CN116810960A

CN116810960A - Composite filling reinforcing agent for soil-out rotten wooden cultural relics in drought environment and preparation method and application thereof

Info

Publication number: CN116810960A
Application number: CN202310906260.4A
Authority: CN
Inventors: 钟磊; 顾文婷; 魏彦飞; 王雪
Original assignee: Gansu Institute Of Cultural Relics And Archaeology
Current assignee: Gansu Institute Of Cultural Relics And Archaeology
Priority date: 2023-07-24
Filing date: 2023-07-24
Publication date: 2023-09-29

Abstract

The invention belongs to the technical field of arid environment unearthed wooden relics reinforcing materials, and discloses a composite filling reinforcing agent for arid environment unearthed rotten wooden relics, a preparation method and application thereof. The composite filling reinforcing agent comprises a natural rosin solution, an ethyl cellulose solution and glycerol; the volume ratio of the natural rosin solution to the ethyl cellulose solution is 1:1, a step of; the volume of glycerol is 1% of the total volume of the composite filling reinforcing agent. The ethyl cellulose used in the invention can be used as retarder and adhesive, and can form tough film, so that the defect of rosin can be overcome; the ethanol is used as a solvent, rosin and ethyl cellulose can be better brought into cavities of wood due to decay, and glycerol contained in the cavities can also provide a moisturizing function for the wood. The composite filling reinforcing agent disclosed by the invention has good permeability, can be suitable for wood with large decay degree, and has acceptable chromatic aberration.

Description

Composite filling reinforcing agent for soil-out rotten wooden cultural relics in drought environment and preparation method and application thereof

Technical Field

The invention relates to the technical field of arid environment unearthed wooden relics reinforcing materials, in particular to a composite filling reinforcing agent for arid environment unearthed rotten wooden relics, a preparation method and application thereof.

Background

Along with development and perfection of archaeological techniques, more and more cultural relics are continuously discovered and mined, the materials and the types of the cultural relics are continuously enriched, and only the original faces of the cultural relics are preserved, the historical value, the artistic value and the scientific value of the cultural relics can be preserved, so that the cultural relic protection technique is also continuously innovated, and the principle of cultural relic protection is also followed in the process of implementing protection, so that the difficulty of cultural relic protection is further improved.

The wooden relics mainly refer to historical relics which take wood as a basic manufacturing material. Wood has been a renewable resource compared to other materials because of its many superior properties that have been of great interest in human social development, and from the original society to date, wood has played an extremely important role in human life. However, wood also has its own drawbacks, such as: 1. wood is an anisotropic heterogeneous material, the deformation of the wood is aggravated due to the uneven expansion and shrinkage, and the wood is easy to crack due to the difference of strength in all directions; 2. the wood is a moisture-absorbing material, and wet expansion and dry shrinkage can occur under natural conditions, so that the dimensional stability of the wood is affected, namely the wood is easy to deform; 3. wood is a natural high molecular organic polymer, is easy to parasitize some insects and fungus (mould and wood rot fungus) so as to degrade the wood and destroy the wood products; 4. wood is inflammable; 5. the main diseases which occur in the dry area and are stored (unearthed) with lower water content are cracking, deformation, decay, worm damage and the like, and the wood with serious decay can lose strength completely, so that the cultural relic value is lost; the water content of the full-water wood is very high, water is rapidly lost in the air after the soil is removed, the wood can crack and deform in the process, and the dehydration problem is considered in the first aspect of protection of the full-water paint wood. Because of the different characteristics of dry and saturated wood, different strengthening agents are required for these characteristics.

Research on wood body reinforcing materials is always a key point and a difficult point of cultural relic protection. WoodBesides its own factors, the change of the buried environment after the soil is unearthed can cause the precious cultural relics to be secondarily damaged. The existing state of the woodware when the woodware is unearthed mainly comprises water saturation and drying, and due to the influence of economic development and other factors, the current research is mainly focused on the woodware shaping and reinforcing protection research under the water saturation state, and the common characteristic of the methods is that the strength of the cultural relics is increased after dehydration. The reinforcement of the dry woodware is mainly as follows: in the 19 th century, mineral water glass (NaSiO ₃ ) Is applied to wood reinforcement; natural products such as natural gums, oils, waxes, resins, and sucrose among organic materials have been used as reinforcement treatments for dry wood. Natural gums including skin gums, bone gums, fish gums, and bean gums have been replaced with widely used synthetic resins in recent years due to their lack of resistance to bacterial and insect damage and poor hygroscopicity. The oil is mainly tung oil, and has the greatest advantages of higher hardness and water repellency; disadvantages are that it is difficult to harden entirely in the cooled condition and that the wood surface is also contaminated. At the beginning of the 20 th century, a method for soaking wood in a hot wax-resin mixed solution was reported, and after sterilization and insecticide treatment, the wax had not only a reinforcing effect but also an antiseptic and insect-proof effect. The wood is impregnated with the beeswax to achieve the dampproof effect, but the beeswax has limited reinforcing effect, and the beeswax has poor weather resistance and is easy to age and become brittle. The beeswax, rosin and gasoline solution of rosin can be directly used as reinforcing agent for wood, and the addition of correspondent insecticide can raise insect-proofing effect. The wood cultural relics reinforced by rosin are heat-resistant and water-repellent, but have poor reinforcing effect, poor corrosion resistance and easy embrittlement. Sucrose is also used for reinforcing wood, but since sucrose is hygroscopic, the treated wood is unstable under environmental changes, and the presence of sugar is liable to cause mildew, decay and worm-eating, the reinforcing treatment is insufficient only for this. The latter approach is to displace the sucrose solution in the wood with an ethanol solution of the phenolic resin, thereby allowing the phenolic resin to eventually set in the wood, without the treated wood having a change in shape.

