CN113480915A

CN113480915A - Pigment for filling color of stone cultural relics and preparation method thereof

Info

Publication number: CN113480915A
Application number: CN202110774215.9A
Authority: CN
Inventors: 张兴; 张超; 司云鹏
Original assignee: Individual
Current assignee: Individual
Priority date: 2021-07-08
Filing date: 2021-07-08
Publication date: 2021-10-08

Abstract

The application provides a pigment for color filling of stone cultural relics and a preparation method thereof, and the pigment comprises the following components in percentage by mass: 36-40% of natural mineral pigment, 24-28% of fish glue, 24-28% of water-based epoxy resin and 6-13% of curing agent. Pulverizing natural ore, grinding, selecting the type and amount of natural mineral pigment according to color filling requirement, cutting air bladder, placing into a pot, adding Alumen and water, and decocting for 1h to obtain air bladder glue. Uniformly stirring fish glue, natural mineral pigment, water-based epoxy resin and curing agent to obtain the pigment for filling the color of the stone cultural relics and the preparation method thereof. The pigment for color filling of stone cultural relics such as Moya stone carving and stele carving has the characteristics of good reversibility, difficult fading, good weather resistance, small interference on the stone cultural relics and the like. The pigment prepared by the method is nontoxic, non-corrosive, good in safety, free of side effects and damages to the bodies of operators, simple in process method, convenient to operate and low in cost.

Description

Pigment for filling color of stone cultural relics and preparation method thereof

Technical Field

The application relates to the field of cultural relic restoration, in particular to a pigment for color filling of stone cultural relics and a preparation method thereof.

Background

The Moya stone carving is a stone carving art in ancient China, and refers to calligraphy, statues or rock paintings carved on the cliff stone wall. As the Mounti gravels are exposed in outdoor environment all year round and are influenced by natural and human factors, the phenomena of upwarping, falling and fading of color filling layers appear in a plurality of Mounti gravels; the same problem is also present in other stone cultural relics such as inscriptions. The traditional color filling pigment for the molya cliff stone adopts mineral pigment mixed with animal and vegetable glue as a binder, and although the pigment is not easy to change color, the weather resistance, especially the water resistance is relatively poor. Modern paint is mostly used for color filling of the moya graves, but the paint is easy to fade and rise, is difficult to remove and does not conform to the principle of reversibility of cultural relic protection.

Accordingly, one skilled in the art provides a pigment for color filling of stone cultural relics and a preparation method thereof, so as to solve the problems in the background art.

Disclosure of Invention

Aiming at the defects of the prior art, the application aims to provide the pigment for the color filling of the stone cultural relic and the preparation method thereof, the pigment is prepared by processing the natural mineral pigment, fish glue, water-based epoxy resin, a curing agent and the like as raw materials, and has the characteristics of good reversibility, difficult fading, good weather resistance, small interference on the stone cultural relic and the like.

The technical scheme adopted by the application is as follows:

the pigment for filling the color of the stone cultural relics comprises the following components in percentage by mass: 36-40% of natural mineral pigment, 24-28% of fish glue, 24-28% of water-based epoxy resin and 6-13% of curing agent.

Further, the pigment for color filling of the stone cultural relics comprises the following components in percentage by mass: 37% of natural mineral pigment, 26% of fish glue, 26% of water-based epoxy resin and 11% of curing agent.

Further, the pigment for color filling of the stone cultural relics comprises the following components in percentage by mass: 38.5 percent of natural mineral pigment, 26.9 percent of fish glue, 26.9 percent of water-based epoxy resin and 7.7 percent of curing agent.

Further, the pigment for filling the color of the stone cultural relics comprises the following components in percentage by mass: 5.7 percent of dry swimming bladder, 3.4 percent of alum and 90.9 percent of water.

Further, the pigment for filling the color of the stone cultural relics is prepared by selecting one or more of cinnabar, hematite, turquoise, bluestone, bronze and stone yellow as raw materials for preparing the natural mineral pigment.

