CN103709917B - A kind of aftertreatment fluid for 3 D-printing device and preparation method thereof and application - Google Patents
A kind of aftertreatment fluid for 3 D-printing device and preparation method thereof and application Download PDFInfo
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- CN103709917B CN103709917B CN201310669671.2A CN201310669671A CN103709917B CN 103709917 B CN103709917 B CN 103709917B CN 201310669671 A CN201310669671 A CN 201310669671A CN 103709917 B CN103709917 B CN 103709917B
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Abstract
The invention discloses a kind of 3 D-printing device aftertreatment fluid preparation method and application. This aftertreatment fluid comprises host A liquid and the host B liquid placed respectively; Host A liquid is for filling hardening agent; Host B liquid is made up of 40～70% aqueous polyurethane emulsion, 5～30% aqueous epoxy emulsions, 10～30% distilled water, 10～40% Ludox, 0.2～0.7% coupling agent, 0.2～0.5% bleeding agent. When preparation, after aqueous polyurethane emulsion and aqueous epoxy emulsion add in distilled water and to mix, add coupling agent and Ludox, disperse; Add again bleeding agent, stir and prepare host B liquid. When use, 3 D-printing device is immersed in host A liquid, after infiltration, then is immersed in host B liquid, dry. Aftertreatment fluid of the present invention can improve intensity and the resistance to water of 3 D-printing device effectively, and has the device of preventing shedding, is applicable to the post processing of starch base, gypsum base or fiber base 3 D-printing device.
Description
Technical field
The present invention relates to a kind of aftertreatment fluid of 3 D-printing device, particularly relate to a kind of post processing for 3 D-printing deviceLiquid and preparation method thereof and application, belong to the Material Field of rapid shaping.
Background technology
Three-dimensional fast shaping successively prints the addition method, is a kind of apply wide and fast forming technique of processing speed. It is applicable toThe geometry structure of hundred kinds of different various complexity of application, and support multiple material type. But, due to binding material threeDimension printing technique bonds dusty material and moulding layer by layer by jet binder, and printout surface and inside exist more microporeStructure, therefore the intensity of printing shaping part is very limited, need to be through post processing strengthening.
The many post-processing approach that use are at present that instant drying adhesive is brushed, and its enhancing is effective, and shortcoming is that reaction speed is too fast,Storage life is short, poor water resistance, and durability is bad, and part instant drying adhesive solidifies glue face jaundice after latter 2 months, brushes and cannot protect simultaneouslyCard film is even.
Summary of the invention
The object of invention is, rough surface poor for 3 D-printing device strength deficiency, water imbibition, the easy problem such as shedding, carriesFor a kind of print device intensity and resistance to water that can effectively improve 3 D-printing, prevent shedding and make the smooth rear place of device surfaceReason liquid and preparation method thereof.
Another object of the present invention is to provide the application process of the described aftertreatment fluid for 3 D-printing device.
Object of the present invention realizes by following technical solution:
A kind of 3 D-printing device aftertreatment fluid that is used for, is characterized in that, by percentage to the quality, and by host A liquid and host BLiquid composition:
Described host A liquid is for filling hardening agent.