Along with the continuous abundance of materials, various synthetic organic materials are also used for impregnating and reinforcing dry wooden relics and achieving certain effects, such as: polyvinyl butyral, styrene, methyl methacrylate, epoxy resins, and the like.

In recent years, reinforcing agents which use rosin and shellac as raw materials are used by the university of southwest forestry to reinforce saturated wooden cultural relics; the reinforcing agent for water-saturated decay wood is developed by using suberic acid and alcohols (methanol, n-butanol and glycerol) as raw materials at Nanjing forestry university; the nano cellulose adopted by the wood industry institute of China forestry science institute is used for carrying out corrosion prevention and reinforcement on the wood, the wood is required to be soaked and vacuumized in the process, and the process is not beneficial to cultural relic protection; the bergamot kernel and chemical coating limited company adopt wood wax oil, hexamethyldisiloxane and the like as raw materials to strengthen the saturated water content, and the method is used for strengthening the saturated water content woodware, but the woodware strengthening of soil yielding in drought environment is not studied.

Therefore, aiming at the problems and the disease characteristics of the dry environment unearthed woodware, the preparation of a convenient and practical reinforcing material is a key problem to be solved at present.

Disclosure of Invention

The invention aims to provide a composite filling reinforcing agent for a soil-bearing rotten wood relic in a drought environment, a preparation method and application thereof, and solves the problems of the existing reinforcing material.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a composite filling reinforcing agent for a soil-out rotten wood relic in a drought environment, which comprises a natural rosin solution, an ethyl cellulose solution and glycerol;

the volume ratio of the natural rosin solution to the ethyl cellulose solution is 1:1, a step of;

the volume of the glycerol is 1% of the total volume of the composite filling reinforcing agent.

Preferably, in the composite filling reinforcing agent for the soil-out rotting wood relics in drought environments, the natural rosin solution is obtained by dissolving natural rosin in absolute ethyl alcohol;

the ethyl cellulose solution is prepared by dissolving ethyl cellulose in absolute ethyl alcohol.

Preferably, in the composite filling reinforcing agent for the soil-out rotting wood relics in drought environments, the concentration of the natural rosin solution is 2-5%;

the concentration of the ethyl cellulose solution is 2-5%.

Preferably, in the composite filling reinforcing agent for the soil-out and rotten wood cultural relics in drought environments, the natural rosin in the natural rosin solution is quaternary or penta-grade rosin.

The invention also provides a preparation method of the composite filling reinforcing agent for the soil-out rotten wood relics in the drought environment, which comprises the following steps:

and mixing the natural rosin solution and the ethyl cellulose solution, and then adding glycerol to obtain the composite filling reinforcing agent for the soil-out and rotten wooden cultural relics in the drought environment.

The invention also provides application of the composite filling reinforcing agent for the soil-out rotten wooden relics in drought environments in reinforcing wooden relics.

Preferably, in the application of the composite filling reinforcing agent for the soil-out and decay wood relics in the drought environment in the reinforcement of wood relics, the method for reinforcing the wood relics comprises the following steps:

spraying the composite filling reinforcing agent on the surface of the wooden relics;

or cotton gauze is stuck on the surface of the wooden relics, and then a composite filling reinforcing agent is sprayed;

or soaking the wooden relics in the composite filling reinforcing agent.

Preferably, in the application of the composite filling reinforcing agent for the soil-out and decay wood relics in the drought environment in the reinforcement of wood relics, the reinforcing frequency of the reinforced wood relics is greater than or equal to 1 time.

