentioned calcification soil rust removal method, and calcification soil rust removal method on a kind of method is simple, cost is low, result of use is good ancient wall and the historical relic colored drawing is provided.
Solving the problems of the technologies described above the technical scheme that is adopted is made up of following step:
1, preparation calcification soil rust remover
With ethanol and massfraction is that 6%～10% oxalic acid aqueous solution is 1: 1～5 to mix by volume, is mixed with calcification soil rust remover.
2, preparation neutralization solution
Hydrated barta and methyl alcohol are placed three-necked flask, be heated to 120 ℃, constant temperature refluxed 4 hours, and hydrated barta is fully dissolved, and naturally cooled to 20 ℃, was mixed with massfraction and is 7% hydrated barta methanol solution; In massfraction is 7% hydrated barta methanol solution, add ethanol, massfraction is that 7% hydrated barta methanol solution and alcoholic acid volume ratio are 1: 1～1.5, stirs, and mixes, and is mixed with neutralization solution.
3, embrocate calcification soil rust remover
Clamp absorbent cotton with tweezers; Dip in and get calcification soil rust remover; Embrocate calcification soil rust remover in ancient times on mural painting and the historical relic colored drawing surface calcification soil rust, embrocate 3～5 times, treat that calcification soil rusty scale is loose; Gently calcification soil rusty scale is removed with absorbent cotton, repetitive operation to coat of colo(u)r shows, mural painting clear till.
4, embrocate neutralization solution
Clamp absorbent cotton with tweezers and dip in and get neutralization solution and embrocate on the wall painting pigment layer, embrocate 3～5 times, dry naturally.
In preparation calcification of the present invention soil rust remover step 1, optimal selection is that 6% oxalic acid aqueous solution is to mix at 1: 5 by volume with ethanol and massfraction, is mixed with the calcification soil remover that becomes rusty.
In preparation neutralization solution step 2 of the present invention, massfraction is that hydrated barta methanol solution and alcoholic acid volume ratio the best of 7% are 1: 1.
The present invention is through a large amount of experiment, test in place; Experimental result proves; Adopt the inventive method and calcification soil rust remover and neutralization solution; Can remove the calcification soil rust on ancient wall and the historical relic colored drawing effectively, and not influence ancient wall and paint-coated pattern of historical relic and color, to the wall painting pigment layer, hold layer and do not damage.The present invention can be used for ancient wall and the paint-coated reparation of historical relic.
Description of drawings
Fig. 1 is the XRD figure of permanently happy princess's tomb wall painting surface calcification soil rust.
Fig. 2 is that the use massfraction is that 4% oxalic acid aqueous solution processing calcification soil rust preceding (left one side of something), the ultra depth of field three-dimensional optical microscope of back (right one side of something) analog sample contrast photo.
Fig. 3 is that the use massfraction is that 5% oxalic acid aqueous solution processing calcification soil rust preceding (left one side of something), the ultra depth of field three-dimensional optical microscope of back (right one side of something) analog sample contrast photo.
Fig. 4 is that the use massfraction is that 6% oxalic acid aqueous solution processing calcification soil rust preceding (left one side of something), the ultra depth of field three-dimensional optical microscope of back (right one side of something) analog sample contrast photo.
Fig. 5 is that the use massfraction is that 10% oxalic acid aqueous solution processing calcification soil rust preceding (left one side of something), the ultra depth of field three-dimensional optical microscope of back (right one side of something) analog sample contrast photo.
Fig. 6 is that to use ethanol and massfraction be that the volume ratio of 6% oxalic acid aqueous solution is to handle that the ultra depth of field three-dimensional optical microscope of (left side is half of), back (right half of) coat of colo(u)r contrasts photo before the calcification soil rust at 0: 1 o'clock.
Fig. 7 is that ethanol and massfraction are that the volume ratio of 6% oxalic acid aqueous solution is to handle the ultra depth of field three-dimensional optical microscope contrast photo of (left side is half of), back (right half of) coat of colo(u)r before the calcification soil rust at 1: 1 o'clock.
