CN111170747A - Ceramic powder and modification method thereof - Google Patents
Ceramic powder and modification method thereof Download PDFInfo
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- CN111170747A CN111170747A CN202010087554.5A CN202010087554A CN111170747A CN 111170747 A CN111170747 A CN 111170747A CN 202010087554 A CN202010087554 A CN 202010087554A CN 111170747 A CN111170747 A CN 111170747A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62894—Coating the powders or the macroscopic reinforcing agents with more than one coating layer
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
Abstract
The invention is suitable for the technical field of materials, and provides a ceramic powder modification method and ceramic powder, wherein the ceramic powder modification method comprises the following steps: in a weakly acidic environment, in an organic solvent, modifying the surface of ceramic powder by using a modifier, and drying to obtain primary modified ceramic powder; the modifier carries carbon-carbon double bonds capable of undergoing polymerization reaction and groups capable of carrying out bonding reaction with hydroxyl on the surface of the ceramic powder; and (2) fully dissolving a thermal initiator in an organic solvent, adding photosensitive resin and the primary modified ceramic powder, heating and stirring fully, and drying to obtain the secondary modified ceramic powder. According to the invention, the surface of the ceramic powder is modified by the modifier, and then the carbon-carbon double bond of the modifier is utilized to carry out polymerization reaction with the photosensitive resin, so that the photosensitive resin and the modified ceramic powder form firm chemical combination, and the ceramic powder and the photosensitive resin have good intersolubility and binding force.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a modification method of ceramic powder and the ceramic powder.
Background
Ceramic photocurable pastes for ceramic 3D printing are mostly applied with non-aqueous photosensitive resin systems because of their wider range of refractive indices, more choice of curing resin properties, such as: hardness, shrinkage, etc. of the resin. The formula of the ceramic light-cured slurry mainly comprises the following components: ceramic powder, oligomer, monomer diluent, dispersant, photoinitiator, plasticizer and the like, and in order to achieve the mechanical properties required by structural ceramics, the mass ratio of the ceramic powder in the formula is required to be as high as possible. However, if the particle diameter of the common structural ceramic powder, such as alumina, zirconia, silica, etc., is smaller, the difficulty of making the high solid content photo-curing slurry is higher, and the reason is that the properties of the particle surface are all hydrophilic structures, the affinity with the non-aqueous photo-curing resin system is not good, and the second reason is that the small-particle ceramic powder tends to agglomerate due to the higher surface energy, which increases the viscosity of the slurry.
The common methods for improving the affinity between the ceramic powder and the photosensitive resin include: however, although the affinity between the powder and the resin can be improved by these means, the improvement of the affinity between the powder and the photosensitive resin is still limited due to the structural difference between the modified powder and the resin, and the stability between the powder and the resin in the photo-curing slurry is also limited.
Therefore, the existing ceramic powder modification means has the problems of limited effect of improving the affinity between the ceramic powder and the photosensitive resin and limited stability.
Disclosure of Invention
The embodiment of the invention provides a method for modifying ceramic powder, aiming at solving the problems of limited effect on improving the affinity between the ceramic powder and photosensitive resin and limited stability of the existing ceramic powder modification means.
The embodiment of the invention is realized in such a way that a method for modifying ceramic powder comprises the following steps:
in a weakly acidic environment, in an organic solvent, modifying the surface of ceramic powder by using a modifier, and drying to obtain primary modified ceramic powder; the modifier carries a carbon-carbon double bond capable of generating polymerization reaction and a group capable of carrying out bonding reaction with hydroxyl on the surface of the ceramic powder;
and (2) fully dissolving a thermal initiator in an organic solvent, adding photosensitive resin and the primary modified ceramic powder, heating and stirring fully, and drying to obtain the secondary modified ceramic powder.
The embodiment of the invention also provides ceramic powder, which is obtained by modifying the ceramic powder by the modification method.
