Color-adjusting and restoration materials for limestone cultural relics and their applications

Abstract

The present invention discloses a coloring and repairing material for limestone cultural relics and its application, and relates to the technical field of limestone restoration. In view of the nature and color change of limestone, burnt granite, quartz sand, oyster ash, Dunhuang soil, fine tile ash, black gold sand and green pumice powder are used as natural mineral raw materials to obtain a cultural relic coloring and repairing material, which has stable color and is not easy to change color even if it is placed in an open-air environment for a long time after restoration; and the natural mineral raw materials have good bonding strength with the materials for repairing and patching or natural raw stones, so that the connection stability of the cultural relic coloring and repairing material is better and it is not easy to fall off, reducing the risk of damage to the cultural relic due to repeated repairs. In addition, by controlling the proportion of each raw material, a variety of colors similar to the color of limestone can be quickly modulated, which reduces the difficulty of limestone coloring and repair, provides a basis for rapid compounding for limestone coloring, and the color of the repaired area is harmonious and unified with the surrounding raw stones.

Description

Technical Field

[0001] The invention relates to the technical field of limestone restoration, and in particular to a coloring restoration material for limestone cultural relics and application thereof. Background Art

[0002] Limestone is a carbonate rock with calcite as its main component. As a relatively hard stone, it was often used in the production of steles in ancient times, such as the Chang Yue Statue Stele of the Northern Wei Dynasty in Guanlin, Luoyang, Henan; there are also many cave statues carved on limestone cliffs, such as the Longmen Grottoes in Luoyang, Henan, the Nanxiangtang Grottoes and Beixiangtang Grottoes in Handan, Hebei; as well as the inscriptions on the walls of Qutang Gorge in Fengjie, Chongqing, the Jiaoshan Stone Carvings in Zhenjiang, Jiangsu, the Southern Dynasties statues and Southern Dynasties tomb stone carvings in Qixia Mountain, Nanjing, and the Feilaifeng statues in Hangzhou, Zhejiang, etc., which are widely distributed.

[0003] The sources of the above-mentioned limestone cultural relics vary slightly depending on the region. For example, the Longmen Grottoes were mainly excavated in the strata formed by the limestone and dolomite of the Middle and Upper Cambrian; the Nanxiangtang Grottoes are located in the Middle Ordovician limestone and dolomite limestone strata; the Beixiangtang Grottoes were excavated in the thick oolitic limestone strata of the Cambrian; the inscriptions on the wall of Qutang Gorge belong to the gray to dark gray medium-thick to thick dolomite limestone strata of the Jialingjiang Formation of the Lower Triassic, which is cryptocrystalline, dense and hard.

[0004] Limestone cultural relics that have been placed outdoors for a long time are prone to cracking, weathering, and damage, which not only affect the safety and stability of the cultural relics, but also cause immeasurable losses to the various values ​​​​endowed by the cultural relics themselves.

[0005] At the same time, during the process of rock formation, affected by physical and chemical factors, the same type of stone will have richer color changes in different locations (for example, light gray and dark gray will appear in limestone, and white blocky porphyroblasts will appear in some areas). In addition, after the cultural relics are carved, they are kept in an outdoor environment for a long time, and are affected by wind, rain, snow and sunlight, and the surface of the cultural relics will also have certain color changes (for example, the surface of the stone in the area that has been eroded by rain for a long time will become darker and yellower). Therefore, in the process of repairing limestone cultural relics, different repair areas of the same type of stone need to be equipped with repair materials with similar colors to achieve a coordinated and unified overall restoration effect of the cultural relics.

[0006] The current restoration method includes reshaping, shaping and coloring the area to be restored to ensure the overall restoration effect of the cultural relics is coordinated and unified. The existing coloring process mainly uses chemical synthetic pigments such as Chinese painting pigments and watercolor pigments for coloring. These materials have poor aging resistance under outdoor natural climate conditions. After a period of restoration, they are prone to discoloration or falling off, which is inconsistent with the color of the surrounding original stones, affecting the appreciation and protection of cultural relics. The area to be restored needs to be repaired repeatedly, which not only increases the cost of restoration, but also may cause irreversible damage to the cultural relics during each restoration process, which is not conducive to the protection of cultural relics.

[0007] In view of this, the present invention is proposed. Summary of the invention

[0008] The purpose of the present invention is to provide a coloring and restoration material for limestone cultural relics and application thereof.

[0009] The present invention is achieved in that:

[0010] In a first aspect, the present invention provides a coloring and restoration material for limestone cultural relics. The cultural relic coloring and restoration material includes, by mass percentage, burned gravel: 5% to 45%, quartz sand: 0% to 35%, oyster lime: 0% to 45%, Dunhuang soil: 0% to 37.5%, fine tile lime: 0% to 40%, black gold sand: 0% to 35% and green pumice powder: 0% to 5%.

[0011] The color value parameters of the burned gravel include: L=74~75, a=4~5, b=14~15.

[0012] The color value parameters of quartz sand include: L=88~90, a=0.1~0.2, b=2.5~3.5.

[0013] The color parameters of oyster gray include: L=86~87, a=-0.4~-1.4, b=10.1~11.1.

[0014] The color parameters of Dunhuang soil include: L = 65 ~ 66, a = 5 ~ 6, b = 11 ~ 12;

[0015] The color value parameters of the fine tile gray include: L=42-43, a=0.1-1.0, b=4-5;

[0016] The color value parameters of the black gold sand include: L=32-33, a=3-4, b=-10--11;

[0017] The color parameters of the green pumice powder include: L=76-77, a=-3-4, b=-2-3

[0018] In a second aspect, the present invention provides an application of a material according to any one of the aforementioned embodiments in limestone-type stone repair.