Fig. 8 is that ethanol and massfraction are that the volume ratio of 6% oxalic acid aqueous solution is to handle the ultra depth of field three-dimensional optical microscope contrast photo of (left side is half of), back (right half of) coat of colo(u)r before the calcification soil rust at 1: 3 o'clock.
Fig. 9 is that ethanol and massfraction are that the volume ratio of 6% oxalic acid aqueous solution is to handle the ultra depth of field three-dimensional optical microscope contrast photo of (left side is half of), back (right half of) coat of colo(u)r before the calcification soil rust at 1: 5 o'clock.
Figure 10 is that to use ethanol and massfraction be that the volume ratio of 6% oxalic acid aqueous solution is to handle that the ultra depth of field three-dimensional optical microscope of (left side is half of), back (right half of) coat of colo(u)r contrasts photo before the calcification soil rust at 1: 6 o'clock.
Figure 11 is the stereoscan photograph of untreated calcification soil rust analog sample.
Figure 12 is the stereoscan photograph of the calcification soil rust analog sample handled.
Figure 13 is the stereoscan photograph of untreated green mural painting analog sample coat of colo(u)r.
Figure 14 is the stereoscan photograph of the green mural painting analog sample coat of colo(u)r handled.
Figure 15 is the ultra depth of field three-dimensional optical microphotograph of green mural painting analog sample coat of colo(u)r of being untreated.
Figure 16 is a ultra depth of field three-dimensional optical microphotograph of having handled green mural painting analog sample coat of colo(u)r.
Embodiment
To further explain of the present invention, but the invention is not restricted to these embodiment below in conjunction with accompanying drawing and embodiment.
Embodiment 1
1, preparation calcification soil rust remover
With ethanol and massfraction is that 6% oxalic acid aqueous solution is to mix at 1: 5 by volume, is mixed with calcification soil rust remover 30mL.
2, preparation neutralization solution
7g hydrated barta, 93g methyl alcohol are placed the 250mL three-necked flask, be heated to 120 ℃, constant temperature refluxed 4 hours, and hydrated barta is fully dissolved, and naturally cooled to 20 ℃, was mixed with massfraction and is 7% hydrated barta methanol solution; Get the 20mL massfraction and be 7% hydrated barta methanol solution, add 20mL ethanol, hydrated barta methanol solution and alcoholic acid volume ratio are 1: 1, and stirring mixes, and is mixed with neutralization solution.
3, embrocate calcification soil rust remover
Clamp absorbent cotton with tweezers, dip in and get calcification soil rust remover, on surperficial calcification soil rust, embrocate calcification soil rust remover; Embrocate 3～5 times; Treat that calcification soil rusty scale is loose, gently native rusty scale removed with absorbent cotton, repetitive operation to coat of colo(u)r shows, mural painting clear till.
4, embrocate neutralization solution
Clamp absorbent cotton with tweezers and dip in and get neutralization solution and embrocate on the wall painting pigment layer, embrocate 3～5 times, dry naturally.
Embodiment 2
In the preparation calcification of the present embodiment soil rust remover step 1, be that 6% oxalic acid aqueous solution is to mix at 1: 3 by volume, be mixed with the calcification soil remover 40mL that becomes rusty ethanol and massfraction.In preparation neutralization solution step 2,7g hydrated barta, 93g methyl alcohol are placed the 250mL three-necked flask, be heated to 120 ℃; Constant temperature refluxed 4 hours; Hydrated barta is fully dissolved, naturally cool to 20 ℃, be mixed with massfraction and be 7% hydrated barta methanol solution; Get the 20mL massfraction and be 7% hydrated barta methanol solution, add 30mL ethanol, hydrated barta methanol solution and alcoholic acid volume ratio are 1: 1.5, and stirring mixes, and is mixed with neutralization solution.Other steps are identical with embodiment 1.
Embodiment 3
In the preparation calcification of embodiment 1～2 soil rust remover step 1, be that 6% oxalic acid aqueous solution is to mix at 1: 1 by volume with ethanol and massfraction, be mixed with the calcification soil remover 40mL that becomes rusty.Other steps are identical with corresponding embodiment.
