CN100404600C - Starch base material system for tridimensional spraying and adhesive bonding and preparation method thereof - Google Patents
Starch base material system for tridimensional spraying and adhesive bonding and preparation method thereof Download PDFInfo
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- CN100404600C CN100404600C CNB200610012721XA CN200610012721A CN100404600C CN 100404600 C CN100404600 C CN 100404600C CN B200610012721X A CNB200610012721X A CN B200610012721XA CN 200610012721 A CN200610012721 A CN 200610012721A CN 100404600 C CN100404600 C CN 100404600C
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Abstract
The present invention relates to a starch base material system for tridimensional spraying and adhesive bonding fast molding technique, which comprises composite base material and adhesive matched with the composite base material, wherein the composite base material is formed by that starch, adhesive, accelerating agent CMC, dispersing agent which is white carbon black, reinforcing agent and borax are uniformly mixed; the adhesive is formed by that oxidizing agent, NaOH, water-based polyurethane adhesive, phenolic resin, non-ionic surface activator and alcohol solutizer are dissolved in deionized water and mixed. According to the characteristics of the tridimensional spraying and adhesive bonding fast molding technique, the present invention selects raw material with low cost to obtain the molding composite base material and the matched adhesive which can completely meet the use requirements through the simple preparation process of technology.
Description
Affiliated technical field
The present invention relates to rapid shaping technique, specifically, the present invention relates to a kind of material system that uses for the 3-D spraying binding rapid shaping technique, comprise base-material and with the supporting caking agent of this base-material, particularly based on the base-material and the adhesive material system supporting of starch with it.
Background technology
3 D-printing (the Three Dimensional Printing that at first proposes by (US patent 5204055) such as the Sachs of Massachusetts Institute Technology, 3DP) Rapid Prototyping technique is the most vital technology in the at present quick shaping industry, it has the height process flexibility that traditional production is had no precedent, various tool that need not conventional powder machine-shaping is not subjected to the restriction of any geometrical shape.Because spraying position, spraying number of times, spraying rate can arbitrarily be controlled, different materials can be by different shower nozzle sprayings, spraying substance can be solution, suspension, emulsion and melt substance etc., therefore, the 3DP forming technique can be controlled local material composition, microtexture and surface property at an easy rate.Because the 3DP forming technique for constantly to repeat process of agglutinating on a machine, is easy to design studies, the technology stability problem that does not exist mass-producing to amplify with numerous conventional processes unifications in the industrial production conversion process.The advantage that the 3DP forming technique is the most outstanding is to need not mechanical workout or any mould, just can directly from computer graphics data, generate the part of Any shape, thereby greatly shorten the lead time of product, boost productivity and reduce production costs, really embody the advantage of Rapid Prototyping technique.
3 D-printing is similar to ink-jet printer as a kind of forming technique that does not rely on laser.Concrete printing technological process is at first according to product requirement, set up cad model by computer aided design (CAD), characterize the image of object with this cad file,, cad file is converted into stereolithography form (STL) through the digital processing simulation, by computer control 3 D-printing equipment, notion according to " successively print, be layering " is successively made entity, finishes overall print process, carry out aftertreatment subsequently again, thereby prepare object with special external form or complex internal structure.
Traditional detail design all is two-dimentional three-view diagram, though present design software such as UG, Pro/ENGINEER etc. can design three-dimensional view, does not realize real pattern layout, just conceptual design.The 3DP forming technique will make solid model be designed to possibility.Only need convert the part of common software design to the STL form, utilize the 3 D stereo printer again, need not be how long, real three-dimensional stereo model will appear at the planner in face of.So just can reduce expenses greatly, reduce unnecessary waste, but also can accelerate Products Development, dominate the market rapidly.
The 3 D-printing Rapid Prototyping technique mainly contains following three kinds of main modes: spraying microparticles, spray ink Printing moulding, 3-D spraying binding.
