CN104230289A - 3D printing composition as well as preparation method and applications thereof - Google Patents
3D printing composition as well as preparation method and applications thereof Download PDFInfo
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Abstract
The invention relates to a 3D printing composition as well as a preparation method and applications thereof. The composition comprises gypsum powder, oxide powder, a binding material, a fortifier, a solid lubricant and a preservative, and preferably comprises auxiliaries. The composition is low in cost, good in stability, high in forming strength, good in tenacity, difficult to deform, can be used in the field of 3D printing technology, and the preparation method has the advantages of being pollution-free, green, environment-friendly and the like. Therefore, the 3D printing composition as well as the preparation method and applications thereof have excellent scientific research values and industrial application potential.
Description
Technical field
The present invention relates to a kind of printing composition and method of making the same and purposes, more particularly, relate to a kind of 3D and print composition and method of making the same and purposes, belong to rapid shaping printed material field.
Background technology
Along with the progress and development of science and technology, at the end of 20th century 80, people have developed rapid shaping (Rapid Prototyping is called for short RP) technology, are also called rapid prototyping technique, and are described as significant innovation and progress that material manufactures field.
In RP technical field, 3 D-printing (Three Dimensional Printing, namely 3D prints) a kind of important rapid shaping technique, the manufacturing theory of this technology utilizes three-dimensional CAD data, by rapidform machine, sprays binding agent with shower nozzle, thus optionally powdered material is bonded to two-dimensional section, then repeating this process according to computer design program, by piling up layer by layer, finally obtaining required 3D solid raw product.
3D printing technique, owing to adopting powdered material, does not need to make supporting, simultaneously owing to there is not the processing means such as cutting, thus significantly reduces material loss, significant for cost control.In addition, owing to have employed the mode that layer is piled up, and there is the plurality of advantages such as working process is pollution-free, shaping speed is fast, precision controlling is high, not only can make conceptual model, and can product model be made.Therefore, shaping industry, architectural design, medical equipment preparation, automobile making and all many-sides such as design, aircraft industry can be widely used in.
Just because of the above-mentioned excellent characteristics of 3D printing technique, researcher has carried out a large amount of further investigations to it, have developed miscellaneous powdered material printed for 3D, such as:
CN103205107A discloses a kind of high caking ability 3D printing shaping material being rich in toughness, described material comprises powdered material and matrix material, wherein, described powdered material comprises 40-85 part polyamide resin, 5-40 part pigment, 5-30 part filler, 1-6 part color stuffing dispersion moistening auxiliary agent, 0.1-1.5 part flow agent, 0.1-0.5 part air release agent by weight; Described matrix material comprises 60-95 part epoxy resin, 5-40 part filler, 1-10 part toughner, 0.1-1.5 part flow agent, 1-4 part color stuffing dispersion moistening auxiliary agent, 0.1-0.5 part air release agent, 0.1-0.5 part powder flow aid by weight.The described material physical components printed is used to have cohesive strength and firmness is higher, the good and advantage of damage resistant of snappiness.
CN103497414A discloses a kind of crosslinked polypropylene printed for 3D, described crosslinked polypropylene is α-crosslinked with silicane polypropylene, described crosslinked polypropylene raw material comprises the component of following weight part: polypropylene 100 parts, superoxide 0.1-0.5 part, α-silane 2-6 part.Described crosslinked polypropylene can be suitable as 3D printed material, foam material, ribbon stretch-proof material and replace other Application Areas of nylon, and not only than nylon material light weight, environmental protection, and cost is low, has important industrial application value.
CN103467950A discloses a kind of 3D and prints modified polylactic acid material, and its weight part is composed as follows: poly(lactic acid) 70-85 part, chainextender 1-5 part, linking agent 1-5 part, nucleator 0.5-1 part, low-molecular weight polymer 5-10 part, toughner 5-10 part, strengthening agent 1-5 part, oxidation inhibitor 0.3-0.8 part; This invention utilizes pulverize at low temperature hybrid reaction technology, thus carries out modification to poly(lactic acid), all has significant improvement, make poly(lactic acid) have more wide application prospect in 3D printed material to the toughness of poly(lactic acid), shock strength and heat-drawn wire.