According to the method for modifying the ceramic powder, provided by the embodiment of the invention, the surface of the ceramic powder is modified by the modifier carrying the carbon-carbon double bond capable of generating polymerization reaction and the group capable of performing bonding reaction with hydroxyl, and then the carbon-carbon double bond of the modifier is utilized to perform polymerization reaction with photosensitive resin, so that the photosensitive resin and the modified ceramic powder form firm chemical bonding, and therefore, the ceramic powder and the photosensitive resin have good intersolubility and bonding force and good stability; meanwhile, the modification method is favorable for improving the dispersibility and the affinity of the ceramic powder in a resin system.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a method for modifying ceramic powder for ceramic 3D printing based on the current situation, wherein the surface of the ceramic powder is modified by a modifier carrying carbon-carbon double bonds capable of undergoing polymerization reaction and groups capable of undergoing bonding reaction with hydroxyl, and then the carbon-carbon double bonds of the modifier are utilized to carry out polymerization reaction with photosensitive resin, so that the photosensitive resin and the modified ceramic powder form firm chemical bonding, and therefore, the ceramic powder and the photosensitive resin have good intersolubility and bonding force and good stability; meanwhile, the modification method is favorable for improving the dispersibility and the affinity of the ceramic powder in a resin system.
In an embodiment of the present invention, a method for modifying ceramic powder includes:
in a weakly acidic environment, in an organic solvent, modifying the surface of ceramic powder by using a modifier, and drying to obtain primary modified ceramic powder; the modifier carries a carbon-carbon double bond capable of generating polymerization reaction and a group capable of carrying out bonding reaction with hydroxyl on the surface of the ceramic powder;
and (2) fully dissolving a thermal initiator in an organic solvent, adding photosensitive resin and the primary modified ceramic powder, heating and stirring fully, and drying to obtain the secondary modified ceramic powder.
In the embodiments of the present invention, the specific type of the organic solvent is not limited, and in the following specific embodiments, the organic solvent is absolute ethyl alcohol, a mixed solution of glacial acetic acid and water, or absolute ethyl alcohol, and the type of the organic solvent used has a very small and negligible effect on the system performance.
In the embodiment of the present invention, the ceramic powder is an oxide ceramic powder, and may be an alumina ceramic powder, or a silica ceramic powder, or a zirconia ceramic powder, and the surface of the ceramic powder contains hydroxyl groups, and the ceramic powder is obtained by purchasing the ceramic powder from alumina manufacturers such as Alteo corporation, products of sumitomo corporation, zirconia manufacturers such as oriental zirconium industry, sai china corporation, etc., and silica manufacturers such as himei powder technology ltd, etc.; it D50：0.2-10μm，BET：1-15m2The ceramic powder used in the invention is not limited by the purchasing manufacturer.
In the embodiment of the invention, the modifier is one or more of vinyl trimethoxy silane, vinyl methyl diethoxy silane, vinyl methyl dimethoxy silane, allyl trimethoxy silane, gamma-methacryloxypropyl trimethoxy silane, methacryloxyethyl maleic acid monoester and alkyl acrylate phosphate.
In the embodiment of the invention, the mass ratio of the modifier to the ceramic powder is 0.001-0.02: 1; the modifier is used as a main action reagent for primary modification, and the type and the dosage of the modifier determine the quality of the modification effect. The modifier contains a group capable of reacting with the hydroxyl on the surface of the powder and double bonds. When the amount of the modifier used is too small, the modifier grafted to the surface of the powder is too small, so that the amount of the resin bound to the modifier during secondary modification is limited, and if the amount of the resin modified on the surface of the powder is insufficient, the affinity with the powder is insufficient. On the contrary, if the modifier is excessive, the self-polymerization ratio of the modifier is increased, the modifier really grafted to the surface of the powder is possibly less, and the modification effect is worse for a long time; therefore, the amount of modifier used is critical.
In the embodiment of the invention, the mass ratio of the photosensitive resin to the primary modified ceramic powder is 0.005-0.05: 1.
In the embodiment of the invention, the weight ratio of the thermal initiator to the photosensitive resin is 0.01-0.1: 1; the secondary modification is a thermal polymerization reaction of the resin and the modifier used, and the amount of the thermal initiator used is directly related to the effect of the thermal polymerization reaction as a necessary condition for the thermal polymerization reaction. Too little results in low efficiency of polymerization of the resin and the modifier on the surface of the powder, too high results in difficulty in controlling thermal polymerization of the resin, too long or too high a degree of steric crosslinking, and affects the affinity between the powder and the resin.
