CN111334109A - Cultural relic protection coating hardening capsule and preparation method and application thereof - Google Patents
Cultural relic protection coating hardening capsule and preparation method and application thereof Download PDFInfo
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- CN111334109A CN111334109A CN202010180980.3A CN202010180980A CN111334109A CN 111334109 A CN111334109 A CN 111334109A CN 202010180980 A CN202010180980 A CN 202010180980A CN 111334109 A CN111334109 A CN 111334109A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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Abstract
The invention discloses a cultural relic protection coating hardening capsule which is mainly prepared from the following raw materials in parts by weight: 0.5-10 parts of alginate, 5-15 parts of resin and 9-50 parts of calcium solution. Correspondingly, the invention also discloses a preparation method and application of the cultural relic protection coating hardening capsule. The hardening capsule belongs to micro-nano-grade particles, can improve the adhesive force of the cultural relic protective coating to a cultural relic substrate, and can effectively release substances in the capsule to repair the coating when the coating is damaged; in addition, the microcapsules of the present invention can be applied to various types of coatings.
Description
Technical Field
The invention relates to the field of coatings, in particular to a cultural relic protection coating hardening capsule and a preparation method and application thereof.
Background
With the increasing importance of our country on the salvage of marine cultural relics, in recent years, a great amount of underwater cultural relics are discharged. After fishing, the environmental conditions change, which leads to a great increase in the corrosion rate of the metal cultural relics, and therefore, the surfaces of the cultural relics need to be sealed and protected. However, at present, metal cultural relics which are discharged under a plurality of marine environments lose efficacy in a short time after corrosion inhibition and sealing protection, and the corrosion phenomenon appears on the surface of the metal again, and the iron ware and the copper ware are the most obvious. In addition, different sea areas have different influences on the sealing and protecting materials due to different environmental factors.
On the other hand, the cultural relic protection coating is different from the common anticorrosive coating. The cultural relic protection coating needs to play a protection role on the premise of not changing the original texture and appearance of the cultural relic, namely, the cultural relic protection coating needs to follow the principle of 'repairing the cultural relic as old'. Moreover, the material of the metal cultural relics is different from the material of the modern metal material, and the corrosion products and the corrosion mechanism are different, so that the requirements on the cultural relic protective coating are different; in addition, conventional metal anticorrosion coatings are typically applied to smooth metal fixture surfaces; and the surface of the cultural relic can not be completely cleaned, which also puts higher requirements on the cultural relic protection coating. The existing cultural relic protection mainly comprises acrylic resin, acrylic acid-polyurethane, polyester-polyurethane and the like, but the existing cultural relic protection is mostly used for protecting outdoor gilded cultural relics and sculptures, and the research on underwater metal cultural relic protective coating is relatively less at present.
Disclosure of Invention
The invention aims to provide a microcapsule for a cultural relic protection coating, which can effectively improve the adhesive force of the coating, improve the corrosion resistance of the coating and prolong the service life of the coating.
The technical problem to be solved by the present invention is to provide a method for preparing the above microcapsules.
The technical problem to be solved by the present invention is to provide an application of the above microcapsule.
In order to solve the technical problem, the invention provides a cultural relic protection coating hardening capsule, which comprises a capsule wall substance and a capsule inner substance; wherein the capsule wall material is formed by the reaction of calcium-containing solution and alginate; the capsule substance comprises resin and alginate;
the cultural relic protection coating hardening capsule comprises the following raw materials in parts by weight: 0.2-10 parts of alginate, 5-15 parts of resin and 9-50 parts of calcium-containing solution.
As an improvement of the technical scheme, the alginate is selected from one or more of alginic acid, calcium alginate, sodium alginate and potassium alginate;
the resin is one or more of epoxy resin, fluorocarbon resin, alkyd resin, polyurethane and organic silicon resin;
the calcium-containing solution is one of a calcium chloride saturated solution, a calcium hydroxide saturated solution and a calcium carbonate saturated solution.
As an improvement of the technical scheme, the resin is epoxy resin;
the calcium-containing solution is a calcium chloride solution, and the concentration of calcium in the calcium-containing solution is 0.5-5 wt%.
