CN116083023A - Epoxy resin-based adhesive for repairing ceramic cultural relics, preparation method and application - Google Patents
Epoxy resin-based adhesive for repairing ceramic cultural relics, preparation method and application Download PDFInfo
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- CN116083023A CN116083023A CN202310150851.3A CN202310150851A CN116083023A CN 116083023 A CN116083023 A CN 116083023A CN 202310150851 A CN202310150851 A CN 202310150851A CN 116083023 A CN116083023 A CN 116083023A
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- epoxy resin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention discloses an epoxy resin adhesive for repairing ceramic cultural relics, a preparation method and application thereof, belonging to the technical field of cultural relic protection and repair, and specifically comprising the following technical scheme: the adhesive consists of A, B components, wherein the component A comprises the following components in parts by weight: 52-68 parts of epoxy resin, 2-8 parts of diluent, 0.35-1 part of defoamer and 3.5-15 parts of flexibilizer; the component B comprises the following components in parts by weight: 18-25 parts of amine curing agent and 0-5 parts of curing accelerator; the preparation method comprises the following steps: the component A and the component B are respectively prepared, uniformly mixed and defoamed in vacuum to obtain the epoxy resin adhesive, and the prepared adhesive has the characteristics of high transparency, excellent weather resistance and high bonding strength.
Description
Technical Field
The invention belongs to the technical field of cultural relic repair, and particularly relates to an epoxy resin-based adhesive for ceramic cultural relic repair, a preparation method and application thereof.
Background
The Chinese ancient ceramic is the most glaring pearl in the human history culture artistic treasury, and has a certain artistic appreciation value and extremely high history research value. However, the porcelain is fragile, and most porcelain relics have incomplete loss, so that not only is the artistic aesthetic feeling of the porcelain itself lost, but also the historical research value of the porcelain relics is greatly influenced, and therefore, the porcelain relics must be repaired.
The porcelain relic repair generally comprises the steps of removing impurities, bonding, reinforcing, repairing and matching incomplete, coloring and glaze imitation, and the like. Wherein, the bonding reinforcement is to repair the broken part of the porcelain relics by using an adhesive. The epoxy resin adhesive is widely applied to the bonding reinforcement of cultural relics due to excellent performances such as good processability, high bonding strength, water resistance, oil resistance and the like. However, epoxy resin is easy to change color after being irradiated by ultraviolet rays, mainly because bisphenol A structure is easy to oxidize to generate carbonyl to form yellowing, and free amine generated by a curing agent is directly polymerized with epoxy groups, so that the temperature rise of a local range of the adhesive is increased, the yellowing is accelerated, meanwhile, the reaction polymerization is incomplete, the internal stress is not easy to release, and the mechanical property of the adhesive is damaged. The yellowing problem of the epoxy resin not only affects the appearance of the cultural relics, but also worsens the mechanical properties of the adhesive, and the requirement of repairing the cultural relics is not met.
For the research of improving the weatherability of epoxy resin, patent CN201811348480.5 proposes an adhesion protection method for porcelain relics, wherein the adhesive is prepared from porcelain powder, bisphenol A epoxy resin, nano titanium dioxide, nano calcium carbonate, beeswax, rosin, bentonite, ethylene glycol monobutyl ether, zinc oxide and castor oil triglycidyl ether according to a certain proportion to form a component A; the component B is prepared by a modified amine curing agent, surface modified talcum powder, xanthan gum, DMP-30, 2, 6-di-tert-butyl-p-cresol and 2-hydroxy-2-methyl phenyl propane-1-ketone according to a certain proportion. Although the adhesive strength and the UV resistance are improved, the adhesive has the advantages of multiple ingredients, complex preparation process, realization of curing under the heating condition and certain damage to cultural relics.
