CN104493952A - Gel-casting 3D printing preparation method for ceramic gradient material - Google Patents

Gel-casting 3D printing preparation method for ceramic gradient material Download PDF

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CN104493952A
CN104493952A CN201510004372.6A CN201510004372A CN104493952A CN 104493952 A CN104493952 A CN 104493952A CN 201510004372 A CN201510004372 A CN 201510004372A CN 104493952 A CN104493952 A CN 104493952A
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ceramic
printing
print
gradient
moulding
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CN201510004372.6A
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CN104493952B (en
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彭晓领
徐靖才
李静
杨艳婷
王新庆
葛洪良
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彭晓领
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B28WORKING CEMENT, CLAY, OR STONE
    • B28BSHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00Producing shaped prefabricated articles from the material
    • B28B1/001Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B28WORKING CEMENT, CLAY, OR STONE
    • B28BSHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B11/00Apparatus or processes for treating or working the shaped or preshaped articles
    • B28B11/24Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening
    • B28B11/243Setting, e.g. drying, dehydrating or firing ceramic articles
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/14Shaped 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 silica
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    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/26Shaped 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 ferrites
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    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/50Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • C04B35/505Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds based on yttrium oxide
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    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped 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
    • C04B35/56Shaped 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
    • C04B35/5607Shaped 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 refractory metal carbides
    • C04B35/5611Shaped 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 refractory metal carbides based on titanium carbides
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped 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
    • C04B35/58Shaped 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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/584Shaped 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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride

Abstract

The invention discloses a gel-casting 3D printing preparation method for ceramic gradient material. The gel-casting 3D printing preparation method for the ceramic gradient material includes steps that 1) building a computer three-dimensional sketch map of the ceramic gradient material, slicing, and building a scanning route; 2) calculating ingredient proportions of different positions; 3) setting corresponding printing parameters; 4) preparing ceramic ingredient, organic monomer, cross-linking agent, initiator, catalyst and the like; 5) starting printing equipment to perform sol-gel 3D printing, pouring the ceramic ingredient, organic premixed liquid, initiator and catalyst to a printing head, and printing to form according to a set track and a set speed after mixing; 6) sintering the green body to prepare the ceramic gradient material. The gel-casting 3D printing preparation method for the ceramic gradient material has advantages that the gradient distribution for the ingredients is really realized through using a computer to control the ingredient proportions at different positions; the 3D printing technology belongs to a material increase preparing method, compared with a traditional technique, raw material is saved.

Description

The gel injection-moulding 3D printing preparation method of gradient ceramic
Technical field
The present invention relates to a kind of gel injection-moulding 3D printing preparation method of gradient ceramic, belong to field of material preparation.
Background technology
Function-graded material and homogeneous material, composite are different, it is the material selecting two kinds of (or multiple) performances different, by changing the Nomenclature Composition and Structure of Complexes of these two kinds of (or multiple) materials continuously, its interface is disappeared causes the performance of material slowly to change along with the change of the Nomenclature Composition and Structure of Complexes of material, forms function-graded material.
From the combination of material, FGM can be divided into metal/alloy, metal/non-metal, and the multiple combination modes such as nonmetal/pottery, metal/ceramic, pottery/pottery, therefore can obtain the material of multiple specific function.
Ceramic material has been widely used in the industrial circles such as electronics, machinery, national defence because of the performance of its uniqueness.But be difficult to carry out machined after ceramic material sintering, old friends are seeking the dead size forming method of complicated shape ceramic component always, this has become the key link ensureing ceramic component quality and make developed material acquisition practical application.The forming method of ceramic material, generally can be divided into dry method and the large class of wet method two.Comparatively speaking, wet therapy forming process equipment is simple, molding blank component is even, defect is few, be easy to the advantages such as shaping complicated shape part, and practicality is stronger.But traditional wet-forming technique all exists some problems, if injection forming realizes by plaster mold water suction, cause in base substrate and form density gradient distribution and inhomogeneous deformation, and blank strength is low, be easy to damage.Injection moulding or injection moulding need add mass fraction up to 20% wax or organic matter, cause skimming processes loaded down with trivial details, the thawing of bonding agent or evaporation make the intensity of base substrate reduce, and easily form defect and even collapse.These problems improve the production cost of ceramic material, reduce the stability of its quality.The beginning of the nineties, U.S.'s Oak Ridge National Laboratory has invented a kind of brand-new ceramic material wet-forming technique---Gelcasting Technique, and main production process is: the mixing of ceramic raw material and medium → shaping (solidifying) → get rid of medium → drying → sintering.