[0019] Preferably, the material application method comprises mixing the raw materials of the material with water in proportion and then applying the mixture to the surface of the limestone-like stone.

[0020] Preferably, the mass ratio of the raw material to water is 1:0.35-0.4.

[0021] The present invention has the following beneficial effects:

[0022] The present invention provides a color-adjusting and repairing material for limestone cultural relics and its application. According to the nature and color change of limestone, the color-adjusting and repairing material for limestone cultural relics is obtained by mixing natural mineral raw materials. The cultural relic color-adjusting and repairing material is natural and stable in color. It is not easy to change color even if it is in an open-air environment for a long time after repair, and the color stability is good. The natural mineral raw materials have good bonding force with the repairing and patching materials or natural raw stones, so that the connection stability of the cultural relic color-adjusting and repairing material is good and it is not easy to fall off, which reduces the risk of damage to the cultural relic by repeated repair of the cultural relic. In addition, by controlling the proportion of each raw material, a variety of colors similar to the color of limestone can be quickly modulated, which reduces the difficulty of color-adjusting and repairing limestone, provides a basis for rapid compounding for color-adjusting limestone, realizes color-adjusting and repairing limestone of different colors, and the color of the repaired area is harmonious and unified with the surrounding raw stones. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without creative work.

[0024] Figure 1 This is a color difference diagram of limestone in different locations;

[0025] Figure 2 A color comparison diagram of the color-adjusting restoration material for limestone cultural relics provided in Example 2 of the present invention and the corresponding limestone original stone;

[0026] Figure 3 A color comparison diagram of the color-adjusting restoration material for limestone cultural relics provided in Example 3 of the present invention and the corresponding limestone original stone;

[0027] Figure 4 A color comparison diagram of the color-adjusting restoration material for limestone cultural relics provided in Example 6 of the present invention and the corresponding limestone original stone;

[0028] Figure 5 A comparison diagram of the color-adjusting restoration material for limestone cultural relics provided in Example 3 of the present invention before and after restoration;

[0029] Figure 6 A comparison diagram of the color-adjusting restoration material for limestone cultural relics provided in Example 7 of the present invention before and after restoration;

[0030] Figure 7 This is a comparison diagram before and after restoration of the color-adjusting restoration material for limestone cultural relics provided in Example 10 of the present invention. DETAILED DESCRIPTION

[0031] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0032] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0033] First of all, it should be noted that the color value parameters L, a and b mentioned in the present invention are color representation parameters in the CIELAB color space, which is a device-independent color space and is widely used in color theory and color difference calculation.

[0034] L stands for lightness, which indicates how light or dark a color is. L values ​​usually range from 0 (black) to 100 (white), with lower values ​​representing darker colors and higher values ​​representing lighter colors.

[0035] a represents the range from green to red, with positive values ​​indicating a reddish color and negative values ​​indicating a greenish color.

[0036] b represents the range from blue to yellow, with positive values ​​indicating yellowish color and negative values ​​indicating bluish color.

[0037] By controlling the values ​​of L, a and b of each substance (raw material or coloring and restoration material of limestone cultural relics), the color uniformity of each substance can be ensured; and the L, a and b parameters can be directly detected by equipment, such as using a spectrophotometer, and the detection method is simple and easy to obtain.

[0038] In a first aspect, the present invention provides a coloring and restoration material for limestone cultural relics. The cultural relic coloring and restoration material includes, by mass percentage, burned gravel: 5% to 45%, quartz sand: 0% to 35%, oyster lime: 0% to 45%, Dunhuang soil: 0% to 37.5%, fine tile lime: 0% to 40%, black gold sand: 0% to 35% and green pumice powder: 0% to 5%.

[0039] By compounding with natural mineral raw materials such as burnt gravel, quartz sand, oyster ash, Dunhuang soil, fine tile ash, black gold sand and green pumice powder, the color stability of the cultural relic coloring and restoration materials is better, and it is not easy to change color even if it is placed in an open-air environment for a long time after restoration; and the natural mineral raw materials have good bonding with the repair materials or natural raw stones, so that the connection stability of the cultural relic coloring and restoration materials is better and it is not easy to fall off, reducing the risk of damage to the cultural relics caused by repeated restoration of cultural relics. In addition, by controlling the proportion of each raw material, a variety of colors similar to the color of limestone can be quickly adjusted, which reduces the difficulty of limestone coloring and restoration, provides a basis for rapid compounding for limestone coloring, realizes the coloring and restoration of limestone of different colors, and the color of the repaired area is harmonious and unified with the surrounding raw stones.

[0040] Among them, burnt gravel is the main cementing material of the restoration material, which plays a bonding role; in addition, the color of burnt gravel is light gray with a white tint, and can be used as a raw material to reduce the saturation of the color restoration material of cultural relics. The content of burnt gravel can be, for example, any value among 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40% or 45%, or a range between any two values.

[0041] In order to ensure the overall uniformity of the color of the limestone restoration materials for cultural relics, the color value parameters of the burned gravel include: L=74~75, a=4~5, b=14~15.

