CN113173792A - Resin suitable for 3D printing of ceramic and preparation method thereof - Google Patents
Resin suitable for 3D printing of ceramic and preparation method thereof Download PDFInfo
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- CN113173792A CN113173792A CN202110380301.1A CN202110380301A CN113173792A CN 113173792 A CN113173792 A CN 113173792A CN 202110380301 A CN202110380301 A CN 202110380301A CN 113173792 A CN113173792 A CN 113173792A
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- 239000011347 resin Substances 0.000 title claims abstract description 49
- 229920005989 resin Polymers 0.000 title claims abstract description 49
- 239000000919 ceramic Substances 0.000 title claims abstract description 41
- 238000010146 3D printing Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000003085 diluting agent Substances 0.000 claims abstract description 45
- 238000002474 experimental method Methods 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000007639 printing Methods 0.000 claims abstract description 9
- 239000003086 colorant Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 7
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 7
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 7
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 4
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 2
- JZEXORLUKMQOFA-UHFFFAOYSA-N 2-(1-ethoxyethyl)-2-(hydroxymethyl)propane-1,3-diol prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCOC(C)C(CO)(CO)CO JZEXORLUKMQOFA-UHFFFAOYSA-N 0.000 claims description 2
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 2
- FHNINJWBTRXEBC-UHFFFAOYSA-N Sudan III Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC(C=C1)=CC=C1N=NC1=CC=CC=C1 FHNINJWBTRXEBC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004364 calculation method Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 2
- 238000000691 measurement method Methods 0.000 claims description 2
- 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 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 2
- 238000010187 selection method Methods 0.000 claims description 2
- 229940099373 sudan iii Drugs 0.000 claims description 2
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 3
- 239000002002 slurry Substances 0.000 abstract description 18
- 239000007787 solid Substances 0.000 abstract description 6
- 238000005457 optimization Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 description 11
- 238000000498 ball milling Methods 0.000 description 9
- 238000001723 curing Methods 0.000 description 9
- 101000720524 Gordonia sp. (strain TY-5) Acetone monooxygenase (methyl acetate-forming) Proteins 0.000 description 8
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000000110 selective laser sintering Methods 0.000 description 1
- 210000004916 vomit Anatomy 0.000 description 1
- 230000008673 vomiting Effects 0.000 description 1
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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
- C04B35/63—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 using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63424—Polyacrylates; Polymethacrylates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- 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
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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
- C04B35/62605—Treating the starting powders individually or as mixtures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
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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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—Carbon
- C04B2235/424—Carbon black
Abstract
The invention discloses a resin suitable for 3D printing of ceramics, which is characterized in that the raw materials of the resin comprise a photoinitiator, a prepolymer, a diluent and a coloring agent, the prepolymer and the diluent are selected, a gradient experiment is carried out on the addition amount of the initiator, and the initiator with the highest gel content is calculated; under the condition of fixing the content of the prepolymer, adding different diluents, adding an initiator with the highest gel content, calculating the curing thickness measured under different curing energies, and selecting the diluent with the smallest critical exposure; fixing the types of the prepolymer and the diluent, performing a gradient experiment on the addition amount of the diluent, and selecting the diluent with the highest gel content as the addition amount of the diluent. The invention can obtain the slurry which has low resin viscosity, high curing speed, high solid content and good rheological property and is mixed with the ceramic powder, and the slurry meets the printing requirement; the optimization method is simple, and the resin preparation period is short.
Description
Technical Field
The invention relates to a resin suitable for 3D printing of ceramic and a preparation method thereof, and belongs to the technical field of additive manufacturing.
Background
The ceramic material has excellent properties of high strength, wear resistance, corrosion resistance and the like, and is widely applied in the fields of aerospace, petrochemical industry, biomedical use and the like. The traditional forming process is to dry the ceramic slurry into a green body after opening the die and then to sinter the green body at high temperature to obtain the ceramic product. This forming method is limited by the opening of the mold, which limits the development of ceramic products with complications.