Gel casting forming is the technology that a kind of practicality is very strong, and it has following distinguishing feature: (1) is applicable to various ceramic material, the ceramic part of shaping various complicated shape and size.(2) because type-approval process is separated completely with injection moulding operation, sizing forms the cancellated gelinite of interlinkage by organic monomer in-situ polymerization in slurry and realizes.So molding blank component is even, even density, defect are few.(3) slurry to solidify shaping time shorter and controlled.Different with the addition of catalyst according to polymerization temperature, solidify shaping time generally controlled at 5 ~ 60 min.(4) this technique mould therefor is non-porous mold, and to mould without particular/special requirement, can be metal, glass or plastics etc.(5) in base substrate, content of organics is less, and its mass fraction is generally 3% ~ 5%.But intensity is higher, generally at more than 10MPa.Machined (car, mill, plane, milling, boring, saw etc.) can be carried out to base substrate, thus cancel or reduce the processing after sintering.(6) this is a kind of dead size forming technique.Due to component and the even density of base substrate, thus can not be out of shape in drying and sintering process, shape and size ratio when sintered body can keep shaping.(7) ceramic material used is high solid phase (volume parts is not less than 50%), low viscosity (being less than 1Pas).The solid concentration of slurry is the factor affecting the density of molding blank, intensity and uniformity, the quality of magnitude relationship to become blank shape of viscosity and the exhaust effect of slurry.
Gradient ceramic lacks easy preparation method at present, and this is the major reason that restriction gradient ceramic further develops.Therefore, if by the ceramic forming material means of maturation, can be used for preparing gradient ceramic, had great importance undoubtedly and vast potential for future development.
Summary of the invention
The object of this invention is to provide a kind of gel injection-moulding 3D printing preparation method of gradient ceramic.
Concrete steps of the present invention are:
1) modeling
First by microcomputer modelling software modeling, then become by the threedimensional model built up " subregion " thickness to be the cross section of 20 ~ 100 μm, namely cut into slices, thus instruct printer successively to print;
2) proportioning is calculated
According to the Composition Design requirement of gradient ceramic, calculate the component proportion of ceramic gradient structural member diverse location, as variable input computer, the powder feeding ratio of diverse location when controlling to print;
3) print parameters is set
Arranging print speed is 0.05 ~ 0.5m/s, print resolution 20 ~ 100 μm, for powder sending quantity is 0.02 ~ 5mm 3/ s;
4) raw material prepares
It is the feed cylinder that the ceramic powder component of 0.1 ~ 10 μm puts into feed appliance after pretreatment respectively by particle diameter; Organic monomer and crosslinking agent are dissolved in deionized water by the weight ratio of 6 ~ 24:1, is made into the premixed liquid that organic matter mass fraction is 10 ~ 25%; Premixed liquid is loaded transfusion rifle 1; Initator and catalyst are loaded transfusion rifle 2;
Described ceramic composition is ZrO 2, SiC, AlN, Si 3n 4, B 4c, SiO 2, TiC, Y 2o 3, Al 2o 3, ferrite;
Described organic monomer is acrylamide, Methacrylamide or vinyl pyrrole ketone;
Described crosslinking agent is methylene-bisacrylamide;
Described initator to be mass fraction be 1 ~ 5% the persulfuric acid aqueous solution;
Described catalyst is tetramethylethylenediamine;
5) gel injection-moulding 3D prints
Start printing device and carry out 3D printing.Feed appliance enters printhead according to the proportioning feeding of setting, and rifle of simultaneously infusing sends into premixed liquid, initator and catalyst to printhead.Above-mentioned raw materials in printhead after mixing, print according to track, the speed of setting.According to trajectory, print forming surface line by line, more successively print formation three-dimensional ceramic functionally gradient material (FGM).In print procedure, control operating room's temperature at 60 ~ 80 DEG C, be beneficial to gel process;
Described premixed liquid addition is 40 ~ 100% of solid phase ceramic powders volume;
Described initator addition is 2 ~ 10% of premixed liquid volume;
Described catalyst charge is 0.3 ~ 3% of premixed liquid volume;
6) sinter
Take out green compact and put into sintering furnace, be filled with argon gas or nitrogen is protected, sintering temperature, between 600 ~ 1400 DEG C, cools to 100 ~ 300 DEG C of taking-ups with the furnace.