[0042] Quartz sand is a filling material for restoration materials, which plays a role in reducing the shrinkage of restoration materials. In addition, the color of quartz sand is close to white, which can adjust the color depth of cultural relics restoration materials. The content of quartz sand can be, for example, any value among 0%, 5%, 10%, 15%, 20%, 25%, 30% or 35%, or a range between any two values.

[0043] In order to ensure the overall uniformity of the color of the limestone stone cultural relics restoration materials, the color value parameters of quartz sand include: L = 88 ~ 90, a = 0.1 ~ 0.2, b = 2.5 ~ 3.5.

[0044] The role of oyster ash is to increase the plasticity of the repair material, and its own color is also conducive to adjusting the color of the cultural relic coloring repair material. The content of oyster ash can be, for example, any value among 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40% or 45%, or a range between any two values.

[0045] In order to ensure the overall color uniformity of the coloring and restoration materials for limestone cultural relics, the color value parameters of oyster lime include: L=86~87, a=-0.4~-1.4, b=10.1~11.1.

[0046] The main color of limestone is gray or yellow. In addition, there are some limestone stones that are white or bluish. Therefore, in order to meet the color matching needs of limestone stones of different colors, it is necessary to use colorful natural mineral raw materials such as Dunhuang soil, fine tile gray, black gold sand and green pumice powder for color matching to ensure that the color of the cultural relics color restoration materials is coordinated and unified with the surrounding limestone stones.

[0047] Dunhuang soil is used as a yellow rock color to adjust the color of cultural relics color restoration materials, and is particularly suitable for coloring yellowish limestone raw stones. The amount of Dunhuang soil added determines the yellowness of the overall color of the cultural relics color restoration materials, so the amount of Dunhuang soil added can be adjusted according to the color of the limestone raw stone. For example, the content of Dunhuang soil can be any value among 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35% or 37.5%, or a range value between any two values.

[0048] Specifically, in order to ensure that the Dunhuang soil is controlled within the above range to obtain a color that is coordinated and unified with the surrounding raw stones, the color value parameters of the Dunhuang soil include: the color value parameters of the Dunhuang soil include: L=65~66, a=5~6, b=11~12.

[0049] Fine tile gray is used as gray rock color to adjust the color of cultural relic coloring and restoration materials, and can reduce the saturation of cultural relic coloring and restoration materials. By changing the content of fine tile gray, the grayscale of cultural relic coloring and restoration materials can be adjusted. For example, the content of fine tile gray can be any value among 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35% or 40%, or a range value between any two values.

[0050] The higher the grayness of the surrounding limestone raw stone, the more the content of fine tile gray can be increased; the lower the grayness of the surrounding limestone raw stone, for example, when it is white or yellowish, the content of fine tile gray can be reduced.

[0051] Specifically, in order to ensure that the fine tile gray is controlled within the above range to obtain a color that is coordinated and unified with the surrounding raw stones, the color value parameters of the fine tile gray include: L=42~43, a=0.1~1.0, b=4~5.

[0052] Black gold sand is used as a black rock color to adjust the color of cultural relics coloring and restoration materials. For example, it can reduce the darkness of the color of cultural relics coloring and restoration materials to match the color of the surrounding limestone raw stones. Since the color of most limestones is darker, a certain proportion of black gold sand is required for coloring. For example, the content of black gold sand can be any value among 0%, 5%, 10%, 15%, 20%, 25%, 30% or 35%, or a range between any two values.

[0053] Specifically, in order to ensure that the black gold sand is controlled within the above range to obtain a color that is coordinated and unified with the surrounding raw stones, the color value parameters of the black gold sand include: L=32~33, a=3~4, b=-10~-11.

[0054] Green pumice powder is used as green rock color to adjust the color of cultural relics restoration materials. When the color of the limestone is green or blue, the content of green pumice powder can be increased, otherwise the content of green pumice powder can be reduced. The content of green pumice powder can be, for example, any value among 0%, 1%, 2%, 3%, 4% or 5%, or a range between any two values.

[0055] Specifically, in order to ensure that the green pumice powder is controlled within the above range to obtain a color that is coordinated and unified with the surrounding raw stones, the color value parameters of the green pumice powder include: L=76~77, a=-3~-4, b=-2~-3.

[0056] like Figure 1 As shown in the figure, due to the inconsistency of the sedimentation process of rocks during diagenesis, the colors of limestone in different locations are different, and the color of cultural relics will also change to a certain extent after being exposed to the outdoor environment for a long time (such as rain, snow and sun exposure). At the same time, the color of limestone also includes two main colors: gray and yellow. Therefore, for limestones of different colors, the present invention provides the following formula of cultural relic coloring and restoration materials.

[0057] Since the color adjustment process is relatively complicated, the way the color changes after adding raw materials of different colors is not uniquely determined. The original limestone mainly presents gray or yellow, and then presents other colors besides gray according to the deposition method in different locations and the influence of the external environment. For example, the color of the original limestone can be gray of different brightness, such as dark gray, medium gray and light gray; or yellow of different brightness, such as brown yellow, medium yellow and light yellow; the original limestone in some areas is white; and the color of the original limestone in some areas is bluish, such as blue-gray, light blue-gray and yellowish blue-gray. The following is the formula of the color adjustment and restoration materials for limestone cultural relics of different colors and the color value parameters of their corresponding colors.

[0058] In an optional embodiment, when the cultural relics coloring and restoration material presents a dark gray, the composition of the material, by mass percentage, includes burned gravel: 22% to 28%, oyster ash: 22% to 28%, quartz sand: 8% to 12%, fine tile ash: 2% to 8% and black gold sand: 30% to 35%; when the material presents a dark gray, the color value parameters of the material include L = 50 to 52, a = 1 to 2, b = 3.5 to 4.5.

