CN1826393A - 聚电解质墨水 - Google Patents
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Abstract
本发明提供含有溶剂、溶于该溶剂中的阳离子聚电解质和溶于该溶剂中的阴离子聚电解质的聚电解质墨水。至少一种聚电解质在该溶剂中的浓度在亚浓溶液区域。
Description
背景技术
具有微米级特征的三维构件有很多潜在的应用,例如作为光子带隙材料、组织工程支架、生物传感器和药物递送系统。因此,已经开发了几种制造具有小于100微米特征的复杂三维构件的组装技术,如微制造、全息微影蚀刻(holographic lithography)、双光子聚合和胶体自组装。但是,所有这些技术都有限制其用途的局限性。
双光子聚合能够制造出具有亚微米级特征的三维构件,但它的前体是生物不相容的。已经开发了多种制造三维光子晶体的技术,但是它们依赖于昂贵且复杂的设备或耗时的工艺。胶体自组装也被用于制造三维周期性构件,但是很难控制缺陷的形成。
一种制造技术依靠粘弹性胶体墨水(viscoelastic colloidal inks)通常通过自动(robotic)装置的沉积。由于所施加的压力切断粒子间的结合并破坏弹性模量,因此这些墨水就流过沉积喷嘴。离开喷嘴后模量立即恢复,然后墨水凝固以维持其形状并跨过没有支持的区域。墨水中粒子的平均直径约为1微米,这意味着墨水不可能流过直径为1微米的沉积喷嘴而不发生堵塞(clogging)或阻塞(jamming)。事实上,纳米粒子墨水(平均直径~60nm)也会堵塞小于30微米的喷嘴从而限制粘弹性胶体墨水在这一段范围的应用。
在自然界中聚合物溶液被用来制造细丝。例如蜘蛛的丝纤维来自于浓缩的蛋白质生物聚合物溶液,在被拉伸时该溶液凝固形成极结实的细丝。该溶液的伸展流动(extensional flow)使聚合物中的液晶片排成直线,并通过加入离子使溶液在离开吐丝器时胶凝。这一过程通过使重组蛛丝生物聚合物沉积入极性(polar)“沉积浴”以制造具有相似性质的细丝纤维从而得以人工重现。
发明内容
第一方面,本发明提供聚电解质墨水,其含有溶剂、溶于该溶剂中的阳离子聚电解质和溶于该溶剂中的阴离子聚电解质。该溶剂中至少一种聚电解质的浓度在亚浓溶液区域(semidilute regime)。
第二方面,本发明提供一种固体细丝,其含有阳离子聚电解质与阴离子聚电解质的复合物。该细丝的直径至多为10微米。
第三方面,本发明提供制造聚电解质墨水的方法,其包括将含有溶剂、阳离子聚电解质和阴离子聚电解质的成分混合在一起。该溶剂中至少一种聚电解质的浓度在亚浓溶液区域。
第四方面,本发明提供制造细丝的方法,其包括使所述聚电解质墨水流过喷嘴并使墨水与沉积浴接触。该聚电解质墨水在沉积浴中胶凝。
第五方面,本发明提供形成三维构件的方法,其包括制造多条细丝,每条细丝都通过第四方面中的方法制造。
附图说明
图1表示在恒定的聚合物体积分数(Φpoly=0.4)下聚电解质混合物的粘度和弹性模量,它们为可电离基团混合比例的函数。
图2表示在水/IPA沉积浴中反应的墨水的弹性模量,其为沉积池中IPA浓度的函数。
图3A、3B和3C是通过聚电解质墨水的定向组装而制造的构件的电子显微镜照片。(A)缺少一个条杆的可以作为光子晶体的波导管的四层微构件。(B)显示墨水形成跨越(spanning)和空间充填(space-filling)元件的能力的具有外壁的八层构件。(C)显示墨水翻转锐角和钝角的能力的辐射构件。
具体实施方式
本发明提供通过流过10微米或更细的沉积喷嘴而不发生堵塞或阻塞的墨水的沉积来制造微构件的方法。当在沉积浴中沉积时,墨水离开喷嘴后凝固。所得的微构件具有微米级的特征,可用生物相容性材料制造,且制造方法相对简便、价格低廉。
本发明包括通过利用一种墨水来制造具有微米级特征的三维构件。施加的压力使墨水通过连接在活动的x-y-z微定位器上的沉积喷嘴进入沉积浴中,该沉积浴在微定位器移动时使墨水在原位胶凝以在底材上形成二维构件。然后喷嘴在z(垂直)方向逐渐上升以形成该构件的下一层。重复这一过程直至得到期望的三维构件。通过这一技术可以定义和制造任意的三维构件。
本发明的墨水是带有相反电荷的聚电解质的浓缩混合物,也称为聚电解质复合物(PEC)。PEC含有两种带有相反电荷的聚电解质(例如聚(丙烯酸)和聚(氮杂环丙烷))。优选一种聚电解质较另一种大,较大聚电解质的浓度优选在亚浓溶液区域之内:该浓度高于稀溶液区域与亚浓溶液区域的分界浓度c*。低于c*,在稀溶液区域中聚电解质混合物形成粒子而不是形成连续细丝沉积所需要的单相液体。高于c*,在亚浓溶液区域中聚合物牢牢地彼此重叠缠绕在一起,电解质混合物可用于构件沉积。
墨水粘度优选在施加适当的压力时在允许流动连贯并可控的范围内。优选粘度值最小为0.05Pa·sec至最大为600Pa·sec。更优选的粘度值为最小0.1Pa·sec至最大150Pa·sec。更优选的粘度值为最小1Pa·sec至最大20Pa·sec。而且,当墨水与沉积浴接触时便迅速发生凝固反应,这使挤出的细丝在跨越构件中没有支持的区域时仍然保持其形状。
PEC中可以使用的聚电解质的实例是聚(丙烯酸)、聚(氮杂环丙烷)、聚(苯乙烯磺酸酯)、聚(烯丙胺)盐酸盐、聚(二烯丙基二甲基氯化铵)、聚(4-乙烯基吡啶)和阳离子或阴离子表面活性剂。可以使用电学活性聚合物或旋光聚合物,例如聚乙炔、聚苯胺、聚吡咯、聚噻吩、聚(3,4-亚乙二氧基噻吩)(PEDOT)、NAFION(Du Pont,Wilmington,DE)、聚亚苯基亚乙烯、聚苯基苯胺(polyphenylbenzenamine)、磺化聚对亚苯基偶氮苯染料和其它有机染料,它们很适合于涉及有机LED和电路的应用。这些类别的聚合物中有一些聚合物的母体聚合物不含有带电基团,但是这些类别的共聚物和衍生物含有带电基团;例如,可通过含有取代基(该取代基可以被保护至聚合物合成之后)的单体或通过衍生性(derivatizing)反应性基团(例如羟基或苯环上的亲电加成)引入带电基团。