Advantage of the present invention is:
1) strictly controlled the raw material components proportioning at diverse location place by computer, thus truly realize the gradient distribution of composition;
2) adopt 3D to print feeding, mixing, printing and gel are completed simultaneously, improve operating efficiency;
3) 3D printing technique is for increasing material, preparation method, compared with traditional handicraft, saves raw material, avoids waste.
Detailed description of the invention
Describe the present invention below in conjunction with embodiment, to understand objects, features and advantages of the present invention better.Although the present invention is described in conjunction with this specific embodiment, be not intended that the invention be limited to described specific embodiment.On the contrary, to the embodiment substituting, improve and be equal to that the embodiment in the protection domain that can be included in defined in the claims in the present invention carries out, all protection scope of the present invention is belonged to.For the technological parameter of not special mark, can technology carry out routinely.
The concrete steps that the present invention adopts are as follows:
1) modeling
First by microcomputer modelling software modeling, then become by the threedimensional model built up " subregion " thickness to be the cross section of 20 ~ 100 μm, namely cut into slices, thus instruct printer successively to print;
2) proportioning is calculated
According to the Composition Design requirement of gradient ceramic, calculate the component proportion of ceramic gradient structural member diverse location, as variable input computer, the powder feeding ratio of diverse location when controlling to print;
3) print parameters is set
Arranging print speed is 0.05 ~ 0.5m/s, print resolution 20 ~ 100 μm, for powder sending quantity is 0.02 ~ 5mm 3/ s;
4) raw material prepares
It is the feed cylinder that the ceramic powder component of 0.1 ~ 10 μm puts into feed appliance after pretreatment respectively by particle diameter; Organic monomer and crosslinking agent are dissolved in deionized water by the weight ratio of 6 ~ 24:1, is made into the premixed liquid that organic matter mass fraction is 10 ~ 25%; Premixed liquid is loaded transfusion rifle 1; Initator and catalyst are loaded transfusion rifle 2;
Described ceramic composition is ZrO 2, SiC, AlN, Si 3n 4, B 4c, SiO 2, TiC, Y 2o 3, Al 2o 3, ferrite;
Described organic monomer is acrylamide, Methacrylamide or vinyl pyrrole ketone;
Described crosslinking agent is methylene-bisacrylamide;
Described initator to be mass fraction be 1 ~ 5% the persulfuric acid aqueous solution;
Described catalyst is tetramethylethylenediamine;
5) gel injection-moulding 3D prints
Start printing device and carry out 3D printing.Feed appliance enters printhead according to the proportioning feeding of setting, and rifle of simultaneously infusing sends into premixed liquid, initator and catalyst to printhead.Above-mentioned raw materials in printhead after mixing, print according to track, the speed of setting.According to trajectory, print forming surface line by line, more successively print formation three-dimensional ceramic functionally gradient material (FGM).In print procedure, control operating room's temperature at 60 ~ 80 DEG C, be beneficial to gel process;
Described premixed liquid addition is 40 ~ 100% of solid phase ceramic powders volume;
Described initator addition is 2 ~ 10% of premixed liquid volume;
Described catalyst charge is 0.3 ~ 3% of premixed liquid volume;
6) sinter
Take out green compact and put into sintering furnace, be filled with argon gas or nitrogen is protected, sintering temperature, between 600 ~ 1400 DEG C, cools to 100 ~ 300 DEG C of taking-ups with the furnace.
