CN117534470A - Method for preparing finished product by 3D printing boron carbide ceramic slurry - Google Patents
Method for preparing finished product by 3D printing boron carbide ceramic slurry Download PDFInfo
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- CN117534470A CN117534470A CN202311494350.3A CN202311494350A CN117534470A CN 117534470 A CN117534470 A CN 117534470A CN 202311494350 A CN202311494350 A CN 202311494350A CN 117534470 A CN117534470 A CN 117534470A
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- printing
- boron carbide
- carbide ceramic
- ceramic slurry
- finished product
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- 239000000919 ceramic Substances 0.000 title claims abstract description 64
- 239000002002 slurry Substances 0.000 title claims abstract description 55
- 229910052580 B4C Inorganic materials 0.000 title claims abstract description 51
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000010146 3D printing Methods 0.000 title claims abstract description 33
- 238000007639 printing Methods 0.000 claims abstract description 91
- 238000012360 testing method Methods 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 24
- 239000000654 additive Substances 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000002356 single layer Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 35
- 239000003638 chemical reducing agent Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 16
- 229910002804 graphite Inorganic materials 0.000 claims description 14
- 239000010439 graphite Substances 0.000 claims description 14
- 239000000314 lubricant Substances 0.000 claims description 14
- 239000000853 adhesive Substances 0.000 claims description 11
- 230000001070 adhesive effect Effects 0.000 claims description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000001272 pressureless sintering Methods 0.000 claims description 8
- 101000737276 Mus musculus Carbonyl reductase [NADPH] 2 Proteins 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- 238000007667 floating Methods 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- 230000008676 import Effects 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 229920001778 nylon Polymers 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000011368 organic material Substances 0.000 claims description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 7
- 229920005646 polycarboxylate Polymers 0.000 claims description 7
- 229920002635 polyurethane Polymers 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 7
- 238000012805 post-processing Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000004584 polyacrylic acid Substances 0.000 claims description 5
- 238000001746 injection moulding Methods 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 239000002048 multi walled nanotube Substances 0.000 claims description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 238000000518 rheometry Methods 0.000 claims 1
- 238000010008 shearing Methods 0.000 claims 1
- 239000012745 toughening agent Substances 0.000 abstract description 6
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 238000011049 filling Methods 0.000 abstract description 2
- 238000001125 extrusion Methods 0.000 description 7
- 230000000630 rising effect Effects 0.000 description 7
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- 238000002791 soaking Methods 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 5
- 238000000861 blow drying Methods 0.000 description 5
- 238000002955 isolation Methods 0.000 description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011224 oxide ceramic Substances 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
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- 239000002131 composite material Substances 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000012255 powdered metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/563—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on boron carbide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/001—Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
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- 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
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- 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
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- 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
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- C04B35/62605—Treating the starting powders individually or as mixtures
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- C04B35/6263—Wet mixtures characterised by their solids loadings, i.e. the percentage of solids
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- C04B2235/5276—Whiskers, spindles, needles or pins
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- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
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Abstract
A method for preparing a finished product by 3D printing of boron carbide ceramic slurry belongs to the field of ceramic material preparation, and comprises the steps of firstly pre-grinding and premixing boron carbide ceramic powder and a toughening agent, crushing and uniformly mixing sintered two phases with different particle sizes, adding an additive after obtaining dry powder uniformly mixed materials, finally adding water to obtain slurry, and carrying out viscosity test by a viscometer. Corresponding parameters are input by rewriting slicing software, 3D direct writing is carried out on qualified slurry, and variables such as discharge amount, printing speed, printing outlet caliber, printing distance, thermal field temperature and the like are controlled to control important parameters such as single-layer thickness, filling rate and the like of the lattice ceramic. The invention controls the solid content of the ceramic slurry by controlling the proportion of the external additive, and makes the ceramic obtain a clear and tough framework structure under the action of an external heating field, and the toughening agent is added to improve the macroscopic performance of the ceramic. And obtaining the direct-writing 3D printing lattice boron carbide ceramic slurry finished product with high solid content, low porosity and low single-layer material collapse rate.
Description
Technical Field
The invention belongs to the field of ceramic material preparation, and particularly relates to a method for preparing a finished product from high-solid-content direct-writing 3D printing lattice boron carbide ceramic slurry.