对于生物化学、分子生物学和生物医学应用例如生物催化、基因操作和组织工程,可以使用生物电解质。生物电解质的实例有多核苷酸如DNA和RNA、肽、蛋白质、肽核酸、酶、多糖如淀粉和纤维素、酸性多糖如半纤维素(例如阿拉伯葡糖醛酸木聚糖(arabinoglucuronoxylan))、碱性多糖如聚-(1,4)N-乙酰基-D-葡糖胺(壳聚糖)、半乳聚糖如琼脂糖、多糖醛酸苷如海藻酸、角叉菜聚糖、透明质酸、胶原蛋白、纤维蛋白、蛋白聚糖、聚乳酸、聚乙醇酸、有机酸共聚物、阳离子脂质。墨水组合物中还可包括既带有正电荷也带有负电荷的生物聚电解质例如两性离子如聚羧基甜菜碱。
墨水中还可含有生物活性分子,例如带电的或中性的营养分子、分子信使如生长刺激物质,以及细胞粘附分子。还可以加入用于生物分子的分子探针,例如细胞脂质或细胞膜蛋白、细胞组分如离子通道和受体、或细胞器如线粒体或溶酶体。
也可以向墨水中引入有机或无机小物种,其量应不至对墨水的流变学性质产生不良影响。实例包括纳米粒子、量子点、电中性聚合物、有机金属前体和生物分子。视这些物种的离子性质不同,它们可以与聚电解质相互作用以辅助胶凝作用或在墨水中保持惰性。另外,可以通过引入带电基团例如氨基、磺酸基和羧基使聚合物骨架官能化而将许多其它聚合物制成聚电解质。
优选较大聚电解质的分子量高至足以促进链重叠(优选最低5000道尔顿),但也要低至足以形成其粘度使其在适当的压力下能够流动的浓缩墨水(优选最高100,000道尔顿)。墨水优选高浓度以避免构件因干燥而变形。典型的聚合物浓度为最低5重量%至最高95重量%。更优选浓度为最低25重量%至最高75重量%。更优选浓度为最低35重量%至最高45重量%。最优选浓度为最低38重量%至最高42重量%。
较大的聚电解质与较小的聚电解质优选以一定比例混合在一起,该比例应使带电基团之一过量(通常较大聚合物的带电基团),这样产生的混合物偏离化学计量(1∶1)阳离子基团:阴离子基团比例。在这一比例附近,互补的聚电解质之间的强烈相互作用可能导致形成动力学稳定的不均匀聚集体,且该复合物可能形成两相,一相是富含聚合物的聚集体,另一相是聚合物含量很低的流体。
一旦选定了聚电解质和溶剂,就可以绘制与作为聚电解质总浓度(在选定溶剂中)的函数的阴阳离子基团的比例有关的相图,其目的是确定均质墨水的范围。该范围将高于较大聚合物的稀溶液/亚浓溶液临界值且偏离化学计量(1∶1)阳离子基团:阴离子基团的比例。均质墨水的粘度随聚合物浓度升高和混合比例接近于1∶1而增加。因此可以控制粘度以使墨水通过各种尺寸的喷嘴沉积。
选择一种沉积浴经快速凝固反应来制造三维构件。在这些聚电解质墨水中,通过增加带有相反电荷的聚电解质之间的吸引力强度使反应发生。这可以通过例如改变pH、改变离子强度、改变溶液组成或不止一种改变的组合来实现。该反应产生的细丝的强度足以使其在跨越构件中没有支持的区域时仍保持其形状,但是也软至足以使细丝粘附于底材上且可以一致地(consistently)流过喷嘴。
聚电解质含有酸性和/或碱性带电基团时通常使用通过改变pH而引发胶凝的沉积浴。pH的改变通过例如使在墨水pH下为中性的酸性基团离子化来消除带电基团之一的过量。这样得到化学计量(1∶1)阳离子基团:阴离子基团比例的、胶凝成为细丝的混合物。
此外,可以选定沉积浴的pH以诱导已沉积的细丝在维持形状的同时部分溶解。浴pH削弱带有相反电荷的聚电解质之间的结合力,从而导致溶解。构件的表面带有残余的电荷,可以用于吸附带电的纳米粒子。
还可以通过改变溶剂组成来实现凝结。例如,水性墨水可能在含有相对非极性溶剂如乙醇的沉积浴中沉积。由此导致的介电常数的降低引起聚电解质之间的库仑吸引作用增加。此外,可以选择对聚电解质溶解力较弱的非极性溶剂,这将增加聚电解质/聚电解质结合。该反应得到的聚电解质复合物沉淀的正电荷∶负电荷的比例比未反应的墨水更接近1∶1,但还没有达到pH引发的反应的程度。构件的表面带有残余的电荷,可以用于吸附带相反电荷的纳米粒子。
而且,已沉积墨水的机械性质依赖于沉积浴的组成。如图2所示,不同百分比的非极性溶剂通常得到刚性不同的细丝。
沉积墨水的装置可以通过将优选直径为最小0.1微米至最大10微米的沉积喷嘴与微定位器如计算机控制的压电微定位器以及墨水池相连接而制备。这些微定位器用于各种设备如扫描隧道显微镜中,且可商购获得。压力推动墨水通过喷嘴、或两个或更多喷嘴,微定位器控制细丝的沉积式样。或者,喷嘴(或多个喷嘴)可以是静止的,而微构件形成于其上的固定底材的平台可以被微定位器控制。在另一种配置中,喷嘴和平台都可被其自身的微定位器控制。当存在多个喷嘴时也可能有多个底材。此时优选使用与微定位器相配的计算机辅助设计软件制作的式样来进行构件的组装。
用这些材料和方法制造的固体PEC构件具有很多应用。可以用高折光率材料浸润该构件,然后将PEC构件复溶以形成光子晶体。墨水跨越距离的能力使得在功能性光子带隙材料构件中设计缺陷(例如空腔或波导管)成为可能。高孔隙度构件可用于选择性地允许小分子以较快的速率通过的膜。另外,还可以制备不允许细胞或大于某一尺寸的细胞通过的筛。这种类型的筛可以用于例如将血样中较小的细胞与较大的细胞分离。它们也可以用于其中孔隙度对控释而言必不可少的药物递送系统。
带有电荷的复合物可以用作组织工程支架供细胞附着和生长。例如聚(L-乳酸)和聚(L-乙醇酸)的共聚物,这两种FDA批准作为生物可降解聚合物的阴离子聚电解质都可以与一种或多种阳离子聚合物如壳聚糖结合形成用于组织工程应用的生物相容性墨水。为了促进整个构件中细胞的生长,可以向墨水中加入蛋白质和糖类以随着聚电解质的溶解而释放。