Can the functionally gradient material (FGM) of various thickness that in very large range changes of prepared composition by the present invention, and composition consecutive variations.
Embodiment 1:
Step of the present invention is:
1) modeling
First by microcomputer modelling software modeling, then become by the threedimensional model built up " subregion " thickness to be the cross section of 20 μm, namely cut into slices, thus instruct printer successively to print;
2) proportioning is calculated
According to the Composition Design requirement of gradient ceramic, calculate the component proportion of ceramic gradient structural member diverse location, as variable input computer, the powder feeding ratio of diverse location when controlling to print;
3) print parameters is set
Arranging print speed is 0.05m/s, print resolution 20 μm, for powder sending quantity is 0.02mm 3/ s ;
4) raw material prepares
By the ZrO that particle diameter is 0.1 μm 2with the Y of 0.3 μm 2o 3ceramic powder component puts into the feed cylinder of feed appliance after pretreatment respectively; Acrylamide and methylene-bisacrylamide are dissolved in deionized water by the weight ratio of 6:1, is made into the premixed liquid that organic matter mass fraction is 10%; Premixed liquid is loaded transfusion rifle 1; Be persulfuric acid aqueous solution initator and the tetramethylethylenediamine catalyst loading transfusion rifle 2 of 1% by mass fraction;
5) gel injection-moulding 3D prints
Start printing device and carry out 3D printing.Feed appliance enters printhead according to the proportioning feeding of setting, and rifle of simultaneously infusing sends into the catalyst of the premixed liquid of powder volume 40%, the initator of premixed liquid volume 2% and premixed liquid volume 0.3% to printhead.Above-mentioned raw materials in printhead after mixing, print according to track, the speed of setting.According to trajectory, print forming surface line by line, more successively print formation three-dimensional ceramic functionally gradient material (FGM).In print procedure, control operating room's temperature at 60 DEG C, be beneficial to gel process;
6) sinter
Take out green compact and put into sintering furnace, be filled with argon gas protection, 600 DEG C of sintering, cool to 100 DEG C of taking-ups with the furnace.
Electron probe line analysis is carried out to the sample prepared by example 1, finds its composition consecutive variations, ZrO 2reduce to 0% of opposite side by 100% of side, sample interior exists without macroscopic interface.
Embodiment 2:
Step of the present invention is:
1) modeling
First by microcomputer modelling software modeling, then become by the threedimensional model built up " subregion " thickness to be the cross section of 50 μm, namely cut into slices, thus instruct printer successively to print;
2) proportioning is calculated
According to the Composition Design requirement of gradient ceramic, calculate the component proportion of ceramic gradient structural member diverse location, as variable input computer, the powder feeding ratio of diverse location when controlling to print;
3) print parameters is set
Arranging print speed is 0.1m/s, print resolution 50 μm, for powder sending quantity is 0.25mm 3/ s;
4) raw material prepares
It is the feed cylinder that the TiC ceramic powder component of 1 μm SiC and 0.8 μm puts into feed appliance after pretreatment respectively by particle diameter; Methacrylamide and methylene-bisacrylamide are dissolved in deionized water by the weight ratio of 24:1, is made into the premixed liquid that organic matter mass fraction is 25%; Premixed liquid is loaded transfusion rifle 1; Be persulfuric acid aqueous solution initator and the tetramethylethylenediamine catalyst loading transfusion rifle 2 of 5% by mass fraction;
5) gel injection-moulding 3D prints
Start printing device and carry out 3D printing.Feed appliance enters printhead according to the proportioning feeding of setting, and rifle of simultaneously infusing sends into the catalyst of the premixed liquid of powder volume 100%, the initator of premixed liquid volume 10% and premixed liquid volume 3% to printhead.Above-mentioned raw materials in printhead after mixing, print according to track, the speed of setting.According to trajectory, print forming surface line by line, more successively print formation three-dimensional ceramic functionally gradient material (FGM).In print procedure, control operating room's temperature at 60 DEG C, be beneficial to gel process;
6) sinter
Take out green compact and put into sintering furnace, be filled with nitrogen protection, 900 DEG C of sintering, cool to 100 DEG C of taking-ups with the furnace.