CN103756293A discloses a kind of 3D printed material, comprise ink powder and binding agent, described ink powder comprises: polymeric amide 100 weight part, Sumstar 190 50-80 weight part, Gum Rosin 10-30 weight part, pigment 5-80 weight part, filler 5-30 weight part, air release agent 0.1-0.5 weight part; Described binding agent comprises: epoxy resin 100 weight part, Gum Rosin 10-30 weight part, filler 5-30 weight part, flow agent 0.1-1.5 weight part, air release agent 0.1-0.5 weight part.This invention, by adopting thermoplasticity Sumstar 190, makes there is good cementability with epoxy resin, improves the cohesive force between ink powder and binding agent, is conducive to obtaining cohesive strength and the high physical components of firmness.
CN103804862A discloses a kind of high performance 3D printing consumables alloy material, comprises following parts by weight ingredient: poly(lactic acid) 20-50 part, high-impact polystyrene 50-80 part, compatilizer 0.1-5 part, auxiliary agent 0.2-3 part.Described compatilizer comprises maleic anhydride graft polymer, by the terpolymer (SAG) of vinylbenzene, vinyl cyanide, glycidyl methacrylate copolymerization, by terpolymer (MBS) wherein one or more of methyl methacrylate, divinyl, styrol copolymer copolymerization.3D printing consumables alloy plastic prepared by this invention is nontoxic, low-carbon environment-friendly, and at the bottom of alloy material cost, over-all properties is superior, has very high economic worth and wide market outlook.
CN103739954A discloses a kind of polypropylene composite material that can be used for 3D and print, and described material comprises the raw material of following weight percents: polypropylene 70-98%, transparent toughner 1-20%, mineral filler 01-0%, nucleator 0.1-0.5%, stablizer 0.2-2%, other additive 0-5%.
CN103772837A discloses a kind of polystyrene microsphere material printed for 3D, and it is made up of following raw material: polystyrene microsphere 100 parts, light steady agent 0.1-10 part, defoamer 0.1-10 part, flow agent 0.1-10 part, oxidation inhibitor 0.1-5 part.Material scatter prepared by this invention is good, has excellent mechanical property, and preparation technology is simple, environment friendly and pollution-free simultaneously, can directly apply to 3D and print.
CN103923470A discloses a kind of bio-based degradation material printed for 3D, is made up of: vinylformic acid foodstuff glue derivative 20-45%, acrylic acid rosin derivative 10-40%, lauric acid acrylate 5-10%, calcium carbonate superfine powder 5-15%, vinyl silicane coupling agent 1-8%, hydroxy acrylate 20-50%, light trigger 1-5% the raw material of following mass percentage content.The printed material that this invention obtains has good biological decomposition rate and photodegradation rate, has good tensile strength and flexural strength simultaneously.
CN103862040A discloses the metal powder material that a kind of 3D prints, described material is the magnesium powder being enclosed with rosin thin film is basic material, add a certain proportion of nickel powder being enclosed with rosin thin film as support material, adding a certain proportion of aluminium powder is intermediate materials; Then three kinds of metal powders can be become after fully stirring, mixing the magnesium-base metal powder printed for 3D.
As mentioned above, disclosed multiple 3D printing material in prior art, but still there are some shortcomings in these materials, such as, containing some decomposable macromolecular materials, thus easily produce obnoxious flavour and/or material, cause potential safety hazard; Or composition is too numerous and diverse, it is more difficult to control in print procedure.
Therefore, constantly perfect, improve or seek brand-new 3D printed material, being still the target of current vast researcher, is also one of the study hotspot and emphasis in this field, this also just the basic place that is accomplished of the present invention and power lean on.
Summary of the invention
In order to the 3D printed material and its production and use of development of new, the present inventor, to this has been research deep in a large number, is paying sufficient creative work and after deep scientific exploration, thus is completing the present invention.
The present invention relates generally to following several aspect.
More specifically, the present invention relates to three aspects.First aspect, the present invention relates to a kind of 3D and print composition, described composition comprises terra alba, oxide powder, matrix material, toughener, solid lubricant, sanitas, and optionally also comprises auxiliary agent.
Described 3D of the present invention prints composition, and with parts by weight, it comprises the concrete component of following content, and it is made up of following component in other words:
Preferably, described 3D of the present invention prints the auxiliary agent that composition also comprises 0.5-5 weight part.Namely described 3D of the present invention prints composition, and with parts by weight, it comprises the concrete component of following content, and it is made up of following component in other words:
Print in composition at described 3D of the present invention, all " comprising " relating to composition, both contained open " comprising ", " comprising " etc. and similar meaning thereof, also contains enclosed " by ... composition " etc. and similar meaning thereof.
Print in composition at described 3D of the present invention, the weight part of described terra alba is 40-85 part, such as, can be 40 parts, 50 parts, 60 parts, 70 parts, 80 parts or 85 points.