Described host B liquid, by percentage to the quality, formula comprises following component:
Described soluble polyurethane emulsion is water-based aliphaic polyurethane aqueous dispersion, and viscosity is 25～50s, and solid content is35～38% translucent milky emulsion;
Described Ludox is one or more in AJN-830, SKP-27, S-35;
Described coupling agent be type siloxane coupling agent gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane,N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane or γ-(2,3-epoxyThe third oxygen) one or more in propyl trimethoxy silicane;
Described bleeding agent is one in penetrating agent JFC, fast penetrant T, bleeding agent OE-35, superpower penetrating agent JFC-EKind or several;
When preparation, after aqueous polyurethane emulsion and aqueous epoxy emulsion are added and mixed in appropriate distilled water, low whipping speed is300～700rpm, adds coupling agent and Ludox, disperses; Add again bleeding agent, stir 30min～3h, prepare viscosity and beThe aftertreatment fluid of 8～40s;
Described host A is the DL31-concrete sealing reinforcing agent of Dongguan City Hui Zhi Nono-material Science & Technology Ltd., DL32-The agent of concrete infiltration tempering, the silica-based waterproof agent of Dow corning or U.S. high-tech chemical industry Chem-creteCAF140;
Described Ludox is in Foshan, the flood AJN-830 of glass factory, the SKP-27 of Guangzhou Hui Hegui Products Co., Ltd, S-35In one or more;
Described coupling agent is Aladdin reagent gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, γ-shrink sweetOil ether oxygen propyl trimethoxy silicane, West Asia reagent N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, Qingdao rising sun sunriseOne or more in the γ of work Co., Ltd-(2,3-epoxy the third oxygen) propyl trimethoxy silicane;
Described bleeding agent is DOW Chemical penetrating agent JFC, Jiangsu Hai'an Petrochemical Plant's fast penetrant T, bleeding agentOne or more in OE-35, the superpower penetrating agent JFC-E of the luxuriant prosperous chemical industry in Jiangsu;
In order further to realize the object of the invention, described aqueous polyurethane emulsion is Guangzhou Guan Zhi Chemical Co., Ltd.PU-202B, PU-303B, the Acure8110 of Shanghai Yuan He Chemical Co., Ltd., BayhydrolXP2558 or the patina of sky, GuangdongThe TC-103 of work Co., Ltd;
Described aqueous epoxy emulsion be the 3520-WY-55A of Guangzhou Li Baoshi Trade Development Co., Ltd, 3540-WY-55A or3522；
The application process of this aftertreatment fluid is as follows: the 3 D-printing device of moulding is immersed in to 1～30s in host A liquid, treatsAfter host A liquid permeates completely, then being immersed in 1～30s filter paper in host B liquid, to blot the surface on print device surface obviously surplusRemaining liquid dries 1～5h at 30～100 DEG C.
The technical indicator of the aftertreatment fluid of preparation is as follows as stated above:
Outward appearance: milky white liquid
Viscosity: 8～40s
Device compression strength after immersion aftertreatment fluid: > 9MPa
After soaking aftertreatment fluid, device surface is smooth, not dry linting
Device water absorption rate after immersion aftertreatment fluid: < 11%
With respect to prior art, tool of the present invention has the following advantages:
1) of the present invention for 3 D-printing device aftertreatment fluid, selecting commercially available sealing hardening agent or the agent of infiltration tempering is host ALiquid, host B liquid is taking aqueous polyurethane emulsion as main film forming substance. This emulsion have fracture strength large (being greater than 35MPa),Viscosity is little, the fine and smooth tough and tensile and good solvent resistance of film forming, but the film forming at substrate surface is thinner; Add a kind of commercially availableGood to base material adhesive force, admittedly can increase film thickness and hardness containing high aqueous epoxy emulsion.
2) the present invention adds proper amount of silicon colloidal sol. The silanol base activity of the cataloid in Ludox is larger, can be by hairTubule is directly penetrated into base material inside, is firmly adsorbed on substrate surface. After the polyaminoester emulsion blend film forming, can improve filmAdhesive force. Adding of silane coupler, not only play the effect that prevents Ludox cohesion, changed organic-inorganic material simultaneouslyInterface adhesion, has improved adhesive property.
3) aftertreatment fluid that the present invention prepares can long term storage, has overcome instant drying adhesive short shortcoming service time. Adopt waterProperty raw material, raw material is easy to get, and toxicity is lower, lower to the harmful effect of human body and environment, and handling safety is conducive to marketing.
4) the present invention is simple, easy to use for 3 D-printing device aftertreatment fluid preparation method, has a good application prospect.
Detailed description of the invention
For understanding better the present invention, below in conjunction with embodiment, the present invention is elaborated, but protection scope of the present invention is not limitIn the scope of following embodiment statement.
The cube that it is 30cm × 30cm × 30cm that the present invention tests with gypsum base 3 D-printing device is self-control gypsum base powderPrint gained with aqueous binders via the Z310 of ZCorporation company three-dimensional printing machine, rough surface, easily shedding, strongIt is poor to spend, and water proofing property is poor, in soaked 10s, dissolves.