In the embodiment of the invention, the thermal initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide and tert-butyl peroxy-2-ethylhexanoate.
In the examples of the present invention, the photosensitive resin is an epoxy acrylate oligomer, a polyester acrylate oligomer, a urethane acrylate oligomer, an aliphatic urethane acrylate oligomer, an ethoxylated bisphenol A diacrylate, 1, 6-ethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, polyethylene glycol (200) diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (600) diacrylate, propoxylated neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane acrylate, isobornyl acrylate, ethoxylated trimethylolpropane acrylate, di-trimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, a copolymer of ethylene glycol, propylene glycol, Ethoxylated pentaerythritol tetraacrylate.
In a preferred embodiment of the present invention, the step of performing surface modification on the ceramic powder by using a modifier in an organic solvent in a weakly acidic environment, and drying the ceramic powder to obtain a primary modified ceramic powder specifically includes:
adding a modifier into an organic solvent, adjusting the pH value to 4-6, fully stirring, adding ceramic powder, heating and stirring in a water bath at 50-100 ℃, condensing and refluxing for 3-12 hours, carrying out centrifugal cleaning and drying at 50-100 ℃ to obtain the primary modified ceramic powder.
Adding a certain amount of modifier into absolute ethyl alcohol, dropwise adding acetic acid to adjust the pH value to be 4-6 so as to promote the modifier to form a group capable of being combined with hydroxyl on the surface of the ceramic powder, then adding a certain amount of ceramic powder, heating in a water bath at 50-100 ℃ for 3-12 hours, cleaning the slurry after the water bath in a centrifuge, wherein the cleaning solvent is absolute ethyl alcohol, and cleaning for at least 2 times; drying the washed wet powder at 50-100 ℃ for at least 12 hours.
In a preferred embodiment of the present invention, the step of adding the photosensitive resin and the primary modified ceramic powder after sufficiently dissolving the thermal initiator in the organic solvent, heating and stirring the mixture sufficiently, and drying the mixture to obtain the secondary modified ceramic powder specifically includes:
and (2) fully dissolving a thermal initiator in an organic solvent, adding the primary modified ceramic powder, adding the photosensitive resin while stirring, heating and stirring in a water bath at 50-100 ℃, condensing and refluxing for 3-12 hours, then carrying out centrifugal cleaning and drying treatment at 50-100 ℃ to obtain the secondary modified ceramic powder.
In the embodiment of the invention, the alkenyl double bond of the modifier in the first modification process is utilized to carry out polymerization reaction with the photosensitive resin, so that the photosensitive resin can be combined with the modified powder, and the intermiscibility and the associativity between the powder and the resin are improved.
Adding a certain amount of thermal initiator into absolute ethyl alcohol, stirring to completely dissolve the thermal initiator, adding a certain amount of ceramic powder after first modification, adding a certain amount of photosensitive resin while stirring, heating in a water bath at 50-100 ℃ for 3-12 hours, cleaning the slurry after the water bath in a centrifuge, wherein a cleaning solvent is absolute ethyl alcohol, and cleaning for at least 2 times; drying the cleaned wet powder at 50-100 ℃ for at least 12 hours to obtain the ceramic powder after secondary modification.
The embodiment of the invention also provides ceramic powder, which is obtained by modifying the ceramic powder by the modification method.
The method for modifying ceramic powder and the technical effects of the ceramic powder of the present invention will be further described with reference to the following specific examples, but the specific implementation methods mentioned in these examples are only illustrative and explanatory of the technical solution of the present invention, and do not limit the implementation scope of the present invention, and all modifications and substitutions based on the above principles should be within the protection scope of the present invention.