Print in composition at described 3D of the present invention, the weight part of described oxide powder is 2-35 part, such as, can be 2 parts, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts or 35 parts.
Wherein, described oxide compound is any one or the mixture multiple arbitrarily in aluminum oxide, silicon-dioxide, magnesium oxide, titanium oxide, zirconium white, zinc oxide, germanium oxide, strontium oxide, barium oxide.
Print in composition at described 3D of the present invention, the weight part of described matrix material is 5-30 part, such as, can be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts or 30 parts.
Wherein, described binding agent is Sudan Gum-arabic, acrylic styrene copolymer, polyhydroxyalkanoate, ethylene-vinyl acetate copolymer, vinyl acetate polymer, polyvinyl alcohol, acrylic resin, latex powder, poly-epsilon-caprolactone, poly-(2-ethyl-2-
azoles quinoline) or ethylene acrylic acid co polymer in any one or mixture multiple arbitrarily, be preferably the mixture of at least two kinds arbitrarily.
Wherein, concrete selection kind in described binding agent can use concrete material as known in the art, and exemplarily property exemplifies: acrylic styrene copolymer such as can be KT-15, polyhydroxyalkanoate and such as can be PHA D1060, ethylene-vinyl acetate copolymer and such as can be AE-60, vinyl acetate polymer and such as Gelava-700, polyvinyl alcohol such as can be TM500, acrylic resin such as Soluryl-820, described latex powder and such as can be EAA 2002 of latex powder SWF-09, ethylene acrylic acid co polymer such as du pont company etc.
Print in composition at described 3D of the present invention, the weight part of described toughener is 0.5-10 part, such as, can be 0.5 part, 1 part, 2 parts, 4 parts, 6 parts, 8 parts or 10 parts.
Described toughener is the mixture of water reducer, defoamer and derivatived cellulose, the weight ratio of described water reducer, defoamer and derivatived cellulose is 1:0.25-1:4-25, such as, can be 1:0.25:4,1:0.5:10,1:1:20,1:0.25:25,1:0.5:4,1:0.5:20,1:0.5:25,1:1:4,1:1:10 or 1:1:25.
Wherein, described water reducer is selected from sulfonated melamine based water reducer (such as SUNBOSMF-1013), carboxylic acid water reducing agent (such as carboxylic acid water reducer M-1), aminosulfonic water-reducing agent (such as AE-b), most preferably is sulfonated melamine based water reducer.
Wherein, described defoamer is selected from tributyl phosphate, aluminum stearate, silicone oil, alkylphenol polyoxyethylene, TWEEN Series, sapn (sometimes also referred to as this dish) series.
Wherein, concrete selection kind in described defoamer can use concrete material as known in the art, and exemplarily property exemplifies: described alkylphenol polyoxyethylene such as can be Nonyl pheno (10) ether, octyl phenol polyoxyethylene (10) ether etc.; Described tween such as can be Tween-60, tween-80 etc.; Described sapn such as can be Arlacel-60, Arlacel-80 etc.
Wherein, described derivatived cellulose is any one or the mixture multiple arbitrarily in Vltra tears, Walocel MT 20.000PV, Natvosol.
Print in composition at described 3D of the present invention, the weight part of described auxiliary agent is 0.5-5 part, such as, can be 0.5 part, 1 part, 2 parts, 3 parts, 4 parts or 5 parts.
Described auxiliary agent is any one or mixture multiple arbitrarily in quartz sand, molybdenumdisulphide, lithium silicate.
Print in composition at described 3D of the present invention, the weight part of described solid lubricant is 0.1-5 part, such as, can be 0.1 part, 2 parts, 4 parts or 5 parts.
Described solid lubricant is any one or mixture multiple arbitrarily in talcum powder, Yelkin TTS, graphite, tetrafluoroethylene.
Print in composition at described 3D of the present invention, the weight part of described sanitas is 0.1-5 part, such as, can be 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts, 4 parts or 5 parts.
Described sanitas is selected from Sodium Nitrite or strontium nitrate.
Second aspect, the invention still further relates to the preparation method of above-mentioned composition, said method comprising the steps of:
(1) the various components of above-mentioned weight part are taken;
(2) matrix material is joined in solvent, and fully stir, dispersion completely, obtain solution; Then in gained solution, add oxide powder, continue fully to stir, until the bonded material of oxide powder is fully coated, obtain slurries; Last vacuum-drying, except desolventizing, obtains dried powder;
(3) dried powder and terra alba, toughener, solid lubricant, sanitas and the optional auxiliary agent one existed are reinstated ball mill grinding 2-4 hour, cross 100-200 mesh sieve, obtain described composition of the present invention.