The aftertreatment fluid method of testing that the each example of the present invention is implemented preparation is all according to following standard testing
Appearance milky white liquid
Viscosity is pressed GB/T2794-1995 standard test
Compression strength is pressed GB/T15231.2-94 standard test
After surface characteristics is soaked and is dried, observe surface and have or not granular sensation, whether whether hand is touched smooth, glossy
Water suction takes the lead in weighing detected sample and is designated as m1, then immerse (23 ± 0.5) DEG C. In distilled waterAfter (24 ± 1) h, take out sample and wipe the specimen surface globule with filter paper, again weighBe designated as m2(measurement is accurate to 1mg). This job requirement completes in lmin.
Sample water suction percentage: W=(m2-m1)/m1*100％
Embodiment 1
A kind of 3 D-printing device aftertreatment fluid host A liquid that is used for is selected DL31-concrete sealing reinforcing agent.
A kind of for 3 D-printing device aftertreatment fluid host B liquid, formed by the raw material of following percentage by weight proportioning:
Aqueous polyurethane PU-202B viscosity for 3 D-printing device aftertreatment fluid host B liquid is 25s, and solid content is 35%Translucent milky.
For the preparation method of 3 D-printing device aftertreatment fluid host B liquid: by 57% aqueous polyurethane emulsion PU-202B andAfter 6% aqueous epoxy emulsion 3540-WY-55A adds in 17% distilled water and to mix, low whipping speed is 500rpm, adds 0.5%Coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane and 19% Ludox AJN-830, disperse; Add again 0.5% superpowerPenetrating agent JFC-E, stirs 30min, and preparing viscosity is the host B liquid of 23s.
Using method for 3 D-printing device aftertreatment fluid: the gypsum base 3 D-printing device of moulding is immersed in to host5s in A liquid, after liquid permeates completely, then is immersed in 5s in host B liquid, and infiltration process finds that infiltration liquid is at printout tableFace rapid diffusion; Dry the remaining liq on print device surface, 80 DEG C of preliminary drying 3h. Carry out respectively compression strength, water imbibition,Surface characteristics, whether shedding is tested, and test result is as shown in table 1.
Embodiment 2
A kind of 3 D-printing device aftertreatment fluid host A liquid that is used for is selected silica-based waterproof agent.
A kind of for 3 D-printing device aftertreatment fluid host B liquid, formed by the raw material of following weight proportion:
Aqueous polyurethane BayhydrolXP2558 viscosity for 3 D-printing device aftertreatment fluid host B liquid is 40s, GuContent is 37% translucent milky.
Preparation method for 3 D-printing device aftertreatment fluid host B liquid: by 60% aqueous polyurethane emulsion BayhydrolXP2558 and 8% after aqueous epoxy emulsion 3540-WY-55A adds in 15% distilled water and to mix, and low whipping speed is 450rpm,Add 0.7% coupling agent N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane and 16% Ludox SKP-27, disperse; AgainAdd 0.3% bleeding agent OE-35, stir 1h, preparing viscosity is the host B liquid of 20s.
Using method for 3 D-printing device aftertreatment fluid: the gypsum base 3 D-printing device of moulding is immersed in to host10s in A liquid, after liquid permeates completely, then is immersed in 10s in host B liquid, and infiltration process finds that infiltration liquid is at printoutSurface rapid diffusion; Dry the remaining liq on print device surface, 70 DEG C of preliminary drying 3h. Carry out respectively compression strength, water imbibition,Surface characteristics, whether shedding is tested, and test result is as shown in table 1.
Embodiment 3
A kind of 3 D-printing device aftertreatment fluid host A liquid that is used for is selected the agent of DL32-concrete infiltration tempering.
A kind of for 3 D-printing device aftertreatment fluid host B liquid, formed by the raw material of following weight proportion:
Aqueous polyurethane PU-303B viscosity for 3 D-printing device aftertreatment fluid host B liquid is 27s, and solid content is 35%Translucent milky.
For the preparation method of 3 D-printing device aftertreatment fluid host B liquid: by 50% aqueous polyurethane emulsion PU-303B andAfter 25% aqueous epoxy emulsion 3522 adds in 7% distilled water and to mix, low whipping speed is 600rpm, adds 0.7% coupling agentGamma-aminopropyl-triethoxy-silane and 17% Ludox SKP-27, disperse; Add again 0.3% fast penetrant T, stir 30min,Preparing viscosity is the host B liquid of 18s.