Background
3D printing (3 DP), a type of rapid prototyping technology, also known as additive manufacturing, is a technology that builds objects by means of layer-by-layer printing, using bondable materials such as powdered metal or plastic, based on digital model files. 3D printing is typically implemented using a digital technology material printer. Often in the fields of mould manufacture, industrial design, etc., are used to manufacture models, and later gradually in the direct manufacture of some products, parts have been printed using this technique. The technology has application in jewelry, footwear, industrial design, construction, engineering and construction (AEC), automotive, aerospace, dental and medical industries, education, geographic information systems, civil engineering, firearms, and other fields. 3D printing of ceramics was proposed in the early 90 th century of the 20 th century, so far, along with development of material science and computer science, mainstream 3D printing applied to ceramic materials is mainly focused on three-dimensional light curing molding (SLA), ink Jet Printing (IJP), three-dimensional printing technology (3 DP), laser selective sintering (SLS), slurry direct writing molding (DIW) and the like, wherein the flow of the direct writing technology (DIW) is simpler and more convenient and suitable for industrial production, and is often used in structural parts and decoration parts with low requirements on near-molding precision, the molding mode is mainly influenced by rheological property of slurry, and the rheological property of slurry is often influenced by solid content and thermal field of the slurry.
With the higher pursuit of army in China for combat capability and equipment weight reduction, high performance B 4 The C ceramic is widely applied to the individual protection field by virtue of the excellent performances of high strength, high toughness, low density, corrosion resistance and the like brought by the unique rhombohedral structure, 3D printing boron carbide is always ignored by ceramic printing in the process of boron carbide research in China, one of the reasons is that the cost of the boron carbide is too high, the ceramic is used for the military field, and the other reasons are that the solid content of the ceramic is low in the direct writing process and the material collapse phenomenon is serious.
Disclosure of Invention
With the further application of the boron carbide ceramic, people have higher requirements on the shape of the ceramic, in particular to the boron carbide ceramic in a lattice form, which has higher specific surface area and can be widely used in explosion-proof and bulletproof materials and neutron absorbing materials. If the boron carbide ceramic with the lattice porous structure is to be obtained through a direct-writing 3D printing mode, the problem that the solid content of ceramic slurry is not high is solved, and a small amount of organic additives are added, so that the lattice ceramic is more compact in the pressureless sintering process. Aiming at the problems, the invention provides a method for preparing a finished product by 3D printing boron carbide ceramic slurry, and the technical scheme of the invention controls the solid content of the ceramic slurry by controlling the optimal proportion of external additives, and the solid content determines the density of the slurry and also finally determines B 4 Microcosmic morphology and performance of C ceramic. Meanwhile, under the action of an external heating field, the ceramic obtains a clear and tough skeleton structure, and then toughening agents such as SiC whisker, rare earth oxide and the like can be added into the slurry according to the toughening requirement, so that the macroscopic performance of the ceramic is improved. The high solid content (boron carbide powder accounts for 89 percent) of the ceramic can be reduced to 5 percent after sintering, and the single-layer material collapse rate can be controlled to be lower than 1 percent (Y-direction comparison).
The design idea of the invention is as follows:
firstly, pre-grinding and premixing boron carbide ceramic powder and a toughening agent, crushing and uniformly mixing sintered two phases with different particle sizes to obtain a dry powder mixed material, and then addingAdditives were added, and finally water was added to obtain a slurry, and viscosity test was performed by a rotary viscometer. Corresponding parameters are input by rewriting slicing software, 3D direct writing is carried out on qualified slurry, and important parameters such as single-layer thickness, filling rate and the like of the lattice ceramic are controlled by controlling variables such as discharge amount, printing speed, printing outlet caliber, printing distance, thermal field temperature and the like. The strength of the finally obtained lattice green blank can be improved by 20 percent (compared with the solid content of 65 percent), the highest hardness can reach 15GPa, and the highest fracture toughness can reach 2.5MPa.m 1/2 Provides a better choice for the preparation of the continuous phase composite material.
The invention aims at realizing the following technical scheme:
a method for preparing a finished product by 3D printing boron carbide ceramic slurry, wherein the slurry of 3D printing boron carbide ceramic is high-solid-content direct-writing 3D printing lattice boron carbide ceramic slurry, and specifically comprises the following steps:
1.B 4 c, premixing powder and toughening phase: mixing boron carbide ceramic with the grain diameter of 0.5-1.0 mu m and a toughening phase in the mass ratio of 9:1-10:0.1, performing ball milling, putting grinding balls into zirconium dioxide balls with the grain diameter of 6mm, 8mm and 10mm in the mass ratio of 1:2:1, controlling the ball-material ratio to be 2.5:1-3.5:1, and controlling the powder loading amount to be 1/3-1/2 of the barrel body and the rotating speed of a rolling rod to be 10-15 r/min.
2. Printing paste preparation: and (2) adding a small amount of additive in batches into the mixture prepared in the step (1), wherein the additive comprises a water reducing agent, a binder and a lubricant, adding pure water to mechanically stir at a speed of 5-15 r/min for 30-40 h, so that the water reducing agent is fully combined with the surface functional groups of the powder, and controlling the solid content of the ceramic slurry to be more than 85%. Then testing by using a rheometer, adopting a flat plate with the diameter of 30-35 mm to test a rotor, wherein the gap is 1-2 mm, and the testing temperature is room temperature; the test interval for the viscosity test is a shear rate of from 0.1s -1 Increase to 200s -1 The modulus test section is a shear force of 1Pa to 1000Pa.