In the preparation method of composition of the present invention, the solvent in step (2) is any one or mixture multiple arbitrarily in water, alcohols, ethers, ketone or ester class.
Wherein, in non-limiting manner, such as can be any one or the mixture multiple arbitrarily in water, ethanol, ethyl acetate, ethylene glycol monomethyl ether or acetone.
The consumption of described solvent is not particularly limited, as long as can by matrix material dispersion completely.
In the preparation method of composition of the present invention, the granularity of the powder (namely described 3D of the present invention prints composition) obtained in step (3) is 100-300 order, such as, can be 100 orders, 200 orders or 300 orders.
3rd aspect, the invention still further relates to the purposes of above-mentioned composition for 3D printing shaping, described composition can be used for 3D and print field, thus obtain various shaped component.
Compared with printing composition with 3D of the prior art, described composition of the present invention has obvious advantage and positive effect, such as:
(1) 3D printing powdered material of the present invention adopts gypsum powder as the material of rapid shaping, coordinate matrix material, oxide powder, toughener, solid lubricant and sanitas again, all raw materials are cheap to be easy to get, and greatly reduces the production cost of model manufacturing.
(2) fully stir by the solution that oxide powder joined matrix material, be then dried to solid, make oxide powder and sticky material more uniformly to disperse in the final composition, serve the effect strengthening powder compacting intensity,
(3) described composition of the present invention is by using suitable coated processing mode, such that printed profiled member intensity is high, good toughness, yielding, and in print procedure all components without decomposition, odorlessness, environmental protection.
Embodiment
Below by specific embodiment, the present invention is described in detail; but the purposes of these exemplary embodiments and object are only used for exemplifying the present invention; not any type of any restriction is formed to real protection scope of the present invention, more non-protection scope of the present invention is confined to this.
Embodiment 1
(1) 40 weight part terra albas are taken respectively, 2 parts by weight of alumina powder, 5 parts by weight binder are (by 1.5 weight part gum arabic powder, 0.5 weight part latex powder SWF-09 and 3 parts by weight propylene acid esters-styrol copolymer KT-15 forms), 0.5 weight part toughener is (by water reducer, defoamer becomes with cellulose derivative group, the weight ratio of three is 1:0.25:4, wherein water reducer is sulfonated melamine based water reducer SUNBO SMF-1013, defoamer is tributyl phosphate and derivatived cellulose is Vltra tears), 0.1 parts by weight solids lubricant talcum powder and 0.1 weight part sanitas Sodium Nitrite,
(2) above-mentioned matrix material is added to the water, and fully stir, dispersion completely, obtain solution; Then in gained solution, add above-mentioned oxide powder, continue fully to stir, until the bonded material of oxide powder is fully coated, obtain slurries; Last vacuum-drying, except desolventizing, obtains dried powder;
(3) dried powder and above-mentioned terra alba, above-mentioned toughener, above-mentioned solid lubricant and foregoing preservatives one are reinstated ball mill grinding 2 hours, cross 100 mesh sieves, obtain described composition of the present invention, called after DY-1.
Embodiment 2
(1) 55 weight part terra albas are taken respectively, 10 parts by weight of silica powder, 15 parts by weight binder are (by 5 weight part polyhydroxyalkanoates D1060, 5 parts by weight of ethylene-vinyl acetate copolymer AE-60 and 5 parts by weight acetic acid vinyl ester polymers Gelava-700 forms), 5 weight part tougheners are (by water reducer, defoamer becomes with cellulose derivative group, the weight ratio of three is 1:0.5:20, wherein water reducer is sulfonated melamine based water reducer SUNBOSMF-1013, defoamer is aluminum stearate and derivatived cellulose is Walocel MT 20.000PV), 2 parts by weight solids lubricant Yelkin TTS and 2 weight part sanitas strontium nitrates,
(2) above-mentioned matrix material is joined in ethanol, and fully stir, dispersion completely, obtain solution; Then in gained solution, add above-mentioned oxide powder, continue fully to stir, until the bonded material of oxide powder is fully coated, obtain slurries; Last vacuum-drying, except desolventizing, obtains dried powder;
(3) dried powder and above-mentioned terra alba, above-mentioned toughener, above-mentioned solid lubricant and foregoing preservatives one are reinstated ball mill grinding 3 hours, cross 200 mesh sieves, obtain described composition of the present invention, called after DY-2.
