CN113956025B - Photocuring 3D printing impregnation reinforced ceramic core and preparation method thereof - Google Patents
Photocuring 3D printing impregnation reinforced ceramic core and preparation method thereof Download PDFInfo
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- CN113956025B CN113956025B CN202111362650.7A CN202111362650A CN113956025B CN 113956025 B CN113956025 B CN 113956025B CN 202111362650 A CN202111362650 A CN 202111362650A CN 113956025 B CN113956025 B CN 113956025B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- 238000000034 method Methods 0.000 claims abstract description 33
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- 238000001035 drying Methods 0.000 claims abstract description 21
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- 238000001764 infiltration Methods 0.000 claims abstract description 13
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- 238000010438 heat treatment Methods 0.000 claims description 33
- 239000011248 coating agent Substances 0.000 claims description 26
- 238000000576 coating method Methods 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 18
- 238000005728 strengthening Methods 0.000 claims description 18
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- 239000002131 composite material Substances 0.000 claims description 12
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- OTRIMLCPYJAPPD-UHFFFAOYSA-N methanol prop-2-enoic acid Chemical compound OC.OC.OC(=O)C=C.OC(=O)C=C OTRIMLCPYJAPPD-UHFFFAOYSA-N 0.000 claims description 5
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 claims description 5
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- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 4
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 4
- 229910006501 ZrSiO Inorganic materials 0.000 claims description 4
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 4
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Abstract
The invention relates to a photocuring 3D printing dipping enhanced ceramic core and a preparation method thereof, wherein the preparation method of the photocuring 3D printing dipping enhanced ceramic core comprises the following steps: 1) Preparing light-emitting curing 3D printing ceramic core slurry; 2) Carrying out photocuring 3D printing treatment on the photocuring 3D printing ceramic core slurry to obtain a ceramic core biscuit; 3) Degreasing and sintering the ceramic core biscuit to obtain a photocuring 3D printing ceramic core body; 4) Carrying out infiltration treatment and drying treatment on the photocuring 3D printing ceramic core body to obtain an infiltrated photocuring 3D printing ceramic core body; the method comprises the following steps of (1) carrying out infiltration treatment on a photocuring 3D printing ceramic core body by adopting a ceramic precursor resin solution; 5) Carrying out re-sintering treatment on the impregnated photocuring 3D printing ceramic core body to obtain a photocuring 3D printing impregnation enhanced ceramic core; the photocuring 3D printing impregnation reinforced ceramic core has excellent strength.
Description
Technical Field
The invention relates to the technical field of additive manufacturing ceramic materials, in particular to a photocuring 3D printing impregnation reinforced ceramic core and a preparation method thereof.
Background
Aircraft engines and heavy duty gas turbines are moving toward high thrust-to-weight ratios and high power, which require increased pre-turbine temperatures (i.e., pre-turbine temperatures) of the engines. In order to increase the temperature before the vortex, the prior art develops from the original polycrystalline blade to the current single crystal blade and from the manufacture of a solid blade to the manufacture of a hollow blade, and aims to continuously improve the temperature resistance of the blade of the engine so as to increase the temperature before the vortex of the engine. Due to the limitation of the metal melting point, the improvement of the temperature resistance of the alloy material meets the bottleneck, and the complex air-cooling inner cavity structure of the blade becomes an important way for improving the temperature resistance of the blade. The ceramic core is the key for forming a complex air-cooling inner cavity structure of the blade, so the performance and quality of the ceramic core directly influence the yield of the blade.
For the ceramic core, several key indexes include bending strength, open porosity, firing shrinkage and high-temperature creep resistance. With the increasing complexity of the ceramic cores, the traditional preparation process of hot-pressing injection has difficulty in preparing ceramic cores with more complex structures. Due to the fact that a mold is not needed, a reliable preparation mode is provided for preparation of a more complex ceramic core.
For the photo-curing 3D printing ceramic core, since the ceramic core requires high open porosity, a bonding portion (sintering neck) between ceramic particles is limited during degreasing and sintering, so that the strength of the ceramic core is low (e.g., bending strength is low). Therefore, a method is needed to strengthen the sintering neck of the photocuring 3D printing ceramic core to improve the strength of the photocuring 3D printing ceramic core.
Disclosure of Invention
In view of this, the invention provides a photocuring 3D printing impregnation enhanced ceramic core and a preparation method thereof, and mainly aims to strengthen a sintering neck of the ceramic core so as to improve the strength of the ceramic core.
In order to achieve the purpose, the invention mainly provides the following technical scheme:
in one aspect, an embodiment of the present invention provides a method for preparing a photocuring 3D printing ceramic core, which includes the following steps:
1) Preparing light-emitting curing 3D printing ceramic core slurry;
2) Carrying out photocuring 3D printing treatment on the photocuring 3D printing ceramic core slurry to obtain a ceramic core biscuit;
3) Degreasing and sintering the ceramic core biscuit to obtain a photocuring 3D printing ceramic core body;
4) Performing infiltration treatment and drying treatment on the photocuring 3D printing ceramic core body to obtain the infiltrated photocuring 3D printing ceramic core body; performing infiltration treatment on the photocuring 3D printing ceramic core body by adopting a ceramic precursor resin solution; wherein the viscosity of the ceramic precursor resin solution is 0.1-30cp;
5) And carrying out re-sintering treatment on the impregnated photocuring 3D printing ceramic core body, so that the ceramic precursor resin on the impregnated photocuring 3D printing ceramic core body is converted into a dipping strengthening coating for strengthening a sintering neck, and thus the photocuring 3D printing dipping strengthening ceramic core is obtained.