3. Model import and slicing software setting: firstly, importing a file in an STL (Standard template) format of three-dimensional drawing software into slicing software Ultimaker Cure, and printing a range X: 90-180 mm; y: 90-180 mm; z: 10-50 mm; the number of prints was 1; the size of the nozzle is 1.2-1.5, a surface mode is selected, and the outer contour is set to be smooth; the diameter of the discharged material is 0.4-0.6 mm, and the compensation value is 0.1mm; the single layer is 0.3-0.5 mm in height, the first layer is 0.5-1 mm in height, and the double-line is 1-2 mm in height; the thickness of the outer wall of the model does not have technical requirements; the capping thickness is set to be 0.5-1 mm; setting the printing temperature to be 30-50 ℃; the printing speed is 0.7-5 mm/s; the wall and top/bottom speeds are 10-15 mm/s.
4. Pre-printing, actual printing and post-processing: the edge agent material time is 30 s-1 min, the hard block of the plug of the feeding barrel is discharged, and the total printing height is 10-50 mm. And after printing, soaking the extrusion barrel into pure water to prevent dry materials. Vacuum drying is selected, and the surface floating ash is dried for standby.
5. Setting a pressureless sintering system: and placing the raw materials after printing and drying in a graphite mold, and paving 1-2 layers on the upper and lower periphery by taking 0.1-0.2 mm graphite paper on the upper, lower, left and right sides as an isolating layer. The sintering schedule is as follows: the temperature is 0-500 ℃, and the temperature rising rate is 5-10 ℃/min; after 500 ℃, different temperature gradients are required to be set according to different additives. Cooling along with the furnace.
The preparation method comprises the following steps:
in the step 1, the toughening phase is selected from multi-wall Carbon Nanotubes (CNTs), rare earth oxides, siC whiskers and Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The content of the toughening phase in the mixture of the boron carbide ceramic and the toughening phase is not more than 15 percent.
In the step 1, a three-bar double-layer horizontal dry ball mill is selected for ball milling, and the barrel material is selected from polyurethane or nylon polymer organic materials;
in the step 2, the polycarboxylate water reducer is selected, and the addition amount is controlled to be 0.5% -1.5%; the adhesive is polyacrylic acid aqueous solution resin or adhesive NE-119 (wax system) for injection molding, and the addition amount is 0.01-0.05%; the lubricant is stearic acid emulsion AP27, and the addition amount is controlled to be 0.1-0.5%.
In the step 3, certain Z-axis compensation is carried out, and the compensation amount is 0.3-0.5 mm;
in the step 4, the first layer printing height in the actual printing process needs to be adjusted by 0.3-0.5 mm;
in the step 4, the vacuum drying temperature is 60-80 ℃ and the drying time is 36-48 h;
the edge extrusion time refers to the time for removing gas and solvent precipitation in a charging barrel without printing in front.
The invention has the beneficial effects and key points that:
the invention adopts high-solid-content slurry to directly write and generate the boron carbide ceramic in the lattice form, firstly, the slurry with high solid content has profound effects on the micro morphology and macro performance of the subsequent pressureless sintered boron carbide product, and gives more added value to the high-content ceramic slurry for controlling the critical point of the rheological property of the slurry, and the porous array boron carbide provides a new idea for compounding metals such as steel/aluminum and the like with the metals by virtue of a unique point reinforcing framework form, thereby being expected to replace single materials (hot-pressed sintered boron carbide) to be applied to the military industry and other fields. In addition, the boron carbide ceramic with the system can be applied to the field of nuclear radiation protection by virtue of the higher specific surface area and the controllable void ratio. Finally, the traditional hot-pressing sintering is abandoned, and the method is more green, energy-saving and suitable for industrial production.
As previously mentioned, boron carbide slurries are not uncommon because they are expensive and have poor slurry forming properties themselves. The 3D direct writing printing has higher requirements on rheological property of the slurry, and the influence of different toughening agents on the slurry property is increased, the boron carbide is prepared into the slurry with high solid content, and the toughening agents and the additives are added to improve the properties of toughness, bending strength and the like of the finished product, so that an innovative scheme is provided for the preparation of the boron carbide slurry suitable for 3D printing.
Detailed Description
Example 1
A method for preparing a finished product from high-solid-content (89%) direct-writing 3D printing lattice boron carbide/CNTs ceramic slurry specifically comprises the following steps:
1.B 4 c, premixing powder and toughening phase: ball milling is carried out by a three-bar double-layer horizontal dry ball mill, and boron carbide with the grain diameter of 0.5 mu m is obtainedCeramic and toughening phase multiwall Carbon Nanotubes (CNTs) are mixed according to the mass ratio of 9.7:0.3, the materials of the ball barrel are high molecular organic materials such as polyurethane or nylon, the grinding balls are zirconium dioxide balls with the mass ratio of 6mm, 8mm and 10mm, the ball material ratio is controlled at 2.5:1, and the powder loading amount is 1/3 of the rotational speed of the roller of the barrel body, 15r/min.