Further, a preparation method of the pigment for color filling of the stone cultural relics comprises the following steps:

(1) preparation of natural mineral pigments: crushing and grinding natural ore, and selecting the type and the quantity of natural mineral pigments according to color filling requirements;

(2) cutting dry and non-mildewed swimming bladder into pieces, soaking in water for 3h, putting the swimming bladder into a pot, adding alum which is 0.6 time of the weight of the swimming bladder and water which is 16 times of the weight of the swimming bladder, and decocting for 1h to obtain swimming bladder glue;

(3) uniformly stirring fish glue, a natural mineral pigment, water-based epoxy resin and a curing agent to obtain the pigment for filling the color of the stone cultural relics.

The beneficial effect of this application lies in:

the natural mineral pigment, the fish maw glue, the water-based epoxy and the curing agent are compounded and blended into the novel stone carving color filling material through scientific proportioning, and the novel stone carving color filling material has the characteristics of good reversibility, difficult fading, good weather resistance, small interference on stone cultural relics and the like. The pigment prepared by the method is nontoxic, non-corrosive, good in safety, free of side effects and damages to the bodies of operators, simple in process method, convenient to operate and low in cost.

Detailed Description

The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

Example 1

The pigment for filling the color of the stone cultural relics comprises the following components in percentage by mass: 37% of natural mineral pigment, 26% of fish glue, 26% of water-based epoxy resin and 11% of curing agent. The preparation method comprises the following steps:

(3) 26g of fish glue, 37g of natural mineral pigment, 26g of water-based epoxy resin and 11g of curing agent are uniformly stirred to obtain the pigment for filling the color of the stone cultural relic.

Example 2

The pigment for filling the color of the stone cultural relics comprises the following components in percentage by mass: 38.5 percent of natural mineral pigment, 26.9 percent of fish glue, 26.9 percent of water-based epoxy resin and 7.7 percent of curing agent.

(3) 26.9g of fish glue, 38.5g of natural mineral pigment, 26.9g of water-based epoxy resin and 7.7g of curing agent are uniformly stirred to obtain the pigment for filling the color of the stone cultural relic.

1. Performance testing of the adhesive

The pigment is required to be uniformly coated and firmly attached to the surface of a coated object, so that a binder with excellent performance is required, the binder is the basis of all coating materials and is an essential basic component, and the properties of the binder play a role in determining the hardness, flexibility, wear resistance, impact resistance, weather resistance, water resistance, heat resistance and state of a formed coating film, and a drying and hardening method, such as normal-temperature drying, curing of a curing agent and the like.

Animal glue commonly used by ancient traditional adhesives in China, such as bone glue, hide glue, fish glue and the like, has the greatest advantage of very good reversibility, which also accords with the basic principle of cultural relic protection, so that the animal glue and mineral pigments are often selected to be mixed for performance test comparison, and the components are shown in table 1:

TABLE 1 Components

Group of	Bone glue (%)	Skin glue (%)	Fish maw glue (%)	Mineral pigment (%)
					First group	62	0	0	38
Second group	0	62	0	38
					Third group	0	0	62	38

(1) Comparison of Water Permeability

Since the stone carving needs to maintain proper moisture to maintain self balance, the color filling material is selected to ensure that the pores on the surface of the stone are not completely closed, and the stone has good weather resistance and certain air permeability and water permeability.

The method comprises the following steps of coating 3 groups of pigments on the surface of a stone sample block, respectively labeling, carrying out a free water permeability test on the stone sample block after drying, and comparing the stone sample block with an original stone, wherein the water repellency of a first group of materials is reduced by 42.8% compared with that of the original stone, the water repellency of a second group of materials is increased by 14.3% compared with that of the original stone, and the water repellency of a third group of materials is increased by 42.8% compared with that of the original stone. Through the data analysis, the three materials have certain pores, so that the stone maintains moisture balance; the reason why the water-repellent capacity of the bone glue pigment is reduced by looking up data is probably that the bone glue has relatively high water absorption, so that the water-repellent capacity of the fish maw glue is relatively optimal.