Preferably, in the step 4): the viscosity of the ceramic precursor resin solution is 0.1-30cp; preferably, the ceramic precursor resin solution is prepared from a ceramic precursor resin and a solvent, and the volume ratio of the ceramic precursor resin to the solvent is (1-2): (10-20), preferably 1: (10-20); preferably, the solvent is 1, 6-hexanediol diacrylate.
Preferably, in the step 4): the ceramic precursor resin in the ceramic precursor resin solution is one or more of polysiloxane, polycarbosilane, polysilazane, polyborosilazane, polysilane and polytitanocarbosilane.
Preferably, the step 4) includes: putting the photocuring 3D printing ceramic core body into the ceramic precursor resin solution, soaking for 1-5h for infiltration, then taking out, and drying to obtain the infiltrated photocuring 3D printing ceramic core body; preferably, the steps of impregnating and drying are performed at least once, and preferably, the steps of impregnating and drying are repeated 2 to 5 times; preferably, the temperature of the drying treatment is 120-180 ℃, and the time of the drying treatment is 1-3h.
Preferably, in the step 5), the impregnation strengthening coating is a composite coating, and the components of the composite coating comprise amorphous non-oxide ceramics, crystalline non-oxide ceramics and crystalline oxide ceramics; the step of the re-sintering treatment comprises the following steps: heating the impregnated photocuring 3D printing ceramic core body to 600-700 ℃, preserving heat for 600-1200min, and cooling; preferably, the heating rate is 40-60 ℃/h, and the cooling rate is 40-60 ℃/h; preferably, the atmosphere of the re-sintering treatment is N 2 And O 2 A mixed atmosphere of the composition; wherein N is 2 In a volume fraction of 50-80%, O 2 The volume fraction of (A) is 20-50%.
Preferably, in the step 1): the photo-curing 3D printing ceramic core slurry comprises 50-80 parts by weight of a reinforcing agent, 10-30 parts by weight of a mineralizer and 20-40 parts by weight of a photo-curing resin premixed liquid; preferably, the enhancer is SiO 2 、Al 2 O 3 One or two of them; preferably, the grain size of the enhancer is 50-100 μm; preferably, the particle size of the mineralizer is 10-100nm; preferably, the mineralizer is ZrO 2 、ZrSiO 4 、Na 2 O、K 2 One or more of O; preferably, the light-cured resin premix is formed by mixing a photosensitive resin and a diluent; wherein the volume fraction of the photosensitive resin is 60-80%; the volume fraction of the diluent is 20-40%; preferably, the photosensitive resin is one or more of tricyclodecyl dimethanol diacrylate, octadecyl acrylate, propoxylated neopentyl glycol diacrylate and alkoxylated pentaerythritol tetraacrylate; preferably, the diluent is one or two of 1, 6-hexanediol diacrylate and tripropylene glycol diacrylate.
Preferably, the step 1) includes: mechanically mixing the enhancer and the mineralizer to obtain mixed powder; and (3) keeping the temperature of the light-cured resin premixed solution at 60-120 ℃, stirring, adding the mixed powder into the light-cured resin premixed solution while stirring, keeping the temperature and stirring for 3-4h to obtain the light-cured 3D printing ceramic core slurry.
Preferably, in the step 2), the parameters of the photocuring 3D printing process are set as follows: the curing thickness is set to 50-150 μm, and the curing power is set to 25-45nW/cm 2 The single-layer curing time is set to be 5-30s.
Preferably, in the step 3):
the step of degreasing treatment comprises: heating the ceramic core biscuit to 550-600 ℃, preserving heat for 120-180min, and then cooling; preferably, the heating rate is 60-100 ℃/h, and the cooling rate is 60-100 ℃/h; preferably, the degreasing atmosphere is composed of N 2 And O 2 A mixed atmosphere of the composition; wherein N is 2 In a volume fraction of 50-80%, O 2 The volume fraction of (A) is 20-50%; and/or
The sintering treatment step comprises: heating the degreased ceramic core biscuit to 1000-1700 ℃, preserving heat for 240-360min, and cooling; preferably, the heating rate is 60-120 ℃/h, and the cooling rate is 60-120 ℃/h; preferably, the atmosphere of the sintering treatment is N 2 And O 2 A mixed atmosphere of the composition; wherein N is 2 In a volume fraction of 50-80%, O 2 The volume fraction of (A) is 20-50%.
On the other hand, the embodiment of the invention provides a photocuring 3D printing impregnation reinforced ceramic core, wherein the bending strength of the photocuring 3D printing ceramic core is 15-40MPa, and the porosity of the opening is 25-40%; preferably, the photocuring 3D printing dipping reinforced ceramic core is prepared by any one of the preparation methods of the photocuring 3D printing dipping reinforced ceramic core.
