Inorganic bonding agent for repairing ceramic cultural relic material and use method thereof

Abstract

The invention discloses an inorganic bonding agent for repairing a ceramic cultural relic material and a use method of the inorganic bonding agent. The bonding agent is prepared from the following raw materials in percentage by mole: 50%-60% of magnesium aluminate spinel powder, 15%-20% of Na2CO3 powder, 15%-20% of K2CO3 powder and 1%-10% of Li2CO3 powder. The inorganic bonding agent and a ceramic interface are sintered at the temperature lower than the melting temperature of the ceramic interface, a chemical reaction occurs between the bonding layer and the ceramic interface, an aluminosilicate system is generated, then long-time connection and stability of the ceramic interface are achieved, firm connection is formed, and the problems of aging, falling and the like of a traditional organic adhesive are solved.

Description

Technical Field

[0001] The present invention belongs to the field of materials and relates to ceramic cultural relic restoration technology, in particular to an inorganic connector for restoring ceramic cultural relic materials and a method of using the same. Background Art

[0002] Ceramics are an ancient and precious cultural relic, prized for their unique colors and simple shapes. They played a vital role in daily life, ritual culture, and international exchanges in ancient China. Over time, many ceramic artifacts have suffered varying degrees of damage, such as breakage, flaking, and cracking, significantly diminishing their integrity, aesthetic appeal, and research value.

[0003] Traditional restoration methods primarily use organic adhesives, which offer high bond strength but poor durability. These adhesives are susceptible to aging, discoloration, and peeling when exposed to high temperature and humidity for extended periods. Furthermore, their chemical properties differ significantly from those of ceramics, causing varying degrees of damage to ceramic artifacts. Furthermore, these organic adhesives are expensive and pose environmental risks. Therefore, the development of a novel inorganic linker and its preparation method are of great significance for the protection and restoration of ceramic artifacts. Summary of the Invention

[0004] The purpose of the present invention is to provide an inorganic connector for repairing ceramic cultural relic materials and a method of using the same, so as to ensure the stability and reliability of the connection of ceramic materials.

[0005] The present invention is achieved through the following technical solutions:

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] An inorganic connector for repairing ceramic cultural relic materials. The raw materials comprise, by molar percentage, 50% to 60% of magnesia-alumina spinel powder, 15% to 20% of Na2CO3 powder, 15% to 20% of K2CO3 powder, and 1% to 10% of Li2CO3 powder.

[0008] Preferably, the average particle size of the magnesia-alumina spinel powder is 35 μm to 50 μm, and the average particle size of the Na 2 CO 3 powder, K 2 CO 3 powder and Li 2 CO 3 powder is 0.1 μm to 2 μm.

[0009] Preferably, the mass percentage of spinel in the magnesium-aluminum spinel powder is greater than 88%, the mass percentage of Al2O3 is between 50% and 70%, and the mass percentage of MgO is between 25% and 35%.

[0010] Preferably, the magnesia alumina spinel powder is fused magnesia alumina spinel powder or sintered magnesia alumina spinel powder.

[0011] The method for using an inorganic linker for repairing ceramic cultural relic materials comprises the following steps:

[0012] S1. Weigh 50% to 60% of magnesia-alumina spinel powder, 15% to 20% of Na2CO3 powder, 15% to 20% of K2CO3 powder, 1 to 10% of Li2CO3 powder by molar percentage and mix by wet ball milling and drying;

[0013] S2. PVA or anhydrous ethanol and PVA were added to the dried mixed powder to prepare a suspension;

[0014] S3. The prepared suspension is evenly applied to the surface of the ceramic artifact sample to be connected and pressurized;

[0015] S4. Place the pressurized ceramic artifact connection sample in a muffle furnace and heat it from room temperature to 900℃~1100℃ at 2℃ / min~5℃ / min, keep it warm for 2h~4h, and then cool it to room temperature at a cooling rate of 3℃ / min~10℃ / min to obtain a ceramic artifact sample connection part with good interface bonding.