Wherein, the process principle of 3-D spraying binding is according to the three-dimensional data model in the computer, and prototype or part are carried out hierarchy slicing, obtains the outline data of each layer cross section.Computer is the printing head on the data message control three-dimensional printer in view of the above, layering cross section profile according to prototype or part, on the material powder layer that each layer completed in advance, spray one deck liquid adhesive selectively, the path material that sprayed caking agent is bonded in together, form a sheet entity profile, and elsewhere remains bulky powder with small thickness.After one deck powder forming is finished, following one deck powder bonding, so circulation successively is piled into one after bonding layer by layer, obtains a three-dimensional space entity, removes powder and carry out the back sintering just to produce designed product innovation exemplar, model or mould.
The material system of 3-D spraying binding Rapid Prototyping technique comprises suitable powder binder and the adhesive solution that matches with it.Wherein require to have at least following performance for powder binder:
1, particle is little, even, does not have obviously and reunites;
2, mobility of particle is good, can be paved into thin layer;
3, when the solution jet impact, base-material can not produce depression, splatter and hole;
4, with the adhesive solution effect after can very fast curing.
Also require to possess following performance at least for adhesive solution:
1, stable performance, the energy standing storage;
2, printer head there is not corrosive nature;
3, have enough low viscosity and sufficiently high surface tension, so that can from printer head, extrude according to the flow of expection;
4, be difficult for drying up, can prolong the anti-duration of congestion of printer head.
In addition, should guarantee that also employed base-material and caking agent are all nontoxic, pollution-free.
Summary of the invention
The purpose of this invention is to provide a kind of material system that is suitable for the 3-D spraying binding rapid shaping technique, and the preparation method of this material system.
Material system of the present invention comprises a kind of composite base-material and supporting with it caking agent, and wherein, described composite base-material is by following portions by weight:
Starch 75～85
Binding agent 10～15
Accelerating chemicals CMC 1～2
The white carbon black 0.5～3 of dispersion agent
Toughener 1～3
Borax 1～5
Be mixed and made into;
Described caking agent is by following portions by weight:
Oxygenant clorox or potassium permanganate 0.5～3
NaOH 0.5～3
Waterbased urethane tackiness agent 0.5～3
Phenolic resin 0.5～2
Nonionogenic tenside 0.5～3
Co-solvent 1～3
Deionized water 90～95
Be mixed and made into.
Wherein, the framework ingredient during the starch base composite base-material is formed is a starch, and described starch is W-Gum or potato starch preferably.
In other component, the binding agent that uses is polyvinyl alcohol or Emulsion acrylic resin.Polyvinyl alcohol is a kind of water miscible poly-hydroxy high molecular polymer, and its aqueous solution has certain viscosity, and filamentary material is had good affinity and reasonable wettability and cohesiveness.Emulsion acrylic resin is that acrylic ester monomer is dispersion medium with water, and under emulsifying agent and mechanical agitation, through the macromolecular compound water miscible liquid that letex polymerization forms, it is nontoxic, pollution-free, raw material is easy to get, clinging power is strong.
In the starch base composite base-material, also be added with accelerating chemicals Xylo-Mucine (CMC) and the white carbon black of dispersion agent, and add glass fibre, lithium silica flour or anhydrous calcium sulfate whisker as toughener.
At last, the present invention also is added with borax as mineral filler in the starch base composite base-material.The molecular formula of borax is Na
2(H
2O)
8(B
4O
5(OH)
4), soluble in water, have the bonding effect of crosslinked enhancing usually, help improving initial bonding strength and increase quick-drying speed.Add borax in the starch base composite base-material, the Sumstar 190 that can make short chain is with its hydroxyl or hydroxyl and boron atom formation complex compound, irregular crosslinked by these, form reticulated structure, has crosslinked viscosifying action, help improving initial bonding strength and accelerate rate of drying, also play anticorrosion, antiseepage and termination reaction effect in addition.But the consumption of borax is not The more the better, and too much consumption can make the mobile variation of base-material.