[0059] Preferably, when the cultural relics coloring and restoration material presents a dark gray, the composition of the material, by mass percentage, includes burnt gravel: 25%, oyster ash: 25%, quartz sand: 10%, fine tile ash: 5% and black gold sand: 35%; when the material presents a dark gray, the color value parameters of the material include L=50.5~51.5, a=1.2~1.8, b=3.5~4.2.

[0060] In an optional embodiment, when the cultural relics coloring and restoration material presents a medium gray color, the composition of the material, calculated by mass percentage, includes burned gravel: 5% to 10%, quartz sand: 12% to 18%, oyster ash: 40% to 45%, fine tile ash: 2% to 8% and black gold sand: 28% to 32%; when the material presents a medium gray color, the color value parameters of the material include L=58 to 60, a=1 to 2, b=3 to 4.

[0061] Preferably, when the cultural relics coloring and restoration material presents a medium gray color, the composition of the material, by mass percentage, includes burnt gravel: 5%, oyster ash: 45%, quartz sand: 15%, fine tile ash: 5% and black gold sand: 30%; when the material presents a medium gray color, the color value parameters of the material include L=58.5~59.5, a=1~1.5, b=3~3.5.

[0062] In an optional embodiment, when the cultural relics coloring and restoration material presents a light gray color, the composition of the material, by mass percentage, includes burned gravel: 22% to 28%, quartz sand: 12% to 18%, oyster ash: 22% to 28%, fine tile ash: 22% to 28% and black gold sand: 8% to 12%; when the material presents a light gray color, the color value parameters of the material include L=60 to 62, a=0.5 to 1.5, and b=3 to 4.

[0063] Preferably, when the cultural relics coloring and restoration material presents a light gray color, the composition of the material, by mass percentage, includes burnt gravel: 25%, oyster ash: 25%, quartz sand: 15%, fine tile ash: 25% and black gold sand: 10%; when the material presents a light gray color, the color value parameters of the material include L=61~62, a=0.8~1.2, b=3.4~4.

[0064] In an optional embodiment, when the cultural relics coloring and restoration material is brownish yellow, the composition of the material, by mass percentage, includes burned gravel: 10% to 15%, quartz sand: 22% to 28%, Dunhuang soil: 35% to 37.5% and black gold sand: 22% to 28%; when the material is brownish yellow, the color value parameters of the material include L=48 to 51, a=2 to 3, b=7.5 to 8.5.

[0065] Preferably, when the cultural relics coloring and restoration material is brownish yellow, the composition of the material, by mass percentage, includes burned gravel: 12.5%, quartz sand: 25%, Dunhuang soil: 37.5% and black gold sand: 25%; when the material is brownish yellow, the color value parameters of the material include L=49~50, a=2.5~3, b=7.8~8.4.

[0066] In an optional embodiment, when the cultural relics coloring and restoration material presents a medium yellow color, the composition of the material, calculated by mass percentage, includes burned gravel: 22% to 28%, quartz sand: 30% to 35%, Dunhuang soil: 22% to 28% and fine tile ash: 12% to 18%; when the material presents a medium yellow color, the color value parameters of the material include L = 68 to 70, a = 3 to 4, b = 11 to 12.5.

[0067] Preferably, when the cultural relics coloring and restoration material presents a medium yellow color, the composition of the material, by mass percentage, includes burned gravel: 25%, quartz sand: 35%, Dunhuang soil: 25% and fine tile ash: 15%; when the material presents a medium yellow color, the color value parameters of the material include L=69~70, a=3.2~3.8, b=11.5~12.5.

[0068] In an optional embodiment, when the cultural relics coloring and restoration material appears light yellow, the composition of the material, by mass percentage, includes burned gravel: 40% to 45%, quartz sand: 28% to 32%, Dunhuang soil: 2% to 8% and fine tile ash: 18% to 22%; when the material appears light yellow, the color value parameters of the material include L=71 to 74, a=1.5 to 3, and b=9 to 10.

[0069] Preferably, when the cultural relics coloring and restoration material appears light yellow, the composition of the material, by mass percentage, includes burned gravel: 45%, quartz sand: 30%, Dunhuang soil: 5% and fine tile ash: 20%; when the material appears light yellow, the color value parameters of the material include L=72~73, a=1.8~2.4, b=9~9.5.

[0070] In an optional embodiment, when the cultural relics coloring and restoration material appears whitish, the composition of the material, by mass percentage, includes burned gravel: 5% to 10%, quartz sand: 18% to 22%, oyster ash: 40% to 45%, fine tile ash: 2% to 8%, black gold sand: 18% to 22% and green pumice powder: 3% to 5%; when the material appears whitish, the color value parameters of the material include L = 63 to 65, a = 0.5 to 1.5, b = 3 to 4.5.

[0071] Preferably, when the cultural relics coloring and restoration material appears whitish, the composition of the material, by mass percentage, includes burnt gravel: 5%, quartz sand: 20%, oyster ash: 45%, fine tile ash: 5%, black gold sand: 20% and green pumice powder: 5%; when the material appears whitish, the color value parameters of the material include L=63.5~64.5, a=0.8~1.2, b=3~4.