Embodiment 3
(1) 85 weight part terra albas are taken respectively, 30 part by weight of zinc oxide powder, 30 parts by weight binder are (by 5 parts by weight propylene acid resin Soluryl-820, 10 weight account polyethylene alcohol TM500, 5 weight part latex powder SWF-09 and 10 parts by weight of ethylene acrylic copolymer du pont company EAA 2002 form), 10 weight part tougheners are (by water reducer, defoamer becomes with cellulose derivative group, the weight ratio of three is 1:1:4, wherein water reducer is sulfonated melamine based water reducer SUNBO SMF-1013, defoamer is silicone oil and derivatived cellulose is Natvosol), 5 parts by weight solids lubricant graphite and 5 weight part sanitas Sodium Nitrites,
(2) above-mentioned matrix material is joined in ethyl acetate, and fully stir, dispersion completely, obtain solution; Then in gained solution, add above-mentioned oxide powder, continue fully to stir, until the bonded material of oxide powder is fully coated, obtain slurries; Last vacuum-drying, except desolventizing, obtains dried powder;
(3) dried powder and above-mentioned terra alba, above-mentioned toughener, above-mentioned solid lubricant and foregoing preservatives one are reinstated ball mill grinding 4 hours, cross 300 mesh sieves, obtain described composition of the present invention, called after DY-3.
Embodiment 4
(1) 70 weight part terra albas, 5 weight part strontium oxide powder, 10 parts by weight binder are taken respectively (by 2 weight part poly-epsilon-caprolactones, the poly-(2-ethyl-2-of 3 weight parts
azoles quinoline), 4 parts by weight propylene acid esters-styrol copolymer KT-15 and 1 parts by weight propylene acid resin Soluryl-820 form), 4 weight part tougheners are (by water reducer, defoamer becomes with cellulose derivative group, the weight ratio of three is 1:0.5:25, wherein water reducer is sulfonated melamine based water reducer SUNBO SMF-1013, defoamer is Nonyl pheno (10) ether, the mixture of derivatived cellulose to be Natvosol and Vltra tears with weight ratio be 1:1), 1 parts by weight solids lubricant tetrafluoroethylene and 2 weight part sanitas strontium nitrates,
(2) above-mentioned matrix material is joined in ethylene glycol monomethyl ether, and fully stir, dispersion completely, obtain solution; Then in gained solution, add above-mentioned oxide powder, continue fully to stir, until the bonded material of oxide powder is fully coated, obtain slurries; Last vacuum-drying, except desolventizing, obtains dried powder;
(3) dried powder and above-mentioned terra alba, above-mentioned toughener, above-mentioned solid lubricant and foregoing preservatives one are reinstated ball mill grinding 2 hours, cross 100 mesh sieves, obtain described composition of the present invention, called after DY-4.
Embodiment 5-8
Except also comprising 0.5 weight part auxiliary agent quartz sand, (namely also comprise 0.5 weight part auxiliary agent quartz sand), implement embodiment 5 with the embodiment identical with embodiment 1, resulting composition called after DY-5.
Except also comprising 2 weight part auxiliary agent molybdenumdisulphide, (namely also comprise 2 weight part auxiliary agent molybdenumdisulphide), implement embodiment 6 with the embodiment identical with embodiment 2, resulting composition called after DY-6.
Except also comprising 5 weight part auxiliary agent lithium silicates, (namely also comprise 5 weight part auxiliary agent lithium silicates), implement embodiment 7 with the embodiment identical with embodiment 3, resulting composition called after DY-7.
Except also comprising 1 weight part auxiliary agent quartz sand, (namely also comprise 1 weight part auxiliary agent quartz sand), implement embodiment 8 with the embodiment identical with embodiment 4, resulting composition called after DY-8.
Embodiment 9-16
Except respectively the sulfonated melamine based water reducer SUNBOSMF-1013 in embodiment 1-4 toughener being replaced with carboxylic acid water reducer as except M-1, respectively to implement embodiment 9-12 with the same way of embodiment 1-4, resulting composition is called after DY-9, DY-10, DY-11 and DY-12 in turn.
Except respectively the sulfonated melamine based water reducer SUNBOSMF-1013 in embodiment 1-4 toughener being replaced with aminosulfonic water-reducing agent as except AE-b, respectively to implement embodiment 13-16 with the same way of embodiment 1-4, resulting composition is called after DY-13, DY-14, DY-15 and DY-16 in turn.