2. Printing paste preparation: adding a small amount of additives into the mixture prepared in the step 1 in batches, wherein the additives comprise a water reducing agent, a binder and a lubricant; the water reducer is a polycarboxylate water reducer, and the addition amount is controlled at 0.5%; the adhesive is polyacrylic acid aqueous solution with the addition amount of 0.01%; the lubricant is stearic acid emulsion AP27, and the addition amount is 0.5%. And adding pure water to mechanically stir at a speed of about 5r/min for 40h, so that the water reducer is fully combined with the powder surface functional groups, and the solid content of the ceramic slurry is controlled to be more than 89%. Then testing by using a rheometer, adopting a flat plate with the diameter of 35mm to test a rotor, wherein the gap is 1mm, and the testing temperature is room temperature; the test interval for the viscosity test is a shear rate of from 0.1s -1 Increase to 200s -1 The modulus test section is a shear force of 1Pa to 1000Pa.
3. Model import and slicing software setting: firstly, importing a file in an STL (Standard template) format of three-dimensional drawing software into slicing software Ultimaker Cure, and printing a range X:180mm; y:180mm; z:50mm; the number of prints was 1; the size of the nozzle is 1.5, a surface mode is selected, and the outer contour is set to be smooth; the diameter of the discharged material is 0.6mm, and the compensation value is 0.1mm; performing certain Z-axis compensation, wherein the compensation amount is 0.5mm; the single layer is 0.5mm in height, the first layer is 1mm in height, and the double lines are 2mm in height; the thickness of the outer wall of the model does not have technical requirements; setting the capping thickness to be 1mm, and encrypting and printing without setting; setting the printing temperature to 50 ℃; printing speed is 0.7mm/s; the wall and top/bottom speeds were 10mm/s.
4. Pre-printing, actual printing and post-processing: the edge agent material time is 1min, the hard block of the plug of the feeding barrel is discharged, the total printing height is 50mm, and the first layer printing height in the actual printing process needs to be manually adjusted by 0.3-0.5 mm. And after printing, soaking the extrusion barrel into pure water to prevent dry materials. Vacuum drying is selected, the drying temperature is 80 ℃, and the drying time is 48 hours. Blow-drying the surface floating ash for standby.
5. Setting a pressureless sintering system: and placing the raw materials after printing and drying in a graphite die, and paving 2 layers of graphite paper with the thickness of 0.1mm on the upper, lower, left and right sides serving as isolation layers. The sintering schedule is as follows: the temperature is 0-500 ℃, and the temperature rising rate is 5 ℃/min; the temperature rising rate is 10 ℃/min after 500 ℃, and the temperature is kept for 30min after the temperature rises to 1950 ℃. Cooling along with the furnace.
The strength of the finally obtained lattice green body can be improved by 21.5 percent (compared with the solid content of 65 percent), the average hardness is 1.9GPa, and the average fracture toughness is 0.56MPa.m 1/2 The average hardness after sintering is 12GPa, and the average fracture toughness is 1.98MPa.m 1/2 。
Example 2
A method for preparing a finished product from high-solid-content (85%) direct-writing 3D printing lattice boron carbide/cerium oxide ceramic slurry specifically comprises the following steps:
1.B 4 c, premixing powder and toughening phase: ball milling is carried out by a three-bar double-layer horizontal dry ball mill, boron carbide ceramic with the grain diameter of 1.0 mu m and toughened phase cerium oxide are mixed according to the mass ratio of 9.5:0.5, the materials of a ball barrel are high molecular organic materials such as polyurethane or nylon, the materials of the ball barrel are zirconium dioxide balls with the mass ratio of 6mm, 8mm and 10mm, the ball material ratio is controlled to be 3.5:1, and the powder loading amount is 1/3 of the rotational speed of a roller of 15r/min.
2. Printing paste preparation: adding a small amount of additives into the mixture prepared in the step 1 in batches, wherein the additives comprise a water reducing agent, a binder and a lubricant; the water reducer is a polycarboxylate water reducer, and the addition amount is controlled at 1.5%; the adhesive is selected from adhesive NE-119 (wax system) for injection molding, and the addition amount is 0.05%; the lubricant is stearic acid emulsion AP27, and the addition amount is controlled to be 0.5%. And adding pure water to mechanically stir at a speed of about 15r/min for 30h, so that the water reducer is fully combined with the powder surface functional groups, and the solid content of the ceramic slurry is controlled to be 85%. Then testing by using a rheometer, adopting a flat plate with the diameter of 30mm to test a rotor, wherein the gap is 2mm, and the testing temperature is room temperature; the test interval for the viscosity test is a shear rate of from 0.1s -1 Increase to 200s -1 The modulus test section is a shear force of 1Pa to 1000Pa.