[0016] Preferably, the medium for wet ball milling in step S1 is deionized water or anhydrous ethanol, and the grinding balls are alumina balls or yttrium-stabilized zirconia balls.

[0017] Preferably, the wet ball milling in step S1 adopts a planetary ball mill with a rotation speed of 300 r / min and a ball milling time of 12 h to 16 h.

[0018] Preferably, the PVA used in step S2 accounts for 1 wt% to 5 wt% of the mixed powder.

[0019] Preferably, the suspension preparation process in step S2 is to mix PVA + dried powder and grind them in a mortar; or to mix PVA + anhydrous ethanol + dried powder and perform ultrasonic vibration, the ultrasonic time is 5min to 30min, and the suspension concentration is 0.1g / mL to 0.8g / mL.

[0020] Preferably, the suspension in step S3 is applied to a thickness of 0.3 mm to 3 mm.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] The magnesium-aluminum spinel powder in the inorganic connector used in this invention has the same chemical composition as the ceramic. Therefore, the thermal expansion coefficient and other physical and chemical properties of the connector layer are similar to those of the ceramic. This ensures that the ceramic sample reacts at high temperatures while maintaining a certain level of stability and reliability at room temperature. A true connection is achieved by chemically reacting the intermediate layer, the inorganic connector, with the ceramic interface.

[0023] The present invention uses an intermediate layer, i.e., an inorganic bonding agent, and a ceramic interface to be sintered below the melting temperature of the ceramic interface. A chemical reaction occurs between the bonding layer and the ceramic interface to generate an aluminum silicate system, thereby ensuring long-term connection and stability of the ceramic interface, forming a strong connection and saying goodbye to the problems of aging and shedding of traditional organic adhesives.

[0024] The connector of the present invention is environmentally friendly. Traditional organic ones will release toxic substances after restoration and disposal, while the present invention adopts inorganic mineral materials, which do not contain volatile organic substances and are in line with the concept of green restoration; it has certain antibacterial properties. Organic glues will be corroded by mold, bacteria and other organisms, while inorganic materials themselves have antibacterial properties, which prolongs the life of cultural relics; the temperature stability of the present invention is higher than that of organic materials, because the present invention performs connection below the melting temperature of ceramics, which is lower than the melting temperature of ceramics, but much higher than the aging and melting limit temperature of organic materials; the cost is low, which is much lower than that of organic materials and the price is cheap; it can be widely used in the restoration of ceramic cultural relics, realize long-term connection of ceramic cultural relics, and provide new ideas for the restoration of ceramic cultural relics. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 is a flow chart of the preparation method of the present invention;

[0026] Figure 2 This is a physical picture of the ceramic connection sample of the present invention;

[0027] Figure 3 This is a light microscope image of the interface of the ceramic connection sample of the present invention;

[0028] Figure 4 A three-dimensional optical microscope image of the interface of the ceramic connection sample of the present invention;

[0029] Figure 5 This is the SEM image of the ceramic connection sample interface of the present invention. DETAILED DESCRIPTION

[0030] The present invention will be further described in detail below with reference to specific embodiments, which are intended to explain the present invention rather than to limit it.

[0031] Example 1

[0032] This embodiment provides an inorganic connector for repairing ceramic cultural relic materials, which includes, by mole percentage, 60% of magnesia-alumina spinel powder, 20% of Na2CO3, 19% of K2CO3, and 1% of Li2CO3 powder.

[0033] like Figure 1 As shown, the method of use specifically includes the following steps:

[0034] S1 measured by molar percentage weighed 60% of magnesium aluminum spinel powder, 20% of Na2CO3, 19% of K2CO3 powder, 1% of Li2CO3 powder for wet ball milling and drying; deionized water as the milling medium, alumina balls as the milling time 16h, speed 300r / min;

[0035] S2. Add 2% PVA to the dried mixed powder of S1 and grind it in a mortar to mix it evenly to prepare a 0.5g / mL suspension;

[0036] S3. Evenly apply the suspension prepared in S2 to the surface of the ceramic artifact sample to be connected and apply pressure to it; the coating thickness of the connecting agent is 1.5 mm. The pressure is to better ensure good contact between the ceramic sample interface and the connecting agent layer;

[0037] S4. Place the pressurized ceramic artifact connection sample in S3 into a muffle furnace and heat it from room temperature to 1000°C at a rate of 5°C / min, keep it warm for 4 hours, and then cool it to room temperature at a cooling rate of 5°C / min to obtain a ceramic artifact sample connection part with good interface bonding.