所述微构件上还可以连接生物学有意义的分子。这些分子的实例包括核酸、多肽和其它有机分子。核酸包括多核苷酸(至少具有两个核苷酸)、脱氧核糖核酸(DNA)如已表达序列标志(EST)、基因片段或互补DNA(cDNA)或可能影响基因转录的内含子序列如启动子、增强子或结构元件。但是所述核酸不需要与基因或基因表达有关,因为也可以使用适体(aptamer)(与目标分子特异性结合的小核酸序列)。也可以使用核糖核酸(RNA),如信使RNA(mRNA)、转移RNA(tRNA)或核糖体RNA(rRNA)。核酸还可以被修饰,例如用非天然核酸如肌苷取代核酸。也可以使用核酸的化学修饰,例如于底材能够提供稳定性或促进固定化的修饰。被修饰的核酸的另一个实例是肽核酸(PNA),它是一种核酸模拟物(例如DNA模拟物),其中脱氧核糖磷酸骨架被伪肽骨架代替,只保留了四种天然核酸碱基。PNA的中性骨架使之能够在低离子强度条件下与DNA和RNA杂交。PNA低聚物的合成可以使用标准固相肽合成方案进行。与所述微构件连接的核酸可以用于例如诊断和预后检测、基因表达阵列、药物基因组分析等。
多核苷酸可以通过与引入微构件中的金纳米粒子的巯基介导的自组装联接从而连接至微构件。可以通过向未沉积的墨水混合物中加入金或在沉积后使金例如通过墨水中存在的巯基与微构件相联接的方法将金引入微构件中。
具有至少两个氨基酸残基的多肽可以应用于底材上或底材内。多肽类别的实例包括抗体及衍生物、蛋白质激素(例如人生长激素和胰岛素)、细胞外基质分子如层粘连蛋白、胶原蛋白或巢蛋白;与信号传导有关的多肽如磷酸酶和激酶;受体如多巴胺受体和激素受体(可以有利地以天然形式连接,或者在为同型二聚物、三聚物等的情况下可与其它多肽链混合或作为单链)等。将多肽与本发明的底材联接可以有广泛的应用,包括药物筛选、诊断和预后检测、与酶联免疫吸附分析(ELISA)相似的分析、蛋白组学分析甚至细胞粘附研究。
有机分子在微构件上也有用途。例如微构件上可以联接甾体激素如雌激素和睾酮。这种偶联可以促进与这些分子结合的分子如抗体或适体的筛选。同样,微构件上可以联接候选的小分子拮抗剂或激动剂以促进药物筛选。
也可以联接朊病毒、病毒、细菌和真核细胞等实体。朊病毒是错折叠的蛋白质聚集体,它能将它的错折叠状态传播给天然蛋白质;实例包括引起疯牛病(牛海绵状脑病(BSE))或克-雅二氏病的聚集体。病毒的实例包括单纯疱疹、正痘病毒(天花)或人免疫缺陷病毒。感兴趣的细菌可以包括霍乱弧菌、产气荚膜梭菌或炭疽杆菌(炭疽)。真核细胞例如从受试者或植物中或从细胞系(例如可以从American Type CultureCollection(ATCC);Manassus,VA获得的细胞系)中分离出来的原代培养物可以固定于微构件上以达到各种目的,包括药物筛选、对细胞-底物的粘附情况的研究或各种分子的结合。
通过改变溶剂而胶凝的任何墨水都可以用于由电学活性聚合物、旋光聚合物或生物活性聚合物组装三维构件。通过使用溶胶凝胶前体还可制造无机构件以生产例如传感器或无模板光子带隙材料。
实施例
1)墨水混合物
在水溶液中将线性多元酸聚(丙烯酸)(MW~10,000)和高度分支的多元碱聚(氮杂环丙烷)结合,得到聚合物分数Φpoly=0.4的溶液。当这些聚离子被结合时,聚(丙烯酸)(PAA)的羧酸根基团(carboxylate group)与聚(氮杂环丙烷)(PEI)的胺基形成离子键。开始先将聚合物在微酸性条件(pH~3.6)下混合,其中PAA上的部分电荷只允许潜在的可电离基团的一部分参与复合过程。如图1的相图所示,Φpoly保持恒定,且不同的PAA与PEI比例所得到的混合物具有不同的流变学性质。在该图中,左右y轴表示在Φpoly=0.4时纯PAA和纯PEI的值。PAA的稀溶液-亚浓溶液交叉浓度c*表示在底部的x轴上。两相区域由稠密的、富含聚合物的相与流体样、聚合物含量低的相组成,在该区域无法获得数据。随着比例接近两相区域,混合物的弹性模量和粘度增加。
在富含PAA与PEI区域中的混合比例处观察到了均质的单相。电荷的不平衡形成了非化学计量的亲水性复合物。化学计量混合比例附近的两相区域包括稠密的、富含聚合物并具有化学计量的疏水性复合物的相以及流体样、聚合物含量低的相。
在不同的混合比例处观察到的粘度差异可用于组装不同的长度范围的构件。在小号喷嘴处,较低粘度的墨水可在施加适当的压力时沉积,而较大号的喷嘴通常需要粘度更高的墨水以使流动具有可控的速率。
2)墨水沉积装置
将如实施例1中所述制备的墨水载至制造微构件的沉积装置中。该装置包括NanoCubeTM XYZ NanoPositioning System(Polytec PI,Auburn,MA),它控制μ-Tip(World Precision Instruments,Sarasota,FL)沉积喷嘴,且墨水被具有3ml ULTRA Barrel Reservoirs(EFD,Providence,RI)的Model 800 ULTRA Dispensing System从装置中分配出去。
3)在异丙醇和水中制造构件
在含有异丙醇(IPA)和水的混合物的沉积浴中,使根据实施例1的方法制备的Φpoly=0.4、PAA∶PEI比例为~5.7∶1的墨水以20微米/秒的速度通过1微米的喷嘴沉积。由于对于聚电解质而言溶剂质量下降和可电离基团之间的库仑吸引作用的增强而发生胶凝作用,得到发生反应的墨水细丝。NMR光谱数据(未给出)显示在发生反应的复合物和未发生反应的复合物之间结合的类型不存在可辨认的差异,这表明所述反应只是引起结合数目和结合强度的变化。发生反应的墨水的机械性质高度依赖于沉积浴,如图2所示。
4)在水沉积浴中制造构件
重复实施例3的实验,这次使用PAA∶PEI比例为~4.8的墨水和去离子水沉积浴。pH的变化通过将在墨水pH下为中性的酸性基团离子化而消除了带有正电荷的基团的过量。这样得到的混合物胶凝成为细丝,其具有近乎化学计量的阳离子基团∶阴离子基团比例(表1)。