3. Model import and slicing software setting: firstly, importing a file in an STL (Standard template) format of three-dimensional drawing software into slicing software Ultimaker Cure, and printing a range X:90; y:90mm; z:50mm; the number of prints was 1; the size of the nozzle is 1.2, a surface mode is selected, and the outer contour is set to be smooth; the diameter of the discharged material is 0.4mm, and the compensation value is 0.1mm; performing certain Z-axis compensation, wherein the compensation amount is 0.5mm; the single layer is 0.5mm in height, the first layer is 1mm in height, and the double lines are 2mm in height; the thickness of the outer wall of the model is not required to be technically required; setting the capping thickness to be 1mm, and encrypting and printing without setting; setting the printing temperature to be 30 ℃; printing speed is 1.6mm/s; the wall and top/bottom speeds were 15mm/s.
4. Pre-printing, actual printing and post-processing: the edge agent time is 30s, the plug hard block of the feeding barrel is discharged, the total printing height is 50mm, and the first layer printing height in the actual printing process needs to be manually adjusted by 0.3mm. And after printing, soaking the extrusion barrel into pure water to prevent dry materials. Vacuum drying is selected, the drying temperature is 60 ℃, and the drying time is 36 hours. Blow-drying the surface floating ash for standby.
5. Setting a pressureless sintering system: and placing the raw materials after printing and drying in a graphite die, and paving 2 layers of graphite paper with the thickness of 0.1mm on the upper, lower, left and right sides serving as isolation layers. The sintering schedule is as follows: the temperature is 0-500 ℃, and the temperature rising rate is 5 ℃/min; the temperature rise rate is 10 ℃/min between 500 ℃ and 900 ℃, and the temperature is kept for 20min when reaching 900 ℃; the temperature is raised to 900-1400 ℃ at a speed of 5 ℃/min, and the temperature is kept at 1400 ℃ for 30min; the temperature rise rate from 1400 ℃ to 1900 ℃ is 10 ℃/min, and the temperature is kept for 30min after the temperature reaches 1900 ℃. Cooling along with the furnace.
The strength of the finally obtained lattice green body can be improved by 17.5 percent (compared with the solid content of 65 percent), the average hardness is 1.3GPa, and the average fracture toughness is 0.33MPa.m 1/2 An average hardness after sintering of 11GPa and an average fracture toughness of 1.52MPa.m 1/2 。
Example 3
A method for preparing a finished product from high-solid-content (85%) direct-writing 3D printing lattice boron carbide/lanthanum oxide ceramic slurry specifically comprises the following steps:
1.B 4 c, premixing powder and toughening phase: ball milling is carried out by a three-bar double-layer horizontal dry ball mill, boron carbide ceramic with the grain diameter of 1.0 mu m and toughened phase lanthanum oxide are mixed according to the mass ratio of 9.5:0.5, the materials of a ball barrel are high molecular organic materials such as polyurethane or nylon, the materials of the ball barrel are zirconium dioxide balls with the mass ratio of 6mm, 8mm and 10mm, the ball material ratio is controlled to be 3.5:1, and the powder loading amount is 1/3 of the rotational speed of a roller of 15r/min.
2. Printing paste preparation: adding a small amount of additives into the mixture prepared in the step 1 in batches, wherein the additives comprise a water reducing agent, a binder and a lubricant; the water reducer is a polycarboxylate water reducer, and the addition amount is controlled at 1.5%; the adhesive is selected from adhesive NE-119 (wax system) for injection molding, and the addition amount is 0.05%; the lubricant is stearic acid emulsion AP27, and the addition amount is controlled to be 0.5%. And adding pure water to mechanically stir at a speed of 15r/min for 30h, so that the water reducer is fully combined with the powder surface functional groups, and the solid content of the ceramic slurry is controlled to be 85%. Then testing by using a rheometer, adopting a flat plate with the diameter of 30mm to test a rotor, wherein the gap is 2mm, and the testing temperature is room temperature; the test interval for the viscosity test is a shear rate of from 0.1s -1 Increase to 200s -1 The modulus test section is a shear force of 1Pa to 1000Pa.
3. Model import and slicing software setting: firstly, importing a file in an STL (Standard template) format of three-dimensional drawing software into slicing software Ultimaker Cure, and printing a range X:90; y:90mm; z:50mm; the number of prints was 1; the size of the nozzle is 1.2, a surface mode is selected, and the outer contour is set to be smooth; the diameter of the discharged material is 0.4mm, and the compensation value is 0.1mm; performing certain Z-axis compensation, wherein the compensation amount is 0.5mm; the single layer is 0.5mm in height, the first layer is 1mm in height, and the double lines are 2mm in height; the thickness of the outer wall of the model is not required to be technically required; setting the capping thickness to be 1mm, and encrypting and printing without setting; setting the printing temperature to be 30 ℃; printing speed is 1.6mm/s; the wall and top/bottom speeds were 15mm/s.