Patent CN201910594211.5 proposes a highly transparent UV-resistant epoxy resin adhesive and a preparation method thereof, which is preferably liquid hydrogenated bisphenol a epoxy resin and solid hydrogenated bisphenol a epoxy resin as main resins, and is equipped with silicone modified epoxy resin, and the weather resistance is greatly improved on the basis of adding an ultraviolet absorber. The method requires the hydrogenation treatment of the main epoxy resin and the addition of an ultraviolet absorber, which makes the preparation cost too high.
Disclosure of Invention
The invention discloses an epoxy resin-based adhesive for repairing ceramic cultural relics, which is preferably a low-viscosity hydroxyl end group linear polyether additive, improves the toughness of bisphenol A epoxy resin, improves the weather resistance and greatly improves the yellowing resistance time of products.
The invention also discloses a preparation method of the epoxy resin-based adhesive for repairing ceramic cultural relics, which is simple by optimizing the proportion of materials on the basis of meeting the basic requirements of cultural relic protection.
The invention also discloses application of the epoxy resin-based adhesive for repairing ceramic cultural relics, and weather resistance is improved and yellowing resistance time is greatly prolonged on the premise that mechanical properties are kept to meet cultural relic protection requirements.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the epoxy resin-based adhesive for repairing ceramic cultural relics consists of a component A and a component B:
the component A comprises the following components in parts by weight: 52-68 parts of epoxy resin, 2-8 parts of diluent, 0.35-1 part of defoamer and 3.5-15 parts of flexibilizer;
wherein the epoxy resin is composed of bisphenol A epoxy resin and chemically modified liquid epoxy resin. The proportion of bisphenol A epoxy resin in the epoxy resin component is 70-80 parts, and the proportion of the chemically modified liquid epoxy resin in the epoxy resin component is 20-30 parts;
the component B comprises the following components in parts by weight: 18-25 parts of an amine curing agent and 0-5 parts of a curing accelerator.
The bisphenol A epoxy resin is one or the combination of more than one of DER-330, E-51 and EP4100 with the epoxy equivalent of 170-250; the chemical modified liquid epoxy resin is organosilicon modified epoxy resin.
The defoamer is one or a combination of any plurality of Surfynol 104E with decane tetramethyl decylenol as the main component, BYK-022 with polysiloxane and hydrophobic particles as the main component, and Foamex 830 with organic polymer containing aerosil as the main component.
The diluent in the component A of the epoxy resin adhesive for repairing cultural relics is one or a combination of more of butyl glycidyl ether, trimethylolpropane triglycidyl ether, ethylene glycol diglycidyl ether and 1, 6-hexanediol diglycidyl ether.
The toughening agent in the component A of the epoxy resin adhesive for repairing cultural relics is a hydroxyl end group linear polyether compound with low viscosity.
The amine curing agent in the epoxy resin adhesive B component for repairing cultural relics is one or a combination of more of alicyclic amine curing agents isophorone diamine (IPDA), polyetheramine D-230 and polyetheramine D-400.
The curing accelerator in the component B of the epoxy resin adhesive for repairing cultural relics is one or a combination of any more of benzyl dimethylamine, triethylamine, triethanolamine, dimethylethanolamine and pyridine.
The adhesive has the characteristics of high transparency and yellowing resistance, the tensile shear strength is more than or equal to 5Mpa, and the impact strength is more than or equal to 50KJ/m 2 The light transmittance is more than or equal to 90 percent; in an ultraviolet aging test chamber, at 0.68W/m 2 And irradiation at 50 ℃ with yellowing resistance time not less than 150 hours.