表1
聚电解质 | 碳 | 氢 | 氮 | (-∶+)电荷比例 |
PAA | 39.48 | 4.80 | NA | |
PEI | 52.04 | 11.78 | 31.68 | NA |
未反应的PEC | 40.12 | 5.21 | 2.27 | 4.8∶1 |
发生反应的PEC | 41.92 | 5.58 | 2.90 | 1.1∶1 |
4)微构件
图3A至3C表示用1微米的喷嘴在83%IPA(余量水)沉积浴中制造的构件。图3A表示中间缺失细丝的FCT构件,它可以用作光子晶体中的波导管。图3B表示具有壁的8层构件,显示了形成固体构件以及跨越元件的能力。图3C表示在不同的长度范围处具有孔隙的辐射构件。发生反应的复合物能够跨越远远大于细丝直径的长度。波导管和辐射构件得以制造表明制造具有锐角或钝角的结构特征的能力。还使用不同的喷嘴和墨水(Φpoly=0.4且PAA∶PEI比例~5.7∶1;Φpoly=0.4且PAA∶PEI比例~5∶1;Φpoly=0.43且PAA∶PEI比例~2∶1)制造了具有不同特征尺寸的周期性构件,其中构件的特征尺寸是它最细的细丝的直径。
如果沉积在微酸性环境中进行,就会发生复合物仍维持其形状但部分溶解的现象,从而产生弹性较差的高孔隙度构件。该构件的表面具有残余的负电荷,并可用于吸附纳米粒子。
微构件还可以经过热处理并保持其完整性。例如将微构件在空气中以5℃/min的速度加热至240℃。温度在240℃保持30分钟,然后以5℃/min的速度冷却。所述构件保持着它们的原始形状,并变得比加热前更坚硬。这种硬化可能还由于热诱导的聚电解质间键的形成,例如PAA的羧基与PEI的胺基之间形成的酰胺键。
Claims (48)
1.一种聚电解质墨水,其包含:
(a)溶剂,
(b)溶于该溶剂中的阳离子聚电解质,和
(c)溶于该溶剂中的阴离子聚电解质,
其中至少一种所述聚电解质在该溶剂中的浓度在亚浓溶液区域。
2.权利要求1的墨水,其中该墨水中所述阳离子聚电解质的阳离子基团与所述阴离子聚电解质的阴离子基团的比例不是1比1。
3.权利要求1的墨水,其中所述聚电解质选自以下组中:聚(丙烯酸)、聚(氮杂环丙烷)、聚(苯乙烯磺酸酯)、聚(烯丙胺)盐酸盐、聚(二烯丙基二甲基氯化铵)、聚(4-乙烯基吡啶)、聚乙炔、聚苯胺、聚吡咯、聚噻吩、聚(3,4-亚乙二氧基噻吩)、聚(四氟乙烯)羧酸酯、聚(四氟乙烯)磷酸酯、聚亚苯基亚乙烯、聚苯基苯胺、磺化聚对亚苯基偶氮苯、多核苷酸、肽、蛋白质、肽核酸、酶、多糖、淀粉、纤维素、酸性多糖、半纤维素、阿拉伯葡糖醛酸木聚糖、碱性多糖、聚-(1,4)N-乙酰基-D-葡糖胺、半乳聚糖、琼脂糖、多糖醛酸苷、海藻酸、角叉菜聚糖、透明质酸、胶原蛋白、纤维蛋白、蛋白聚糖、聚乳酸、聚乙醇酸、有机酸共聚物、阳离子脂质、两性离子聚电解质、聚羧基甜菜碱。
4.权利要求1的墨水,其中所述阳离子聚电解质是聚(氮杂环丙烷),而所述阴离子聚电解质是聚(丙烯酸)。
5.权利要求1的墨水,其中还含有另一种聚电解质。
6.权利要求1的墨水,其中所述墨水的粘度为0.05-600Pa·sec。
7.权利要求1的墨水,其中所述墨水的粘度为0.1-150Pa·sec。
8.权利要求1的墨水,其中所述墨水的粘度为1-20Pa·sec。
9.权利要求1的墨水,其中所述溶剂包含水。
10.一种固体细丝,其包含阳离子聚电解质和阴离子聚电解质的复合物,其中所述细丝的直径最大为10微米。
11.权利要求10的固体细丝,其中所述细丝的直径最大为1微米。
12.权利要求10的固体细丝,其中所述聚电解质选自以下组中:聚(丙烯酸)、聚(氮杂环丙烷)、聚(苯乙烯磺酸酯)、聚(烯丙胺)盐酸盐、聚(二烯丙基二甲基氯化铵)、聚(4-乙烯基吡啶)、聚乙炔、聚苯胺、聚吡咯、聚噻吩、聚(3,4-亚乙二氧基噻吩)、聚(四氟乙烯)羧酸酯、聚(四氟乙烯)磷酸酯、聚亚苯基亚乙烯、聚苯基苯胺、磺化聚对亚苯基偶氮苯、多核苷酸、肽、蛋白质、肽核酸、酶、多糖、淀粉、纤维素、酸性多糖、半纤维素、阿拉伯葡糖醛酸木聚糖、碱性多糖、聚-(1,4)N-乙酰基-D-葡糖胺、半乳聚糖、琼脂糖、多糖醛酸苷、海藻酸、角叉菜聚糖、透明质酸、胶原蛋白、纤维蛋白、蛋白聚糖、聚乳酸、聚乙醇酸、有机酸共聚物、阳离子脂质、两性离子聚电解质、聚羧基甜菜碱。
13.权利要求11的固体细丝,其中所述聚电解质选自以下组中:聚(丙烯酸)、聚(氮杂环丙烷)、聚(苯乙烯磺酸酯)、聚(烯丙胺)盐酸盐、聚(二烯丙基二甲基氯化铵)、聚(4-乙烯基吡啶)、聚乙炔、聚苯胺、聚吡咯、聚噻吩、聚(3,4-亚乙二氧基噻吩)、聚(四氟乙烯)羧酸酯、聚(四氟乙烯)磷酸酯、聚亚苯基亚乙烯、聚苯基苯胺、磺化聚对亚苯基偶氮苯、多核苷酸、肽、蛋白质、肽核酸、酶、多糖、淀粉、纤维素、酸性多糖、半纤维素、阿拉伯葡糖醛酸木聚糖、碱性多糖、聚-(1,4)N-乙酰基-D-葡糖胺、半乳聚糖、琼脂糖、多糖醛酸苷、海藻酸、角叉菜聚糖、透明质酸、胶原蛋白、纤维蛋白、蛋白聚糖、聚乳酸、聚乙醇酸、有机酸共聚物、阳离子脂质、两性离子聚电解质、聚羧基甜菜碱。
14.权利要求10的固体细丝,其中所述阳离子聚电解质是聚(氮杂环丙烷),而所述阴离子聚电解质是聚(丙烯酸)。
15.权利要求11的固体细丝,其中所述阳离子聚电解质是聚(氮杂环丙烷)且阴离子聚电解质是聚(丙烯酸)。
16.一种制备聚电解质墨水的方法,其包括将各成分混合在一起,其中所述成分包含:
(a)溶剂,
(b)阳离子聚电解质,和
(c)阴离子聚电解质,
其中至少一种所述聚电解质在该溶剂中的浓度在亚浓溶液区域。
17.权利要求16的方法,其中所述阳离子聚电解质的阳离子基团与所述阴离子聚电解质的阴离子基团的比例不是1比1。