As an improvement of the technical scheme, the feed also comprises the following raw materials in parts by weight:
0.2-5 parts of hydrocarbyl benzylamine and 2-20 parts of mercaptan.
As an improvement of the technical scheme, the hydrocarbyl benzylamine is selected from one or more of N, N-dimethylbenzylamine, N-methylbenzylamine, N-diethylbenzylamine, N-ethylbenzylamine and 4-vinylbenzylamine;
the mercaptan is selected from one or more of pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate) polythiol and pentaerythritol tetrakis (mercaptoacetate).
As the improvement of the technical proposal, the hydrocarbyl benzylamine is N, N-dimethylbenzylamine; the mercaptan is pentaerythritol tetrakis (3-mercaptopropionate).
Correspondingly, the invention also discloses a preparation method of the cultural relic protection coating hardening capsule, which is characterized by comprising the following steps:
(1) preparing 5-30 g/L alginate solution and calcium-containing solution;
(2) gradually adding resin into an alginate solution with the total volume of alginate being 30-50% to form an oil-in-water emulsion;
(3) adding the rest alginate solution into the oil-in-water emulsion, and uniformly mixing to obtain a core emulsion;
(4) and carrying out electric spraying on the nuclear emulsion into a calcium-containing solution, solidifying for 0.2-5 h, filtering, washing and drying to obtain a hardened capsule finished product.
As an improvement of the technical scheme, the step (4) comprises the following steps:
(4.1) carrying out electric spraying on the nuclear emulsion into a calcium-containing solution, and solidifying for 0.2-5 h;
(4.2) adding hydrocarbyl benzylamine and mercaptan, and mixing and reacting for 0.1-5 h;
and (4.3) filtering, washing and drying to obtain a hardened capsule finished product.
Correspondingly, the invention also discloses an application of the cultural relic protection coating hardening capsule in the cultural relic protection coating.
As an improvement of the technical scheme, the coating is epoxy coating, polyurethane coating, organosilicon coating or acrylic coating;
the addition amount of the hardening capsule is 1-10 wt%.
The implementation of the invention has the following beneficial effects:
1. the hardened capsule is prepared into resin-alginate core-shell structure microspheres by an electrospray method, and a large amount of resin and a small amount of alginate are taken as cores; the reaction product of alginate and calcium-containing solution is used as the shell. The particle size reaches the micro-nano level; after the cultural relic protection coating is added, the permeability and the bonding capacity of the coating can be effectively improved, and particularly, the coating has good adhesion capacity to corrosion products generated on the surfaces of the cultural relics and the copper ware, so that the coating cannot fall off along with a surface corrosion layer, and the service life of the coating is greatly prolonged.
2. The hardening capsule of the invention grafts carbonyl, hydroxyl, ether and other functional groups on the surface of the core-shell microsphere, thus improving the compatibility between the hardening capsule and various types of coatings and ensuring that the hardening capsule of the invention can be suitable for various coatings.
3. The hardening capsule additive can be effectively dispersed in the cultural relic protection coating, and the shielding effect of the coating on corrosive particles is increased, so that the service life of the coating is prolonged.
4. The hardening capsule additive is embedded in the coating, and when the coating is damaged, the repairing agent can be effectively released, the damaged position is filled, and the protection effect on cultural relics is improved.
Drawings
FIG. 1 is a method for preparing microcapsules for a coating for cultural relics protection according to the present invention;
FIG. 2 is an infrared spectrum of a microcapsule of the present invention;
FIG. 3 is a photograph of a sample of example 4 prior to 5% citric acid soak (brush ZS-922);
FIG. 4 is a photograph of the 5% citric acid soaked sample of example 4 (brush ZS-922);
FIG. 5 is a photograph of a sample of example 4 before 5% citric acid soak (painting ZS-922+ 10% of example 3 microcapsules);
fig. 6 is a photograph of the sample after 5% citric acid soak in example 4 (with ZS-922+ 10% of the example 3 microcapsules brushed).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and examples.