Embodiment 4
In the preparation calcification of embodiment 1～3 soil rust remover step 1, with massfraction be 6% oxalic acid aqueous solution to use isopyknic massfraction be 10% oxalic acid aqueous solution replacement, other steps are identical with corresponding embodiment.
In order to confirm top condition of the present invention, the contriver has carried out a large amount of laboratories and production site experiment, and various test situation are following:
The full-automatic X-ray diffractometer of laboratory apparatus: D/Max2550VB+/PC is produced test condition: voltage 45kV, electric current 80mA, copper target, graphite monochromator filtering by Japanese Rigalcu company; The ultra depth of field three-dimensional optical of VHX-600K microscope is produced by Japanese Keyen company; Quanta 200 environmental scanning electronic microscopes are produced by Dutch Philips-FEI company; The full-automatic colour-difference meter of DC-P3 type is produced by the emerging flash ranging look in Beijing instrument company; The KBF240 climatic chamber is produced by Buchbinder, Germany company.
1, calcification soil rust composition on the ancient wall is analyzed
The hidden surface soil rust of mural painting is chosen in this experiment in the permanently happy princess's tomb of Tang Zhaoling mural painting, cut with scalpel and put into sample sack on a small quantity, adopts X-ray diffractometer that calcification soil rust sample is analyzed, and test result is seen Fig. 1.
Visible by Fig. 1, mainly contain CaCO in permanently happy princess's tomb wall painting surface soil rust
3And SiO
2CaCO
3In a single day usually can not cause damage, yet form hard dirt layer, extremely is difficult to remove mural painting.And the SiO in the soil rust
2Can form white Si0 along with the evaporation of moisture is slowly moved to wall painting surface
2Or the crust layer of silicate.
2, the concentration of oxalic acid aqueous solution is to the influence of calcification soil rust removal effect
With earth 40g, lime carbonate 5g uniform mixing, water squirts, and uses grinding tool to be pressed into diameter as 5cm, thick 4 calcification soil rust analog samples as 1cm, dries, and is subsequent use.
It is to mix at 1: 5 by volume that ethanol and massfraction are respectively 4%, 5%, 6%, 10% oxalic acid aqueous solution, is mixed with calcification soil rust remover 5mL respectively.Clamp absorbent cotton with tweezers, dip in the calcification soil rust remover of getting the preparation of different mass fractional oxalic acid aqueous solution respectively, embrocate respectively on 4 calcification soil rust analog samples, dry.Adopt ultra depth of field three-dimensional optical observation by microscope calcification soil rust remover to handle the morphology change of front and back calcification soil rust analog sample; The result sees Fig. 2～5, and wherein Fig. 2 is that the use massfraction is that 4% oxalic acid aqueous solution processing calcification soil rust preceding (left one side of something), the ultra depth of field three-dimensional optical microscope of back (right one side of something) analog sample contrast photo; Fig. 3 is that the use massfraction is that 5% oxalic acid aqueous solution processing calcification soil rust preceding (left one side of something), the ultra depth of field three-dimensional optical microscope of back (right one side of something) analog sample contrast photo; Fig. 4 is that the use massfraction is that 6% oxalic acid aqueous solution processing calcification soil rust preceding (left one side of something), the ultra depth of field three-dimensional optical microscope of back (right one side of something) analog sample contrast photo; Fig. 5 is that the use massfraction is that 10% oxalic acid aqueous solution processing calcification soil rust preceding (left one side of something), the ultra depth of field three-dimensional optical microscope of back (right one side of something) analog sample contrast photo.
Visible by Fig. 2～5; The massfraction of oxalic acid aqueous solution is 4% and 5% o'clock; The calcification that is mixed with soil rust remover is little to the effect of calcification soil rust analog sample, and the soil particle structure does not have considerable change, and the massfraction of oxalic acid aqueous solution is 6% and 10% o'clock; The soil particle of calcification soil rust analog sample is loosely organized, helps the removal of soil rust in conjunction with mechanical means.