Example 1
Adding 500ml of absolute ethyl alcohol into a 2L conical flask, adjusting the pH value to 4 by dripping acetic acid, adding 33g of distilled water and 10g of glacial acetic acid into the conical flask, adding magnetons into the conical flask, adding 0.25g of gamma-methacryloxypropyl trimethoxysilane into the conical flask under the stirring of a magnetic stirrer, and then continuing stirring for 60 min; adding 250g of alumina ceramic powder, keeping the temperature of the mixture in a water bath at 80 ℃ for 4h under the condition of magnetic stirring, then cleaning the slurry twice by adopting absolute ethyl alcohol in a centrifuge, wherein the centrifuge is a Luxiang instrument TD4, the rotating speed of the centrifuge is 3000rpm, and the single centrifugation time is 5 min. Drying the cleaned powder at 80 ℃ for 12h to obtain primary modified ceramic powder;
adding 300ml of absolute ethyl alcohol into a 2L conical flask, starting magnetic stirring, adding 0.25g of thermal initiator dibenzoyl peroxide, adding 250g of primary modified ceramic powder after the thermal initiator is dissolved, adding 12.5g of (2) propylene oxide neopentyl glycol diacrylate, keeping the temperature in a water bath at 80 ℃ for 4h, keeping the magnetic stirring started state in the whole process, cleaning the slurry twice in a centrifuge, wherein the centrifuge is a Luxiang instrument TD4, the rotation speed of the centrifuge is 3000rpm, and the single centrifugation time is 5 min. And drying the cleaned powder at 60 ℃ for 12h to obtain the ceramic powder after secondary modification.
Example 2
Adding 500ml of absolute ethyl alcohol into a 2L conical flask, adjusting the pH value to 6 by dripping acetic acid, adding magnetons into the conical flask, adding 0.5g of vinyl trimethoxy silane under the stirring of a magnetic stirrer, and then continuing to stir for 60 min; adding 250g of alumina ceramic powder, keeping the temperature of the mixture in a water bath at 80 ℃ for 4h under the condition of magnetic stirring, then cleaning the slurry twice by adopting absolute ethyl alcohol in a centrifuge, wherein the centrifuge is a Luxiang instrument TD4, the rotating speed of the centrifuge is 3000rpm, and the single centrifugation time is 5 min. Drying the cleaned powder at 80 ℃ for 12h to obtain primary modified ceramic powder;
adding 300ml of absolute ethyl alcohol into a 2L conical flask, starting magnetic stirring, adding 0.4g of thermal initiator azobisisobutyronitrile, adding 250g of primary modified ceramic powder after the thermal initiator is dissolved, adding 10g of 1, 6-ethylene glycol diacrylate, keeping the temperature in a water bath at 80 ℃ for 4 hours, keeping the magnetic stirring started in the whole process, cleaning the slurry twice by adopting the absolute ethyl alcohol in a centrifugal machine, wherein the centrifugal machine is a Luxiang instrument TD4, the rotating speed of the centrifugal machine is 3000rpm, and the single centrifugation time is 5 min. And drying the cleaned powder at 60 ℃ for 12h to obtain the ceramic powder after secondary modification.
Example 3
Adding 500ml of absolute ethyl alcohol into a 2L conical flask, adjusting the pH value to 6 by dripping acetic acid, adding magnetons into the conical flask, adding 2.5g of vinyl methyl dimethoxysilane under the stirring of a magnetic stirrer, and then continuing to stir for 60 min; adding 250g of alumina ceramic powder, keeping the temperature of the mixture in a water bath at 80 ℃ for 4h under the condition of magnetic stirring, then cleaning the slurry twice by adopting absolute ethyl alcohol in a centrifuge, wherein the centrifuge is a Luxiang instrument TD4, the rotating speed of the centrifuge is 3000rpm, and the single centrifugation time is 5 min. Drying the cleaned powder at 80 ℃ for 12h to obtain primary modified ceramic powder;
adding 300ml of absolute ethyl alcohol into a 2L conical flask, starting magnetic stirring, adding 0.0125g of thermal initiator tert-butyl 2-ethylhexanoate peroxide, adding 250g of first-time modified ceramic powder after the thermal initiator is dissolved, adding 1.25g of (2) ethoxylated bisphenol A diacrylate, then preserving heat for 4 hours in a water bath at 80 ℃, keeping the magnetic stirring started state in the whole process, then cleaning the slurry twice in a centrifuge, wherein the centrifuge is a Luxiang instrument TD4, the rotating speed of the centrifuge is 3000rpm, and the single centrifugation time is 5 min. And drying the cleaned powder at 60 ℃ for 12h to obtain the ceramic powder after secondary modification.