[0038] Example 2

[0039] This embodiment provides an inorganic connector for repairing ceramic cultural relic materials, which includes 59% magnesia-alumina spinel powder, 20% Na2CO3, 20% K2CO3, and 1% Li2CO3 powder in molar percentage.

[0040] The specific method of use includes the following steps:

[0041] S1 measured by molar percentage weighed 59% of magnesium aluminum spinel powder, 20% Na2CO3, 20% K2CO3, 1% Li2CO3 powder was wet milled and dried; deionized water was used as the milling medium, alumina balls were used as the milling balls, milling time was 16h, speed was 300r / min;

[0042] S2. Add 2% PVA to the dried mixed powder of S1 and grind it in a mortar to mix it evenly to prepare a 0.5g / mL suspension;

[0043] S3. Evenly apply the suspension prepared in S2 to the surface of the ceramic artifact sample to be connected and apply pressure to it; the coating thickness of the connecting agent is 1.5 mm. The pressure is to better ensure good contact between the ceramic sample interface and the connecting agent layer;

[0044] S4. Place the pressurized ceramic artifact connection sample in S3 into a muffle furnace and heat it from room temperature to 1000°C at a rate of 5°C / min, keep it warm for 4 hours, and then cool it to room temperature at a cooling rate of 5°C / min to obtain a ceramic artifact sample connection part with good interface bonding.

[0045] Example 3

[0046] This embodiment provides an inorganic connector for repairing ceramic cultural relic materials, which includes 58% magnesia-alumina spinel powder, 20% Na2CO3, 20% K2CO3, and 2% Li2CO3 powder in molar percentage.

[0047] The specific method of use includes the following steps:

[0048] S1 measured by molar percentage weighed 58% of magnesium aluminum spinel powder, 20% Na2CO3, 20% K2CO3, 2% Li2CO3 powder wet milling mixing, drying; deionized water as the milling medium, alumina balls as the milling time 16h, speed 300r / min;

[0049] S2. Add 2% PVA to the dried mixed powder of S1 and grind it in a mortar to mix it evenly to prepare a 0.5g / mL suspension;

[0050] S3. Evenly apply the suspension prepared in S2 to the surface of the ceramic artifact sample to be connected and apply pressure to it; the coating thickness of the connecting agent is 1.5 mm. The pressure is to better ensure good contact between the ceramic sample interface and the connecting agent layer;

[0051] S4. Place the pressurized ceramic artifact connection sample in S3 into a muffle furnace and heat it from room temperature to 1000°C at a rate of 5°C / min, keep it warm for 4 hours, and then cool it to room temperature at a cooling rate of 5°C / min to obtain a ceramic artifact sample connection part with good interface bonding.

[0052] Example 4

[0053] This embodiment provides an inorganic connector for repairing ceramic cultural relic materials, which is composed of 57% magnesia-alumina spinel powder, 18% Na2CO3, 19% K2CO3, and 6% Li2CO3 powder measured in molar percentage.

[0054] The specific method of use includes the following steps:

[0055] S1. Weigh 57% of magnesium aluminum spinel powder, 18% of Na2CO3, 19% of K2CO3, and 6% of Li2CO3 powder by molar percentage and mix them by wet ball milling and drying; deionized water was used as the milling medium, and alumina balls were used as milling balls for 16h at a speed of 300r / min;

[0056] S2. Add 2% PVA to the dried mixed powder of S1 and grind it in a mortar to mix it evenly to prepare a 0.5g / mL suspension;

[0057] S3. Evenly apply the suspension prepared in S2 to the surface of the ceramic artifact sample to be connected and apply pressure to it; the coating thickness of the connecting agent is 1.5 mm. The pressure is to better ensure good contact between the ceramic sample interface and the connecting agent layer;

[0058] S4. Place the pressurized ceramic artifact connection sample in S3 into a muffle furnace and heat it from room temperature to 1000°C at a rate of 5°C / min, keep it warm for 4 hours, and then cool it to room temperature at a cooling rate of 5°C / min to obtain a ceramic artifact sample connection part with good interface bonding.