Compared with the prior art, the photocuring 3D printing impregnation reinforced ceramic core and the preparation method thereof have at least the following beneficial effects:
according to the preparation method of the photocuring 3D printing impregnation enhanced ceramic core, after photocuring 3D printing slurry is subjected to photocuring 3D printing treatment and degreasing-sintering treatment, further impregnation treatment and drying treatment are carried out on a photocuring 3D printing ceramic core body obtained after degreasing and sintering treatment, so that ceramic precursor resin is adhered to a sintering neck of the photocuring 3D printing ceramic core body in a liquid form (the sintering neck formed by mutually adhering ceramic particles); and finally, carrying out re-sintering treatment to convert the ceramic precursor resin adhered to the photocuring 3D printing ceramic core body into an impregnation strengthening coating, thereby achieving the purpose of strengthening the sintering neck. Therefore, the scheme of the embodiment of the invention can improve the mechanical property of the ceramic core. Here, it should be noted that: in the infiltration treatment step, a low-viscosity ceramic precursor resin solution with the viscosity of 0.1-30cp is adopted, and the solution with the viscosity range ensures that the ceramic precursor resin solution can be infiltrated into the sintering neck of the photocuring 3D printing ceramic core body, so that the phenomenon that micro pores cannot be infiltrated or closed pores are formed due to infiltration is avoided, and the porosity of the photocuring 3D printing ceramic core is ensured.
Further, in the preparation method of the photocuring 3D printing impregnation reinforced ceramic core provided by the embodiment of the invention, in the final re-sintering treatment step, the control of the ceramic degree, the ceramic crystallization rate and the oxide ceramic content of the ceramic precursor resin is realized by controlling the temperature, the time and the atmosphere of the re-sintering treatment, so that the strength and the open porosity of the photocuring 3D printing ceramic core are regulated and controlled. The photocuring 3D printing ceramic core prepared by the embodiment of the invention can realize regulation and control of different strengths and open porosity according to pouring requirements of different alloys. Specifically, through the control of the re-sintering treatment process (temperature, time and atmosphere), the ceramic precursor resin is converted into the composite coating containing the components of amorphous non-oxide ceramic, crystalline non-oxide ceramic and crystalline oxide ceramic, and the composite coating of the components has excellent strength and certain toughness, so that the problem of cracking of the composite coating can be avoided, and the strength (such as bending strength) of the ceramic core is further ensured.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to make the technical solutions of the present invention practical in accordance with the contents of the specification, the following detailed description is given of preferred embodiments of the present invention with reference to the accompanying drawings.
Drawings
FIG. 1 is a process flow diagram of a method of making a photocured 3D printed impregnated reinforced ceramic core provided by an embodiment of the present invention;
FIG. 2 is an SEM photograph of a photocured 3D printed dip-enhanced ceramic core prepared according to example 1 of the invention;
FIG. 3 is an SEM photograph of a ceramic core prepared according to comparative example 1 of the present invention;
FIG. 4 is a schematic representation of an embodiment of the present invention employing an immersion strengthening coating to strengthen the sintering neck.
Detailed Description
To further explain the technical means and effects of the present invention adopted to achieve the predetermined object, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The technical problem to be solved by the embodiment of the invention is as follows: the ceramic core prepared by the existing photocuring 3D printing process can generate a large amount of microcracks in the degreasing-sintering process, so that the mechanical property of the ceramic core is obviously reduced. In order to solve the problem, the invention provides the following technical scheme:
the embodiment of the invention provides a preparation method of a photocuring 3D printing impregnation reinforced ceramic core, which comprises the following steps of:
1) Preparing light-emitting curing 3D printing ceramic core slurry.
The method comprises the following steps: mechanically mixing the reinforcer and the mineralizer to obtain mixed powder; and (3) stirring the light-cured resin premix liquid at the temperature of 60-120 ℃ in a heat preservation manner, slowly adding the mixed powder while stirring, and stirring for 3-4h in a heat preservation manner to obtain the light-cured 3D printing ceramic core slurry.
Wherein the photocuring 3D printing ceramic core slurry comprises 50-80 parts by weight of strong acid10-30 parts of mineralizer and 20-40 parts of light-cured resin premix. Wherein the enhancer is SiO 2 、Al 2 O 3 One or two of them. The grain size of the reinforcer is 50-100 μm. Wherein the particle size of the mineralizer is 10-100nm. The mineralizing agent being ZrO 2 、ZrSiO 4 、Na 2 O、K 2 One or more of O. Wherein the light-cured resin premix is prepared by mixing photosensitive resin and a diluent; wherein, the volume fraction of the photosensitive resin is 60-80%; the volume fraction of the diluent is 20-40%; wherein the photosensitive resin is one or more of tricyclodecyl dimethanol diacrylate, octadecyl acrylate, propoxylated neopentyl glycol diacrylate and alkoxylated pentaerythritol tetraacrylate; wherein the diluent is one or two of 1, 6-hexanediol diacrylate and tripropylene glycol diacrylate.
2) And carrying out photocuring 3D printing treatment on the photocuring 3D printing ceramic core slurry to obtain a ceramic core biscuit.
Specifically, setting photocuring 3D printing parameters, and curing the slurry through photocuring 3D printing equipment to obtain the ceramic core biscuit. The photocuring 3D printing process parameters are set as follows: the curing thickness is set to be 50-150 μm, and the curing power is set to be 25-45nW/cm 2 The single-layer curing time is set to be 5-30s.