Embodiment 17
(1) 40 weight part terra albas are taken respectively, 2 parts by weight of alumina powder, 5 parts by weight binder are (by 1.5 weight part gum arabic powder, 0.5 weight part latex powder SWF-09 and 3 parts by weight propylene acid esters-styrol copolymer KT-15 forms), 0.5 weight part toughener is (by water reducer, defoamer becomes with cellulose derivative group, the weight ratio of three is 1:0.25:4, wherein water reducer is sulfonated melamine based water reducer SUNBO SMF-1013, defoamer is tributyl phosphate and derivatived cellulose is Vltra tears), 0.1 parts by weight solids lubricant talcum powder, 0.1 weight part sanitas Sodium Nitrite and 0.5 weight part auxiliary agent quartz sand,
(2) above-mentioned all material is added to the water, and fully stir, dispersion completely, obtain slurries; Last vacuum-drying, except desolventizing, obtains drying composite;
(3) by described drying composite ball mill grinding 2 hours, cross 100 mesh sieves, obtain described composition of the present invention, called after DY-17.
Namely all components kind of the present embodiment, consumption are all same as embodiment 5, but do not carry out the fully coated process of the bonded material of oxide powder.
Embodiment 18
(1) 55 weight part terra albas are taken respectively, 10 parts by weight of silica powder, 15 parts by weight binder are (by 5 weight part polyhydroxyalkanoates D1060, 5 parts by weight of ethylene-vinyl acetate copolymer AE-60 and 5 parts by weight acetic acid vinyl ester polymers Gelava-700 forms), 5 weight part tougheners are (by water reducer, defoamer becomes with cellulose derivative group, the weight ratio of three is 1:0.5:20, wherein water reducer is sulfonated melamine based water reducer SUNBOSMF-1013, defoamer is aluminum stearate and derivatived cellulose is Walocel MT 20.000PV), 2 parts by weight solids lubricant Yelkin TTS, 2 weight part sanitas strontium nitrates and 2 weight part auxiliary agent molybdenumdisulphide,
(2) above-mentioned matrix material is joined in ethanol, and fully stir, dispersion completely, obtain slurries; Last vacuum-drying, except desolventizing, obtains drying composite;
(3) by described drying composite ball mill grinding 3 hours, cross 200 mesh sieves, obtain described composition of the present invention, called after DY-18.
Namely all components kind of the present embodiment, consumption are all same as embodiment 6, but do not carry out the fully coated process of the bonded material of oxide powder.
Embodiment 19
(1) 85 weight part terra albas are taken respectively, 30 part by weight of zinc oxide powder, 30 parts by weight binder are (by 5 parts by weight propylene acid resin Soluryl-820, 10 weight account polyethylene alcohol TM500, 5 weight part latex powder SWF-09 and 10 parts by weight of ethylene acrylic copolymer du pont company EAA 2002 form), 10 weight part tougheners are (by water reducer, defoamer becomes with cellulose derivative group, the weight ratio of three is 1:1:4, wherein water reducer is sulfonated melamine based water reducer SUNBO SMF-1013, defoamer is silicone oil and derivatived cellulose is Natvosol), 5 parts by weight solids lubricant graphite, 5 weight part sanitas Sodium Nitrites and 5 weight part auxiliary agent lithium silicates,
(2) above-mentioned matrix material is joined in ethyl acetate, and fully stir, dispersion completely, obtain slurries; Last vacuum-drying, except desolventizing, obtains drying composite;
(3) by described drying composite ball mill grinding 4 hours, cross 300 mesh sieves, obtain described composition of the present invention, called after DY-19.
Namely all components kind of the present embodiment, consumption are all same as embodiment 7, but do not carry out the fully coated process of the bonded material of oxide powder.
Embodiment 20
(1) 70 weight part terra albas, 5 weight part strontium oxide powder, 10 parts by weight binder are taken respectively (by 2 weight part poly-epsilon-caprolactones, the poly-(2-ethyl-2-of 3 weight parts
azoles quinoline), 4 parts by weight propylene acid esters-styrol copolymer KT-15 and 1 parts by weight propylene acid resin Soluryl-820 form), 4 weight part tougheners are (by water reducer, defoamer becomes with cellulose derivative group, the weight ratio of three is 1:0.5:25, wherein water reducer is sulfonated melamine based water reducer SUNBO SMF-1013, defoamer is Nonyl pheno (10) ether, the mixture of derivatived cellulose to be Natvosol and Vltra tears with weight ratio be 1:1), 1 parts by weight solids lubricant tetrafluoroethylene, 2 weight part sanitas strontium nitrates and 1 weight part auxiliary agent quartz sand,
(2) above-mentioned matrix material is joined in ethylene glycol monomethyl ether, and fully stir, dispersion completely, obtain slurries; Last vacuum-drying, except desolventizing, obtains drying composite;
(3) by described drying composite ball mill grinding 2 hours, cross 100 mesh sieves, obtain described composition of the present invention, called after DY-20.