Compared with the prior art, the invention has the following beneficial effects:

the invention adopts natural rosin, ethyl cellulose and glycerol to carry out a series of proportioning and combination, and the mixture is dissolved by ethanol to form the composite filling reinforcing agent. If the wood cultural relics reinforced by rosin are used singly, although the wood cultural relics are heat-resistant and water-repellent, the reinforcing effect is poor, the corrosion resistance is poor, the wood cultural relics are easy to become brittle, the ethyl cellulose used in the invention can be used as a retarder and an adhesive, and a tough film can be formed, so that the defects of the rosin can be overcome; the ethanol is used as a solvent, so that rosin and ethyl cellulose can be better brought into a cavity of wood due to decay, and after the ethanol volatilizes, a mixture formed by the rosin and the ethyl cellulose can play a better role in reinforcement; the glycerol contained therein can also provide moisture retention to the wood. The composite filling reinforcing agent disclosed by the invention has good permeability, can be suitable for wood with large decay degree, and has acceptable chromatic aberration.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.

FIG. 1 is a schematic representation of the penetration depth of the composite filled reinforcing agent of example 1;

FIG. 2 is a schematic representation of the penetration depth of the composite filled reinforcing agent of example 2;

FIG. 3 is a schematic representation of the penetration depth of the composite filled reinforcing agent of example 3;

FIG. 4 is a graph showing the results of compressive strength testing prior to reinforcement of a cultural relic sample;

fig. 5 is a graph showing the results of compressive strength testing after reinforcement of a cultural relic sample.

Detailed Description

the volume ratio of the natural rosin solution to the ethyl cellulose solution is preferably 1:1, a step of;

the volume of the glycerol is preferably 1% of the total volume of the composite filling and reinforcing agent.

In the invention, the natural rosin solution is preferably obtained by dissolving natural rosin in absolute ethyl alcohol;

the ethyl cellulose solution is preferably prepared by dissolving ethyl cellulose in absolute ethyl alcohol.

In the present invention, the concentration of the natural rosin solution is preferably 2 to 5%, more preferably 2, 3, 4 or 5%, still more preferably 3%;

the concentration of the ethylcellulose solution is preferably 2 to 5%, more preferably 2, 3, 4 or 5%, and still more preferably 4%.

In the present invention, the natural rosin in the natural rosin solution is preferably a quaternary or quaternary rosin, more preferably a quaternary rosin. The natural rosin used in the subsequent examples of the present invention was a commercially available Qinbao violin specific rosin No.602#.

In the invention, the method for reinforcing the wooden relics comprises the following steps:

or soaking the wooden relics in the composite filling reinforcing agent.

In the present invention, the number of times of reinforcement of the reinforced wooden relics is preferably 1 or more, more preferably 3 to 10 times, and still more preferably 7 times.

The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

Example 1

The embodiment provides a composite filling reinforcing agent for soil-out rotten wood cultural relics in drought environments, which comprises a natural rosin solution with the concentration of 3% (the natural rosin is obtained by dissolving natural rosin in absolute ethyl alcohol), an ethyl cellulose solution with the concentration of 3% (the ethyl cellulose is obtained by dissolving ethyl cellulose in absolute ethyl alcohol), and glycerol accounting for 1% of the total volume of the composite filling reinforcing agent, wherein the volume ratio of the natural rosin solution to the ethyl cellulose solution is 1:1.

the preparation method of the composite filling reinforcing agent comprises the following steps:

and (3) uniformly mixing the natural rosin solution and the ethyl cellulose solution, and then adding glycerol for uniform mixing to obtain the composite filling reinforcing agent.

Example 2

The embodiment provides a composite filling reinforcing agent for soil-out rotten wood cultural relics in drought environments, which comprises a natural rosin solution with the concentration of 4% (the natural rosin is obtained by dissolving natural rosin in absolute ethyl alcohol), an ethyl cellulose solution with the concentration of 4% (the ethyl cellulose is obtained by dissolving ethyl cellulose in absolute ethyl alcohol), and glycerol accounting for 1% of the total volume of the composite filling reinforcing agent, wherein the volume ratio of the natural rosin solution to the ethyl cellulose solution is 1:1.

Example 3

The embodiment provides a composite filling reinforcing agent for soil-out rotten wood cultural relics in drought environments, which comprises a natural rosin solution with the concentration of 5% (obtained by dissolving natural rosin in absolute ethyl alcohol) and an ethyl cellulose solution with the concentration of 5% (obtained by dissolving ethyl cellulose in absolute ethyl alcohol), wherein glycerol accounts for 1% of the total volume of the composite filling reinforcing agent, and the volume ratio of the natural rosin solution to the ethyl cellulose solution is 1:1.