3) And (4) degreasing and sintering the ceramic core biscuit to obtain the photocuring 3D printing ceramic core body.
Wherein the step of degreasing comprises: heating the ceramic core biscuit to 550-600 ℃, preserving the heat for 120-180min and then cooling; preferably, the heating rate is 60-100 ℃/h, and the cooling rate is 60-100 ℃/h; preferably, the degreasing atmosphere is composed of N 2 And O 2 A mixed atmosphere of the composition; wherein, N 2 In a volume fraction of 50-80%, O 2 The volume fraction of (A) is 20-50%.
Wherein, the step of sintering treatment comprises: heating the ceramic core biscuit to 1000-1700 ℃, and cooling after keeping the temperature for 240-360 min; preferably, the heating rate is 60-120 ℃/h, and the cooling rate is 60-120 DEG CH; preferably, the atmosphere of the sintering treatment is N 2 And O 2 A mixed atmosphere of the composition; wherein N is 2 In a volume fraction of 50-80%, O 2 The volume fraction of (A) is 20-50%.
4) Carrying out infiltration treatment and drying treatment on the photocuring 3D printing ceramic core body to obtain an infiltrated photocuring 3D printing ceramic core body; wherein, the ceramic precursor resin solution with the viscosity of 0.1-30cp is adopted to carry out infiltration treatment on the photocuring 3D printing ceramic core body.
Wherein the steps are as follows: and (3) soaking the photocuring 3D printing ceramic core body in the ceramic precursor resin solution for 1-5h, and then drying in an oven at 120-180 ℃ for 1-3h (preferably, circularly soaking and drying for 2-5 times) to obtain the impregnated photocuring 3D printing ceramic core body.
It should be noted here that: the ceramic precursor resin is a resin that can react to form a ceramic material in a sintering step (during the sintering process, most of the ceramic precursor resin is converted into ceramic, and a small part of the ceramic precursor resin overflows in the form of gas such as carbon monoxide and carbon dioxide).
The ceramic precursor resin is one or more of polysiloxane, polycarbosilane, polysilazane, polyborosilazane, polysilane and polytitanocarbosilane.
The molecular structure of the polysiloxane is as follows:
the molecular structure of polycarbosilane is as follows:
the molecular structure of polysilazane is as follows:
the molecular structure of polyborosilazane is as follows:
the molecular structure of polysilane is as follows:
the molecular structure of the polytitanocarbosilane is as follows:
it should be noted here that: the ceramic precursor resin is selected by ensuring the viscosity of the ceramic precursor resin solution prepared from the ceramic precursor resin and the solvent to be 0.1-30cp, and the side chain group (such as R) of the ceramic precursor resin 1 、R 2 、R 3 、R 4 ) The selection of the ceramic precursor resin is not particularly limited, and the ceramic precursor resin may be partially decomposed into gas which overflows and partially converted into ceramics (mostly crystalline oxide ceramics, crystalline non-oxide ceramics, and less amorphous non-oxide ceramics) in the re-sintering treatment step. Therefore, through the control of the re-sintering treatment process (temperature, time and atmosphere), the ceramic precursor resin is converted into the composite coating containing the amorphous non-oxide ceramic, the crystalline non-oxide ceramic and the crystalline oxide ceramic, and the composite coating containing the components has excellent strength (such as bending strength) and certain toughness, so that the problem of cracking of the composite coating can be avoided. Here, the crystalline oxide ceramic has excellent high-temperature strength, but is highly brittle and easily cracked; the amorphous non-oxide ceramic and the crystalline non-oxide ceramic have good toughness but low high-temperature strength; while the composite coating combines the advantages of both.
In order to ensure the open porosity (reduce the closed porosity) of the finally obtained photocuring 3D printing ceramic core, the invention selects a ceramic precursor resin solution with the viscosity of 0.1-30 cp. Preferably, the ceramic precursor resin solution is prepared from a ceramic precursor resin and a solvent, and the volume ratio of the ceramic precursor resin to the solvent is (1-2): (10-20), preferably 1: (10-20). Preferably, the solvent is 1, 6-hexanediol diacrylate.
5) And (4) carrying out re-sintering treatment on the impregnated photocuring 3D printing ceramic core body to obtain the photocuring 3D printing impregnation enhanced ceramic core.
Here, in order to convert the impregnated ceramic precursor resin into a composite coating including amorphous non-oxide ceramics, crystalline non-oxide ceramics, and crystalline oxide ceramics. The steps for the re-sintering treatment are as follows:
wherein, the step of the re-sintering treatment comprises the following steps: heating the impregnated photocuring 3D printing ceramic core body to 600-700 ℃, preserving heat for 600-1200min, and cooling; preferably, the heating rate is 40-60 ℃/h, and the cooling rate is 40-60 ℃/h; preferably, the atmosphere of the re-sintering treatment is N 2 And O 2 A mixed atmosphere of the composition; wherein N is 2 In a volume fraction of 50-80%, O 2 The volume fraction of (A) is 20-50%.
In summary, the above scheme of the embodiment of the present invention mainly has the following three creations:
(1) Higher strength (e.g., flexural strength) is desirable because the ceramic core needs to maintain an open porosity of about 20%. The higher porosity necessarily results in a limited bonding portion (sintering neck) between the ceramic particles, resulting in a lower strength of the core. In order to increase the strength, the sintering neck is reinforced by impregnation (as shown in fig. 4).