The method for preparing the epoxy resin-based adhesive for repairing ceramic cultural relics comprises the following specific steps:
1. sequentially adding bisphenol A epoxy resin and chemically modified liquid epoxy resin into a reaction kettle according to a proportion, heating the reaction kettle to 90-110 ℃ and stirring for 2-3 hours to fully and uniformly mix the epoxy resins, then cooling to 60 ℃, adding a diluent, a defoaming agent and a toughening agent into the reaction kettle according to a proportion, stirring for 1.5 hours, taking out, and vacuumizing and defoaming at room temperature to obtain a component A;
2. the method comprises the steps of (1) adding an amine curing agent and a curing accelerator into a reaction kettle in proportion, and stirring for 1-2 hours at 40-60 ℃ to obtain a component B;
3. and uniformly mixing A, B components, and carrying out vacuum defoaming for 5-10 min to obtain the high-transparency yellowing-resistant epoxy resin adhesive for repairing cultural relics.
The application of the epoxy resin-based adhesive for repairing ceramic cultural relics comprises the following specific steps:
1. thoroughly cleaning the ceramic relic bonding surface, uniformly smearing an epoxy resin adhesive on the ceramic relic bonding surface, fully contacting porcelain fragments to be bonded with the ceramic relic, and overflowing the redundant adhesive;
2. and (3) removing redundant adhesive on the surface of the cultural relics, and airing the ceramic cultural relics in the air at room temperature for 10-24 hours to be solidified, so that the adhesion repair of the ceramic cultural relics is completed.
Compared with the prior art, the concrete beneficial effects are as follows:
1. according to the invention, raw materials are optimized, bisphenol A epoxy resin with the epoxy equivalent of 170-250 is selected as a main matrix, and a small amount of silane modified epoxy resin is mixed, so that the repairing cost of cultural relics is reduced, and the yellowing resistance of the adhesive is improved; the curing agent adopts alicyclic amine and polyether amine curing agents, the curing agent is a normal temperature curing agent, and is suitable for repairing cultural relics, heating is not needed in the curing process, and damage to the cultural relics is avoided. According to the reactivity of the epoxy resin and the curing agent, the proportion of raw materials is optimized, so that the curing reaction can be fully carried out, the generation of free amine is reduced, and the yellowing resistance of the epoxy resin is greatly improved.
2. The invention optimizes the formula and selects the low-viscosity hydroxyl end group linear polyether compound as the toughening agent. The polyether compound itself contains a large amount of linear ether bond structures, so that when the polyether compound is introduced into the epoxy resin matrix material, the content of the flexible chain segments in the material can be increased, thereby achieving the toughening effect and ensuring the excellent mechanical property of the adhesive. In addition, the active end group of the low-viscosity polyether can participate in the curing reaction of the epoxy resin to form a stable cross-linking structure, so that the curing exothermic peak value is reduced, the curing reaction of the epoxy resin is stable, the yellowing caused by local severe temperature rise is avoided, and the anti-yellowing performance of the epoxy resin is improved. Meanwhile, the linear polyether compound greatly increases the proportion of an ether network in the crosslinked network structure of the epoxy resin cured product, and the ether bond has strong polarity, can form a hydrogen bond with phenolic hydroxyl in the bisphenol A structure, so that the stability of the epoxy resin is improved, the yellowing caused by the carbonylation of the phenolic hydroxyl is further reduced, and the yellowing resistance of the resin is improved.
3. The adhesive formula provided by the invention has the advantages that the light transmittance of the obtained product can reach more than 93%, the product belongs to a high light transmittance material, the strength is excellent, and the light transmittance is 0.68W/m 2 The ultraviolet rapid weathering test box at 50 ℃ starts to generate yellowing after 150 hours, and compared with the conventional adhesive for cultural relic protection, the yellowing-resistant time is greatly prolonged, and the requirements of cultural relic protection on the deficiency-supplementing and bonding materials can be fully met.
4. The adhesive formula provided by the invention is only composed of an epoxy resin matrix, a curing agent, a defoaming agent and a polyether additive, and has the advantages of simple formula, simple and convenient operation and good product performance.