Correspondingly, mix by oxygenant, paste agent, tackiness agent, incremental dose, wetting agent and solubility promoter with the supporting caking agent of above-mentioned starch base composite base-material and form.
Oxygenant commonly used is clorox and potassium permanganate.In order to make the starch base composite base-material have processability preferably, oxidation is suitable, and the starch dissolution performance improves, and film forming ability is good, and bonding force is strong, should add clorox or potassium permanganate oxidant in caking agent.
In caking agent, also be added with NaOH as paste agent.The effect of paste agent is the alcohol radical chemical combination that makes in its molecule and the starch, destroys the part hydrogen bond, makes the reaction force attenuation between starch polymer, and molecular change gets comparatively and releives, and helps the generation of oxidizing reaction; Secondly, paste agent can be emitted a large amount of heat after being dissolved in starch, makes that starch molecule expands, gelatinization, thereby makes starch have very strong cohesive force; In addition, paste agent also makes caking agent have good mobility.
Add the waterbased urethane tackiness agent as tackiness agent in caking agent, add phenolic resin as incremental dose, incremental dose effect is the surface tension that reduces caking agent, does not cause it to stop up shower nozzle.
Also be added with nonionogenic tenside as wetting agent, described nonionogenic tenside is sorbitan mono-laurate class or alkyl polyoxyethylene esters surface active agent.
In addition, also be added with co-solvent, the effect of solubility promoter is to make the solubleness of starch base-material in caking agent reach maximum, thereby makes the even structure of final molding part, strength of joint height.Described co-solvent is one or more in ethanol, glycerine, propylene glycol, the polyoxyethylene glycol.
The preparation method of above-mentioned starch base composite base-material is to be major ingredient with starch, is aided with other auxiliary agent and carries out modification and handle, and final sizing obtains composite base-material, and concrete preparation method is:
A), with starch cool to-60 ℃～-150 ℃, pulverize, screening makes starch dust;
B), binding agent, accelerating chemicals CMC, the white carbon black of dispersion agent, toughener and borax are added in a) the fine powder successively, mix with high-speed mixer;
C), the b that mixes) powder obtains the composite base-material of required fineness after the reciprocating sieve screening.
Wherein, starch sieves the fine powder of selecting its 40～60 μ m for use after crushed.
With the preparation method of the supporting caking agent of above-mentioned composite base-material be:
A), with deionized water dissolved oxidant clorox or potassium permanganate;
B), add NaOH and make dissolving fully;
C), add waterbased urethane tackiness agent, phenolic resin, nonionogenic tenside successively;
D), add co-solvent, mixing and stirring obtains required caking agent.
Starch base material system for tridimensional spraying and adhesive bonding provided by the invention is made up of starch base composite base-material and supporting with it caking agent, and wherein, the starch base composite base-material has following characteristics:
1, powder appearance white, median size 50 μ m;
2, the powder particle level prepares, and shop powder density height does not have obviously and reunites;
3, mobility of particle is good, can be paved into thin layer;
4, when the solution jet impact, base-material can not produce depression, splatter and hole;
5, with the adhesive solution effect after can very fast curing, time of coagulation≤4min;
6, profiled member precision height, the size distortion made are little, profiled member scale error≤0.02mm;
7, the profiled member aftertreatment is simple and convenient, can make profiled member elegant in appearance.
Correspondingly, the caking agent supporting with above-mentioned composite base-material has good flowing property, can controlled high-density spray in the nozzle of the following aperture of 60 μ m, do not stop up shower nozzle; By having certain surface tension, flow is controlled simultaneously; And nontoxic pollution-free, shower nozzle there is not corrosive nature.
At present, with respect to other rapid shaping technique, the 3DP technical development is rapid, need further research and develop out the shaped material that has more good over-all properties.The present invention is directed to the characteristics of 3-D spraying binding Rapid Prototyping technique, select the cheap relatively raw material of cost for use,, obtained to satisfy fully the moulding composite base-material and the supporting with it caking agent of service requirements through simple prepared process.