3, oxalic acid aqueous solution and alcoholic acid volume ratio are to the influence of ancient wall and historical relic coloured drawing pigment layer
(1) makes the mural painting analog sample
Select the malachite green coloured drawing pigment, pigment is Chinese painting color, is produced by pigment factory of attached middle school of Central Academy of Fine Arts (being Beijing green vegetarian art painting of gold factory), and the pigment plate is pigment and adds gelatin.The pigment board manufacturing method is following:
1. 408g earth is mixed with the long straw 6g of 1cm, the zero(ppm) water that adds 118g stirs, and makes ground battle analog sample with the wooden model tool of 15cm * 12cm.
2. the thick gypsum of 1mm is smeared as bottom in battle analog sample surface on ground, dries naturally.
3. get malachite green 5g, with massfraction be that 1% aqueous gelatin solution 3g is modulated into pigment paste, with writing brush it is evenly coated in the gypsic horizon surface, thickness is 0.1～0.2mm.
4. room temperature is dried naturally, prepares 5 mural painting analog samples.
(2) treatment process of mural painting analog sample
With ethanol and massfraction is that 6% oxalic acid aqueous solution is to mix in 0: 1,1: 1,1: 3,1: 5,1: 6 by volume; Be mixed with calcification soil rust remover 5mL respectively; Clamp absorbent cotton with tweezers; Dip in respectively and get calcification soil rust remover, embrocate on coat of colo(u)r, adopt the pattern of ultra depth of field three-dimensional optical microscopic examination coat of colo(u)r; The result sees Fig. 6～10, and wherein Fig. 6 is that to use ethanol and massfraction be that the volume ratio of 6% oxalic acid aqueous solution is to handle that the ultra depth of field three-dimensional optical microscope of (left side is half of), back (right half of) coat of colo(u)r contrasts photo before the calcification soil rust at 0: 1 o'clock; Fig. 7 is that ethanol and massfraction are that the volume ratio of 6% oxalic acid aqueous solution is to handle the ultra depth of field three-dimensional optical microscope contrast photo of (left side is half of), back (right half of) coat of colo(u)r before the calcification soil rust at 1: 1 o'clock; Fig. 8 is that ethanol and massfraction are that the volume ratio of 6% oxalic acid aqueous solution is to handle the ultra depth of field three-dimensional optical microscope contrast photo of (left side is half of), back (right half of) coat of colo(u)r before the calcification soil rust at 1: 3 o'clock; Fig. 9 is that ethanol and massfraction are that the volume ratio of 6% oxalic acid aqueous solution is to handle the ultra depth of field three-dimensional optical microscope contrast photo of (left side is half of), back (right half of) coat of colo(u)r before the calcification soil rust at 1: 5 o'clock; Figure 10 is that to use ethanol and massfraction be that the volume ratio of 6% oxalic acid aqueous solution is to handle that the ultra depth of field three-dimensional optical microscope of (left side is half of), back (right half of) coat of colo(u)r contrasts photo before the calcification soil rust at 1: 6 o'clock.
Visible by Fig. 6～10; Ethanol and massfraction be the volume ratio of 6% oxalic acid aqueous solution be 1: 1,1: 3,1: 5 o'clock to not influence of coat of colo(u)r; Be full of cracks does not appear in coat of colo(u)r, explains that calcification soil rust remover injures less than coat of colo(u)r in calcification soil rust removal process.Ethanol and massfraction are that the volume ratio of 6% oxalic acid aqueous solution is 0: 1,1: 6 o'clock, and the coat of colo(u)r be full of cracks is explained to have injured coat of colo(u)r.
Comprehensive test 2 and 3; It is that 6%～10% oxalic acid aqueous solution is 1: 1～5 to be mixed with calcification soil rust remover by volume that the present invention selects ethanol and massfraction, and optimal selection ethanol and massfraction are that 6% oxalic acid aqueous solution is to be mixed with the calcification soil remover that becomes rusty at 1: 5 by volume.
4, with the native microscopic appearance of analog sample that become rusty of scanning electron microscopic observation calcification with calcification soil rust remover processing front and back
With earth 40g, lime carbonate 5g uniform mixing, water squirts, and uses grinding tool to be pressed into diameter as 5cm, thick 2 calcification soil rust analog samples as 1cm, dries, and is subsequent use.