18.权利要求16的方法,其中所述聚电解质选自以下组中:聚(丙烯酸)、聚(氮杂环丙烷)、聚(苯乙烯磺酸酯)、聚(烯丙胺)盐酸盐、聚(二烯丙基二甲基氯化铵)、聚(4-乙烯基吡啶)、聚乙炔、聚苯胺、聚吡咯、聚噻吩、聚(3,4-亚乙二氧基噻吩)、聚(四氟乙烯)羧酸酯、聚(四氟乙烯)磷酸酯、聚亚苯基亚乙烯、聚苯基苯胺、磺化聚对亚苯基偶氮苯、多核苷酸、肽、蛋白质、肽核酸、酶、多糖、淀粉、纤维素、酸性多糖、半纤维素、阿拉伯葡糖醛酸木聚糖、碱性多糖、聚-(1,4)N-乙酰基-D-葡糖胺、半乳聚糖、琼脂糖、多糖醛酸苷、海藻酸、角叉菜聚糖、透明质酸、胶原蛋白、纤维蛋白、蛋白聚糖、聚乳酸、聚乙醇酸、有机酸共聚物、阳离子脂质、两性离子聚电解质、聚羧基甜菜碱。
19.权利要求16的方法,其中所述阳离子聚电解质是聚(氮杂环丙烷),而所述阴离子聚电解质是聚(丙烯酸)。
20.权利要求16的方法,其中所述成分还包含另一种聚电解质。
21.权利要求16的方法,其中所述墨水的粘度为0.05-600Pa·sec。
22.权利要求16的方法,其中所述墨水的粘度为0.1-150Pa·sec。
23.权利要求16的方法,其中所述墨水的粘度为1-20Pa·sec。
24.权利要求16的方法,其中所述溶剂包括水。
25.通过权利要求16的方法制备的墨水。
26.通过权利要求18的方法制备的墨水。
27.通过权利要求19的方法制备的墨水。
28.通过权利要求20的方法制备的墨水。
29.一种制造细丝的方法,其包括:
使权利要求1的聚电解质墨水流过喷嘴;且
使该墨水与沉积浴接触;
其中所述聚电解质墨水在该沉积浴中胶凝。
30.权利要求29的方法,其中所述喷嘴的直径最大为10微米。
31.权利要求29的方法,其中所述喷嘴的直径最大为1微米。
32.权利要求30的方法,其中所述聚电解质选自以下组中:聚(丙烯酸)、聚(氮杂环丙烷)、聚(苯乙烯磺酸酯)、聚(烯丙胺)盐酸盐、聚(二烯丙基二甲基氯化铵)、聚(4-乙烯基吡啶)、聚乙炔、聚苯胺、聚吡咯、聚噻吩、聚(3,4-亚乙二氧基噻吩)、聚(四氟乙烯)羧酸酯、聚(四氟乙烯)磷酸酯、聚亚苯基亚乙烯、聚苯基苯胺、磺化聚对亚苯基偶氮苯、多核苷酸、肽、蛋白质、肽核酸、酶、多糖、淀粉、纤维素、酸性多糖、半纤维素、阿拉伯葡糖醛酸木聚糖、碱性多糖、聚-(1,4)N-乙酰基-D-葡糖胺、半乳聚糖、琼脂糖、多糖醛酸苷、海藻酸、角叉菜聚糖、透明质酸、胶原蛋白、纤维蛋白、蛋白聚糖、聚乳酸、聚乙醇酸、有机酸共聚物、阳离子脂质、两性离子聚电解质、聚羧基甜菜碱。
33.权利要求30的方法,其中所述阳离子聚电解质是聚(氮杂环丙烷),而所述阴离子聚电解质是聚(丙烯酸)。
34.权利要求30的方法,其中所述墨水的粘度为0.05-600Pa·sec。
35.权利要求30的方法,其中所述墨水的粘度为0.1-150Pa·sec。
36.权利要求30的方法,其中所述墨水的粘度为1-20Pa·sec。
37.权利要求30的方法,其中所述溶剂包括水。
38.权利要求30的方法,其中所述沉积浴的pH与所述墨水的pH不同。
39.权利要求30的方法,其中所述沉积浴的离子强度与所述墨水的离子强度不同。
40.权利要求30的方法,其中所述沉积浴包含与所述墨水中的溶剂不同的溶剂。
41.权利要求30的方法,其中所述沉积浴含有醇。
42.一种形成三维构件的方法,其包括制造多条细丝,每条细丝都通过权利要求29的方法制造。
43.一种形成三维构件的方法,其包括制造多条细丝,每条细丝都通过权利要求30的方法制造。
44.一种形成三维构件的方法,其包括制造多条细丝,每条细丝都通过权利要求33的方法制造。
45.一种制造微构件的装置,其包括:
(1)直径最大为10微米的喷嘴,
(2)支持底材的平台,在喷嘴下方,
(3)可操作地与所述喷嘴、平台或与喷嘴和平台两者连接的微定位器,和
(4)可流通地(fluidly)与喷嘴相连的墨水池。
46.权利要求40的装置,其还包括可操作地与墨水池连接的压力分配系统。
47.权利要求45的装置,其中所述喷嘴的直径最大为1微米。
48.权利要求45的装置,其包括多个喷嘴。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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CN107974131A (zh) * | 2017-11-16 | 2018-05-01 | 华南师范大学 | 一种碳点墨水及其制备方法和应用 |
WO2019075866A1 (zh) * | 2017-10-16 | 2019-04-25 | 深圳市华星光电半导体显示技术有限公司 | 电子传输层喷墨打印墨水及其制备方法 |
Families Citing this family (45)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030091647A1 (en) * | 2001-11-15 | 2003-05-15 | Lewis Jennifer A. | Controlled dispersion of colloidal suspensions via nanoparticle additions |
US20040226620A1 (en) | 2002-09-26 | 2004-11-18 | Daniel Therriault | Microcapillary networks |
US7141617B2 (en) | 2003-06-17 | 2006-11-28 | The Board Of Trustees Of The University Of Illinois | Directed assembly of three-dimensional structures with micron-scale features |
