CN109337229A - 一种用于温控可逆变形的4d打印材料 - Google Patents
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- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 1
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- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
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- 229920001296 polysiloxane Polymers 0.000 claims 1
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- 238000000016 photochemical curing Methods 0.000 abstract description 10
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- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
- B29C64/129—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask
- B29C64/135—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask the energy source being concentrated, e.g. scanning lasers or focused light sources
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- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
本发明属于3D打印材料领域，具体属于光固化成型的3D打印材料，该材料在光固化成型后，通过外界环境可控范围的不同温度感应，呈现形态的可逆改变，这种可逆改变的温度范围在‑15‑95℃之间，当温度大于该温度范围，材料失活，呈现不可逆变化，小于该温度范围，材料形貌变化与温度无关。由于该材料的上述特性导致温控可逆变形的4D打印材料不适用于FDM（熔融沉积）成型技术，因此本发明材料属于SLA（光固化）成型树脂范畴。该材料包括以下重量百分比的各组分制备而成：聚合反应体25份，光引发剂10份，热敏助剂5份，抗高温老化剂0.5份，温敏变形单体8份，稀释剂30份，光反应助剂3份，柔性填料5份。本发明提供的4D打印材料制备过程简单，产率高，同时解决了目前3D打印材料的形状不受温度控制的弊端，该材料具有重要的科学意义和使用前景。
Description
技术领域
本发明涉及一种光固化的4D打印树脂材料，具体属于光固化成型，成型后形状在一定温度区间内随温度变化形貌可逆的树脂材料。
背景技术
3D打印技术和材料目前已经运用非常广泛，而4D打印技术则更是当前新兴的行业。4D打印的成型本质其实与3D打印是一样的。它们的区别在于打印材料的不同。3D打印材料在打印成型后，其形貌不再发生变化。而4D打印则不同，4D打印结构成型后，其打印材料的形貌会随着外界环境的刺激发生相应的变化，这种材料属于敏感材料，这种变化有的是可逆的，而有的则是不可逆的。当前的4D打印材料主要为不可逆敏感材料，而可逆敏感材料则罕有报道。本发明涉及的材料则是属于一种4D打印可逆敏感材料。它由紫外光光照固化成型，在-15-95℃之间，随环境温度变化呈现可逆的形貌改变。因此开发一种温控可逆变形的4D打印材料对于智能制造，智能材料等领域有着非常重要的意义。
发明内容
本发明所述的一种光固化的4D打印树脂材料，在固化前为黏性液态，黏度为13200mPa.S。颜色为淡黄色，光照固化后在25℃温度下为柔性固态，其邵氏硬度为55。
为了获得上述性能的树脂材料，本发明采用的制备方案如下：
1）将聚合反应体25份，柔性填料5份，稀释剂25份加入密闭反应釜中，冲入氮气，在75℃搅拌30r/min匀速搅拌60min;
2）再向反应釜中缓慢加入光引发剂10份，热敏助剂5份，抗高温老化剂0.5份，温敏变形单体8份，光反应助剂3份，升温至110℃，搅拌40min后，降低温度至60℃，再加入5份稀释剂，继续搅拌30min后降温取出，获得目标产物。
本发明所述的树脂材料适用于恒温光固化3D打印机，打印过程温度范围在0-35℃之间。整个打印成型过程温差不得超过±1℃。