(2) In order to prevent the ceramic precursor resin solution from blocking the open pores of the core in the impregnation process, the viscosity of the ceramic precursor resin solution (the ratio of the ceramic precursor resin to the solvent) is regulated to prevent the pores of the core from being blocked.
(3) In order to solve the problem of cracking of the dip reinforced coating formed by dipping, a composite coating concept is provided, the components of the dip reinforced coating are regulated and controlled through controlling the atmosphere of re-sintering, and the cracking problem of the dip reinforced coating is improved through the components.
The invention is further illustrated by the following specific experimental examples:
example 1
The photocuring 3D printing ceramic core is prepared in this embodiment, wherein the raw materials and the parts by weight are as follows: 50 parts by weight of a reinforcing agent, 30 parts by weight of a mineralizer, and 20 parts by weight of a light-curable resin premix (wherein, in the light-curable resin premix, the volume fraction of the photosensitive resin is 80%, and the volume fraction of the diluent is 20%). The enhancer is SiO with particle size of 80 μm 2 Powder and 50 μm Al 2 O 3 Powder (SiO) 2 Powder and Al 2 O 3 The mass ratio of the powder is 7; the mineralizer is ZrO with particle size of 10nm 2 Powder; the photosensitive resin is prepared by mixing 3:2, tricyclodecyl dimethanol diacrylate and octadecyl acrylate; the diluent is 1, 6-hexanediol diacrylate; the ceramic precursor resin solution is obtained by mixing polysiloxane, polycarbosilane and 1, 6-hexanediol diacrylate according to the volume ratio of 1.
The preparation method specifically comprises the following steps:
1) Mechanically mixing the reinforcer and the mineralizer to obtain mixed powder;
and (3) stirring the light-cured resin premix liquid at the temperature of 80 ℃ while keeping the temperature, slowly adding the mixed powder into the light-cured resin premix liquid while stirring, and keeping the temperature and stirring for 3.5 hours to obtain the light-cured 3D printing ceramic core slurry.
2) Setting photocuring 3D printing parameters: the curing thickness was set at 100 μm and the curing power was set at 35nW/cm 2 The single layer curing time was set to 10s. And carrying out 3D printing photocuring treatment on the photocuring 3D printing ceramic core slurry through photocuring 3D printing equipment to obtain a ceramic core biscuit.
3) And degreasing and sintering the ceramic core biscuit to obtain the photocuring 3D printing ceramic core body.
Wherein the degreasing is carried outThe processing steps include: at N 2 And O 2 In a mixed atmosphere of (N) 2 Is 70% by volume, O 2 The volume fraction of (b) is 30%), heating to 550 ℃ at a heating rate of 60 ℃/h, keeping the temperature for 180min, and then cooling at a cooling rate of 60 ℃/h.
The sintering treatment comprises the following steps: at N 2 And O 2 In a mixed atmosphere of (N) 2 Is 50% by volume of O 2 50 percent of the total volume of the mixture), heating to 1250 ℃ at the heating rate of 120 ℃/h, preserving heat for 360min, and then cooling at the cooling rate of 120 ℃/h.
4) And (3) putting the photocuring 3D printing ceramic core body into a ceramic precursor resin solution for soaking for 1h, taking out, and putting into a 120 ℃ drying oven for drying for 1h. And (5) circularly performing the step to obtain the impregnated photocuring 3D printing ceramic core body.
5) And placing the infiltrated photocuring 3D printing ceramic core body into a sintering furnace for re-sintering treatment to obtain the photocuring 3D printing ceramic core.
Wherein, the step of the re-sintering treatment is as follows: at N 2 And O 2 In a mixed atmosphere of (N) 2 Is 50% by volume of O 2 The volume fraction of the water is 50 percent), the temperature is increased to 700 ℃ at the heating rate of 40 ℃/h, the temperature is kept for 800min, and then the temperature is reduced at the cooling rate of 40 ℃/h.
Fig. 2 shows an SEM image of the photocured 3D printed ceramic core prepared in this example, and it can be seen from fig. 2 that: the sintering neck of the photocuring 3D printing ceramic core prepared by the embodiment is strengthened, and the open pore is not blocked; and the impregnation strengthening coating for strengthening the sintering neck has no cracks.
Example 2
The photocuring 3D printing ceramic core is prepared in the embodiment, wherein the core comprises the following raw materials in parts by weight: 60 parts by weight of a reinforcing agent, 10 parts by weight of a mineralizer, and 30 parts by weight of a light-curable resin premix (wherein, in the light-curable resin premix, the volume fraction of the photosensitive resin is 60% and the volume fraction of the diluent is 40%). The enhancer is SiO with particle size of 50 μm 2 Powder and 100 μm Al 2 O 3 Powder (SiO) 2 Powder and Al 2 O 3 The mass ratio of the powder is 1; zrSiO with the grain diameter of 50nm is selected as the mineralizer 2 Powder and K 2 O powder (ZrSiO) 2 Powder and K 2 The mass ratio of O powder is 1); the photosensitive resin is prepared from a mixture of 1:3, propoxylated neopentyl glycol diacrylate and alkoxylated pentaerythritol tetraacrylate; the diluent is tripropylene glycol diacrylate; the ceramic precursor resin solution is obtained by mixing polysilazane, polyborazane and 1, 6-hexanediol diacrylate according to the volume ratio of 1.