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US8895111B2 (en) | 2007-03-14 | 2014-11-25 | Kimberly-Clark Worldwide, Inc. | Substrates having improved ink adhesion and oil crockfastness |
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US20090101278A1 (en) * | 2007-10-17 | 2009-04-23 | Louis Laberge-Lebel | Methods for preparing freeform three-dimensional structures |
US20090221736A1 (en) * | 2008-02-29 | 2009-09-03 | Mccurry Charles Douglas | Water-based ink composition for improved crockfastness |
US8216666B2 (en) | 2008-02-29 | 2012-07-10 | The Procter & Gamble Company | Substrates having improved crockfastness |
US7922939B2 (en) | 2008-10-03 | 2011-04-12 | The Board Of Trustees Of The University Of Illinois | Metal nanoparticle inks |
US8187500B2 (en) | 2008-10-17 | 2012-05-29 | The Board Of Trustees Of The University Of Illinois | Biphasic inks |
US9400219B2 (en) * | 2009-05-19 | 2016-07-26 | Iowa State University Research Foundation, Inc. | Metallic layer-by-layer photonic crystals for linearly-polarized thermal emission and thermophotovoltaic device including same |
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US9474269B2 (en) | 2010-03-29 | 2016-10-25 | The Clorox Company | Aqueous compositions comprising associative polyelectrolyte complexes (PEC) |
US9309435B2 (en) | 2010-03-29 | 2016-04-12 | The Clorox Company | Precursor polyelectrolyte complexes compositions comprising oxidants |
US20110236582A1 (en) * | 2010-03-29 | 2011-09-29 | Scheuing David R | Polyelectrolyte Complexes |
JP2013060570A (ja) * | 2010-10-28 | 2013-04-04 | Kao Corp | 変性ポリウロン酸又はその塩 |
US8742406B1 (en) | 2011-02-16 | 2014-06-03 | Iowa State University Research Foundation, Inc. | Soft lithography microlens fabrication and array for enhanced light extraction from organic light emitting diodes (OLEDs) |
US9643358B2 (en) | 2011-07-01 | 2017-05-09 | The Board Of Trustees Of The University Of Illinois | Multinozzle deposition system for direct write applications |
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CN106163581B (zh) | 2013-11-05 | 2019-10-25 | 哈佛学院院长及董事 | 打印具有包埋的脉管系统的组织构建体的方法 |
EP3071939B1 (en) | 2013-11-18 | 2019-07-31 | President and Fellows of Harvard College | Printed stretchable strain sensor |
US8975220B1 (en) | 2014-08-11 | 2015-03-10 | The Clorox Company | Hypohalite compositions comprising a cationic polymer |
JP2016098313A (ja) * | 2014-11-21 | 2016-05-30 | セイコーエプソン株式会社 | セルロース系材料、液状組成物、造形物および造形物の製造方法 |