Carry out electron probe line analysis to the sample prepared by example 2, find its composition consecutive variations, SiC reduces to 0% of opposite side by 100% of side, and sample interior exists without macroscopic interface.
Embodiment 3:
Step of the present invention is:
1) modeling
First by microcomputer modelling software modeling, then become by the threedimensional model built up " subregion " thickness to be the cross section of 100 μm, namely cut into slices, thus instruct printer successively to print;
2) proportioning is calculated
According to the Composition Design requirement of gradient ceramic, calculate the component proportion of ceramic gradient structural member diverse location, as variable input computer, the powder feeding ratio of diverse location when controlling to print;
3) print parameters is set
Arranging print speed is 0.5m/s, print resolution 100 μm, for powder sending quantity is 5mm 3/ s;
4) raw material prepares
Be the Si of 8 μm AlN and 10 μm by particle diameter 3n 4ceramic powder component puts into the feed cylinder of feed appliance after pretreatment respectively; Vinyl pyrrole ketone and methylene-bisacrylamide are dissolved in deionized water by the weight ratio of 12:1, is made into the premixed liquid that organic matter mass fraction is 15%; Premixed liquid is loaded transfusion rifle 1; Be persulfuric acid aqueous solution initator and the tetramethylethylenediamine catalyst loading transfusion rifle 2 of 3% by mass fraction;
5) gel injection-moulding 3D prints
Start printing device and carry out 3D printing.Feed appliance enters printhead according to the proportioning feeding of setting, and rifle of simultaneously infusing sends into the catalyst of the premixed liquid of powder volume 60%, the initator of premixed liquid volume 5% and premixed liquid volume 1% to printhead.Above-mentioned raw materials in printhead after mixing, print according to track, the speed of setting.According to trajectory, print forming surface line by line, more successively print formation three-dimensional ceramic functionally gradient material (FGM).In print procedure, control operating room's temperature at 80 DEG C, be beneficial to gel process;
6) sinter
Take out green compact and put into sintering furnace, be filled with nitrogen protection, 1400 DEG C of sintering, cool to 300 DEG C of taking-ups with the furnace.
Carry out electron probe line analysis to the sample prepared by example 3, find its composition consecutive variations, AlN reduces to 0% of opposite side by 100% of side, and sample interior exists without macroscopic interface.
Embodiment 4:
Step of the present invention is:
1) modeling
First by microcomputer modelling software modeling, then become by the threedimensional model built up " subregion " thickness to be the cross section of 50 μm, namely cut into slices, thus instruct printer successively to print;
2) proportioning is calculated
According to the Composition Design requirement of gradient ceramic, calculate the component proportion of ceramic gradient structural member diverse location, as variable input computer, the powder feeding ratio of diverse location when controlling to print;
3) print parameters is set
Arranging print speed is 0.2m/s, print resolution 50 μm, for powder sending quantity is 0.5mm 3/ s;
4) raw material prepares
By the B that particle diameter is 4 μm 4the TiC ceramic powder component of C and 6 μm puts into the feed cylinder of feed appliance after pretreatment respectively; Vinyl pyrrole ketone and methylene-bisacrylamide are dissolved in deionized water by the weight ratio of 16:1, is made into the premixed liquid that organic matter mass fraction is 20%; Premixed liquid is loaded transfusion rifle 1; Be persulfuric acid aqueous solution initator and the tetramethylethylenediamine catalyst loading transfusion rifle 2 of 4% by mass fraction;
5) gel injection-moulding 3D prints
Start printing device and carry out 3D printing.Feed appliance enters printhead according to the proportioning feeding of setting, and rifle of simultaneously infusing sends into the catalyst of the premixed liquid of powder volume 80%, the initator of premixed liquid volume 8% and premixed liquid volume 2% to printhead.Above-mentioned raw materials in printhead after mixing, print according to track, the speed of setting.According to trajectory, print forming surface line by line, more successively print formation three-dimensional ceramic functionally gradient material (FGM).In print procedure, control operating room's temperature at 70 DEG C, be beneficial to gel process;
6) sinter
Take out green compact and put into sintering furnace, be filled with nitrogen protection, 1200 DEG C of sintering, cool to 100 DEG C of taking-ups with the furnace.