Description of the embodiments
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Examples
An epoxy resin-based adhesive for repairing ceramic cultural relics comprises a component A and a component B. Wherein the component A comprises epoxy resin E-51, DER-330, organosilicon modified epoxy resin, defoamer BYK-022, diluent n-butyl glycidyl ether and flexibilizer which is a hydroxyl end group linear polyether compound with low viscosity; the component B comprises isophorone diamine as an amine curing agent and triethanolamine as a curing accelerator.
The preparation method comprises the following steps:
1. and (3) preparing a component A: adding 43.5 parts of epoxy resin E-51, 10.1 parts of DER-330 and 13.4 parts of organic silicon modified epoxy resin into a reaction kettle in sequence, heating the reaction kettle to 100 ℃ and stirring for 3 hours, fully mixing the epoxy resin, then cooling to 60 ℃, adding 1 part of defoamer BYK-022,5 parts of diluent n-butyl glycidyl ether into the reaction kettle in sequence, continuously stirring for 1.5 hours, and then carrying out vacuum defoaming to obtain a component A;
2. and (2) preparing a component B: adding 25 parts of amine curing agent IPDA and 2 parts of curing accelerator triethanolamine into a reaction kettle at one time, heating the reaction kettle to 40 ℃, and stirring for 1h to uniformly mix the components to obtain a component B;
all parts are parts by weight.
3. In the subsequent work, A, B components are mixed, fully stirred and then vacuum defoamed for 10min at room temperature, thus obtaining the required adhesive.
The application of the epoxy resin-based adhesive for repairing ceramic cultural relics comprises the following specific steps:
1. thoroughly cleaning the ceramic relic bonding surface, uniformly smearing an epoxy resin adhesive on the ceramic relic bonding surface, fully contacting porcelain fragments to be bonded with the ceramic relic, and overflowing the redundant adhesive;
2. and (3) removing redundant adhesive on the surface of the cultural relics, and airing the ceramic cultural relics in the air at room temperature for 10-24 hours to be solidified, so that the adhesion repair of the ceramic cultural relics is completed.
The gel time and cure time of the adhesive prepared in example one are shown in Table one.
The adhesive gel performance test results obtained in example one are shown in Table two.
Examples
An epoxy resin-based adhesive for repairing ceramic cultural relics, which consists of a component A and a component B, wherein:
and (3) a component A: 40.3 parts of epoxy resin E-51, 9.3 parts of DER-330, 12.4 parts of organosilicon modified epoxy resin, 5 parts of diluent n-butyl glycidyl ether, 1 part of defoamer BYK-022 and 5 parts of toughening agent;
and the component B comprises the following components: 25 parts of amine curing agent IPDA and 2 parts of curing accelerator triethanolamine;
all parts are parts by weight.
The preparation method and application of this embodiment are the same as those of the first embodiment.
The gel time and cure time of the adhesive prepared in example two are shown in Table one.
The adhesive gel performance test results obtained in example two are shown in Table two.
Examples
An epoxy resin-based adhesive for repairing ceramic cultural relics, which consists of a component A and a component B, wherein:
and (3) a component A: 37.7 parts of epoxy resin E-51, 8.7 parts of DER-330, 11.6 parts of organosilicon modified epoxy resin, 5 parts of diluent n-butyl glycidyl ether, 1 part of defoamer BYK-022 and 9 parts of toughening agent;
and the component B comprises the following components: 25 parts of amine curing agent IPDA and 2 parts of curing accelerator triethanolamine;
all parts are parts by weight.
The preparation method and application of this embodiment are the same as those of the first embodiment.
The gel time and curing time of the adhesive prepared in example three are shown in Table one.
The adhesive gel performance test results obtained in example three are shown in Table two.
Examples
An epoxy resin-based adhesive for repairing ceramic cultural relics, which consists of a component A and a component B, wherein:
and (3) a component A: 35.1 parts of epoxy resin E-51, 8.1 parts of DER-330, 10.8 parts of organosilicon modified epoxy resin, 5 parts of diluent n-butyl glycidyl ether, 1 part of defoamer BYK-022 and 13 parts of toughening agent;
and the component B comprises the following components: 25 parts of amine curing agent IPDA and 2 parts of curing accelerator triethanolamine;
all parts are parts by weight.