Using method for 3 D-printing device aftertreatment fluid: the gypsum base 3 D-printing device of moulding is immersed in to host15s in A liquid, after liquid permeates completely, then is immersed in 5s in host B liquid, and infiltration process finds that infiltration liquid is at printout tableFace rapid diffusion; Dry the remaining liq on print device surface, 85 DEG C of preliminary drying 2h. Carry out respectively compression strength, water imbibition,Surface characteristics, whether shedding is tested, and test result is as shown in table 1.
Embodiment 4
A kind of 3 D-printing device aftertreatment fluid host A liquid that is used for is selected the agent of DL32-concrete infiltration tempering.
A kind of for 3 D-printing device aftertreatment fluid host B liquid, formed by the raw material of following weight proportion:
Aqueous polyurethane TC-103 viscosity for 3 D-printing device aftertreatment fluid host B liquid is 30s, and solid content is 33%Translucent milky.
Preparation method for 3 D-printing device aftertreatment fluid host B liquid: by 70% aqueous polyurethane emulsion TC-103 and 5%After aqueous epoxy emulsion 3520-WY-55A adds in 13.9% distilled water and to mix, low whipping speed is 400rpm, adds 0.6%Coupling agent γ-aminopropyltrimethoxysilane and 10% Ludox AJN-830, disperse; Add again 0.5% bleeding agent OE-35,Stir 2h, preparing viscosity is the host B liquid of 20s.
Using method for 3 D-printing device aftertreatment fluid: the gypsum base 3 D-printing device of moulding is immersed in to host5s in A liquid, after liquid permeates completely, then is immersed in 15s in host B liquid, and infiltration process finds that infiltration liquid is at printout tableFace rapid diffusion; Dry the remaining liq on print device surface, 80 DEG C of preliminary drying 2h. Carry out respectively compression strength, water imbibition,Surface characteristics, whether shedding is tested, and test result is as shown in table 1.
Embodiment 5
A kind of 3 D-printing device aftertreatment fluid host A liquid that is used for is selected Chem-creteCAF140.
A kind of for 3 D-printing device aftertreatment fluid host B liquid, formed by the raw material of following weight proportion:
Aqueous polyurethane Acure8110 viscosity for 3 D-printing device aftertreatment fluid host B liquid is 40s, and solid content is35% translucent milky.
Preparation method for 3 D-printing device aftertreatment fluid host B liquid: by 45% aqueous polyurethane emulsion Acure8110After adding in 19% distilled water and to mix with 15% aqueous epoxy emulsion 3520-WY-55A, low whipping speed is 450rpm, adds0.5% coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane and 20% Ludox S-35, disperse; Add again 0.5% infiltrationAgent JFC, stirs 50min, and preparing viscosity is the host B liquid of 14s.
Using method for 3 D-printing device aftertreatment fluid: the gypsum base 3 D-printing device of moulding is immersed in to host20s in A liquid, after liquid permeates completely, then is immersed in 10s in host B liquid, and infiltration process finds that infiltration liquid is at printoutSurface rapid diffusion; Dry the remaining liq on print device surface, 50 DEG C of preliminary drying 4h. Carry out respectively compression strength, water imbibition,Surface characteristics, whether shedding is tested, and test result is as shown in table 1.
Embodiment 6
A kind of 3 D-printing device aftertreatment fluid host A liquid that is used for is selected Chem-creteCAF140.
A kind of for 3 D-printing device aftertreatment fluid host B liquid, formed by the raw material of following weight proportion:
Aqueous polyurethane PU-202B viscosity for 3 D-printing device aftertreatment fluid host B liquid is 25s, and solid content is 35%Translucent milky.
For the preparation method of 3 D-printing device aftertreatment fluid host B liquid: by 60% aqueous polyurethane emulsion PU-202B andAfter 15% aqueous epoxy emulsion 3540-WY-55A adds in 11% distilled water and to mix, low whipping speed is 325rpm, adds 0.4%Coupling agent gamma-aminopropyl-triethoxy-silane and 13% Ludox S-35, disperse; Add again 0.6% superpower penetrating agent JFC-E,Stir 2h, preparing viscosity is the host B liquid of 18s.