4. Pre-printing, actual printing and post-processing: the edge agent time is 30s, the plug hard block of the feeding barrel is discharged, the total printing height is 50mm, and the first layer printing height in the actual printing process needs to be manually adjusted by 0.3mm. And after printing, soaking the extrusion barrel into pure water to prevent dry materials. Vacuum drying is selected, the drying temperature is 60 ℃, and the drying time is 36 hours. Blow-drying the surface floating ash for standby.
5. Setting a pressureless sintering system: and placing the raw materials after printing and drying in a graphite die, and paving 2 layers of graphite paper with the thickness of 0.1mm on the upper, lower, left and right sides serving as isolation layers. The sintering schedule is as follows: the temperature is 0-500 ℃, and the temperature rising rate is 5 ℃/min; the temperature is raised to 500-900 ℃ at a speed of 10 ℃/min, and the temperature is kept at 900 ℃ for 20min; the temperature is raised to 900-1400 ℃ at a speed of 5 ℃/min, and the temperature is kept at 1400 ℃ for 30min; heating to 1400 deg.C at 10 deg.C/min, and maintaining at 1900 deg.C for 30min. Cooling along with the furnace.
The strength of the finally obtained lattice green body can be improved by 17.7 percent (the ratio of the solid content is 65 percent), the average hardness is 1.1GPa, and the average fracture toughness is 0.45MPa.m 1/2 The average hardness after sintering was 10.54GPa and the average fracture toughness was 1.22MPa.m 1/2 。
Example 4
A method for preparing a finished product from high-solid-content (88%) direct-writing 3D printing lattice boron carbide/SiC whisker ceramic slurry specifically comprises the following steps:
1.B 4 c, premixing powder and toughening phase: the method comprises the steps of ball milling by a three-bar double-layer horizontal dry ball mill, mixing boron carbide ceramic with the particle size of 0.5 mu m and toughened phase SiC whisker in a mass ratio of 9.0:1.0, wherein a ball barrel is made of polyurethane or nylon and other high polymer organic materials, a grinding ball is made of 6mm, 8mm and 10mm zirconium dioxide balls in a mass ratio of 1:2:1, the ball material ratio is controlled to be 2.5:1, and the powder loading amount is 1/3 of the rotational speed of a roller of 11r/min.
2. Printing paste preparation: adding a small amount of additives into the mixture prepared in the step 1 in batches, wherein the additives comprise a water reducing agent, a binder and a lubricant; the water reducer is a polycarboxylate water reducer, and the addition amount is controlled at 1.5%; the adhesive is polyacrylic acid aqueous solution with the addition amount of 0.01%; the lubricant is stearic acid emulsion AP27, and the addition amount is 0.5%. Adding pure water, mechanically stirring at a speed of about 5r/minThe mixing time is 40h, so that the water reducer is fully combined with the powder surface functional groups, and the solid content of the ceramic slurry is controlled to 88%. Then testing by using a rheometer, adopting a flat plate with the diameter of 35mm to test a rotor, wherein the gap is 1mm, and the testing temperature is room temperature; the test interval for the viscosity test is a shear rate of from 0.1s -1 Increase to 200s -1 The modulus test section is a shear force of 1Pa to 1000Pa.
3. Model import and slicing software setting: firstly, importing a file in an STL (Standard template) format of three-dimensional drawing software into slicing software Ultimaker Cure, and printing a range X:180mm; y:180mm; z:50mm; the number of prints was 1; the size of the nozzle is 1.5, a surface mode is selected, and the outer contour is set to be smooth; the diameter of the discharged material is 0.6mm, and the compensation value is 0.1mm; performing certain Z-axis compensation, wherein the compensation amount is 0.5mm; the single layer is 0.5mm in height, the first layer is 1mm in height, and the double lines are 2mm in height; the thickness of the outer wall of the model does not have technical requirements; setting the capping thickness to be 1mm, and encrypting and printing without setting; setting the printing temperature to 50 ℃; printing speed is 0.7mm/s; the wall and top/bottom speeds were 10mm/s.
4. Pre-printing, actual printing and post-processing: the edge agent material time is 1min, the hard block of the plug of the feeding barrel is discharged, the total printing height is 50mm, and the first layer printing height in the actual printing process needs to be manually adjusted by 0.3-0.5 mm. And after printing, soaking the extrusion barrel into pure water to prevent dry materials. Vacuum drying is selected, the drying temperature is 80 ℃, and the drying time is 48 hours. Blow-drying the surface floating ash for standby.