Namely all components kind of the present embodiment, consumption are all same as embodiment 8, but do not carry out the fully coated process of the bonded material of oxide powder.
Embodiment 21-24
Except not comprising except Vltra tears, (namely toughener is still 0.5 weight part to implement embodiment 21 with the embodiment identical with embodiment 5, be that the water reducer of 1:0.25 and defoamer form by the weight ratio in embodiment 5), resulting composition called after DY-21.
Except not comprising except Walocel MT 20.000PV, (namely toughener is still 5 weight parts to implement embodiment 22 with the embodiment identical with embodiment 6, be that the water reducer of 1:0.5 and defoamer form by the weight ratio in embodiment 6), resulting composition called after DY-22.
Except not comprising except Natvosol, (namely toughener is still 10 weight parts to implement embodiment 23 with the embodiment identical with embodiment 7, be that the water reducer of 1:1 and defoamer form by the weight ratio in embodiment 7), resulting composition called after DY-23.
Except not comprising mixture that Natvosol and Vltra tears take weight ratio as 1:1, (namely toughener is still 4 weight parts to implement embodiment 24 with the embodiment identical with embodiment 8, be that the water reducer of 1:0.5 and defoamer form by the weight ratio in embodiment 8), resulting composition called after DY-24.
Performance test
1, according to GB9776-88 " plaster of Paris ", test time of coagulation is carried out to the composition of above-described embodiment gained.
2, each composition of above-described embodiment gained is used, the well-known operations mode printed according to 3D prints, and the test of anti-folding, ultimate compression strength is carried out according to " ceramic die terra alba quantitative measurement method " QB/T1640-92, wherein pressure is 200kN, indication error≤1.0%.
3, after each composition be uniformly mixed, get the sample of identical amount respectively, place and estimate after 5-10 minute, observe its mode of appearance.
Wherein, it should be noted: below in all forms " outward appearance " for subject matter be that described 3D of the present invention prints composition, and interlocutory 3D prints shaped piece.
To the test of embodiment 1-16
Print shaped piece to embodiment 1-16 resulting composition and final 3D to test, acquired results sees the following form 1.
The test result of table 1. embodiment 1-16
Note: A represents " evenly, without obviously reuniting ", and B represents " reuniting to some extent ", and C represents " uneven, to have obvious reunion ".
From upper table 1,3D of the present invention prints composition (i.e. DY-1 to DY-4) and has good presetting period and final setting time, and is within the scope of the time requirement that is suitable for carrying out 3D printing.And the final 3D of gained prints shaped piece has very excellent folding strength and ultimate compression strength.
But contriver finds unexpectedly, when comprising auxiliary agent further, its presetting period and final setting time obtain optimization further, and respective time span shortens further, physical appearance performance improves further, the more important thing is: the final 3D of gained prints shaped piece significant raising on folding strength and ultimate compression strength.This demonstrate that in the present composition when adding specific auxiliary agent, can improve each performance index further, played unforeseeable synergy together with other component, this is non-obvious.
In addition, as can be seen from DY-9 to DY-12, DY-13 to DY-16, the kind of the water reducer in toughener is selected extremely important, the impact of highly significant is had for the physicals of resulting composition, the performance of final 3D printing shaped piece, also namely when adopting carboxylic acid water reducer, aminosulfonic water-reducing agent, cause no matter being presetting period, final setting time, or mode of appearance, and the performance that final 3D prints shaped piece has significant reduction, be inferior to composition of the present invention far away, especially contain the present composition of auxiliary agent.Even if this demonstrate that and be all water reducer, but the selection of its concrete kind, there is conclusive impact to various index performance.
To the test of embodiment 17-20
Print shaped piece to embodiment 17-20 resulting composition and final 3D to test, acquired results sees the following form 2, but in order to more clearly contrast, and will the result of embodiment 1-16 together list.
The test result of table 2. embodiment 17-20
Note: A represents " evenly, without obviously reuniting ", and B represents " reuniting to some extent ", and C represents " uneven, to have obvious reunion ".
From upper table 2, when not carrying out the fully coated process of the bonded material of oxide powder, although the composition of resulting composition is identical, the result of embodiment 17-20 is far inferior to corresponding embodiment 7-8: reunite in appearance serious; Longer on presetting period and final setting time; In intensity, more there is the reduction of highly significant simultaneously.