With ethanol and massfraction is that 6% oxalic acid aqueous solution is to mix at 1: 5 by volume, is mixed with calcification soil rust remover 5mL; Clamp absorbent cotton with tweezers, dip in and get calcification soil rust remover, embrocate therein on 1 calcification soil rust analog sample, dry, 1 calcification soil rust analog sample is not embrocated calcification soil rust remover as control sample in addition.Adopt environmental scanning electronic microscope to observe the morphology change of 2 calcification soil rust analog samples; The result sees Figure 11 and 12; Wherein Figure 11 is a stereoscan photograph of not embrocating the control sample of calcification soil rust remover, and Figure 12 is a stereoscan photograph of embrocating the calcification soil rust analog sample of calcification soil rust remover.
By Figure 11 and 12 visible, do not embrocate the calcification soil rust analog sample of calcification soil rust remover, soil particle is piled up dense; And the native analog sample that becomes rusty of the calcification of embrocating the native rust of calcification remover; Soil particle is loosely organized, and it is big that the space becomes, and adopts hand work to remove calcification soil rust easily.Remove in the process of the soil of calcification on ancient wall, the historical relic colored drawing rust effect on the spot obvious.
5, observe the microscopic appearance that calcification soil rust remover is handled calcification soil rust back coat of colo(u)r
Method according to experiment (1) in the experiment 3 is made 4 mural painting analog samples; Wherein clamp absorbent cotton with tweezers for 2; Dipping in and getting ethanol and massfraction is that 6% oxalic acid aqueous solution is the calcification soil rust remover that is mixed with at 1: 5 by volume, embrocates 3～5 times on the left side of mural painting analog sample, to be infiltrated intact after; Use tweezers to clamp absorbent cotton and dip in that to get massfraction be that 7% hydrated barta methanol solution and alcoholic acid volume ratio are the neutralization solution that is mixed with at 1: 1; Wall painting pigment layer embrocating calcification soil rust remover is embrocated 3～5 times, dries as the mural painting analog sample, other two as the blank sample.Morphology change with environmental scanning electronic microscope and ultra depth of field three-dimensional optical microscopic examination mural painting analog sample coat of colo(u)r; The result sees Figure 13～16; Wherein Figure 13 is the stereoscan photograph of untreated malachite green mural painting analog sample coat of colo(u)r; Figure 14 is the stereoscan photograph of the malachite green mural painting analog sample coat of colo(u)r handled; Figure 15 is the ultra depth of field three-dimensional optical microphotograph of untreated malachite green mural painting analog sample coat of colo(u)r, and Figure 16 is the ultra depth of field three-dimensional optical microphotograph of the malachite green mural painting analog sample coat of colo(u)r handled.
Visible by Figure 13～16, untreated mural painting analog sample coat of colo(u)r, granules of pigments accumulative facies are to densification, and the mural painting analog sample coat of colo(u)r that adopts removal method of the present invention to handle is compared microtexture with untreated mural painting analog sample coat of colo(u)r is not had considerable change.Experimental result shows that when the present invention removed the calcification soil rust on ancient wall, the historical relic colored drawing, the remover of the wall painting pigment layer that permeates, remains in did not have obvious influence to the wall painting pigment layer.
6, observe the mural painting analog sample and remove front and back aberration variation
Make respectively 4 of cinnabar, malachite green, iron oxide red, carbon black mural painting analog samples according to the method for experiment (1) in the experiment 3; Wherein to embrocate ethanol and massfraction earlier be that 6% oxalic acid aqueous solution is the calcification soil rust remover that is mixed with at 1: 5 by volume for 2 blocks of cinnabar, 2 blocks of malachite greens, 2 blocks of iron oxide reds, 2 carbon black mural painting analog samples; Embrocating massfraction again and be 7% hydrated barta methanol solution and ethanol is the neutralization solution that is mixed with at 1: 1 by volume; Dry; It is that 80 ℃, relative humidity are aging 28 days of 65% KBF240 climatic chamber that 1 block of cinnabar, 1 block of malachite green, 1 block of iron oxide red, 1 carbon black mural painting analog sample place temperature; 1 block of cinnabar, 1 block of malachite green, 1 block of iron oxide red, 1 carbon black mural painting analog sample place power to be 25W, highly to wear out 28 days for the uv lamp of 20cm is following in addition; Whenever observed once at a distance from 7 days, the record observations adopts CIE L in 1976
*a
*b
*The chromaticity coordinates system is estimated (the full-automatic colour-difference meter of DC-P3 type) aging front and back colour-change, and value of chromatism is calculated as follows:
ΔE＝[(ΔL
*)
2+(Δa
*)
2+(Δb
*)
2]
1/2
Δ E is value of chromatism, Δ L in the formula
*, Δ a poor for lightness
*, Δ b poor for the red green degree
*Be the champac colour difference, the big more account for color of Δ E value changes big more, otherwise then account for color changes more little.Δ E evaluation criterion sees Table 1, and test and result of calculation see Table 2.