Performance test:

permeability test: taking a wood sample, placing the wood sample into the composite filling reinforcing agents with the depth of 5mm in examples 1-3 respectively, placing the wood sample for 30min, taking out, placing the wood sample at room temperature, and drying in the shade, wherein the specification of the wood sample is 10 x 0.2 x 0.8 cm; then put into an iodine jar for 10min, taken out, and the penetration depth (when the penetration depth reaches more than 10mm, the requirements can be met) is measured, and the results are shown in figures 1-3. As can be seen from fig. 1 to 3, the penetration depth of the wood sample into the composite filling and reinforcing agent of example 1 was about 4cm, the penetration depth of the wood sample into the composite filling and reinforcing agent of example 2 was about 3cm, and the penetration depth of the wood sample into the composite filling and reinforcing agent of example 3 was about 5cm.

Color difference analysis: placing a wood sample in a color measuring instrument, and recording an initial value of the wood sample; then coating the composite filling reinforcing agents prepared in the examples 1-3 on the surface of a sample respectively, placing the sample at room temperature, drying in the shade, measuring the numerical value again, and calculating the chromatic aberration; repeatedly coating the composite filling reinforcing agent, and measuring again; the results of the statistical color difference values are shown in tables 1 to 3.

Table 1 color difference statistics of the composite filler reinforcing agent of coating example 1

TABLE 2 color difference statistics of the composite filled reinforcing agent of coating example 2

TABLE 3 color difference statistics of the composite filled reinforcing agent of coating example 3

As is clear from tables 1 to 3, the average color difference of the composite filled reinforcing agent of example 1 was 0.48, the average color difference of the composite filled reinforcing agent of example 2 was 0.82, the average color difference of the composite filled reinforcing agent of example 3 was 0.65, and the change in the color of the wood after the reinforcement was slight or slight (the correspondence relationship between Δe value and color change is shown in table 4).

TABLE 4 correspondence of delta E values to color changes

Solvent permeability: reinforcing the wood samples with the composite filling reinforcing agents of examples 1 to 3, respectively, and drying in the shade at room temperature; and then respectively dripping purified water, ethanol, acetone and ethyl acetate on the surface of the sample, and observing the permeability of the sample to judge the reversibility of the composite filling reinforcing agent. The results were: pure water is respectively dripped on the surfaces of the reinforced samples with the three concentrations in the examples 1-3, the pure water can not permeate, the pure water still keeps in a water drop shape after half an hour, and the edges slightly permeate (wet); ethanol, acetone and ethyl acetate are respectively dripped on the surfaces of the reinforced samples with the three concentrations in examples 1-3, and the solution is quickly infiltrated, paved on the samples and quickly dried.

And (5) reinforcing a cultural relic sample: the concrete experimental contents of applying the composite filling reinforcing agent of the embodiment 3 to the reinforcement of the unearthed tomb gate are as follows: selecting relatively straight wood strips from tomb gate residues, lightly coating a composite filling reinforcing agent on the surface of wood by using a hooking pen, and reinforcing for 2 times according to the wood decay degree; measuring the compressive strength of the reinforced concrete; the test results before and after reinforcement are shown in fig. 4 to 5. As can be seen from the experimental data of fig. 4 to 5, the reinforced precursor sample has little compressive strength, and the sample becomes powder after a little pressure is applied; the pressure that the cultural relic sample can bear after strengthening can reach 28N, so that the effectiveness of the composite filling strengthening agent can be demonstrated.

The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims

1. The composite filling reinforcing agent for the soil-out rotten wood relics in drought environments is characterized by comprising a natural rosin solution, an ethyl cellulose solution and glycerol;

2. The composite filling and reinforcing agent for the soil-out and rotten wood cultural relics in drought environments according to claim 1, wherein the natural rosin solution is obtained by dissolving natural rosin in absolute ethyl alcohol;

3. The composite filling and reinforcing agent for the soil-out and rotten wood cultural relics in drought environments according to claim 2, wherein the concentration of the natural rosin solution is 2-5%;

the concentration of the ethyl cellulose solution is 2-5%.

4. A composite filling and reinforcing agent for soil-working and decaying wood relics in arid environments according to claim 2 or 3, wherein the natural rosin in the natural rosin solution is a quaternary or a penta rosin.

5. The method for preparing the composite filling reinforcing agent for the soil-out and decay of the wooden relics in the drought environment according to any one of claims 1 to 4, which is characterized by comprising the following steps:

6. The use of a composite filling strengthening agent for the soil-out and decay of wooden relics in arid environments as claimed in any one of claims 1 to 4 for strengthening wooden relics.

7. The use of a composite filling and reinforcing agent for the soil-out and decay of wooden relics in arid environments according to claim 6, wherein the method for reinforcing wooden relics comprises the following steps:

or soaking the wooden relics in the composite filling reinforcing agent.

8. The use of a composite filling and reinforcing agent for the soil-out and decay of wooden relics in arid environments according to claim 6 or 7, wherein the number of reinforcing times of the reinforcing wooden relics is 1 or more.