5. Setting a pressureless sintering system: and placing the raw materials after printing and drying in a graphite die, and paving 2 layers of graphite paper with the thickness of 0.1mm on the upper, lower, left and right sides serving as isolation layers. The sintering schedule is as follows: the temperature is 0-500 ℃, and the temperature rising rate is 5 ℃/min; the temperature is raised to between 500 and 1600 ℃ at the speed of 10 ℃/min and the temperature is kept at 1600 ℃ for 30 DEG CminThe method comprises the steps of carrying out a first treatment on the surface of the Then heating to 2000 ℃ at 10 ℃ per minute, and then preserving heat for 30 minutes. Cooling along with the furnace.
The strength of the finally obtained lattice green body can be improved by 27 percent (compared with the solid content of 65 percent), the average hardness is 2.0GPa, and the average fracture toughness is 0.36MPa.m 1/2 The average hardness after sintering was 13.1GPa and the average fracture toughness was 1.78MPa.m 1/2 。
Example 5
High-solid-content (89%) direct-writing 3D printing lattice boron carbide/Al 2 O 3 The method for preparing the finished product by the ceramic slurry specifically comprises the following steps:
1.B 4 c, premixing powder and toughening phase: ball milling is carried out by a three-bar double-layer horizontal dry ball mill, boron carbide ceramics with the grain diameter of 0.5 mu m and toughening phase Al are mixed 2 O 3 Mixing at a mass ratio of 9.0:1.0, wherein the ball barrel is made of high polymer organic materials such as polyurethane or nylon, the grinding balls are made of zirconium dioxide balls with a mass ratio of 6mm, 8mm and 10mm, the ball material ratio is controlled at 2.5:1, and the powder loading amount is 1/3 of the rotational speed of the rolling rod of the barrel body and 10r/min.
2. Printing paste preparation: adding a small amount of additives into the mixture prepared in the step 1 in batches, wherein the additives comprise a water reducing agent, a binder and a lubricant; the water reducer is a polycarboxylate water reducer, and the addition amount is controlled at 0.8%; the adhesive is polyacrylic acid aqueous solution with the addition amount of 0.01%; the lubricant is stearic acid emulsion AP27, and the addition amount is 0.5%. And adding pure water to mechanically stir at a speed of about 5r/min for 40h, so that the water reducer is fully combined with the powder surface functional groups, and the solid content of the ceramic slurry is controlled to be more than 89%. Then testing by using a rheometer, adopting a flat plate with the diameter of 35mm to test a rotor, wherein the gap is 1mm, and the testing temperature is room temperature; the test interval for the viscosity test is a shear rate of from 0.1s -1 Increase to 200s -1 The modulus test section is a shear force of 1Pa to 1000Pa.
3. Model import and slicing software setting: firstly, importing a file in an STL (Standard template) format of three-dimensional drawing software into slicing software Ultimaker Cure, and printing a range X:180mm; y:180mm; z:50mm; the number of prints was 1; the size of the nozzle is 1.5, a surface mode is selected, and the outer contour is set to be smooth; the diameter of the discharged material is 0.6mm, and the compensation value is 0.1mm; performing certain Z-axis compensation, wherein the compensation amount is 0.5mm; the single layer is 0.5mm in height, the first layer is 1mm in height, and the double lines are 2mm in height; the thickness of the outer wall of the model does not have technical requirements; setting the capping thickness to be 1mm, and encrypting and printing without setting; setting the printing temperature to 50 ℃; printing speed is 0.7mm/s; the wall and top/bottom speeds were 10mm/s.
4. Pre-printing, actual printing and post-processing: the edge agent material time is 1min, the hard block of the plug of the feeding barrel is discharged, the total printing height is 50mm, and the first layer printing height in the actual printing process needs to be manually adjusted by 0.3-0.5 mm. And after printing, soaking the extrusion barrel into pure water to prevent dry materials. Vacuum drying is selected, the drying temperature is 80 ℃, and the drying time is 48 hours. Blow-drying the surface floating ash for standby.
5. Setting a pressureless sintering system: and placing the raw materials after printing and drying in a graphite die, and paving 2 layers of graphite paper with the thickness of 0.1mm on the upper, lower, left and right sides serving as isolation layers. The sintering schedule is as follows: the temperature is 0-1100 ℃, and the temperature rising rate is 5 ℃/min; preserving heat at 1100 ℃ for 30min; then the temperature is raised to 1900 ℃ at a heating rate of 10 ℃/min, and then the temperature is kept for 30min. Cooling along with the furnace.