Electron probe line analysis is carried out to the sample prepared by example 4, finds its composition consecutive variations, B 4c reduces to 0% of opposite side by 100% of side, and sample interior exists without macroscopic interface.
Embodiment 5:
Step of the present invention is:
1) modeling
First by microcomputer modelling software modeling, then become by the threedimensional model built up " subregion " thickness to be the cross section of 50 μm, namely cut into slices, thus instruct printer successively to print;
2) proportioning is calculated
According to the Composition Design requirement of gradient ceramic, calculate the component proportion of ceramic gradient structural member diverse location, as variable input computer, the powder feeding ratio of diverse location when controlling to print;
3) print parameters is set
Arranging print speed is 0.4m/s, print resolution 50 μm, for powder sending quantity is 1mm 3/ s;
4) raw material prepares
By the Al that particle diameter is 3 μm 2o 3with the SiO of 2 μm 2ceramic powder component puts into the feed cylinder of feed appliance after pretreatment respectively; Acrylamide and methylene-bisacrylamide are dissolved in deionized water by the weight ratio of 8:1, is made into the premixed liquid that organic matter mass fraction is 14%; Premixed liquid is loaded transfusion rifle 1; Be persulfuric acid aqueous solution initator and the tetramethylethylenediamine catalyst loading transfusion rifle 2 of 2% by mass fraction;
5) gel injection-moulding 3D prints
Start printing device and carry out 3D printing.Feed appliance enters printhead according to the proportioning feeding of setting, and rifle of simultaneously infusing sends into the catalyst of the premixed liquid of powder volume 60%, the initator of premixed liquid volume 3% and premixed liquid volume 0.8% to printhead.Above-mentioned raw materials in printhead after mixing, print according to track, the speed of setting.According to trajectory, print forming surface line by line, more successively print formation three-dimensional ceramic functionally gradient material (FGM).In print procedure, control operating room's temperature at 70 DEG C, be beneficial to gel process;
6) sinter
Take out green compact and put into sintering furnace, be filled with nitrogen protection, 1100 DEG C of sintering, cool to 200 DEG C of taking-ups with the furnace.
Electron probe line analysis is carried out to the sample prepared by example 5, finds its composition consecutive variations, Al 2o 3reduce to 0% of opposite side by 100% of side, sample interior exists without macroscopic interface.
Embodiment 6:
Step of the present invention is:
1) modeling
First by microcomputer modelling software modeling, then become by the threedimensional model built up " subregion " thickness to be the cross section of 50 μm, namely cut into slices, thus instruct printer successively to print;
2) proportioning is calculated
According to the Composition Design requirement of gradient ceramic, calculate the component proportion of ceramic gradient structural member diverse location, as variable input computer, the powder feeding ratio of diverse location when controlling to print;
3) print parameters is set
Arranging print speed is 0.4m/s, print resolution 50 μm, for powder sending quantity is 1mm 3/ s;
4) raw material prepares
It is the feed cylinder that the MnZn ferrite of 0.5 μm and the NiZn ferrite powder component of 0.8 μm put into feed appliance after pretreatment respectively by particle diameter; Methacrylamide and methylene-bisacrylamide are dissolved in deionized water by the weight ratio of 18:1, is made into the premixed liquid that organic matter mass fraction is 12%; Premixed liquid is loaded transfusion rifle 1; Be persulfuric acid aqueous solution initator and the tetramethylethylenediamine catalyst loading transfusion rifle 2 of 2% by mass fraction;
5) gel injection-moulding 3D prints
Start printing device and carry out 3D printing.Feed appliance enters printhead according to the proportioning feeding of setting, and rifle of simultaneously infusing sends into the catalyst of the premixed liquid of powder volume 70%, the initator of premixed liquid volume 6% and premixed liquid volume 0.5% to printhead.Above-mentioned raw materials in printhead after mixing, print according to track, the speed of setting.According to trajectory, print forming surface line by line, more successively print formation three-dimensional ceramic functionally gradient material (FGM).In print procedure, control operating room's temperature at 80 DEG C, be beneficial to gel process;
6) sinter
Take out green compact and put into sintering furnace, be filled with nitrogen protection, 900 DEG C of sintering, cool to 150 DEG C of taking-ups with the furnace.