Table 1 Δ E judgement criteria
Table 2 mural painting analog sample hydrothermal aging, ultraviolet ageing aberration change
It is that 6% oxalic acid aqueous solution is the calcification soil rust remover that is mixed with at 1: 3 by volume that other 2 blocks of cinnabar, 2 blocks of malachite greens, 2 blocks of iron oxide reds, 2 carbon black mural painting analog samples are embrocated ethanol and massfraction earlier; Embrocating massfraction again and be 7% hydrated barta methanol solution and ethanol is the neutralization solution that is mixed with at 1: 1 by volume; Dry; It is that 80 ℃, relative humidity are aging 28 days of 65% KBF240 climatic chamber that 1 block of cinnabar, 1 block of malachite green, 1 block of iron oxide red, 1 carbon black mural painting analog sample place temperature; 1 block of cinnabar, 1 block of malachite green, 1 block of iron oxide red, 1 carbon black mural painting analog sample place power to be 25W, highly to wear out 28 days for the uv lamp of 20cm is following in addition; Whenever observed once the record observations at a distance from 7 days.The testing method of aberration is identical with aforesaid method with the method for calculation of value of chromatism.Test result is seen table 3.
Table 3 mural painting analog sample is damp and hot, the ultraviolet ageing aberration changes
Visible by table 2 and table 3; The aberration of mural painting analog sample behind ultraviolet ageing, hydrothermal aging all has change in various degree with the prolongation of digestion time, change smaller, from imperceptible change in color visually; Show when the calcification soil of the present invention on removing ancient wall becomes rusty; Can not impact wall painting pigment layer color, satisfy historical relic and repair requirement, removal effect is good on the spot.
7, observe the mural painting analog sample and remove front and back sticking power variation
Make 3 of malachite green mural painting analog samples according to the method for experiment (1) in the experiment 3,1 is blank sample; Other 2 to embrocate ethanol and massfraction earlier be that 6% oxalic acid aqueous solution is the calcification soil rust remover that is mixed with at 1: 5 by volume; Embrocating massfraction again and be 7% hydrated barta methanol solution and ethanol is the neutralization solution that is mixed with at 1: 1 by volume; Dry; 1 places temperature is that 80 ℃, relative humidity are aging 28 days of 65% hydrothermal aging case, and 1 places that power is 25W, highly the uv lamp for 20cm wore out 28 days down in addition.Sticking power by " paint film adhesion assay method " (GB 1720-79 (89)) test hydrothermal aging sample, ultraviolet ageing sample, blank sample.Test procedure is on malachite green mural painting analog sample, to cut parallel cut channel with blade, the long 10～20mm of cut channel, and the cut channel spacing is 1mm; Cut the entire depth of wearing malachite green mural painting analog sample, on parallel cut channel, vertically cut same cut channel, form many lattices; Using wide translucent Pressuresensitive Tape as 25mm to be attached to whole square cut channel draws on the lattice; The wrench adhesive tape, the number of the last grid in malachite green mural painting analog sample surface is used for characterizing the adhesion strength of malachite green mural painting analog sample coat of colo(u)r, wherein 0 grade best; 5 grades the poorest, and sticking power grading standard is seen table 4.Whenever observed once at a distance from 7 days, the record observations, test result is seen table 5.