在一个大气压下本发明所述的树脂材料可逆热变形范围在-15-95℃之间，光固化前熔点为-30℃，固化后熔点在135℃。光固化波长范围为320-340nm。固化成型后，环境温度低于-15℃，该材料不与温度变化发生变形，环境温度在-15-95℃之间时，该固化材料与温度变化发生可逆的变形；环境温度大于95℃小于135℃时该材料发生变性，变性后当温度降至-15-95℃之间，材料不再发生温度相关的形变；温度大于135℃时，该固化材料融化。
附图说明
图1为不同温度下，采用本发明所述的树脂材料打印的样品在不同温度下的形貌特征。
图2为光固化前本发明所述的液态树脂材料。
图3 为本发明所述材料光固化打印机的打印成型原理。
具体实施方式
下面结合本发明所述的打印树脂的成型举例说明：
实施例1
1) 采用本发明所述的液体树脂材料，放置于紫外光固化3D打印机中，光波长设定为330nm，打印室温度设定为20℃，打印过程温差不超过±0.5摄氏度。
2)在树脂槽中盛满液态光敏树脂，可升降工作台处于液体下一个界面层厚度的高度，聚焦后的激光束在计算机控制下沿着液面进行扫描，被扫描的区域树脂固化，从而得到该截面的一层树脂固化薄片。
3)升降工作台下降一个层厚的距离，液体树脂再次暴露在光线下，再次扫描固化，如此重复，直到整个产品成型。
4)升降台升出液体树脂表面，取出工件，进行相关后处理，通过强光，电镀，喷漆或着色等处理得到最终所需产品。
5)需要注意的是由于本树脂材料黏度较大，流动性不强，使得在每层照射固化之后，液面很难在短期内恢复流平。所以，本光固化打印机需配备有刮刀布阵，在每层打印台下降后通过刮刀进行刮切操作，便可以将树脂均匀的涂覆在下一叠层之上。
6)光固化逐层打印完毕后，取出打印样品，将该样品放置于-15-95℃变温环境中，会随着环境温度的变化发生可逆的形貌改变。
Claims (10)
1.一种温控可逆变形的4D打印材料，其特征在于，该材料组分配比（质量份数）按以下成份构成：聚合反应体25份，光引发剂10份，热敏助剂5份，抗高温老化剂0.5份，温敏变形单体8份，稀释剂30份，光反应助剂3份，柔性填料5份。
2.如权利要求1所述的一种温控可逆变形的4D打印材料，其特征在于，所述的聚合反应体为PS-b-PMMA共聚物，其分子结构为：
。
3.如权利要求1所述的一种温控可逆变形的4D打印材料，其特征在于，所述的光引发剂为2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮。
4.如权利要求1所述的一种温控可逆变形的4D打印材料，其特征在于，所述的热敏助剂为聚乙烯甲基醚。
5.如权利要求1所述的一种温控可逆变形的4D打印材料，其特征在于，所述的抗高温老化剂为受阻酚类CHEMNOX1076，其分子式为：
。
6.如权利要求1所述的一种温控可逆变形的4D打印材料，其特征在于，所述的温敏变形单体为聚N一异丙基丙烯酞胺。
7.如权利要求1所述的一种温控可逆变形的4D打印材料，其特征在于，所述的稀释剂为3-羟甲基-1-氧杂环丁烷。
8.如权利要求1所述的一种温控可逆变形的4D打印材料，其特征在于，所述的光反应助剂为2-羟基-4-烷氧基二苯甲酮。
9.如权利要求1所述的一种温控可逆变形的4D打印材料，其特征在于，所述的柔性填料为刚性聚硅氧烷，其结构为：
。
10.如权利要求1所述的一种温控可逆变形的4D打印材料，其特征在于成型为光固化成型，光照波长在320-340nm之间，打印环境为恒温环境，打印温度范围控制在0-35℃之间,
整个打印成型过程温差不得超过±1℃。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111248473A (zh) * | 2020-03-18 | 2020-06-09 | 南京财经大学 | 一种猴头菇凝胶食品的4d打印方法 |
| CN112140535A (zh) * | 2020-07-23 | 2020-12-29 | 西安交通大学 | 一种基于4d打印的可调声学超材料的制备方法 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111248473A (zh) * | 2020-03-18 | 2020-06-09 | 南京财经大学 | 一种猴头菇凝胶食品的4d打印方法 |
| CN112140535A (zh) * | 2020-07-23 | 2020-12-29 | 西安交通大学 | 一种基于4d打印的可调声学超材料的制备方法 |
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