(2) Comparison of stability

In outdoor environments, water is the most important factor affecting the stability of traditional mineral pigments, so dry-wet cycling experiments on three binder-coated mineral pigments were required. Painting the 3 groups of pigments on the surface of the stone sample block, then spraying the sample block with water for 1h, putting the sample block into an electrothermal blowing drying oven, setting the temperature of the sample block at 80 ℃, keeping the temperature for 1h, and taking out the sample block to be used as a primary dry-wet cycle. And repeating the experiment, observing the phenomena of warping and falling of the pigment layers of the sample blocks, and recording the dry-wet cycle times when the pigment layers are warped and fall.

The experimental results are as follows: after 3 times of dry-wet circulation, the first group of materials have the phenomena of warping and falling off of local pigment layers of the pigment layers; after the 6 th dry-wet cycle, the first group of materials are basically completely peeled off, and the second group of materials are also partially peeled off; after 15 dry-wet cycles, the second group of materials also substantially completely fell off; the third group of materials only slightly warps after 50 times of dry-wet cycles, and the whole effect is good. Therefore, the fish glue is selected as the main adhesive material in the three adhesives.

2. Comprehensive performance test

Although the fish glue is relatively stable in the traditional animal glue, the fish glue still slowly raises under the condition of repeated alternation of dryness and wetness, the rock massage is exposed in the outdoor environment all the year round, is influenced by factors such as wind, sunshine, rain and the like, and has great test on the weather resistance. Therefore, the swimming bladder glue is tried to be modified, a proper amount of modern adhesive material is compounded with the swimming bladder glue, the modern paint pigment is compared, the relevant performances of various materials are compared, and the raw materials in each group are selected as shown in the table 2:

TABLE 2 Components

Group of

Fish maw glue

Natural mineral pigments

Nano silicon dioxide

Aqueous epoxy resin

Acrylic acid

Alkyd paint

Example 1

√

Comparative example 1

√

Comparative example 2

√

Comparative example 3

√

Comparative example 4

√

Comparative example 5

√

(1) Ultrasonic detection:

the influence of the painting pigment layer on the surface porosity of the stone is judged by comparing the changes of the sound wave time, the wave speed and the wave amplitude of the original stone through the sample block of ultrasonic detection. Experimental data table 3 shows:

TABLE 3 ultrasonic testing data

Combining the above data, it can be seen that the sound time and sound velocity index of example 1 is closest to the original stone, followed by comparative example 1; the materials of comparative example 2 and comparative example 5 had the highest exponential rate of change in sound time and sound velocity. The amplitude index of the material in example 1 is closest to that of the original stone, and then the material in comparative example 2, and the amplitude index change rate of the material in comparative example 4 is the largest. In conclusion, the ultrasonic indexes of the sample block coated with the material of the embodiment 1 are closest to those of the original stone, and the influence on the porosity of the surface of the stone is minimum.

(2) And (3) detecting the free water permeability:

before testing, the test block is put into an electrothermal blowing drying oven to be dried for 1 hour, the water content of the test block is measured to be 4.7%, free water permeability experiments are respectively carried out on each pigment layer, the data of the test block is compared with the free water permeability of the original stone, and the water permeability of the material is evaluated. The experimental data are shown in table 4:

TABLE 4 free Water Permeability test data

The data show that all the materials have certain water repellency, the moisture can not permeate into the materials of the comparative examples 2, 4 and 5 almost completely, however, the application of the materials on the carved surface of the rock massage can not only prevent the water in the external environment from permeating into the gaps of the stone, but also influence the seepage of the moisture in the stone, and influence the self moisture and stress balance to a certain degree. In contrast, the material of comparative example 1 has the most similar free water permeability to the original stone, and the material of example 1 is inferior.