The preparation method specifically comprises the following steps:
1) Mechanically mixing the reinforcer and the mineralizer to obtain mixed powder;
and (3) stirring the light-cured resin premix liquid at the temperature of 120 ℃ while keeping the temperature, slowly adding the mixed powder into the light-cured resin premix liquid while stirring, and keeping the temperature and stirring for 4 hours to obtain the light-cured 3D printing ceramic core slurry.
2) Setting photocuring 3D printing parameters: the curing thickness was set at 150 μm and the curing power was set at 40nW/cm 2 The monolayer cure time was set to 15s. And carrying out 3D printing photocuring treatment on the photocuring 3D printing ceramic core slurry through photocuring 3D printing equipment to obtain a ceramic core biscuit.
3) And (4) degreasing and sintering the ceramic core biscuit to obtain the photocuring 3D printing ceramic core body.
Wherein the degreasing treatment comprises the following steps: at N 2 And O 2 In a mixed atmosphere of (N) 2 Is 70% by volume, O 2 The volume fraction of (b) is 30%), heating to 600 ℃ at a heating rate of 100 ℃/h, keeping the temperature for 120min, and then cooling at a cooling rate of 100 ℃/h.
The sintering treatment comprises the following steps: in N 2 And O 2 In a mixed atmosphere of (N) 2 Is 50% by volume, O 2 The volume fraction of (b) is 50%), heating to 1500 ℃ at a heating rate of 80 ℃/h, keeping the temperature for 300min, and then cooling at a cooling rate of 80 ℃/h.
4) And (3) putting the photocuring 3D printing ceramic core body into a ceramic precursor resin solution for soaking for 5h, taking out, putting into a drying oven at 180 ℃ for drying for 3h, and obtaining the impregnated photocuring 3D printing ceramic core body.
5) And putting the impregnated photocuring 3D printing ceramic core body into a sintering furnace for re-sintering treatment to obtain the photocuring 3D printing ceramic core.
Wherein, the step of the re-sintering treatment is as follows: in N 2 And O 2 In a mixed atmosphere of (N) 2 Is 50% by volume, O 2 The volume fraction of (b) is 50%), heating to 600 ℃ at a heating rate of 60 ℃/h, keeping the temperature for 1200min, and then cooling at a cooling rate of 60 ℃/h.
Example 3
This example prepared a photocurable 3D printing ceramic core, differing from example 1 in that: the ceramic precursor resin is polysilane, wherein the ceramic precursor resin solution is obtained by mixing polysilane and 1, 6-hexanediol diacrylate according to the volume ratio of 1; and the viscosity of the ceramic precursor resin solution was 10cp.
The other steps and parameters were identical to those of example 1.
Example 4
This example prepared a photocurable 3D printing ceramic core, differing from example 1 in that: the ceramic precursor resin is selected from poly-titanium carbosilane, wherein the ceramic precursor resin solution is obtained by mixing poly-titanium carbosilane and 1, 6-hexanediol diacrylate according to the volume ratio of 1; and the viscosity of the ceramic precursor resin solution was 30cp.
The other steps and parameters were identical to those of example 1.
Comparative example 1
Comparative example 1 a photo-cured 3D printed ceramic core was prepared, differing from example 1 in that no infiltration treatment was performed. The other steps and parameters were identical to those of example 1.
Specifically, comparative example 1 prepares a photocuring 3D printing ceramic core, wherein the raw materials and parts by weight are as follows: 50 parts by weight of a reinforcing agent, 30 parts by weight of a mineralizer, and 20 parts by weight of a light-curable resin premix (c) ((ii))Wherein, in the photo-curing resin premix, the volume fraction of the photosensitive resin is 80%, and the volume fraction of the diluent is 20%). The enhancer is SiO with particle size of 80 μm 2 Powder and 50 μm Al 2 O 3 Powder (SiO) 2 Powder and Al 2 O 3 The mass ratio of the powder is 7; the mineralizer is ZrO with particle size of 10nm 2 Powder; the photosensitive resin is prepared by mixing 3:2 tricyclodecyl dimethanol diacrylate and octadecyl acrylate; the diluent is 1, 6-hexanediol diacrylate. The preparation steps are as follows:
1) Mechanically mixing the enhancer and the mineralizer to obtain mixed powder;
and (3) stirring the light-cured resin premix liquid at the temperature of 80 ℃ while keeping the temperature, slowly adding the mixed powder into the light-cured resin premix liquid while stirring, and keeping the temperature and stirring for 3.5 hours to obtain the light-cured 3D printing ceramic core slurry.
2) Setting photocuring 3D printing parameters: the curing thickness was set at 100 μm and the curing power was set at 35nW/cm 2 The monolayer curing time was set to 10s. And carrying out 3D printing photocuring treatment on the photocuring 3D printing ceramic core slurry through photocuring 3D printing equipment to obtain a ceramic core biscuit.
3) And degreasing and sintering the ceramic core biscuit to obtain the photocuring 3D printing ceramic core.
Wherein the degreasing treatment comprises the following steps: at N 2 And O 2 In a mixed atmosphere of (N) 2 Is 70% by volume, O 2 The volume fraction of (b) is 30%), heating to 550 ℃ at a heating rate of 60 ℃/h, keeping the temperature for 180min, and then cooling at a cooling rate of 60 ℃/h.