[0072] In an optional embodiment, when the cultural relics coloring and restoration material presents a bluish gray color, the composition of the material, by mass percentage, includes burned gravel: 22% to 28%, quartz sand: 28% to 32%, oyster ash: 22% to 28%, fine tile ash: 8% to 12% and black gold sand: 8% to 12%; when the material presents a bluish gray color, the color value parameters of the material include L = 62 to 64, a = 1 to 2, b = 4.5 to 5.5.

[0073] Preferably, when the cultural relics coloring and restoration material presents a bluish-gray color, the composition of the material, by mass percentage, includes burned gravel: 25%, quartz sand: 30%, oyster ash: 25%, fine tile ash: 10% and black gold sand: 10%; when the material presents a bluish-gray color, the color value parameters of the material include L=62.5~63.8, a=1.2~1.8, b=4.5~5.

[0074] In an optional embodiment, when the cultural relics coloring and restoration material presents a light bluish gray color, the composition of the material, by mass percentage, includes burned gravel: 22% to 28%, quartz sand: 12% to 18%, oyster ash: 22% to 28%, fine tile ash: 8% to 12% and black gold sand: 22% to 28%; when the material presents a light bluish gray color, the color value parameters of the material include L = 53 to 55, a = 1 to 2, b = 3.5 to 4.5.

[0075] Preferably, when the cultural relics coloring and restoration material presents a light bluish gray color, the composition of the material, by mass percentage, includes burned gravel: 25%, quartz sand: 15%, oyster ash: 25%, fine tile ash: 10% and black gold sand: 25%; when the material presents a light bluish gray color, the color value parameters of the material include L=53.5~54.8, a=1.2~1.8, b=4~4.5.

[0076] In an optional embodiment, when the cultural relics coloring and restoration material presents a yellowish bluish gray color, the composition of the material, calculated by mass percentage, includes burned gravel: 40% to 45%, oyster ash: 2% to 8%, fine tile ash: 35% to 40%, black gold sand: 2% to 8% and green pumice powder: 3% to 5%; when the material presents a yellowish bluish gray color, the color value parameters of the material include L=62 to 65, a=1 to 2, b=6 to 7.

[0077] Preferably, when the cultural relic coloring and restoration material presents a yellowish bluish gray color, the composition of the material, by mass percentage, includes burned gravel: 45%, oyster ash: 5%, fine tile ash: 40%, black gold sand: 5% and green pumice powder: 5%; when the material presents a yellowish bluish gray color, the color value parameters of the material include L=63~64, a=1~1.8, b=6.2~6.8.

[0078] In an optional embodiment, the particle size of the quartz sand is 120-160 meshes, and the particle size of the black gold sand is 120-160 meshes. By controlling the particle sizes of the quartz sand and the black gold sand within the above range, the overall fineness of the material and the surrounding limestone raw stones can be coordinated and unified, and the tightness of the connection between the material and the supplementary material and / or the limestone raw stone can be ensured to prevent the material from falling off.

[0079] In a second aspect, the present invention provides an application of a material according to any one of the aforementioned embodiments in limestone-type stone repair.

[0080] Preferably, the application method of the cultural relic coloring and restoration material includes mixing the raw materials of the material with water in proportion and then applying the mixture to the surface of the limestone-like stone.

[0081] Preferably, the mass ratio of the total mass of the raw materials of the cultural relics coloring and restoration material to water is 1:0.35-0.4.

[0082] The cultural relic coloring and restoration material provided by the present invention has natural raw materials and does not require any chemical additives. It only uses water as a mixing medium for the various raw materials and does not require high-temperature heating for consolidation and molding. It does not cause any physical or chemical damage to the cultural relic itself, and the material has strong compatibility and reversibility.

[0083] In some preferred embodiments, when the materials provided by the present invention are applied to the restoration of limestone, it is only necessary to detect the color value parameters of the area to be restored, and then mix them according to the formula corresponding to the color value parameters provided by the present invention, so that a cultural relic coloring restoration material with uniform color can be quickly obtained, which reduces the difficulty of coloring, reduces the number of repeated color tests, and reduces the requirements for the restoration experience or professional knowledge of the restoration personnel, thereby ensuring the accuracy of the color restoration of cultural relics, while avoiding the increase in costs and the possibility of damage to cultural relics caused by repeated repairs.

[0084] Example 1

[0085] The present embodiment provides a coloring and restoration material for limestone cultural relics. The cultural relic coloring and restoration material includes, by mass percentage, burned gravel: 25%, oyster lime: 25%, quartz sand: 10%, fine tile ash: 5% and black gold sand: 35%, and can be used to repair dark gray limestone raw stones.

[0086] Example 2

[0087] The present embodiment provides a coloring and restoration material for limestone cultural relics. The cultural relic coloring and restoration material includes, by mass percentage, burned gravel: 5%, oyster lime: 45%, quartz sand: 15%, fine tile ash: 5% and black gold sand: 30%, and can be used to repair medium-gray limestone raw stones.

[0088] Example 3

[0089] The present embodiment provides a coloring and restoration material for limestone cultural relics. The cultural relic coloring and restoration material includes, by mass percentage, 50% burned granite, 5% quartz sand, 30% fine tile ash and 15% black gold sand, and can be used to repair light gray limestone raw stones.

[0090] Example 4

[0091] The present embodiment provides a coloring and restoration material for limestone cultural relics. The cultural relic coloring and restoration material includes, by mass percentage, burned gravel: 10% to 15%, quartz sand: 22% to 28%, Dunhuang soil: 35% to 37.5% and black gold sand: 22% to 28%, and can be used to repair brown-yellow limestone raw stones.