The preparation method and application of this embodiment are the same as those of the first embodiment.
The gel time and curing time of the adhesive prepared in example four are shown in Table one.
The adhesive gel performance test results obtained in example four are shown in Table two.
List one
In order to verify that the adhesive disclosed by the invention is excellent in performance, the conventional adhesive for repairing the cultural relics at present is selected for performance comparison, and the result is as follows:
watch II
According to the performance test results of Table II, the adhesive prepared in examples 1-4 has hardness, adhesive force, tensile shear strength and transmittance reaching the use requirements, and is suitable for the adhesion repair of porcelain; next, at 0.68W/m 2 Yellowing can occur in an ultraviolet rapid weathering test box at 50 ℃ for more than 150 hours, and compared with the conventional adhesive in the market at present, the adhesive is greatly improved. In the first embodiment, no linear polyether toughening agent is added, and compared with a commercial reagent (Araldite 2020.), the yellowing resistance is improved, which indicates that the yellowing resistance can be improved to a certain extent through optimization of the epoxy resin matrix and the curing agent and optimization of the proportion. In the second to fourth examples, the linear polyether toughening agent is added, and compared with the first example, the linear polyether toughening agent has tensile shear strength and impact strengthThe impact strength is improved, and the ultraviolet yellowing resistance time is prolonged, so that the linear polyether compound used in the invention can improve the yellowing resistance of the epoxy resin. Compared with the epoxy resin adhesive in the prior art, the adhesive disclosed by the invention has a good yellowing resistance effect.
The invention achieves the effect without adding an antioxidant, an ultraviolet absorber and an ultraviolet shielding agent, and after adding a certain amount of compounds such as the antioxidant, the ultraviolet absorber and the ultraviolet shielding agent, the yellowing resistance of the anti-yellowing agent is improved to a certain extent again.
The foregoing description of the preferred embodiment of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The epoxy resin-based adhesive for repairing ceramic cultural relics is characterized by comprising a component A and a component B:
the component A comprises the following components in parts by weight: 52-68 parts of epoxy resin, 2-8 parts of diluent, 0.35-1 part of defoamer and 3.5-15 parts of flexibilizer;
the epoxy resin consists of bisphenol A epoxy resin and chemically modified liquid epoxy resin, wherein the proportion of the bisphenol A epoxy resin in the epoxy resin component is 70-80 parts, and the proportion of the chemically modified liquid epoxy resin in the epoxy resin component is 20-30 parts;
the component B comprises the following components in parts by weight: 18-25 parts of an amine curing agent and 0-5 parts of a curing accelerator.
2. The epoxy resin-based adhesive for repairing ceramic cultural relics according to claim 1, wherein the epoxy equivalent of the bisphenol a epoxy resin is 170-250, and the chemically modified liquid epoxy resin is an organosilicon modified epoxy resin.
3. The epoxy-based adhesive for repairing ceramic cultural relics according to claim 1, wherein the defoaming agent is one or a combination of any more of Surfynol 104E containing decyltetramethyl decylenediol, BYK-022 containing polysiloxane and hydrophobic particles, and Foamex 830 containing fumed silica organic polymer.
4. The epoxy resin-based adhesive for repairing ceramic cultural relics according to claim 1, wherein the diluent is one or a combination of any more of butyl glycidyl ether, trimethylolpropane triglycidyl ether, ethylene glycol diglycidyl ether and 1, 6-hexanediol diglycidyl ether.
5. The epoxy resin-based adhesive for repairing ceramic cultural relics according to claim 1, wherein the toughening agent is a hydroxyl-terminated linear polyether compound.