Example 4
Adding 500ml of absolute ethyl alcohol into a 2L conical flask, adjusting the pH value to 5 by dripping acetic acid, adding magnetons into the conical flask, adding 5g of allyltrimethoxysilane into the conical flask under the stirring of a magnetic stirrer, and then continuing stirring for 60 min; adding 250g of alumina ceramic powder, keeping the temperature of the mixture in a water bath at 80 ℃ for 4h under the condition of magnetic stirring, then cleaning the slurry twice by adopting absolute ethyl alcohol in a centrifuge, wherein the centrifuge is a Luxiang instrument TD4, the rotating speed of the centrifuge is 3000rpm, and the single centrifugation time is 5 min. Drying the cleaned powder at 80 ℃ for 12h to obtain primary modified ceramic powder;
adding 300ml of absolute ethyl alcohol into a 2L conical flask, starting magnetic stirring, adding 0.25g of thermal initiator azobisisoheptonitrile, adding 250g of primary modified ceramic powder after the thermal initiator is dissolved, adding 2.5g of tricyclodecane dimethanol diacrylate, keeping the temperature in a water bath at 80 ℃ for 4h, keeping the magnetic stirring started in the whole process, cleaning the slurry twice in a centrifuge by adopting the absolute ethyl alcohol, wherein the centrifuge is a Luxiang instrument TD4, the rotation speed of the centrifuge is 3000rpm, and the single centrifugation time is 5 min. And drying the cleaned powder at 60 ℃ for 12h to obtain the ceramic powder after secondary modification.
Example 5
Adding 500ml of absolute ethyl alcohol into a 2L conical flask, adjusting the pH value to 5 by dripping acetic acid, adding magnetons into the conical flask, adding 5g of vinyl methyl diethoxy silane under the stirring of a magnetic stirrer, and then continuing to stir for 60 min; adding 250g of alumina ceramic powder, keeping the temperature of the mixture in a water bath at 80 ℃ for 4h under the condition of magnetic stirring, then cleaning the slurry twice by adopting absolute ethyl alcohol in a centrifuge, wherein the centrifuge is a Luxiang instrument TD4, the rotating speed of the centrifuge is 3000rpm, and the single centrifugation time is 5 min. Drying the cleaned powder at 80 ℃ for 12h to obtain primary modified ceramic powder;
adding 300ml of absolute ethyl alcohol into a 2L conical flask, starting magnetic stirring, adding 1.25g of thermal initiator azobisisoheptonitrile, adding 250g of primary modified ceramic powder after the thermal initiator is dissolved, adding 12.5g of dipropylene glycol diacrylate, keeping the temperature in a water bath at 80 ℃ for 4h, keeping the magnetic stirring started in the whole process, cleaning the slurry twice by adopting the absolute ethyl alcohol in a centrifuge, wherein the centrifuge is a Luxiang instrument TD4, the rotation speed of the centrifuge is 3000rpm, and the single centrifugation time is 5 min. And drying the cleaned powder at 60 ℃ for 12h to obtain the ceramic powder after secondary modification.
Preparing slurry from the ceramic powder obtained by the method for modifying ceramic powder of the embodiment 1-5 (preparing slurry: mixing 47.8g of modified ceramic powder, 0.48g of BYK111 and 20g of 1, 6-hexanediol diacrylate and stirring the mixture to prepare ceramic slurry) to perform viscosity test and anti-settling test, wherein the viscosity test is directly tested by a viscometer (SNB-2 type rotational viscometer) and the anti-settling property is observed by standing the mixture to observe the bottom settling condition; the test results are shown in table 1.
TABLE 1
| Viscosity (Pa. s) | Bottom precipitation conditions | |
| Example 1 | 2.34 | Standing for 15d without caking |
| Example 2 | 2.23 | Standing for 15d without caking |
| Example 3 | 2.21 | Standing for 15d without caking |
| Example 4 | 2.18 | Standing for 15d without caking |
| Example 5 | 2.20 | Standing for 15d without caking |
In summary, as can be seen from table 1, in the ceramic powder prepared by the method for modifying ceramic powder provided in embodiments 1 to 5 of the present invention, the surface of the ceramic powder is modified by the modifier carrying the carbon-carbon double bond capable of undergoing polymerization and the group capable of undergoing a bonding reaction with the hydroxyl group, and then the carbon-carbon double bond of the modifier is utilized to undergo a polymerization reaction with the photosensitive resin, so that the photosensitive resin and the modified ceramic powder form a firm chemical bond, and thus the ceramic powder and the photosensitive resin have good intersolubility and bonding force, and do not cake after standing for 15d, and have good stability, which is beneficial to improving the dispersibility and affinity of the ceramic powder in a resin system.