The strength of the finally obtained lattice green body can be improved by 21.1 percent (the ratio of the solid content is 65 percent), the average hardness is 1.4GPa, and the average fracture toughness is 0.55MPa.m 1/2 The average hardness after sintering is 12.4GPa, and the average fracture toughness is 0.8MPa.m 1/2 。
Claims (9)
1. The method for preparing a finished product by 3D printing of boron carbide ceramic slurry is characterized in that the solid content of the 3D printing of boron carbide ceramic slurry is more than 85 percent, and the method for preparing the finished product by direct writing of 3D printing of lattice boron carbide ceramic slurry comprises the following steps:
1.B 4 c, premixing powder and toughening phase: mixing boron carbide ceramic with the grain diameter of 0.5-1.0 mu m and toughening phase, performing ball milling, wherein the grinding balls are zirconium dioxide balls with the grain diameter of 6mm, 8mm and 10mm, the ball-material ratio is controlled to be 2.5:1-3.5:1, and the powder loading amount is 1/3-1/2 of the rolling rod rotating speed of the barrel body and is 10-15 r/min;
2. printing paste preparation: adding a small amount of additive in batches into the mixture prepared in the step 1, wherein the additive comprises a water reducing agent, a binder and a lubricant, adding pure water to mechanically stir, so that the water reducing agent is fully combined with the powder surface functional groups, and controlling the solid content of the ceramic slurry to be more than 85%; followed by rheology testingThe instrument is used for testing, a flat plate with the diameter of 30-35 mm is used for testing the rotor, the gap is 1-2 mm, and the testing temperature is room temperature; the test interval for the viscosity test is a shear rate of from 0.1s -1 Increase to 200s -1 The modulus test section is that the shearing force is from 1Pa to 1000Pa;
3. model import and slicing software setting: firstly, importing a file in an STL (Standard template) format of three-dimensional drawing software into slicing software Ultimaker Cure, and printing a range X: 90-180 mm; y: 90-180 mm; z: 10-50 mm; the number of prints was 1; the size of the nozzle is 1.2-1.5, a surface mode is selected, and the outer contour is set to be smooth; the diameter of the discharged material is 0.4-0.6 mm, and the compensation value is 0.1mm; the single layer is 0.3-0.5 mm in height, the first layer is 0.5-1 mm in height, and the double-line is 1-2 mm in height; the capping thickness is set to be 0.5-1 mm; setting the printing temperature to be 30-50 ℃; the printing speed is 0.7-5 mm/s; the wall and the top/bottom speed are 10-15 mm/s;
4. pre-printing, actual printing and post-processing: the edge agent material time is 30 s-1 min, the hard block of the plug of the feeding barrel is discharged, and the total printing height is 10-50 mm; vacuum drying is selected, and surface floating ash is dried for standby;
5. setting a pressureless sintering system: placing the raw materials after printing and drying in a graphite mold, and sintering by taking graphite paper as an isolating layer up, down, left and right; the sintering schedule is as follows: the temperature is 0-500 ℃, the heating rate is 5-10 ℃/min, and different temperature gradients are required to be set according to different additives after 500 ℃; cooling along with the furnace.
2. The method for preparing a finished product by 3D printing boron carbide ceramic slurry according to claim 1, wherein in the step 1, the toughening phase is selected from multi-wall carbon nanotubes, rare earth oxides, siC whiskers and Al 2 O 3 。
3. The method for preparing a finished product by 3D printing of boron carbide ceramic slurry according to claim 1, wherein in the step 1, boron carbide ceramic and toughening phase are mixed according to a mass ratio of 9:1-10:0.1.
4. The method for preparing a finished product by 3D printing of boron carbide ceramic slurry according to claim 1, wherein in the step 1, a three-bar double-layer horizontal dry ball mill is selected for ball milling, and a barrel material is selected from polyurethane or nylon polymer organic materials; the zirconia balls with the mass ratio of 6mm, 8mm and 10mm are put into the reactor according to the mass ratio of 1:2:1.
5. The method for preparing a finished product by 3D printing of boron carbide ceramic slurry according to claim 1, wherein in the step 2, a polycarboxylate water reducer is selected as the water reducer, and the addition amount is controlled to be 0.5% -1.5%; the adhesive is polyacrylic acid aqueous solution resin or adhesive NE-119 for injection molding, and the addition amount is 0.01-0.05%; the lubricant is stearic acid emulsion AP27, and the addition amount is controlled to be 0.1-0.5%.
6. The method for preparing a finished product by 3D printing of boron carbide ceramic slurry according to claim 1, wherein in the step 2, the stirring speed is 5-15 r/min, and the stirring time is 30-40 h.
7. The method for preparing a finished product by 3D printing of boron carbide ceramic slurry according to claim 1, wherein in the step 3, certain Z-axis compensation is performed, and the compensation amount is 0.3-0.5 mm.
8. The method for preparing a finished product by 3D printing boron carbide ceramic slurry according to claim 1, wherein in the step 4, the first layer printing height in the actual printing process needs to be adjusted by 0.3-0.5 mm.
9. The method for preparing a finished product by 3D printing of boron carbide ceramic slurry according to claim 1, wherein in the step 4, the vacuum drying temperature is 60-80 ℃ and the drying time is 36-48 h.
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