The invention provides a cultural relic protection coating hardening capsule which is mainly prepared from the following raw materials in parts by weight:
0.5-10 parts of alginate, 5-15 parts of resin, 9-50 parts of calcium solution, 0.2-5 parts of alkyl benzylamine and 2-20 parts of mercaptan;
wherein alginate is a natural polymer salt, which can be mixed with Ca2+Forming a gel to form hardened capsules; in addition, the alginate can also be combined with corrosion products and the like, so that the binding force of the coating to a corrosion device is improved. In the invention, the alginate can be one or more of alginic acid, calcium alginate, sodium alginate and potassium alginate, but is not limited to the above; preferably, sodium alginate is selected. The alginate is used in an amount of 0.2 to 10 parts, preferably 0.4 to 5 parts.
The resin is a hardened intracapsular material which, after release, has the function of repairing damaged coatings. The resin in the present invention may be one or more of epoxy resin, fluorocarbon resin, alkyd resin, polyurethane, and silicone resin, but is not limited thereto. Preferably, an epoxy resin is selected. Specifically, bisphenol a type epoxy resins such as E51, E42, E55 may be used, but not limited thereto. The amount of the resin is 5 to 15 parts, preferably 5 to 8 parts.
The calcium-containing solution provides calcium ions to form a gel with the alginate. The concentration of calcium ions in the calcium-containing solution is 0.5 to 5 wt%, preferably 0.5 to 2 wt%. Specifically, the calcium-containing solution can be one of saturated calcium chloride solution, saturated calcium hydroxide solution, and saturated calcium carbonate solution; preferably, a calcium chloride solution is used. The amount of the calcium-containing solution is 9 to 50 parts, preferably 9 to 20 parts.
The hydrocarbyl benzylamine is selected from one or more of N, N-dimethylbenzylamine, N-methylbenzylamine, N-diethylbenzylamine, N-ethylbenzylamine, and 4-vinylbenzylamine, but is not limited thereto. Preferably, N-dimethylbenzylamine is used. The amount of the hydrocarbyl benzylamine is 0.2 to 5 parts, preferably 0.2 to 2 parts.
The mercaptan is selected from one or more of pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate) polythiol and pentaerythritol tetrakis (mercaptoacetate); but is not limited thereto. Preferably, pentaerythritol tetrakis (3-mercaptopropionate) is used. The amount of the mercaptan is 2-20 parts, preferably 5-10 parts.
Correspondingly, referring to fig. 1, the invention also discloses a preparation method of the cultural relic protection coating hardening capsule, which comprises the following steps:
s1: preparing an alginate solution and a calcium-containing solution;
wherein the concentration of the alginate solution is 5-30 g/L; preferably 10-25 g/L, and the alginate solution with the concentration range can form gel with appropriate viscosity with calcium-containing solution, so that the particle size of the hardened capsule is maintained in micro-nano grade.
Wherein the concentration of calcium ions in the calcium-containing solution is 0.5-5 wt%, preferably 0.5-2 wt%.
Preferably, the method further comprises the step of preparing a 1-10 v/v% hydrocarbyl benzylamine solution. More preferably, the concentration of the alkylbenzylamine is 2 to 5 v/v%.
S2: gradually adding the resin to a portion of the alginate solution to form an oil-in-water emulsion;
specifically, the resin is gradually added into an alginate solution accounting for 30-50% of the total volume of the alginate solution to form an oil-in-water solution. Wherein, the volume of the resin is: alginate solution volume 1: (3-5).
S3: adding the rest alginate solution into the oil-in-water emulsion, and uniformly mixing to obtain a core emulsion;
s4: and (3) carrying out electric spraying on the nuclear emulsion into a calcium-containing solution, solidifying for 0.2-5 h, washing, filtering and drying to obtain a hardened capsule finished product.
Specifically, S4 includes:
s41: carrying out electrospray on the nuclear emulsion into a calcium-containing solution, and curing for 0.2-5 h;
specifically, the volume ratio of the calcium-containing emulsion to the core emulsion is 1: (2-5).
Preferably, the curing time is 0.2-1 h;
s42: adding hydrocarbyl benzylamine and mercaptan, and mixing and reacting for 0.1-5 h;
s43: filtering, washing and drying to obtain the hardened capsule finished product.