Embodiment
Embodiment 1
Get the 75g W-Gum, in refrigerating apparatus, be cooled to-120 ℃, make the W-Gum that median size is 40～60 mu m ranges after grinding and processing, the screening.Add 15g Emulsion acrylic resin, the white carbon black of 2gCMC, 2g, 2g glass fibre, 4g borax in the W-Gum after processing successively, in high-speed mixer, mix.The powder of above-mentioned modification is sieved in reciprocating sieve, and obtaining median size is the compound W-Gum base-material of 40～60 μ m.
The 1g clorox is joined evenly stirring in the 95g deionized water, add 0.8g NaOH again, it is dissolved fully.Add 1g waterbased urethane tackiness agent, 0.5g phenolic resin, 0.7g alkyl polyoxyethylene ether class wetting agent and 1g ethanol successively, stir, obtain supporting with it adhesive solution.
Embodiment 2
Get the 80g W-Gum, in refrigerating apparatus, be cooled to-70 ℃, make the W-Gum that median size is 40～60 mu m ranges after grinding and processing, the screening.Add 12g polyvinyl alcohol, the white carbon black of 2g CMC, 1.5g, 2.5g lithium silica flour, 2g borax in the W-Gum after processing successively, in high-speed mixer, mix.The powder of above-mentioned modification is sieved in reciprocating sieve, and obtaining median size is the compound W-Gum base-material of 40～60 μ m.
1g potassium permanganate is joined evenly stirring in the 92g deionized water.Add 0.5g NaOH again, it is dissolved fully.Add 1.5g waterbased urethane tackiness agent, 0.5g phenolic resin, 0.5g sorbitan mono-laurate class wetting agent and 1g propylene glycol successively, stir, obtain supporting with it adhesive solution.
Embodiment 3
Get the 85g potato starch, in refrigerating apparatus, be cooled to-90 ℃, make the potato starch that median size is 40～60 mu m ranges after grinding and processing, the screening.Add 10g polyvinyl alcohol, the white carbon black of 1.5g CMC, 1g, 1.5g anhydrous calcium sulfate whisker, 1g borax in the potato starch after processing successively, in high-speed mixer, mix.The powder of above-mentioned modification is sieved in reciprocating sieve, and obtaining median size is the compound potato starch base material of 40～60 μ m.
The 2g clorox is joined evenly stirring in the 90g deionized water.Add 1.5g NaOH again, it is dissolved fully.Add 2.5g waterbased urethane tackiness agent, 1g phenolic resin, 1g alkyl polyoxyethylene ether class wetting agent and 2g polyoxyethylene glycol successively, stir, obtain supporting with it adhesive solution.
Claims (8)
1. the material for the use of 3-D spraying binding rapid shaping technique is made up of composite base-material and supporting with it caking agent, wherein,
Described composite base-material is by following portions by weight:
Starch 75～85
Binding agent 10～15
Accelerating chemicals CMC 1～2
The white carbon black 0.5～3 of dispersion agent
Toughener 1～3
Borax 1～5
Be mixed and made into;
Described caking agent is by following portions by weight:
Oxygenant clorox or potassium permanganate 0.5～3
NaOH 0.5～3
Waterbased urethane tackiness agent 0.5～3
Phenolic resin 0.5～2
Nonionogenic tenside 0.5～3
Co-solvent 1～3
Deionized water 90～95
Be mixed and made into.
2. material according to claim 1 is characterized in that described starch is W-Gum or potato starch.
3. material according to claim 1 is characterized in that described binding agent is polyvinyl alcohol or Emulsion acrylic resin.
4. material according to claim 1 is characterized in that described toughener is glass fibre, lithium silica flour or anhydrous calcium sulfate whisker.
5. material according to claim 1 is characterized in that described nonionogenic tenside is sorbitan mono-laurate class or alkyl polyoxyethylene esters surface active agent.