6. The epoxy resin-based adhesive for repairing ceramic cultural relics according to claim 1, wherein the amine curing agent is one or a combination of more of alicyclic amine curing agents isophorone diamine, polyetheramine D-230 and polyetheramine D-400.
7. The epoxy resin-based adhesive for repairing ceramic cultural relics according to claim 1, wherein the curing accelerator is one or a combination of any more of benzyl dimethylamine, triethylamine, triethanolamine, dimethylethanolamine and pyridine.
8. The epoxy resin-based adhesive for repairing ceramic cultural relics according to any one of claims 1 to 7, wherein the adhesive has high transparency and yellowing resistance, tensile shear strength of not less than 5Mpa, impact strength of not less than 50KJ/m 2 The light transmittance is more than or equal to 90 percent; in an ultraviolet aging test chamber, at 0.68W/m 2 And irradiation at 50 ℃ with yellowing resistance time not less than 150 hours.
9. The method for preparing the epoxy resin-based adhesive for repairing ceramic cultural relics is characterized by comprising the following specific steps of:
1. sequentially adding bisphenol A epoxy resin and chemically modified liquid epoxy resin into a reaction kettle according to a proportion, heating the reaction kettle to 90-110 ℃, stirring for 2-3 hours to fully and uniformly mix the epoxy resins, then cooling to 60 ℃, adding a diluent, a defoaming agent and a toughening agent into the reaction kettle according to a proportion, stirring for 1.5 hours, taking out, and vacuumizing and defoaming at room temperature to obtain a component A;
2. the method comprises the steps of (1) adding an amine curing agent and a curing accelerator into a reaction kettle in proportion, and stirring for 1-2 hours at 40-60 ℃ to obtain a component B;
3. and uniformly mixing A, B components, and carrying out vacuum defoaming for 5-10 min to obtain the epoxy resin adhesive.
10. The application of the epoxy resin-based adhesive for repairing ceramic cultural relics is characterized by comprising the following specific steps:
1. thoroughly cleaning the ceramic relic bonding surface, uniformly smearing an epoxy resin adhesive on the ceramic relic bonding surface, fully contacting porcelain fragments to be bonded with the ceramic relic, and overflowing the redundant adhesive;
2. and (3) removing redundant adhesive on the surface of the cultural relics, and airing the ceramic cultural relics in the air at room temperature for 10-24 hours and then curing to finish the adhesion repair of the ceramic cultural relics.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310150851.3A CN116083023A (en) | 2023-02-22 | 2023-02-22 | Epoxy resin-based adhesive for repairing ceramic cultural relics, preparation method and application |
| ZA2023/03111A ZA202303111B (en) | 2023-02-22 | 2023-02-28 | An epoxy resin-based adhesive for ceramic cultural relics restoration, its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310150851.3A CN116083023A (en) | 2023-02-22 | 2023-02-22 | Epoxy resin-based adhesive for repairing ceramic cultural relics, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116083023A true CN116083023A (en) | 2023-05-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310150851.3A Pending CN116083023A (en) | 2023-02-22 | 2023-02-22 | Epoxy resin-based adhesive for repairing ceramic cultural relics, preparation method and application |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN116083023A (en) |
| ZA (1) | ZA202303111B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117303933A (en) * | 2023-11-29 | 2023-12-29 | 佛山东鹏洁具股份有限公司 | Notch repairing process for ceramic glaze |
-
2023
- 2023-02-22 CN CN202310150851.3A patent/CN116083023A/en active Pending
- 2023-02-28 ZA ZA2023/03111A patent/ZA202303111B/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117303933A (en) * | 2023-11-29 | 2023-12-29 | 佛山东鹏洁具股份有限公司 | Notch repairing process for ceramic glaze |
| CN117303933B (en) * | 2023-11-29 | 2024-02-06 | 佛山东鹏洁具股份有限公司 | Notch repairing process for ceramic glaze |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA202303111B (en) | 2023-05-31 |
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