Further, in the research and development process, on the basis of the embodiment 1, only partial changes are made, other components and process conditions are not changed, the following comparative examples 1-5 are carried out, and it is found that the types of the modifier, the mass ratio of the modifier to the ceramic powder, and the mass ratio of the photosensitive resin to the primary modified ceramic powder all have obvious influences on the system performance, and the specific points are as follows:
comparative example 1
Comparative example 1 in the first modification treatment of powder, 0.125g of gamma-methacryloxypropyltrimethoxysilane was added with stirring by a magnetic stirrer, and the other treatment processes and the amounts of the raw materials were the same as those of example 1, as compared with example 1.
Comparative example 2
Comparative example 2 in the first modification treatment of the powder, 7.5g of vinyltrimethoxysilane was added with stirring by a magnetic stirrer, and the other treatment processes and the amounts of the raw materials were the same as those of example 2.
Comparative example 3
Compared with the example 3, in the second step modification treatment of the powder, in the comparative example 3, "0.0025 g of thermal initiator tert-butyl peroxy-2-ethylhexanoate is added, 250g of first modified ceramic powder is added after the thermal initiator is dissolved, and 0.25g of (2) ethoxylated bisphenol A diacrylate is added", and the rest of the treatment process and the amount of the raw materials are the same as those in the example 3.
Comparative example 4
Compared with the example 4, in the second step of the powder modification treatment of the comparative example 4, 1.5g of the thermal initiator azobisisoheptonitrile was added after the magnetic stirring was started, 250g of the first modified ceramic powder was added after the thermal initiator was dissolved, and 15g of tricyclodecane dimethanol diacrylate was added, and the rest of the treatment process and the amount of the raw materials were the same as those of the example 4.
Comparative example 5
Comparative example 5 in the first modification treatment of powder, 5g of 3-aminopropyltrimethoxysilane was added with stirring by a magnetic stirrer, and the other treatment processes and the amounts of the raw materials were the same as those of example 5, as compared with example 5.
The ceramic powders obtained in comparative examples 1 to 5 were subjected to a viscosity test directly measured by a viscometer (SNB-2 type rotational viscometer) and an anti-settling property measured by observing the bottom settling state by standing, and the results of the measurement are shown in Table 2.
TABLE 2
| Viscosity (Pa. s) | Bottom precipitation conditions | |
| Comparative example 1 | 6.28 | Standing for 24h to form bottom block |
| Comparative example 2 | 5.89 | Standing for 24h to form bottom block |
| Comparative example 3 | 6.32 | Standing for 24h to form bottom block |
| Comparative example 4 | 6.24 | Standing for 24h to form bottom block |
| Comparative example 5 | 9.93 | Standing 24h bottom lump |
In summary, from table 2, it can be seen from the test results of comparative example 1 and example 1 that the modifier used in comparative example 1 is too small, the modification of the powder surface grafting is smaller than that of the example, and the modification that can react with the resin at the later stage is relatively smaller. The surface of the powder is linked with fewer resin groups through chemical bonds, namely the affinity with the resin is insufficient, so that the powder cannot be well dispersed and stabilized in the liquid resin in a slurry system, and the system has high viscosity and is rapidly settled; according to the test results of the comparative example 2 and the example 2, the excessive amount of the modifier in the comparative example 2 increases the self-polymerization probability of the modifier, and the modification ratio for grafting the surface of the powder is small, so the results are the same as the above; according to the test results of comparative example 3 and example 3, the amount of the resin used in comparative example 3 is too small, and the amount of the resin used is not large due to the insufficient amount of the resin, although the modifier grafted on the surface of the powder is large, so that the result is the same as the above result; according to the test results of the comparative example 4 and the example 4, the resin in the comparative example 4 is excessive, the excessive resin consumes excessive active groups generated by the thermal initiator due to self-polymerization of the resin, the probability of initiating the polymerization of the resin and the modifier by the thermal initiator is reduced, and the result is the same as the result; according to the test results of comparative example 5 and example 5, the modifier used in comparative example 5 is 3-aminopropyltrimethoxysilane, which can modify the powder, but has low reaction efficiency with the resin and cannot play an effective bridging role, and the result is the same as the above result.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A method for modifying ceramic powder, comprising:
in a weakly acidic environment, in an organic solvent, modifying the surface of ceramic powder by using a modifier, and drying to obtain primary modified ceramic powder; the modifier carries a carbon-carbon double bond capable of generating polymerization reaction and a group capable of carrying out bonding reaction with hydroxyl on the surface of the ceramic powder;
and (2) fully dissolving a thermal initiator in an organic solvent, adding photosensitive resin and the primary modified ceramic powder, heating and stirring fully, and drying to obtain the secondary modified ceramic powder.