[0059] Example 5

[0060] This embodiment provides an inorganic connector for repairing ceramic cultural relic materials, which includes 50% magnesia-alumina spinel powder, 20% Na2CO3, 20% K2CO3, and 10% Li2CO3 powder in molar percentage.

[0061] The specific method of use includes the following steps:

[0062] S1. Weigh 50% of magnesia spinel powder, 20% Na2CO3, 20% K2CO3, 10% Li2CO3 powder by molar percentage and mix by wet ball milling and drying; anhydrous ethanol as the milling medium, yttrium-stabilized zirconia balls as the milling balls for 12h, speed 300r / min;

[0063] S2. 5% PVA was added to the dried mixed powder of S1 and ground in a mortar to mix uniformly to prepare a 0.8 g / mL suspension;

[0064] S3. The suspension prepared in S2 is evenly applied to the surface of the ceramic artifact sample to be connected and pressurized; the thickness of the connecting agent coating is 3.0 mm, and the pressure is applied to better ensure good contact between the ceramic sample interface and the connecting agent layer;

[0065] S4. Place the pressurized ceramic artifact connection sample in S3 into a muffle furnace and heat it from room temperature to 1100°C at a rate of ℃ / min, keep it warm for 2 hours, and then cool it to room temperature at a cooling rate of 3°C / min to obtain a ceramic artifact sample connection part with good interface bonding.

[0066] Example 6

[0067] This embodiment provides an inorganic connector for repairing ceramic cultural relic materials, which includes 60% magnesia-alumina spinel powder, 15% Na2CO3, 15% K2CO3, and 10% Li2CO3 powder in molar percentage.

[0068] The magnesia-alumina spinel powder is fused magnesia-alumina spinel powder or sintered magnesia-alumina spinel powder; the mass percentage of spinel in the magnesia-alumina spinel powder is greater than 88%, the mass percentage of Al2O3 is between 50% and 70%, and the mass percentage of MgO is between 25% and 35%; the average particle size is 35μm to 50μm, and the average particle size of Na2CO3 powder, K2CO3 powder and Li2CO3 powder is 0.1μm to 2μm.

[0069] The specific method of use includes the following steps:

[0070] S1 measured by molar percentage weighed 60% of magnesium aluminum spinel powder, 15% Na2CO3, 15% K2CO3, 10% Li2CO3 powder wet milling mixing, drying; deionized water as the milling medium, alumina balls as the milling time 13h, speed 300r / min;

[0071] S2. Add 1% PVA and anhydrous ethanol to the dried mixed powder of S1 and perform ultrasonic oscillation for 5min to 30min to uniformly mix and prepare a 0.1g / mL suspension;

[0072] S3. The suspension prepared in S2 is evenly applied to the surface of the ceramic artifact sample to be connected and pressurized; the thickness of the connecting agent coating is 0.3 mm, and the pressure is applied to better ensure good contact between the ceramic sample interface and the connecting agent layer;

[0073] S4. Place the pressurized ceramic artifact connection sample in S3 into a muffle furnace and heat it from room temperature to 900°C at a rate of 3°C / min, keep it warm for 3 hours, and then cool it down to room temperature at a cooling rate of 10°C / min to obtain a ceramic artifact sample connection part with good interface bonding.