[0092] Example 5

[0093] The present embodiment provides a coloring and restoration material for limestone cultural relics. The cultural relic coloring and restoration material includes, by mass percentage, 25% burned granite, 35% quartz sand, 25% Dunhuang soil and 15% fine tile ash. The material can be used to repair medium-yellow limestone raw stones.

[0094] Example 6

[0095] The present embodiment provides a coloring and restoration material for limestone cultural relics. The cultural relic coloring and restoration material includes, by mass percentage, 45% burned granite, 30% quartz sand, 5% Dunhuang soil and 20% fine tile ash, and can be used to repair light yellow limestone raw stones.

[0096] Example 7

[0097] The present embodiment provides a coloring and restoration material for limestone cultural relics. The cultural relic coloring and restoration material includes, by mass percentage, burned granite: 5%, quartz sand: 20%, oyster lime: 45%, fine tile lime: 5%, black gold sand: 20% and green pumice powder: 5%, and can be used to repair whitish limestone raw stones.

[0098] Example 8

[0099] The present embodiment provides a coloring and restoration material for limestone cultural relics. The cultural relic coloring and restoration material includes, by mass percentage, burned granite: 25%, quartz sand: 30%, oyster lime: 25%, fine tile lime: 10% and black gold sand: 10%, and can be used to repair blue-gray limestone raw stones.

[0100] Example 9

[0101] The present embodiment provides a coloring and restoration material for limestone cultural relics. The cultural relic coloring and restoration material includes, by mass percentage, burned granite: 25%, quartz sand: 15%, oyster lime: 25%, fine tile lime: 10% and black gold sand: 25%, and can be used to repair light blue-gray limestone raw stones.

[0102] Example 10

[0103] The present embodiment provides a coloring and restoration material for limestone cultural relics. The cultural relic coloring and restoration material includes, by mass percentage, burned granite: 45%, oyster ash: 5%, fine tile ash: 40%, black gold sand: 5% and green pumice powder: 5%, and can be used to repair yellowish bluish-gray limestone raw stones.

[0104] Test Example 1

[0105] The color-adjusting restoration material for limestone cultural relics provided in the above embodiment is applied to the restoration of limestone original stones of corresponding colors, and the color value parameters of the limestone original stones of corresponding colors are detected and recorded in Table 1.

[0106] The color restoration material of the limestone cultural relic in each embodiment was prepared into a cake-shaped sample block with a diameter of 2.5 cm and a thickness of 1 cm, and then the color value parameters of the sample block were detected and recorded in Table 1.

[0107] The sample block preparation method is: after mixing the raw materials of the coloring and restoration materials of the limestone cultural relics in proportion, add an equal mass of deionized water, stir thoroughly, and then prepare it into a cake-shaped sample block, and place the sample block in a cool and dry place to stand until it is fully dried.

[0108] The color value parameters are tested by a spectrophotometer, and the color value parameters of the limestone raw stone and the sample obtained by the test are compared, and the total color difference △E between the two is calculated according to the color space color difference calculation formula in the National Standard of the People's Republic of China - Uniform Color Space and Color Difference Formula "GB / T 7921-1997".

[0109] According to the color difference tolerance range of CIELAB color space:

[0110] ΔE<1: Imperceptible color difference, that is, it is difficult for the naked eye to distinguish the difference between the two colors.

[0111] 1≤ΔE<2: Slight color difference, which can only be detected by careful observation.

[0112] 2≤ΔE<3.5: General color difference, which can be clearly seen by the naked eye.

[0113] ΔE ≥ 3.5: Significant color difference, very easy to detect, may have a significant impact on the appearance quality of the product.

[0114] Table 1 Color parameters of samples and limestone raw stones

[0115]

[0116]

[0117] As can be seen from Table 1, the samples prepared by the color adjustment and restoration materials for limestone cultural relics provided in Examples 1 to 10 of the present invention have a color difference of less than 1 with the original limestone stone, and there is no color difference when observed with the naked eye. The color is very coordinated with the color of the cultural relic itself, has good compatibility, and is suitable for the restoration of cultural relics.

[0118] The samples obtained in Examples 2, 3 and 6 were placed together with the corresponding limestone raw stones and photographed and observed, and the following results were obtained: Figures 2 to 4 The results are shown. Figures 2 to 4 It can be seen that the sample block made by using the cultural relic coloring and restoration material provided by the embodiment of the present invention has almost no difference in color with the original limestone stone, and is suitable for cultural relic restoration.

[0119] Test Example 2

[0120] The coloring and repairing materials of the limestone cultural relics of Examples 3, 7 and 10 were applied to the protection and repair of the body of the limestone cultural relics to obtain the following Figures 5 to 7 Results shown.

[0121] Depend on Figures 5 to 7 It can be seen that after the restoration is carried out using the cultural relic coloring and restoration material provided by the embodiment of the present invention, the damaged and cracked parts disappear, and the area close to the repaired part is coordinated in color with the surrounding limestone original stone, and has good compatibility.

[0122] Comparative Example 1

[0123] This comparative example provides a coloring and restoration material for limestone cultural relics. The cultural relic coloring and restoration material includes, by mass percentage, burned granite: 50%, titanium dioxide: 4%, quartz sand: 40%, light gray: 1% and carbon black: 5%. The material can be used to repair dark gray limestone raw stones.