Carry out electron probe line analysis to the sample prepared by example 6, find its composition consecutive variations, MnZn ferrite reduces to 0% of opposite side by 100% of side, and sample interior exists without macroscopic interface.

Claims (9)

1. the gel injection-moulding 3D printing preparation method of gradient ceramic, is characterized in that its step is:
1) modeling
First by microcomputer modelling software modeling, then become by the threedimensional model built up " subregion " thickness to be the cross section of 20 ~ 100 μm, namely cut into slices, thus instruct printer successively to print;
2) proportioning is calculated
According to the Composition Design requirement of gradient ceramic, calculate the component proportion of ceramic gradient structural member diverse location, as variable input computer, the powder feeding ratio of diverse location when controlling to print;
3) print parameters is set
Arranging print speed is 0.05 ~ 0.5m/s, print resolution 20 ~ 100 μm, for powder sending quantity is 0.02 ~ 5mm 3/ s;
4) raw material prepares
It is the feed cylinder that the ceramic powder component of 0.1 ~ 10 μm puts into feed appliance after pretreatment respectively by particle diameter; Organic monomer and crosslinking agent are dissolved in deionized water by the weight ratio of 6 ~ 24:1, is made into the premixed liquid that organic matter mass fraction is 10 ~ 25%; Premixed liquid is loaded transfusion rifle 1; Initator and catalyst are loaded transfusion rifle 2;
5) gel injection-moulding 3D prints
Start printing device and carry out 3D printing; Feed appliance enters printhead according to the proportioning feeding of setting, and rifle of simultaneously infusing sends into premixed liquid, initator and catalyst to printhead; Above-mentioned raw materials in printhead after mixing, print according to track, the speed of setting; According to trajectory, print forming surface line by line, more successively print formation three-dimensional ceramic functionally gradient material (FGM); In print procedure, control operating room's temperature at 60 ~ 80 DEG C, be beneficial to gel process;
6) sinter
Take out green compact and put into sintering furnace, be filled with argon gas or nitrogen is protected, sintering temperature, between 600 ~ 1400 DEG C, cools to 100 ~ 300 DEG C of taking-ups with the furnace.
2. the gel injection-moulding 3D printing preparation method of gradient ceramic according to claim 1, is characterized in that described ceramic composition is ZrO 2, SiC, AlN, Si 3n 4, B 4c, SiO 2, TiC, Y 2o 3, Al 2o 3, ferrite.
3. the gel injection-moulding 3D printing preparation method of gradient ceramic according to claim 1, is characterized in that described organic monomer is acrylamide, Methacrylamide or vinyl pyrrole ketone.
4. the gel injection-moulding 3D printing preparation method of gradient ceramic according to claim 1, is characterized in that described crosslinking agent is methylene-bisacrylamide.
5. the gel injection-moulding 3D printing preparation method of gradient ceramic according to claim 1, is characterized in that described initator to be mass fraction is the persulfuric acid aqueous solution of 1 ~ 5%.
6. the gel injection-moulding 3D printing preparation method of gradient ceramic according to claim 1, is characterized in that described catalyst is tetramethylethylenediamine.
7. the gel injection-moulding 3D printing preparation method of gradient ceramic according to claim 1, is characterized in that described premixed liquid addition is 40 ~ 100% of solid phase ceramic powders volume.
8. the gel injection-moulding 3D printing preparation method of gradient ceramic according to claim 1, is characterized in that described initator addition is 2 ~ 10% of premixed liquid volume.
9. the gel injection-moulding 3D printing preparation method of gradient ceramic according to claim 1, is characterized in that described catalyst charge is 0.3 ~ 3% of premixed liquid volume.
CN201510004372.6A 2015-01-06 2015-01-06 The gel injection-moulding 3D printing preparation method of gradient ceramic CN104493952B (en)

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