6. material according to claim 1 is characterized in that described co-solvent is one or more in ethanol, glycerine, propylene glycol, the polyoxyethylene glycol.
7. the described preparation methods of claim 1, wherein,
Described composite base-material preparation method is:
A), with starch cool to-60 ℃～-150 ℃, pulverize, screening makes starch dust;
B), binding agent, accelerating chemicals CMC, the white carbon black of dispersion agent, toughener and borax are added in a) the fine powder successively, mix with high-speed mixer;
C), the b that mixes) powder obtains the composite base-material of required fineness after the reciprocating sieve screening;
Described caking agent preparation method is:
A), with deionized water dissolved oxidant clorox or potassium permanganate;
B), add NaOH and make dissolving fully;
C), add waterbased urethane tackiness agent, phenolic resin, nonionogenic tenside successively;
D), add co-solvent, mixing and stirring obtains required caking agent.
8. preparation methods according to claim 7 is characterized in that starch after crushed, and the fine powder of its 40～60 μ m is selected in screening for use.
Priority Applications (1)
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|---|---|---|---|
| CNB200610012721XA CN100404600C (en) | 2006-05-15 | 2006-05-15 | Starch base material system for tridimensional spraying and adhesive bonding and preparation method thereof |
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|---|---|---|---|
| CNB200610012721XA CN100404600C (en) | 2006-05-15 | 2006-05-15 | Starch base material system for tridimensional spraying and adhesive bonding and preparation method thereof |
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| CN100404600C true CN100404600C (en) | 2008-07-23 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093646B (en) * | 2010-10-29 | 2012-07-18 | 华南理工大学 | Material for rapid three dimensional printing forming and preparation method thereof |
| CN103358552B (en) * | 2013-07-30 | 2015-09-30 | 珠海天威飞马打印耗材有限公司 | Three-dimensional modeling Method of printing |
| CN104150915B (en) * | 2014-08-06 | 2015-08-26 | 西安交通大学 | A kind of powder 3D Method of printing based on water-based inorganic binding agent |
| CN105928629A (en) * | 2016-04-29 | 2016-09-07 | 武汉理工大学 | Steel smelting temperature measurement paper clay head and fire-resistant adhesive applied thereto |
| CN106243397A (en) * | 2016-07-26 | 2016-12-21 | 苏州秉创科技有限公司 | A kind of three-dimensional fast shaping composite powder material |
| CN106146910A (en) * | 2016-08-01 | 2016-11-23 | 苏州秉创科技有限公司 | A kind of modified composite material in 3 D-printing |
| CN106146911A (en) * | 2016-08-01 | 2016-11-23 | 苏州秉创科技有限公司 | A kind of starch base modified composite material in 3D prints |
| CN111377699A (en) * | 2020-03-24 | 2020-07-07 | 共享智能铸造产业创新中心有限公司 | Gypsum powder for 3D printing |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5902441A (en) * | 1996-09-04 | 1999-05-11 | Z Corporation | Method of three dimensional printing |
| US6047221A (en) * | 1997-10-03 | 2000-04-04 | Pavilion Technologies, Inc. | Method for steady-state identification based upon identified dynamics |
| US20040056378A1 (en) * | 2002-09-25 | 2004-03-25 | Bredt James F. | Three dimensional printing material system and method |
-
2006
- 2006-05-15 CN CNB200610012721XA patent/CN100404600C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5902441A (en) * | 1996-09-04 | 1999-05-11 | Z Corporation | Method of three dimensional printing |
| US6416850B1 (en) * | 1996-09-04 | 2002-07-09 | Z Corporation | Three dimensional printing materials system |
| US6047221A (en) * | 1997-10-03 | 2000-04-04 | Pavilion Technologies, Inc. | Method for steady-state identification based upon identified dynamics |
| US20040056378A1 (en) * | 2002-09-25 | 2004-03-25 | Bredt James F. | Three dimensional printing material system and method |
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