Using method for 3 D-printing device aftertreatment fluid: the gypsum base 3 D-printing device of moulding is immersed in to host10s in A liquid, after liquid permeates completely, then is immersed in 15s in host B liquid, and infiltration process finds that infiltration liquid is at printoutSurface rapid diffusion; Dry the remaining liq on print device surface, 90 DEG C of preliminary drying 2h. Carry out respectively compression strength, water imbibition,Surface characteristics, whether shedding is tested, and test result is as shown in table 1.
Embodiment 7
A kind of 3 D-printing device aftertreatment fluid host A liquid that is used for is selected DL31-concrete sealing reinforcing agent.
A kind of for 3 D-printing device aftertreatment fluid host B liquid, formed by the raw material of following weight proportion:
Aqueous polyurethane Acure8110 viscosity for 3 D-printing device aftertreatment fluid host B liquid is 40s, and solid content is35% translucent milky.
Preparation method for 3 D-printing device aftertreatment fluid host B liquid: by 55% aqueous polyurethane emulsion Acure8110After adding in 14.2% distilled water and to mix with 20% aqueous epoxy emulsion 3522, low whipping speed is 450rpm, adds 0.4%Coupling agent γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane and 10% Ludox AJN-830, disperses; Add again 0.4% infiltrationAgent JFC, stirs 1h, and preparing viscosity is the host B liquid of 18s.
Using method for 3 D-printing device aftertreatment fluid: the gypsum base 3 D-printing device of moulding is immersed in to host25s in A liquid, after liquid permeates completely, then is immersed in 10s in host B liquid, and infiltration process finds that infiltration liquid is at printoutSurface rapid diffusion; Dry the remaining liq on print device surface, 85 DEG C of preliminary drying 4h. Carry out respectively compression strength, water imbibition,Surface characteristics, whether shedding is tested, and test result is as shown in table 1.
Comparison example 1
According to the preparation method of embodiment 7 and using method, do not add coupling agent γ-(2,3-epoxy the third oxygen) propyl trimethoxySilane.
Comparison example 2
Commercially available 502 instant drying adhesives are brushed on gypsum base 3 D-printing device to 80 DEG C of preliminary drying 3h. Carry out respectively compression strength,Water imbibition, surface characteristics, whether shedding is tested, and test result is as shown in table 1.
Blank assay
Do not pass through the gypsum base 3 D-printing device of any processing.
Table 1 is the key property test of embodiment of the present invention gained aftertreatment fluid.
Table 1 aftertreatment fluid key property
From table 1 test result, the compression strength of embodiment 1-7 is all higher than the device without processing later, with respect to blankThe maximum 5.9Mpa that improves of experiment, water absorption rate is all lower than 11%. The device that aftertreatment fluid prepared by the present invention was processed shows anti-Compressive Strength is high, water-tolerant, and surface smoothness is good, glossy, the excellent properties of not shedding. Immersion process is found host ALiquid infiltration is very fast, and compression strength improves explanation host A liquid and infiltrates through the gap of print device and generated crystallization or harder filmBe filled in device gap, the reduction explanation host B liquid of water absorption rate has formed resistance to water film at device surface.
By water absorption rate in comparison example 1, than having improved 11.4% in embodiment 7, and skin covering of the surface is easily peeled off. Adding of coupling agent, is describedEnter, play the effect of a bridge joint, improved the fusion of host A liquid and host B liquid, formed stable composite membrane system.
By comparison example 2, the water imbibition of the aftertreatment fluid of discovery the present invention preparation is far above commercially available 502 instant drying adhesives. Compression strengthAlso a little more than 502 instant drying adhesives. But the using method of the aftertreatment fluid of the present invention's preparation is simple, pollution-free, and be easy to store.
The above embodiment of the present invention is not determinate. For a person skilled in the art, can on basis of the present invention, do phaseThe changes and improvements of answering, but within should belonging to the protection domain of patent of the present invention.