[0124] Comparative Example 2

[0125] This comparative example provides a coloring and restoration material for limestone cultural relics. The cultural relic coloring and restoration material includes, by mass percentage, burned granite: 50%, titanium dioxide: 6%, quartz sand: 40%, fine tile ash: 1% and carbon black: 3%. The material can be used to repair medium-gray limestone raw stones.

[0126] Comparative Example 3

[0127] This comparative example provides a coloring and restoration material for limestone cultural relics. The cultural relic coloring and restoration material includes, by mass percentage, 50% burned granite, 40% quartz sand, 9% fine tile ash and 1% black gold sand, and can be used to repair light gray limestone raw stones.

[0128] Test Example 3

[0129] The cultural relic coloring and restoration materials provided in Comparative Examples 1 to 3 were prepared into cake-shaped samples of the same size according to the method of Experimental Example 1, and their color value parameters were tested, and the results shown in Table 2 were obtained.

[0130] Then, the samples of Comparative Examples 1 to 3 and Examples 1 to 3 were placed in a natural environment with high temperature, high humidity and abundant rain in summer and low temperature, low humidity and snowfall in winter, and aged for 365 days. The color parameters of the samples after the 365th day were tested and recorded in Table 2. The color parameters tested on the first day (the first day is the day for testing the color after the repair material is naturally dried) and after the 365th day were compared, and the ΔE color difference values ​​of the Examples and Comparative Examples after 365 days of outdoor natural cycle aging were calculated.

[0131] Table 2 Chromaticity parameters of samples of the embodiment and comparative example before and after natural aging

[0132]

[0133]

[0134] It can be seen from Table 2 that the cultural relic coloring and restoration material provided by the embodiment of the present invention has better durability, and has good color stability after long-term storage. Comparative Examples 1 to 3 use chemical synthetic pigments. Although the color difference in the initial stage is small compared with the tuff original stone, after long-term storage, the color changes significantly and the color difference increases. It is not suitable as a coloring and restoration material for cultural relic restoration. It is easy to repeat the restoration of the cultural relic body, which increases the time and labor cost of restoring the cultural relic body and increases the risk of damage to the cultural relic.

[0135] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A coloring and restoration material for limestone cultural relics, characterized in that: The materials for coloring and restoration of cultural relics are calculated by mass percentage, including burnt gravel: 5% to 45%, quartz sand: 0% to 35%, oyster ash: 0% to 45%, Dunhuang soil: 0% to 37.5%, fine tile ash: 0% to 40%, black gold sand: 0% to 35% and green pumice powder: 0% to 5%; The color value parameters of the burnt granite include: L=74-75, a=4-5, b=14-15; The color value parameters of the quartz sand include: L=88-90, a=0.1-0.2, b=2.5-3.5; The color value parameters of the oyster gray include: L=86-87, a=-0.4--1.4, b=10.1-11.1; The color value parameters of the Dunhuang soil include: L=65-66, a=5-6, b=11-12; The color value parameters of the fine tile gray include: L=42-43, a=0.1-1.0, b=4-5; The color value parameters of the black gold sand include: L=32-33, a=3-4, b=-10--11; The color value parameters of the green pumice powder include: L=76-77, a=-3-4, b=-2-3.

2. The material according to claim 1, characterized in that When the material is dark gray, the composition of the material, by mass percentage, includes burnt gravel: 22% to 28%, oyster ash: 22% to 28%, quartz sand: 8% to 12%, fine tile ash: 2% to 8% and black gold sand: 30% to 35%; when the material is dark gray, the color value parameters of the material include L=50 to 52, a=1 to 2, and b=3.5 to 4.5; Preferably, when the material presents a medium gray color, the composition of the material, by mass percentage, includes burnt gravel: 5% to 10%, quartz sand: 12% to 18%, oyster ash: 40% to 45%, fine tile ash: 2% to 8% and black gold sand: 28% to 32%; when the material presents a medium gray color, the color value parameters of the material include L=58 to 60, a=1 to 2, b=3 to 4; Preferably, when the material is light gray, the composition of the material, by mass percentage, includes burnt gravel: 22% to 28%, quartz sand: 12% to 18%, oyster ash: 22% to 28%, fine tile ash: 22% to 28% and black gold sand: 8% to 12%; when the material is light gray, the color value parameters of the material include L=60 to 62, a=0.5 to 1.5, and b=3 to 4.

3. The material according to claim 2, characterized in that When the material is dark gray, the composition of the material, by mass percentage, includes burnt gravel: 25%, oyster ash: 25%, quartz sand: 10%, fine tile ash: 5% and black gold sand: 35%; when the material is dark gray, the color value parameters of the material include L=50.5-51.5, a=1.2-1.8, b=3.5-4.2; Preferably, when the material presents a medium gray color, the composition of the material, by mass percentage, includes burnt gravel: 5%, oyster ash: 45%, quartz sand: 15%, fine tile ash: 5% and black gold sand: 30%; when the material presents a medium gray color, the color value parameters of the material include L=58.5-59.5, a=1-1.5, b=3-3.5; Preferably, when the material is light gray, the composition of the material, by mass percentage, includes burnt gravel: 25%, oyster ash: 25%, quartz sand: 15%, fine tile ash: 25% and black gold sand: 10%; when the material is light gray, the color value parameters of the material include L=61~62, a=0.8~1.2, b=3.4~4.