US9570385B2 (en) | 2015-01-22 | 2017-02-14 | Invensas Corporation | Method for fabrication of interconnection circuitry with electrically conductive features passing through a support and comprising core portions formed using nanoparticle-containing inks |
JP6582485B2 (ja) | 2015-03-27 | 2019-10-02 | セイコーエプソン株式会社 | 組成物、造形物の製造方法および造形物 |
JP2016188283A (ja) | 2015-03-30 | 2016-11-04 | セイコーエプソン株式会社 | 組成物セット、造形物の製造方法および造形物 |
US10597545B2 (en) | 2015-05-18 | 2020-03-24 | President And Fellows Of Harvard College | Foam ink composition and 3D printed hierarchical porous structure |
US10394202B2 (en) | 2015-08-21 | 2019-08-27 | Voxel8, Inc. | 3D printer calibration and control |
WO2017095773A1 (en) * | 2015-11-30 | 2017-06-08 | President And Fellows Of Harvard College | Hydrogel composite ink formulation and method of 4d printing a hydrogel composite structure |
WO2018106705A1 (en) | 2016-12-08 | 2018-06-14 | President And Fellows Of Harvard College | 3d printed core-shell filament and method of 3d printing a core-shell filament |
CN110730800B (zh) | 2017-05-26 | 2022-08-19 | 无限材料解决方案有限公司 | 水性聚合物组合物 |
US11999097B2 (en) * | 2018-05-21 | 2024-06-04 | Virginia Tech Intellectual Properties, Inc. | Selective deposition of materials for composite structures via additive manufacturing |
US20220134301A1 (en) * | 2019-03-12 | 2022-05-05 | Ohio State Innovation Foundation | Ph-sensitive capsule and release system |
US20210053056A1 (en) * | 2019-08-23 | 2021-02-25 | Lawrence Livermore National Security, Llc | Systems and methods for reaction and transport engineering via cellular fluidics |
US11787117B2 (en) * | 2020-04-23 | 2023-10-17 | Rtx Corporation | Fabricating ceramic structures |
US11492547B2 (en) | 2020-06-04 | 2022-11-08 | UbiQD, Inc. | Low-PH nanoparticles and ligands |
WO2022026734A1 (en) * | 2020-07-29 | 2022-02-03 | Ohio State Innovation Foundation | Ph-sensitive capsule and release system |
CN112768611A (zh) * | 2021-01-11 | 2021-05-07 | 陈云 | 一种反式有机无机杂化钙钛矿太阳能电池的制备方法 |
Family Cites Families (138)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2892797A (en) * | 1956-02-17 | 1959-06-30 | Du Pont | Process for modifying the properties of a silica sol and product thereof |
US3546142A (en) * | 1967-01-19 | 1970-12-08 | Amicon Corp | Polyelectrolyte structures |
US3878034A (en) | 1970-06-25 | 1975-04-15 | Du Pont | Refractory laminate based on negative sol or silicate and positive sol |
DE2052749C3 (de) | 1970-10-28 | 1974-09-12 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Verfahren zur Herstellung von duktilem Gold und duktilen Goldlegierungen mit hoher Härte und Warmzugfestigkeit |