Comprehensive upper table 2 is visible, when not carrying out the fully coated process of the bonded material of oxide powder, each performance index all have and significantly reduce, although be better than some embodiment on presetting period and final setting time index, but in intensity, even to be inferior to the intensity of (see in 2H intensity, with the contrast of embodiment 1-4,9-16 product) when not adding auxiliary agent.
To the test of embodiment 21-24
Print shaped piece to embodiment 21-24 resulting composition and final 3D to test, acquired results sees the following form 3, but in order to more clearly contrast, and will the result of embodiment 1-20 together list.
The test result of table 3. embodiment 21-24
Note: A represents " evenly, without obviously reuniting ", and B represents " reuniting to some extent ", and C represents " uneven, to have obvious reunion ".
From upper table 3, when not comprising derivatived cellulose, compared with embodiment 5-8, although also containing auxiliary agent, presetting period and final setting time extend all to some extent, reunite to some extent in appearance; Simultaneously in intensity, there is obvious reduction, even will lower than not containing the respective strengths of the embodiment 1-4 of auxiliary agent.
This demonstrate that the existence of derivatived cellulose decreases for intensity, but the more important thing is the prolongation that result in presetting period and final setting time, and the span of time end points is more wide in range, be more not easy to control than embodiment 5-8.
As can be seen here, although auxiliary agent whether existence has significant impact to final performance, but preparation method of the present invention and derivatived cellulose whether existence has remarkably influenced to final performance equally, only have and there is auxiliary agent, derivatived cellulose and employing preparation method so simultaneously, can play its beyond thought coordination technique effect, this also demonstrates uniqueness and the unobviousness of preparation method of the present invention from the side.
Comprehensive above-mentioned all the elements are visible, and only have and adopt specific components of the present invention, when especially comprising specific adjuvant and adopt preparation method of the present invention, resulting composition just has best performance.
Should be appreciated that the purposes of these embodiments is only not intended to for illustration of the present invention limit the scope of the invention.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various change, amendment and/or modification to the present invention, and these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (10)
1. 3D prints a composition, and with parts by weight, it comprises the concrete component of following content:
2. 3D as claimed in claim 1 prints composition, and it is characterized in that: with parts by weight, it comprises the concrete component of following content:
3. 3D as claimed in claim 1 or 2 prints composition, it is characterized in that: described oxide compound is any one or mixture multiple arbitrarily in aluminum oxide, silicon-dioxide, magnesium oxide, titanium oxide, zirconium white, zinc oxide, germanium oxide, strontium oxide, barium oxide.
4. the 3D as described in any one of claim 1-3 prints composition, it is characterized in that: Sudan Gum-arabic, acrylic styrene copolymer, polyhydroxyalkanoate, ethylene-vinyl acetate copolymer, vinyl acetate polymer, polyvinyl alcohol, acrylic resin, latex powder, poly-epsilon-caprolactone, poly-(2-ethyl-2-
azoles quinoline) or ethylene acrylic acid co polymer in any one or mixture multiple arbitrarily.
5. 3D as described in any one of claim 1-4 prints composition, it is characterized in that: described toughener is the mixture of water reducer, defoamer and derivatived cellulose, and the weight ratio of described water reducer, defoamer and derivatived cellulose is 1:0.25-1:4-25.
6. 3D as described in any one of claim 1-5 prints composition, it is characterized in that: described auxiliary agent is any one or mixture multiple arbitrarily in quartz sand, molybdenumdisulphide, lithium silicate.
7. 3D as described in any one of claim 1-6 prints composition, it is characterized in that: described solid lubricant is any one or mixture multiple arbitrarily in talcum powder, Yelkin TTS, graphite, tetrafluoroethylene.
8. the 3D as described in any one of claim 1-7 prints composition, it is characterized in that: described sanitas is selected from Sodium Nitrite or strontium nitrate.
9. 3D described in any one of claim 1-8 prints the preparation method of composition, said method comprising the steps of:
(1) the various components of above-mentioned weight part are taken;
(2) matrix material is joined in solvent, and fully stir, dispersion completely, obtain solution; Then in gained solution, add oxide powder, continue fully to stir, until the bonded material of oxide powder is fully coated, obtain slurries; Last vacuum-drying, except desolventizing, obtains dried powder;
(3) dried powder and terra alba, toughener, solid lubricant, sanitas and the optional auxiliary agent one existed are reinstated ball mill grinding 2-4 hour, cross 100-300 mesh sieve, obtain described composition of the present invention.
10. 3D described in any one of claim 1-9 prints composition for the purposes in 3D printing shaping.
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