Various 3D printing forming technologies developed in recent years have added another path for ceramic forming and have realized non-mold production. At present, the ceramic 3D printing technology is mainly a selective laser sintering technology (SLM), a fused deposition technology (FDM), a direct writing three-dimensional printing technology (DIM), a stereo photo-curing technology (SL), a digital light processing technology (DLP), and the like. Because the forming mode is different from the printing material, each printing technology has respective advantages and disadvantages.
The DLP type 3D printing technology is a photocuring forming technology which is developed by adopting a Digital Micromirror Device (DMD) as a main key processing original, can enable each layer of image to be directly projected into the whole curing area, realizes surface curing forming, has low requirement on the viscosity of ceramic slurry, and can greatly improve the solid content of the slurry.
Because the DLP type 3D printing technology takes photosensitive slurry prepared from photosensitive resin and ceramic powder as raw materials, a printed blank cannot be directly used as a ceramic material, and the blank needs to be subjected to a degreasing process to remove cured polymers and a sintering process to improve the density and strength of the blank. Therefore, in order to avoid the problems of cracking of a blank body and the like in the processes of degreasing and sintering, the slurry needs to have higher solid content, higher curing speed under the same curing condition and better rheological property so as to be quickly paved in the printing process. The addition of the ceramic powder can greatly increase the viscosity of the photosensitive resin and reduce the rheological property, so that the preparation of the resin suitable for 3D printing of ceramics is of great importance to meet the molding characteristics of high solid content, low viscosity and fast curing.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the existing 3D printing ceramic resin is added with ceramic powder, so that the viscosity is too high and the rheological property is poor.
In order to solve the technical problems, the invention provides a resin suitable for 3D printing of ceramics, the raw materials of the resin comprise a photoinitiator, a prepolymer, a diluent and a coloring agent, and the selection method of the types and the addition amounts of the raw materials comprises the following steps:
step 1): selecting a prepolymer and a diluent, performing a gradient experiment on the addition amount of the initiator, and calculating the type and the addition amount of the initiator when the gel content is highest;
step 2): under the condition of fixing the content of the prepolymer, adding different diluents, adding the initiator with the highest gel content in the step 1) and the addition amount thereof, and measuring the curing thickness under different curing energies according to the calculation of the Beer-Lambert theorem:
Cd＝Dp(lnE-lnEc)
wherein, CdE is the average exposure on the resin side for the cured thickness; ecThe critical exposure is obtained by a fitting curve;
fitting Dp-EcStraight line to obtain projection depth and critical exposure, the projection depth is slope, the critical exposure is the exponent of natural logarithm e, the exponential power is cut offSelecting the diluent type with the minimum critical exposure from the absolute value of the slope;
step 3): fixing the types of the prepolymer and the diluent, and performing a gradient experiment on the addition amount of the diluent; the same gel content measurement method as in S1 was used, and the diluent content having the highest gel content was selected as the amount of diluent to be added.
Preferably, the gradient experiment in step 1) is specifically: introducing the circular slices into a printer, setting printing power and exposure time, obtaining at least 3 circular solidified pieces in each group of experiment, cleaning and drying by using alcohol, weighing, and recording as m0(ii) a Putting the weighed circular cured slices into the same beaker in groups, carrying out ultrasonic treatment for 1 hour under the condition of absolute ethyl alcohol, drying, weighing, and recording as m1(ii) a The gel content is calculated to be m1/m0X 100%, using origin software to draw a gel conversion rate curve, and selecting the initiator type and content with the highest gel content.
Preferably, the resin comprises 0.5-5% of photoinitiator, 30-90% of prepolymer, 10-60% of diluent and the balance of coloring agent in percentage by mass.
Preferably, the photoinitiator is TPO or 819, and the addition amount of the photoinitiator is 1-3%.
Preferably, the prepolymer is at least one of ditrimethylolpropane acrylate, urethane acrylate, epoxy acrylate and 3 (ethoxy) trimethylolpropane triacrylate, and the addition amount of the prepolymer is 57-86%.
Preferably, the diluent is at least one of 4-acryloyl morpholine, 1, 6-hexanediol diacrylate and propoxylated neopentyl glycol diacrylate, and the addition amount of the diluent is 13-42%.