Specifically, after filtering, washing with pure water for 2-5 times, and then drying at 30-60 ℃ for 1-48 h to obtain a hardened capsule finished product.
Correspondingly, the invention also discloses application of the cultural relic protection coating hardening capsule in the cultural relic protection coating. Specifically, the cultural relic protection coating can be epoxy coating, polyurethane coating, organosilicon coating or acrylic coating; the addition amount of the hardening capsule is 1-10 wt%.
The invention is illustrated below in specific examples:
example 1
The embodiment provides a cultural relic protection coating hardening capsule, which is prepared by the following steps:
(1) preparing 15g/L sodium alginate solution and 1 wt% calcium chloride solution (Ca)2+ Concentration 1 wt%);
(2) gradually adding 5mL of E51 epoxy resin into 20mL of sodium alginate solution to obtain an oil-in-water emulsion;
(3) adding 25mL of sodium alginate solution into the oil-in-water emulsion, and uniformly mixing to obtain a nuclear emulsion;
(4) the nuclear emulsion is electrically sprayed into 10mL of calcium chloride solution, and is solidified for 30 minutes; then filtering, washing and drying to obtain a hard capsule finished product.
Example 2
The embodiment provides a cultural relic protection coating hardening capsule
(1) Preparing 20g/L sodium alginate solution and 1 wt% calcium chloride solution (Ca)2+1 wt% concentration), 5 v/v% concentration of N, N-dimethylbenzylamine solution;
(2) gradually adding 8mL of E51 epoxy resin into 25mL of sodium alginate solution to obtain an oil-in-water emulsion;
(3) adding 25mL of sodium alginate solution into the oil-in-water emulsion, and uniformly mixing to obtain a nuclear emulsion;
(4) and (3) carrying out electrospray on the nuclear emulsion into 12mL of calcium chloride solution, solidifying for 30 minutes, then adding 8mL of N, N-dimethylbenzylamine solution and 5mL of pentaerythritol tetrakis (3-mercaptopropionate), mixing and reacting for 1h, and then filtering, washing and drying to obtain a hard capsule finished product.
Example 3
The coatings prepared in examples 1-2 were added to coatings manufactured by Beijing Zhi Shengwei Huake technology development Co., Ltd. with models ZS-511 (fluorocarbon based coating) and ZS-922 (silicone-fluorocarbon based coating). And detecting the related properties of the coating: wherein the adhesive force is measured by the method in GB/T5210-; the salt spray resistance is measured by the method in GB/T1771-2007; the specific measurement results are as follows:
as can be seen from the table, after the hardening capsule of the invention is added, the adhesive force grade, the acid resistance, the alkali resistance and the salt spray resistance of each coating are improved to a certain extent.
Example 4 Effect measurement
4.1 Experimental materials
Selecting a bronze part with No. 1 effluent from south China sea, soaking the bronze part in absolute ethyl alcohol for 2 hours, and brushing a corrosion product on the surface of the bronze part by using a brush after drying; the test specimens were cut to a length of 150mm, a width of 75mm and a thickness of 3 mm.
The ZS-922 paint and ZS-922 paint incorporating 10% of the hardened capsules of example 2 were painted onto the samples, respectively; during painting, only one side is painted, evenly painted for 3 times, and then the paint is used for testing after being kept stand in a fume hood for 48 hours.
4.1 film uniformity test
Soaking the painted sample and the reference substance in 5% NaCl solution for 100 days, and selecting 5 points to measure the thickness of the coating before and after soaking; the specific determination method adopts a related method in GB/T13452.2-2008; the results are as follows:
as can be seen from the table, the coating added with the hardened capsule of the invention has greatly improved the uniformity of the coating thickness.