[0074] Figure 2 This is a diagram of the actual connection of the ceramic samples of Example 5, indicating that the inorganic connecting agent in the middle can achieve the connection of the two ceramic samples at high temperature; Figure 3 This is a picture of the connection interface of the ceramic sample of Example 5 observed under a light microscope after polishing, indicating that the inorganic connecting agent as the intermediate layer can be well filled between the ceramic interfaces; Figure 4 This is a three-dimensional stereogram of the connection interface of the polished ceramic sample of Example 5 observed under a light microscope, indicating that the interface between the inorganic connector and the ceramic sample has good flatness; Figure 5 The SEM image of the interface of the ceramic sample connection in Example 5 shows that during the connection process, the connector can wet the ceramic surface well and form a strong bond after curing. This good interface bonding helps to improve the overall strength and reliability of the connection structure. It also shows that this method can achieve effective restoration of ceramic cultural relics.

[0075] Combination of the above Figure 2-5 However, it should be noted that these specific embodiments are only illustrative explanations of the present invention and do not constitute any limitation on the scope of protection of the present invention.

Claims

1. An inorganic linker for repairing ceramic cultural relic materials, characterized by: The raw materials include 50% to 60% of magnesia-alumina spinel powder, 15% to 20% of Na2CO3 powder, 15% to 20% of K2CO3 powder, and 1% to 10% of Li2CO3 powder by mole percentage.

2. The inorganic linker for repairing ceramic cultural relics according to claim 1, characterized in that: The average particle size of the magnesia-alumina spinel powder is 35 μm to 50 μm, and the average particle size of the Na2CO3 powder, K2CO3 powder and Li2CO3 powder is 0.1 μm to 2 μm.

3. The inorganic linker for repairing ceramic cultural relics according to claim 1, characterized in that: The mass percentage of spinel in the magnesium-aluminum spinel powder is greater than 88%, the mass percentage of Al2O3 is between 50% and 70%, and the mass percentage of MgO is between 25% and 35%.

4. The inorganic linker for repairing ceramic cultural relics according to claim 1, characterized in that: The magnesia alumina spinel powder is fused magnesia alumina spinel powder or sintered magnesia alumina spinel powder.

5. The method for using the inorganic linker for repairing ceramic cultural relics according to any one of claims 1 to 4, characterized in that The following steps are involved: S1. Weigh 50% to 60% of magnesia-alumina spinel powder, 15% to 20% of Na2CO3 powder, 15% to 20% of K2CO3 powder, 1 to 10% of Li2CO3 powder by molar percentage and mix by wet ball milling and drying; S2. PVA or anhydrous ethanol and PVA were added to the dried mixed powder to prepare a suspension; S3. The prepared suspension is evenly applied to the surface of the ceramic artifact sample to be connected and pressurized; S4. Place the pressurized ceramic artifact connection sample in a muffle furnace and heat it from room temperature to 900℃~1100℃ at 2℃ / min~5℃ / min, keep it warm for 2h~4h, and then cool it to room temperature at a cooling rate of 3℃ / min~10℃ / min to obtain a ceramic artifact sample connection part with good interface bonding.

6. The method for using the inorganic linker for repairing ceramic cultural relics according to claim 5, characterized in that: The medium for wet ball milling in step S1 is deionized water or anhydrous ethanol, and the grinding balls are alumina balls or yttrium-stabilized zirconia balls.

7. The method for using the inorganic linker for repairing ceramic cultural relics according to claim 5, characterized in that: In step S1, the wet ball milling is performed using a planetary ball mill with a rotation speed of 300 r / min and a ball milling time of 12 h to 16 h.

8. The method for using the inorganic linker for repairing ceramic cultural relics according to claim 5, characterized in that: The PVA used in step S2 is 1 wt% to 5 wt% of the mixed powder.

9. The method for using the inorganic linker for repairing ceramic cultural relics according to claim 5, characterized in that: The suspension preparation process in step S2 is as follows: PVA + dried powder are mixed and ground in a mortar; or PVA + anhydrous ethanol + dried powder are mixed and ultrasonically shaken, the ultrasonic time is 5 minutes to 30 minutes, and the suspension concentration is 0.1 g / mL to 0.8 g / mL.

10. The method for using the inorganic linker for repairing ceramic cultural relics according to claim 5, characterized in that: The suspension in step S3 is applied with a thickness of 0.3 mm to 3 mm.

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