Preferably, the dyeing agent is carbon black or Sudan III, and the addition amount of the dyeing agent is 0.1-1%.
Preferably, the resin further comprises a dispersant, the resin is matched with the ceramic powder during printing, and the mass ratio of the resin to the ceramic powder is 1: 1-3, preferably 1: 1.2-2.3, wherein the dosage of the dispersant is 0.01-0.15 of the ceramic powder: 1, preferably 2%.
Preferably, the dispersant is at least one of span 80, triton and tween 20.
The invention also provides a preparation method of the resin suitable for 3D printing ceramics, which comprises the steps of adding the photoinitiator into the prepolymer and the diluent, uniformly stirring, adding the coloring agent, stirring and carrying out ultrasonic treatment.
Compared with the prior art, the invention has the following beneficial effects:
(1) by the optimization method of the resin, the obtained resin has low viscosity and high curing speed, and the slurry prepared by mixing the resin with the ceramic powder has high solid content and good rheological property and meets the printing requirement;
(2) the optimization method is simple, the resin preparation period is short, and partial prospects can be provided for industrialization of 3D printing ceramics.
Drawings
FIG. 1 is a flow chart of a method of making a resin provided by the present invention;
FIG. 2 is a graph showing the relationship between the amount of photoinitiator added and the gel content of a polymer;
FIG. 3 shows the cured thickness at different exposure intensities;
FIG. 4 is a graph showing the relationship between the amount of ACMO added and the gel content;
FIG. 5 is a graph of solids content versus viscosity;
FIG. 6 is a graph of shear rate versus viscosity.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Example 1
A preparation method of resin suitable for 3D printing of ceramics comprises the following steps:
s1, selecting Di-TMPTA 16g as prepolymer and HDDA 4g as diluent, adding TPO and 819 at 0.2g, 0.4g, 0.6g, 0.8g and 1g, totally for 10 experiments. A10 mm circular cut piece was introduced into the printer, and the print power was set to 40% (the actual power was 24 mW/cm)2) Exposure time was 5s, 3 round cured parts were obtained for each set of experiments, washed with alcohol, dried and weighed as m0. Will be weighedPutting the circular solidified slices into 10 beakers in groups, carrying out ultrasonic treatment for 1 hour under the condition of absolute ethyl alcohol, weighing after drying, and recording as m1. Gel conversion ═ m1/m0X 100%, using origin software to plot a gel conversion curve, as shown in fig. 2, 819 shows the highest gel content at 2% addition, and the initiator is determined to be 819 while the addition is 2 wt% (S1 is the step of determining the type and addition of the photoinitiator in fig. 1);
s2, selecting Di-TMPTA 16g as prepolymer, 4g each of ACMO, HDDA and (PO)2-NPGDA as diluent, 8190.4 g as initiator, and totally 3 experiments. At 10% (12 mW/cm)2Power) exposure for 2s, 3s, 4s, 5s, 6s, 7s, 8s, 9s to determine the cure thickness, and plotting Dp-Ec curves using origin for 24 sets of data, as shown in fig. 3, lnE without diluent, 30% HDDA, 30% ACMO, 30% NPG2PODAc2.5255, 2.6378, 2.0121 and 2.5781 respectively, and the critical exposure of the resin after the addition of each diluent is calculated to be 12.50mJ/cm2、13.98mJ/cm2、7.48mJ/cm2、13.17mJ/cm2Selecting the diluent as ACMO (S2 is the step of determining the type of the diluent in FIG. 1);
s3, prepolymer measurement was carried out in the same manner as in S1: diluent 9: 1. 8.5: 1.5, 8: 2. 7.5: 2.5, 7: 3. 6.5: 3.5, 6: gel conversion under 4 conditions, as shown in fig. 4, when the ACMO addition amount is 45%, the gel content of the photosensitive resin is the highest, and finally the diluent addition amount is selected to be 45% (S2 is the step of determining the diluent addition amount in fig. 1);
s4, taking 70g of Di-TMPTA and 30g of ACMO resin in an opaque PP bottle, adding 2g of 819 photoinitiator, and performing ultrasonic treatment for 1h at the temperature of 40 ℃; 0.204g of carbon black was weighed before adding the ceramic powder. The viscosity of the photosensitive resin was measured to be 86.8 mPas using a rotational viscometer with a No. 1 spindle at a rotation speed of 200 rpm.