4.2 Corrosion Performance testing
The painted sample was immersed in a 5% citric acid and 5% sulfuric acid solution for 100 days and placed in the air (in the museum of the Guangdong maritime silk road) for 100 days, the change in mass before and after immersion was measured, and the surface condition was photographed and observed. The mass changes are as follows:
appearance observation is performed on the sample after the citric acid and sulfuric acid solution is soaked, and referring to fig. 3, the picture in fig. 3 is a picture of the sample after the ZS-922 is coated and before the citric acid is soaked; the standard color card is arranged below the sample holder, and the sample is arranged above the sample holder. FIG. 4 is a photograph of a sample coated with ZS-922 after immersion in citric acid, in which the standard color chart is shown below and the sample is shown above, and it can be seen that the coating film is broken and peeled off and the copper sheet is corroded. Accordingly, other samples were observed and the results are shown in the following table:
the following table specifically shows; (wherein FIGS. 3-6 are pictures of the sample after citric acid soaking)
As can be seen from the table, the microcapsule additive of the present invention effectively improves the corrosion resistance of the coating under air and acidic conditions.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. A cultural relic protection coating hardening capsule is characterized by comprising a capsule wall substance and a capsule inner substance; wherein the capsule wall material is formed by the reaction of calcium-containing solution and alginate; the capsule substance comprises resin and alginate;
the cultural relic protection coating hardening capsule comprises the following raw materials in parts by weight: 0.2-10 parts of alginate, 5-15 parts of resin and 9-50 parts of calcium-containing solution.
2. The hardening capsule of cultural relic protection coating of claim 1, wherein the alginate is selected from one or more of alginic acid, calcium alginate, sodium alginate and potassium alginate;
the resin is one or more of epoxy resin, fluorocarbon resin, alkyd resin, polyurethane and organic silicon resin;
the calcium-containing solution is one of a calcium chloride saturated solution, a calcium hydroxide saturated solution and a calcium carbonate saturated solution.
3. The cultural relic protection coating hardening capsule of claim 2, wherein the resin is selected from epoxy resin;
the calcium-containing solution is a calcium chloride solution, and the concentration of calcium in the calcium-containing solution is 0.5-5 wt%.
4. The cultural relic protection coating hardening capsule according to any one of claims 1 to 3, which is characterized by further comprising the following raw materials in parts by weight:
0.2-5 parts of hydrocarbyl benzylamine and 2-20 parts of mercaptan.
5. The cultural relic protection coating hardening capsule according to claim 4, wherein the hydrocarbyl benzylamine is selected from one or more of N, N-dimethylbenzylamine, N-methylbenzylamine, N-diethylbenzylamine, N-ethylbenzylamine, 4-vinylbenzylamine;
the mercaptan is selected from one or more of pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate) polythiol and pentaerythritol tetrakis (mercaptoacetate).
6. The cultural relic protection coating hardening capsule according to claim 5, wherein the hydrocarbyl benzylamine is selected from N, N-dimethylbenzylamine; the mercaptan is pentaerythritol tetrakis (3-mercaptopropionate).
7. A method of preparing a cultural relic protection coating hardening capsule according to any of the claims 1 to 6, characterized in that the method comprises:
(1) preparing 5-30 g/L alginate solution and calcium-containing solution;
(2) gradually adding resin into alginate solution accounting for 30-50% of the total volume of the alginate solution to form an oil-in-water emulsion;
(3) adding the rest alginate solution into the oil-in-water emulsion, and uniformly mixing to obtain a core emulsion;
(4) and carrying out electric spraying on the nuclear emulsion into a calcium-containing solution, solidifying for 0.2-5 h, filtering, washing and drying to obtain a hardened capsule finished product.
8. The method for preparing a hardening capsule of cultural relic protection paint according to claim 7, wherein the step (4) comprises:
(4.1) carrying out electric spraying on the nuclear emulsion into a calcium-containing solution, and solidifying for 0.2-5 h;
(4.2) adding hydrocarbyl benzylamine and mercaptan, and mixing and reacting for 0.1-5 h;
and (4.3) filtering, washing and drying to obtain a hardened capsule finished product.
9. Use of a cultural relic protection coating hardening capsule according to any one of claims 1 to 6 in a cultural relic protection coating.
10. The use according to claim 9, wherein the coating is an epoxy-based coating, a polyurethane-based coating, a silicone-based coating or an acrylic-based coating;
the addition amount of the hardening capsule is 1-10 wt%.
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