The sintering treatment comprises the following steps: at N 2 And O 2 In a mixed atmosphere of (N) 2 Is 50% by volume of O 2 50 percent of the total volume of the mixture), heating to 1250 ℃ at the heating rate of 120 ℃/h, preserving heat for 360min, and then cooling at the cooling rate of 120 ℃/h.
FIG. 3 is an SEM image of the ceramic core prepared in comparative example 1; as can be seen from fig. 3: the ceramic particles of the ceramic core which is not subjected to impregnation treatment and re-sintering treatment have an unsintered phenomenon, no obvious sintering necks appear among the particles, and a large number of pores and cracks appear among the ceramic particles.
Comparative example 2
Comparative example 2 a photo-cured 3D printed ceramic core was prepared, differing from example 1 in that the atmosphere of the re-sintering process was vacuum and the other steps and parameters were completely identical.
Comparative example 3
Comparative example 3 a photo-cured 3D printed ceramic core was prepared, differing from example 1 in that the atmosphere of the re-sintering process was pure oxygen, and the other steps and parameters were completely identical.
The ceramic cores prepared in examples 1 to 4 and comparative examples 1 to 3 were tested for room temperature flexural strength, porosity, crack incidence of the dip reinforced coating, and the like, and the test data are shown in table 1.
TABLE 1
Note: the room temperature bending strength in the table is tested according to the aviation industry standard HB 5353.3-2004; the open porosity is tested according to the standard HB5353.1-2004 in the aviation industry; the crack incidence of the dipping strengthening coating adopts a GB/T25995-2010 fine ceramic density and apparent porosity test method.
From the above examples and the data in table 1, it can be seen that:
(1) Compared with the schemes of comparative example 1, comparative example 2 and comparative example 3, the ceramic core prepared by the embodiment of the invention has excellent bending strength on the basis of ensuring higher open porosity, and the crack cracking rate of the impregnation strengthening coating on the ceramic core is low.
(2) With the scheme of comparative example 2, although the impregnation treatment was also performed, since the control of the atmosphere was vacuum, the reinforcing effect of the ceramic core prepared in comparative example 2 was not sufficiently significant.
(3) Although the solution of the comparative example 3 is also subjected to the dipping treatment, the crack cracking rate of the dipping strengthening layer on the ceramic core prepared by the comparative example 3 is high because the atmosphere is controlled to be oxygen, and the strengthening effect is not very obvious.
The above embodiments are only part of the application examples of the present invention, but the present invention is not limited to the above embodiments, and any method or process similar to the above embodiments may be used to achieve the technical effects of the present invention.
Claims (22)
1. A preparation method of a photocuring 3D printing impregnation reinforced ceramic core is characterized by comprising the following steps:
1) Preparing light-emitting curing 3D printing ceramic core slurry;
2) Carrying out photocuring 3D printing treatment on the photocuring 3D printing ceramic core slurry to obtain a ceramic core biscuit;
3) Degreasing and sintering the ceramic core biscuit to obtain a photocuring 3D printing ceramic core body;
4) Performing infiltration treatment and drying treatment on the photocuring 3D printing ceramic core body to obtain an infiltrated photocuring 3D printing ceramic core body; impregnating the photocuring 3D printing ceramic core body with a ceramic precursor resin solution; wherein the viscosity of the ceramic precursor resin solution is 0.1-30cp; the ceramic precursor resin in the ceramic precursor resin solution is one or more of polysiloxane, polycarbosilane, polysilazane, polyborosilazane, polysilane and polytitanocarbosilane; wherein the step 4) comprises: placing the photocuring 3D printing ceramic core body into the ceramic precursor resin solution, soaking for 1-5 hours for infiltration treatment, then taking out, and drying to obtain the photocuring 3D printing ceramic core body after infiltration; wherein, the steps of impregnating treatment and drying treatment are carried out at least once;
5) Carrying out re-sintering treatment on the infiltrated photocuring 3D printing ceramic core body, so that the ceramic precursor resin on the infiltrated photocuring 3D printing ceramic core body is converted into a dipping strengthening coating for strengthening a sintering neck, and obtaining the photocuring 3D printing dipping strengthening ceramic core; the dipping strengthening coating is a composite coating, and the components of the dipping strengthening coating comprise amorphous non-oxide ceramics, crystalline non-oxide ceramics and crystalline oxide ceramics.
2. The method for preparing a photocuring 3D printing impregnated reinforced ceramic core as claimed in claim 1, wherein in step 4):
the ceramic precursor resin solution is prepared from ceramic precursor resin and a solvent, and the volume ratio of the ceramic precursor resin to the solvent is (1-2): (10-20).
3. The method for preparing a photocuring 3D printing impregnation reinforced ceramic core as claimed in claim 2, wherein the volume ratio of the ceramic precursor resin to the solvent is 1: (10-20).
4. The method of making a photocured 3D printing dip-reinforced ceramic core as recited in claim 2 wherein the solvent is 1, 6-hexanediol diacrylate.
5. The method for preparing a photocuring 3D printing dip-enhanced ceramic core as recited in any of claims 1-4 wherein in step 4):
repeating the steps of impregnating and drying for 2-5 times; and/or
The temperature of the drying treatment is 120-180 ℃, and the time of the drying treatment is 1-3h.