4. The material according to claim 1, characterized in that When the material is brownish yellow, the composition of the material, by mass percentage, includes burnt gravel: 10% to 15%, quartz sand: 22% to 28%, Dunhuang soil: 35% to 37.5% and black gold sand: 22% to 28%; when the material is brownish yellow, the color value parameters of the material include L=48 to 51, a=2 to 3, and b=7.5 to 8.5; Preferably, when the material presents a medium yellow color, the composition of the material, by mass percentage, includes burnt gravel: 22% to 28%, quartz sand: 30% to 35%, Dunhuang soil: 22% to 28% and fine tile ash: 12% to 18%; when the material presents a medium yellow color, the color value parameters of the material include L=68 to 70, a=3 to 4, and b=11 to 12.5; Preferably, when the material is light yellow, the composition of the material, by mass percentage, includes burnt gravel: 40% to 45%, quartz sand: 28% to 32%, Dunhuang soil: 2% to 8% and fine tile ash: 18% to 22%; when the material is light yellow, the color value parameters of the material include L=71 to 74, a=1.5 to 3, and b=9 to 10.

5. The material according to claim 4, characterized in that When the material is brownish yellow, the composition of the material, by mass percentage, includes burnt gravel: 12.5%, quartz sand: 25%, Dunhuang soil: 37.5% and black gold sand: 25%; when the material is brownish yellow, the color value parameters of the material include L=49-50, a=2.5-3, b=7.8-8.4; Preferably, when the material presents a medium yellow color, the composition of the material, by mass percentage, includes burnt gravel: 25%, quartz sand: 35%, Dunhuang soil: 25% and fine tile ash: 15%; when the material presents a medium yellow color, the color value parameters of the material include L=69-70, a=3.2-3.8, b=11.5-12.5; Preferably, when the material is light yellow, the composition of the material, by mass percentage, includes burnt gravel: 45%, quartz sand: 30%, Dunhuang soil: 5% and fine tile ash: 20%; when the material is light yellow, the color value parameters of the material include L=72~73, a=1.8~2.4, b=9~9.

5.

6. The material according to claim 1, characterized in that When the material is off-white, the composition of the material, by mass percentage, includes burnt gravel: 5% to 10%, quartz sand: 18% to 22%, oyster ash: 40% to 45%, fine tile ash: 2% to 8%, black gold sand: 18% to 22% and green pumice powder: 3% to 5%; when the material is off-white, the color value parameters of the material include L=63 to 65, a=0.5 to 1.5, and b=3 to 4.5; Preferably, when the material appears whitish, the composition of the material, by mass percentage, includes burnt gravel: 5%, quartz sand: 20%, oyster ash: 45%, fine tile ash: 5%, black gold sand: 20% and green pumice powder: 5%; when the material appears whitish, the color value parameters of the material include L=63.5~64.5, a=0.8~1.2, b=3~4.

7. The material according to claim 1, characterized in that When the material is blue-gray, the composition of the material, by mass percentage, includes burnt gravel: 22% to 28%, quartz sand: 28% to 32%, oyster ash: 22% to 28%, fine tile ash: 8% to 12% and black gold sand: 8% to 12%; when the material is blue-gray, the color value parameters of the material include L=62 to 64, a=1 to 2, and b=4.5 to 5.5; Preferably, when the material is light blue-gray, the composition of the material, by mass percentage, includes burnt gravel: 22% to 28%, quartz sand: 12% to 18%, oyster ash: 22% to 28%, fine tile ash: 8% to 12% and black gold sand: 22% to 28%; when the material is light blue-gray, the color value parameters of the material include L=53 to 55, a=1 to 2, and b=3.5 to 4.5; Preferably, when the material presents a yellowish bluish gray color, the composition of the material, calculated by mass percentage, includes burnt gravel: 40% to 45%, oyster ash: 2% to 8%, fine tile ash: 35% to 40%, black gold sand: 2% to 8% and green pumice powder: 3% to 5%; when the material presents a yellowish bluish gray color, the color value parameters of the material include L=62 to 65, a=1 to 2, b=6 to 7.

8. The material according to claim 7, characterized in that When the material is blue-gray, the composition of the material, by mass percentage, includes burnt gravel: 25%, quartz sand: 30%, oyster ash: 25%, fine tile ash: 10% and black gold sand: 10%; when the material is blue-gray, the color value parameters of the material include L=62.5-63.8, a=1.2-1.8, b=4.5-5; Preferably, when the material is light blue-gray, the composition of the material, by mass percentage, includes burnt gravel: 25%, quartz sand: 15%, oyster ash: 25%, fine tile ash: 10% and black gold sand: 25%; when the material is light blue-gray, the color value parameters of the material include L=53.5-54.8, a=1.2-1.8, b=4-4.5; Preferably, when the material presents a yellowish bluish gray color, the composition of the material, calculated by mass percentage, includes burnt gravel: 45%, oyster ash: 5%, fine tile ash: 40%, black gold sand: 5% and green pumice powder: 5%; when the material presents a yellowish bluish gray color, the color value parameters of the material include L=63~64, a=1~1.8, b=6.2~6.

8.

9. The material according to any one of claims 2 to 8, characterized in that The particle size of the quartz sand is 120-160 meshes, and the particle size of the black gold sand is 120-160 meshes.

10. Use of the material according to any one of claims 1 to 9 in limestone restoration; Preferably, the application method of the material comprises mixing the raw materials of the material with water in proportion and then applying the mixture to the surface of the limestone-like stone; Preferably, the mass ratio of the raw material of the material to water is 1:0.35-0.4.

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