Claims (5)
1. for a 3 D-printing device aftertreatment fluid, it is characterized in that, comprise host A liquid and the host B liquid placed respectively:
Described host A liquid is as filling hardening agent; Described host A liquid is DL31-concrete sealing reinforcing agent, the agent of DL32-concrete infiltration tempering, silica-based waterproof agent or Chem-creteCAF140;
Described host B liquid, by percentage to the quality, formula comprises following component:
Described aqueous polyurethane emulsion is water-based aliphaic polyurethane aqueous dispersion, and viscosity is 25～50s, the translucent milky emulsion that solid content is 35～38%; Viscosity is pressed GB/T2794-1995 standard test;
Described Ludox is one or more in AJN-830, SKP-27 or S-35;
Described coupling agent is one or more in type siloxane coupling agent gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane or γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane;
Described bleeding agent is one or more in penetrating agent JFC, fast penetrant T, bleeding agent OE-35 or superpower penetrating agent JFC-E;
When preparation, after aqueous polyurethane emulsion and aqueous epoxy resin emulsion are added and mixed in distilled water, low whipping speed is 300～700rpm, adds coupling agent and Ludox, disperses; Add bleeding agent again, stir 30min～3h, preparing viscosity is the host B liquid of 8～40s; Viscosity is pressed GB/T2794-1995 standard test.
2. according to claim 1 for 3 D-printing device aftertreatment fluid, it is characterized in that: described aqueous polyurethane emulsion is PU-202B, PU-303B, Acure8110, BayhydrolXP2558 or TC-103.
3. according to claim 1 for 3 D-printing device aftertreatment fluid, it is characterized in that: described aqueous epoxy resin emulsion is 3520-WY-55A or 3540-WY-55A.
4. the preparation method for 3 D-printing device aftertreatment fluid described in claim 1-3 any one, it is characterized in that comprising the following steps: after getting and mixing in the distilled water that the aqueous polyurethane emulsion of prescription quality part and aqueous epoxy resin emulsion add prescription quality part, low whipping speed is 300～700rpm, add coupling agent and the Ludox of prescription quality part, disperse; Add prescription quality part bleeding agent again, stir 30min～3h, preparing viscosity is the host B liquid of 8～40s; Viscosity is pressed GB/T2794-1995 standard test;
Comprise host A liquid and the host B liquid placed respectively for 3 D-printing device aftertreatment fluid: described host A liquid is as filling hardening agent.
5. the application process for 3 D-printing device aftertreatment fluid described in claim 1-3 any one, it is characterized in that comprising the following steps: the 3 D-printing device of moulding is immersed in to 1～30s in host A liquid, after host A liquid permeates completely, be immersed in again 1～30s in host B liquid, blot the obvious raffinate in surface on print device surface with filter paper, at 30～100 DEG C, dry 1～5h.
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| CN105153872A (en) * | 2015-07-29 | 2015-12-16 | 天津城建大学 | Preparation method for composite emulsion waterproof agent used for surface water prevention of raw soil wall |
| CN106380933B (en) * | 2016-08-25 | 2018-06-29 | 湖南新力华纳米科技有限公司 | A kind of printable aqueous polyurethane 3D polishes or 3D ink |
| CN106393663A (en) * | 2016-08-30 | 2017-02-15 | 宁夏共享模具有限公司 | Full-color sandstone dye for 3DP (three dimensional printing) and forming method of full-color sandstone dye product |
| CN107417299B (en) * | 2017-09-07 | 2019-10-22 | 南京工业大学 | A kind of aftertreatment technology of 3D printing plastering |
| EP3684861B1 (en) * | 2017-11-30 | 2023-12-27 | Hewlett-Packard Development Company, L.P. | 3d-printed articles |
| CN112680069B (en) * | 2020-12-14 | 2022-09-13 | 成都展辰涂料有限公司 | Waterborne two-component epoxy woodware coating for sealing tannic acid and high grease and preparation method thereof |
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| JP2013035251A (en) * | 2011-08-10 | 2013-02-21 | Sony Corp | Three-dimensional shaped article, method of manufacturing the same, and liquid composition for manufacturing three-dimensional shaped article |
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| CN1546569A (en) * | 2003-12-18 | 2004-11-17 | 北京工业大学 | Ceramic composite timber precursor liquid and its preparation method |
| CN1624234A (en) * | 2004-10-22 | 2005-06-08 | 上海工程技术大学 | Modified nanometer dxide multifunction finishing agent, preparation method and its use |
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