6. The method of making a photocured 3D printed dip-reinforced ceramic core as recited in any of claims 1-4 wherein in step 5):
the step of the resintering process comprises: and heating the impregnated photocuring 3D printing ceramic core body to 600-700 ℃, and cooling after heat preservation for 600-1200 min.
7. The method of preparing a photocured 3D printed dip-reinforced ceramic core as recited in claim 6, wherein in step 5):
the heating rate is 40-60 ℃/h, and the cooling rate is 40-60 ℃/h; and/or
The atmosphere of the re-sintering treatment is N 2 And O 2 A mixed atmosphere of the composition; wherein N is 2 In a volume fraction of 50-80%, O 2 The volume fraction of (A) is 20-50%.
8. The method of making a photocured 3D printed dip-reinforced ceramic core as recited in any of claims 1-4 wherein in step 1):
the photo-curing 3D printing ceramic core slurry comprises 50-80 parts by weight of a reinforcing agent, 10-30 parts by weight of a mineralizer and 20-40 parts by weight of a photo-curing resin premixed liquid.
9. The method for preparing the photocured 3D printed dip-reinforced ceramic core as recited in claim 8, wherein the reinforcement agent is SiO 2 、Al 2 O 3 One or two of them.
10. The method for preparing the photocuring 3D printing dip-enhanced ceramic core as recited in claim 8, wherein the grain size of the reinforcing agent is 50-100 μ ι η.
11. The method of making a photocured 3D printed dip-reinforced ceramic core as recited in claim 8, wherein the mineralizer has a particle size of 10-100nm.
12. The method of preparing a photocured 3D printed dip-reinforced ceramic core as recited in claim 8, wherein the mineralizer is ZrO 2 、ZrSiO 4 、Na 2 O、K 2 One or more of O.
13. The method for preparing the photocuring 3D printing impregnation reinforced ceramic core as claimed in claim 8, wherein the photocuring resin premix is prepared by mixing a photosensitive resin and a diluent; wherein the volume fraction of the photosensitive resin is 60-80%; the volume fraction of the diluent is 20-40%.
14. The method of making a photocurable 3D printing dip reinforced ceramic core as recited in claim 13 wherein the photosensitive resin is one or more of tricyclodecyl dimethanol diacrylate, octadecyl acrylate, propoxylated neopentyl glycol diacrylate, alkoxylated pentaerythritol tetraacrylate.
15. The method for preparing a photocured 3D printing dip-reinforced ceramic core as recited in claim 13 wherein the diluent is one or both of 1, 6-hexanediol diacrylate and tripropylene glycol diacrylate.
16. The method for preparing a photocured 3D printed impregnated reinforced ceramic core as recited in claim 8, wherein said step 1) comprises:
mechanically mixing the enhancer and the mineralizer to obtain mixed powder;
and (3) preserving heat and stirring the light-cured resin premixed solution at the temperature of 60-120 ℃, adding the mixed powder while stirring, preserving heat and stirring for 3-4h to obtain the light-cured 3D printing ceramic core slurry.
17. The method for preparing a photocured 3D printed dip-reinforced ceramic core as recited in any of claims 1-4, wherein in step 2) the photocured 3D printing process parameters are set as follows:
the curing thickness is set to be 50-150 μm, and the curing power is set to be 25-45nW/cm 2 The single-layer curing time is set to be 5-30s.
18. The method of preparing a photocuring 3D printing dip-enhanced ceramic core as recited in any of claims 1-4 wherein in step 3):
the step of degreasing treatment comprises: and heating the ceramic core biscuit to 550-600 ℃, preserving heat for 120-180min, and cooling.
19. The method for preparing a photocuring 3D printing impregnated reinforced ceramic core as claimed in claim 18, wherein in the step of degreasing treatment:
the heating rate is 60-100 ℃/h, and the cooling rate is 60-100 ℃/h; and/or
The atmosphere of the degreasing treatment is N 2 And O 2 A mixed atmosphere of the composition; wherein, N 2 In a volume fraction of 50-80%, O 2 The volume fraction of (A) is 20-50%.
20. The method of preparing a photocured 3D printing impregnated reinforced ceramic core as claimed in claim 14 wherein in step 3):
the sintering treatment comprises the following steps: and heating the ceramic core biscuit subjected to degreasing treatment to 1000-1700 ℃, and cooling after keeping the temperature for 240-360 min.
21. The method of making a photocured 3D printed dip-reinforced ceramic core as recited in claim 20, wherein in the step of sintering treatment:
the heating rate is 60-120 ℃/h, and the cooling rate is 60-120 ℃/h; and/or
The atmosphere of the sintering treatment is N 2 And O 2 A mixed atmosphere of the composition; wherein N is 2 In a volume fraction of 50-80%, O 2 The volume fraction of (A) is 20-50%.
22. The photocuring 3D printing impregnation reinforced ceramic core is characterized in that the bending strength of the photocuring 3D printing impregnation reinforced ceramic core is 15-40MPa, and the porosity of a hole is 25-40%;
wherein the photocuring 3D printing impregnation reinforced ceramic core is prepared by the preparation method of the photocuring 3D printing impregnation reinforced ceramic core as claimed in any one of claims 1 to 21.
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