S5, 40g of the resin prepared above was put into a 100mL ball mill pot, 0.08g of carbon black was added, and 17.1g of Al was added2O3Finally, 0.342g of Tween 20 is added and ball-milled for 1h, and the viscosity of the slurry is measured; then adding 4.4g of Al into the same ball milling tank2O3Then, 0.088g of vomit was addedBall milling for 1h after the temperature is 20 ℃, and measuring the viscosity of the slurry; then 5.2g of Al are added into the same ball milling tank2O3Then adding 0.104g of Tween 20, ball-milling for 1h, and measuring the viscosity of the slurry; then 6.1g of Al is added into the same ball milling tank2O3Then adding 0.122g of Tween 20, ball-milling for 1h, and measuring the viscosity of the slurry; then 8.9g of Al are added into the same ball milling tank2O3Then adding 0.178g of Tween 20, ball-milling for 1h, and measuring the viscosity of the slurry; then 6.4g of Al are added into the same ball milling tank2O3And then 0.128g of Tween 20 is added and ball milling is carried out for 1h, and the viscosity of the slurry is measured. When Al is shown in FIG. 52When the amount of O3 added was 58%, the viscosity of the slurry increased sharply, but was less than 50000 mPas. Then 58 percent of Al is added2O3The viscosity of the slurry was measured at different rotational speeds, as shown in fig. 6, and as the rotational speed of the rotational viscometer increased, the viscosity of the slurry was measured to decrease, and the slurry appeared as a shear-thinned fluid, satisfying the printing conditions, so 58% Al was selected2O3Is the final addition amount.
Example 2
A preparation method of resin suitable for 3D printing of ceramics comprises the following steps:
s1, selecting Di-TMPTA8g and TMP (EO)3TA 8g as prepolymer, ACMO 4g as diluent, adding TPO 0.2g, TPO 0.4g, TPO 0.6g, TPO 0.8g, TPO 1g and TPO 819 g, and totally 10 sets of experiments. A10 mm circular cut piece was introduced into the printer, and the print power was set to 40% (the actual power was 24 mW/cm)2) Exposure time was 5s, 3 round cured parts were obtained for each set of experiments, washed with alcohol, dried and weighed as m0. Putting the weighed circular solidified slices into 10 beakers in groups, carrying out ultrasonic treatment for 1 hour under the condition of absolute ethyl alcohol, drying, weighing, and recording as m1. Gel conversion ═ m1/m0X 100%, using origin software to draw a gel conversion rate curve, determining that the initiator is 819 and the addition amount is 2 wt%;
s2, selecting Di-TMPTA8g and TMP (EO)3TA 8g as prepolymer, ACMO, HDDA (PO) as diluent24g each of NPGDA and 8190.4 g of initiator, for 3 experiments. At 10% (12 mW/cm)2Power) exposure for 2s, 3s, 4s, 5s, 6s, 7s, 8s, and 9s, curing thickness was measured, 24 sets of data were obtained, and Dp-Ec was plotted using originCalculating critical exposure, and selecting (PO)2-NPGDA as diluent;
s3, prepolymer measurement was carried out in the same manner as in S1: diluent 9: 1. 8.5: 1.5, 8: 2. 7.5: 2.5, 7: 3. 6.5: 3.5, 6: 4, finally selecting the diluent with the addition of 30 percent;
s4, prepolymer 1 was measured by the same method as S1: prepolymer 2 ═ 7: 3. 6: 4. 5: 5. 4: 6. 3: 7 gel conversion rate under the condition, and finally selecting Di-TMPTA: tmp (eo)3TA ═ 6: 4;
s4, taking 42g Di-TMPTA, 28g TMP (EO)3TA and 30g (PO)2-NPGDA resin in a lightproof PP bottle, adding 2g 819 photoinitiator, and carrying out ultrasound treatment for 1h at 40 ℃; 0.204g of carbon black was weighed before adding the ceramic powder. The viscosity of the photosensitive resin was measured to be 76.2 mPas using a rotational viscometer at a spindle No. 1 and a rotational speed of 200 rpm.