Table 4 sticking power grading standard
Sticking power changed before and after table 5 malachite green mural painting analog sample was removed
Visible by table 5, the sticking power of coat of colo(u)r was along with the prolongation of digestion time all has reduction in various degree before and after the mural painting analog sample was removed.And hydrothermal aging sample, ultraviolet ageing sample after handling with calcification soil rust remover and neutralizer are better than the sticking power of blank sample.
8, measure the variation that historical relic colored drawing analog sample is removed front and back coat of colo(u)r cohesive strength
For the influence of the removal method that detects embodiment 1 to historical relic colored drawing analog sample coat of colo(u)r cementability; Adopt homemade bonding strength appearance to measure; The instrument method of modifying is following: the mixer head of DW-1 celestial pole constant speed electric mixer (Yuhua Instrument Co., Ltd., Gongyi City) is adapted as brush, keeps brush to be close to surface of pigments to be measured and rotate polish-brush repeatedly.The power of motor of instrument is 60W, and rotating speed is 0～2000r/min, and is adjustable.Bonding strength measuring method: use brush with 90r/min rotation polish-brush coat of colo(u)r 10min; Observe the variation of surface of pigments state; As whether cut is arranged, come off etc., and assess of the influence of this removal method with this to the coat of colo(u)r bonding strength with the come off quality (M) of pigment of the accurate weighing of balance.
Be 5% aqueous gelatin solution with 5g white pigment and massfraction by mass ratio be to mix at 1: 1, evenly brushing as Tao Yi, is dried on the pottery sheet of sanding of flat naturally; Be 5% aqueous gelatin solution with 5g malachite green and massfraction by mass ratio be to mix at 2: 1; Evenly brushing is dried on Tao Yi naturally, processes 4 of historical relic colored drawing analog samples; Wherein 3 to embrocate ethanol and massfraction earlier be that 6% oxalic acid aqueous solution is the calcification soil rust remover that is mixed with at 1: 5 by volume; Embrocating massfraction again and be 7% hydrated barta methanol solution and ethanol is the neutralization solution that is mixed with at 1: 1 by volume, dries, and is designated as No. 1 sample, No. 2 samples, No. 3 samples respectively.Another piece is a blank sample.Adopt above-mentioned homemade bonding strength appearance test historical relic colored drawing analog sample to remove the cohesive strength of front and back coat of colo(u)r, test result is seen table 6.
Table 6 historical relic colored drawing bonding strength experimental result
Visible by table 6, when adopting the present invention to remove the calcification soil rust on the ancient wall, little to the bonding strength influence of wall painting pigment layer.
In order to prove beneficial effect of the present invention, the contriver adopts the removal method in the embodiment of the invention 1, and the ancient wall agglutinating calcification soil rust of historical relic's protection center, Xianyang collection is removed, and the removal effect situation is following:
1, the calcification soil of removing on the five generation Feng Hui tomb decorative frescos becomes rusty
Situation before five generation Feng Hui tomb decorative frescos are removed: wall painting surface is bonded with serious calcification soil rust, and design and color is smudgy.
Collection unit: historical relic's protection center, Xianyang
The removal method: the operation steps by the embodiment of the invention 1 is carried out.
The removal time: March calendar year 2001
Removal effect: the removal method in the embodiment of the invention 1 has clearly been reproduced the original design and color of five generation Feng Hui tomb decorative frescos after removing the soil rust, does not change so far.
2, remove the permanently happy princess's tomb of Tang Zhaoling mural painting man and wait upon the calcification soil rust on the figure
The permanently happy princess's tomb of Tang Zhaoling mural painting man waits upon figure and removes preceding situation: wall painting surface is bonded with serious calcification soil rust, and design and color is smudgy.
Collection unit: historical relic's protection center, Xianyang
The removal method: the operation steps by the embodiment of the invention 1 is carried out.
The removal time: in June, 2004
Removal effect: after embodiment 1 removes the soil rust, clearly reproduced the permanently happy princess's tomb of Tang Zhaoling mural painting man and waitd upon the original design and color of figure, do not changed so far.
Experiment conclusion: the present invention can get rid of ancient wall and the lip-deep calcification soil of historical relic colored drawing rust, and removal effect is fairly obvious, and does not influence ancient wall and paint-coated pattern of historical relic and color.
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