2. The method for modifying ceramic powder according to claim 1, wherein the modifier is one or more selected from vinyltrimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, allyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, methacryloxyethyl maleic acid monoester, and alkyl acrylate phosphate.
3. The method for modifying ceramic powder according to claim 1, wherein the mass ratio of the modifier to the ceramic powder is 0.001 to 0.02: 1.
4. The method for preparing ceramic powder according to claim 1, wherein the mass ratio of the photosensitive resin to the primary modified ceramic powder is 0.005-0.05: 1.
5. The method for modifying ceramic powder according to claim 1, wherein the weight ratio of the thermal initiator to the photosensitive resin is 0.01 to 0.1: 1.
6. The method for modifying ceramic powder according to claim 1, wherein the thermal initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, and tert-butyl 2-ethylhexanoate peroxide.
7. The method for modifying ceramic powder according to claim 1, wherein the photosensitive resin is an epoxy acrylate oligomer, a polyester acrylate oligomer, a urethane acrylate oligomer, an aliphatic urethane acrylate oligomer, (2) ethoxylated bisphenol A diacrylate, (4) ethoxylated bisphenol A diacrylate, 1, 6-ethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, polyethylene glycol (200) diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (600) diacrylate, (2) propoxylated neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane acrylate, isobornyl acrylate, ethoxylated trimethylolpropane acrylate, (6) ethoxylated trimethylolpropane acrylate, a polyester acrylate oligomer, a urethane acrylate oligomer, an aliphatic urethane acrylate oligomer, a (2) ethoxylated bisphenol A diacrylate, a (4) ethoxylated bisphenol A diacrylate, a 1, 6-ethylene glycol diacrylate, a tripropylene glycol diacrylate, a poly (2) propoxylated neopentyl glycol diacrylate, a tricycl, Di-trimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, and (4) ethoxylated pentaerythritol tetraacrylate.
8. The method for modifying ceramic powder according to claim 1, wherein the step of performing surface modification on the ceramic powder by using a modifier in an organic solvent under a weakly acidic environment and drying the modified ceramic powder to obtain the primary modified ceramic powder specifically comprises:
adding a modifier into an organic solvent, adjusting the pH value to 4-6, fully stirring, adding ceramic powder, heating and stirring in a water bath at 50-100 ℃, condensing and refluxing for 3-12 hours, carrying out centrifugal cleaning, and drying at 50-100 ℃ to obtain the primary modified ceramic powder.
9. The method for modifying ceramic powder according to claim 7, wherein the step of adding a photosensitive resin and the primary modified ceramic powder after sufficiently dissolving a thermal initiator in an organic solvent, heating and stirring the mixture sufficiently, and drying the mixture to obtain the secondary modified ceramic powder specifically comprises:
and (2) fully dissolving a thermal initiator in an organic solvent, adding the primary modified ceramic powder, adding the photosensitive resin while stirring, heating and stirring in a water bath at 50-100 ℃, performing condensation reflux for 3-12 hours, performing centrifugal cleaning and drying at 50-100 ℃ to obtain the secondary modified ceramic powder.
10. A ceramic powder, which is obtained by modifying the ceramic powder according to any one of claims 1 to 9.
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| CN114455946A (en) * | 2022-01-24 | 2022-05-10 | 深圳协同创新高科技发展有限公司 | Zirconia ceramic powder for photocuring 3D printing and preparation method thereof |
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