Claims (10)
1. The resin suitable for 3D printing of ceramics is characterized in that raw materials of the resin comprise a photoinitiator, a prepolymer, a diluent and a coloring agent, and the selection method of the types and the addition amounts of the raw materials comprises the following steps:
step 1): selecting a prepolymer and a diluent, performing a gradient experiment on the addition amount of the initiator, and calculating the type and the addition amount of the initiator when the gel content is highest;
step 2): under the condition of fixing the content of the prepolymer, adding different diluents, adding the initiator with the highest gel content in the step 1) and the addition amount thereof, and measuring the curing thickness under different curing energies according to the calculation of the Beer-Lambert theorem:
Cd＝Dp(lnE-lnEc)；
wherein, CdE is the average exposure on the resin side for the cured thickness; ecCritical exposure amount;
fitting Dp-EcStraight line to obtain projection depth and critical exposure, the projection depth is slope, the critical exposure is the exponent of natural logarithm e, the exponent power is the intercept and the slopeAbsolute value, selecting the diluent type with the minimum critical exposure;
step 3): fixing the types of the prepolymer and the diluent, and performing a gradient experiment on the addition amount of the diluent; the same gel content measurement method as in S1 was used, and the diluent content having the highest gel content was selected as the amount of diluent to be added.
2. The resin suitable for 3D printing of ceramics according to claim 1, wherein the gradient experiment in step 1) is specifically: introducing the circular slices into a printer, setting printing power and exposure time, obtaining at least 3 circular solidified pieces in each group of experiment, cleaning and drying by using alcohol, weighing, and recording as m0(ii) a Putting the weighed circular cured slices into the same beaker in groups, carrying out ultrasonic treatment for 1 hour under the condition of absolute ethyl alcohol, drying, weighing, and recording as m1(ii) a The gel content is calculated to be m1/m0X 100%, using origin software to draw a gel conversion rate curve, and selecting the initiator type and content with the highest gel content.
3. The resin for 3D printing of ceramics according to claim 1, wherein the resin comprises 0.5-5% of photoinitiator, 30-90% of prepolymer, 10-60% of diluent and the balance of colorant by mass percent.
4. The resin suitable for 3D printing of ceramics according to claim 1 or 3, wherein the photoinitiator is TPO or 819, and the addition amount is 1-3%.
5. The resin suitable for 3D printing of ceramics according to claim 1 or 3, wherein the prepolymer is at least one of ditrimethylolpropane acrylate, urethane acrylate, epoxy acrylate and 3 (ethoxy) trimethylolpropane triacrylate, and the addition amount is 57-86%.
6. The resin suitable for 3D printing of ceramics according to claim 1 or 3, wherein the diluent is at least one of 4-acryloyl morpholine, 1, 6-hexanediol diacrylate and propoxylated neopentyl glycol diacrylate, and the addition amount is 13-42%.
7. The resin suitable for 3D printing of ceramics according to claim 1 or 3, wherein the colorant is carbon black or Sudan III, and the addition amount is 0.1-1%.
8. The resin suitable for 3D printing of ceramics according to claim 1 or 3, wherein the resin further comprises a dispersant, the resin is matched with the ceramic powder when being printed, and the mass ratio of the resin to the ceramic powder is 1: 1-3, wherein the dosage of the dispersant is 0.01-0.15 of the ceramic powder: 1.
9. the resin suitable for 3D printing of ceramics according to claim 8, wherein the dispersant is at least one of span 80, triton and tween 20.
10. The method for preparing the resin suitable for 3D printing of ceramics according to any one of claims 1 to 9, wherein the photoinitiator is added to the prepolymer and the diluent, the coloring agent is added after the mixture is uniformly stirred, the mixture is stirred, the ceramic powder is added, and the mixture is subjected to ultrasonic treatment.
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