(3) And (3) dry-wet cycle detection:

and spraying the sample block for 1h, putting the sample block into an electrothermal blowing drying oven, setting the temperature of the sample block at 100 ℃, keeping the temperature for 1h, taking the sample block out, performing one dry-wet cycle, and observing after 100 dry-wet cycles, wherein the materials in comparative example 1 and comparative example 2 have the phenomenon of local upwarping and dropping, and other materials have no obvious change. Therefore, the pure fish glue, the natural mineral pigment, the fish glue and the nano sio are shown₂+ natural mineral pigments two color-filling materials have relatively weaker water resistance than several others.

(4) And (3) reversibility detection:

because the cultural relics are non-renewable, the materials of the example 1 group and the comparative example 1, the comparative example 2, the comparative example 3, the comparative example 4 and the comparative example 5 need to be subjected to cleaning experiments while the exhibition and utilization value of the cultural relics are fully exerted and the principle of minimum intervention and reversibility is necessarily followed, and the experiments show that the materials of the example 1 group and the comparative example 1 and the comparative example 2 can be easily removed by using warm water with the temperature of more than 70 ℃ or using a steam cleaning machine; the materials of comparative example 3 and comparative example 4 can be partially removed only by physical methods, but are difficult to remove cleanly; comparative example 5 the material was difficult to remove. From this, it can be seen that the comparison of the materials of the group of example 1 and the materials of the comparative examples 1 and 2 conforms to the principle of reversibility of cultural relic protection.

From the experimental results, the change of the porosity and the water permeability of the stone surface by the materials of the example 1 and the comparative example 1 is minimum, the carving effect of the rock on the rock can be improved, the reversible principle of cultural relics protection can be simultaneously met, the subsequent reprocessing is convenient, and the material of the example 1 is obviously superior to the material of the comparative example 1 in the aspect of water resistance.

According to the experimental results of the performance of the adhesive and the detection results of all indexes of the comprehensive performance, the natural fish glue, the mineral pigment and the waterborne epoxy resin are finally selected to be matched with the curing agent to be used as the color filling pigment, and the color filling pigment is reasonably and scientifically matched to be prepared into the novel stone carving color filling material, so that the novel stone carving color filling material has the characteristics of good reversibility, difficult fading, good weather resistance, small interference on stone cultural relics and the like.

The above description is only for the purpose of illustrating the preferred embodiments of the present application and is not to be construed as limiting the present application, and all equivalent variations and modifications within the scope of the present application are intended to be covered by the present application. Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims

1. A pigment for color filling of stone cultural relics, which is characterized in that: the paint consists of the following components in percentage by mass: 36-40% of natural mineral pigment, 24-28% of fish glue, 24-28% of water-based epoxy resin and 6-13% of curing agent.

2. A pigment for the color-filling of stone relics according to claim 1, characterized in that: the paint consists of the following components in percentage by mass: 37% of natural mineral pigment, 26% of fish glue, 26% of water-based epoxy resin and 11% of curing agent.

3. The pigment for color-filling of stone cultural relics as claimed in claim 1, and the preparation method thereof, characterized in that: the paint consists of the following components in percentage by mass: 38.5 percent of natural mineral pigment, 26.9 percent of fish glue, 26.9 percent of water-based epoxy resin and 7.7 percent of curing agent.

4. A pigment for the color-filling of stone relics according to claim 1, characterized in that: the fish glue comprises the following components in percentage by mass: 5.7 percent of dry swimming bladder, 3.4 percent of alum and 90.9 percent of water.

5. A pigment for the color-filling of stone relics according to claim 1, characterized in that: the natural mineral pigment is selected from one or more of cinnabar, hematite, turquoise, bluestone, chrysolite and stone yellow.

6. A method of preparing a pigment for color-filling of stone relics as claimed in claim 1, characterized in that: the method comprises the following steps:

(3) putting the fish glue, the natural mineral pigment, the waterborne epoxy resin and the curing agent into a container and stirring uniformly to obtain the pigment for filling the color of the stone cultural relic.