US4137217A (en) * | 1972-07-01 | 1979-01-30 | Eishun Tsuchida | Polyion complex and method for preparing the same |
US4181532A (en) * | 1975-10-22 | 1980-01-01 | United Kingdom Atomic Energy Authority | Production of colloidal dispersions |
JPS53106682A (en) | 1977-03-01 | 1978-09-16 | Hitachi Ltd | Supporting method for hydrated metal oxide on carrier |
US4414354A (en) | 1977-06-16 | 1983-11-08 | Monsanto Company | Aqueous polymeric latex coating compositions, products produced thereby, methods for preparing such compositions, and methods for using such compositions |
US4446174A (en) | 1979-04-27 | 1984-05-01 | Fuiji Photo Film Company, Ltd. | Method of ink-jet recording |
AU534964B2 (en) | 1980-11-05 | 1984-02-23 | Square D Company | Contact material and method of making |
DE3260845D1 (en) | 1981-01-16 | 1984-11-08 | Nippon Catalytic Chem Ind | Copolymer and method for manufacture thereof |
JPS57201700A (en) | 1981-03-03 | 1982-12-10 | Shii Fuitsushiyaa Pooru | Ball pen marking tool and its ink composition |
JPS57185316A (en) * | 1981-05-11 | 1982-11-15 | Sumitomo Metal Mining Co Ltd | Electrically conductive resin paste |
CA1198556A (en) | 1982-05-14 | 1985-12-31 | Martyn C. Barker | Compositions comprising inorganic particles |
US4426356A (en) | 1982-09-30 | 1984-01-17 | E. I. Du Pont De Nemours And Company | Method for making capacitors with noble metal electrodes |
US4818614A (en) | 1985-07-29 | 1989-04-04 | Shiseido Company Ltd. | Modified powder |
JPH0725689B2 (ja) | 1986-10-07 | 1995-03-22 | 中外製薬株式会社 | 顆粒球コロニ−刺激因子を含有する徐放性製剤 |
US4960465A (en) | 1986-12-09 | 1990-10-02 | W. R. Grace & Co. | Hydraulic cement additives and hydraulic cement compositions containing same |
JP2541218B2 (ja) | 1987-05-15 | 1996-10-09 | 日本油脂株式会社 | セメント用添加剤 |
DE3805879C1 (zh) * | 1988-02-25 | 1989-08-10 | Huels Ag, 4370 Marl, De | |
KR0159921B1 (ko) * | 1988-10-03 | 1999-01-15 | 마이클 비. 키한 | 양이온성 및 음이온성 중합체의 혼합물, 그 제법 및 종이용 건조강도 개선 첨가제로서의 용도 |
EP0402563B1 (de) | 1989-05-17 | 1994-08-10 | Sika AG, vorm. Kaspar Winkler & Co. | Wasserlösliche Copolymere, ein Verfahren zu ihrer Herstellung und ihre Verwendung als Fliessmittel in Feststoffsuspensionen |
GB2233928B (en) * | 1989-05-23 | 1992-12-23 | Brother Ind Ltd | Apparatus and method for forming three-dimensional article |
JP2836875B2 (ja) | 1989-12-27 | 1998-12-14 | 株式会社クラレ | イミド化アクリル樹脂の製造方法 |
US5284894A (en) | 1990-02-22 | 1994-02-08 | Basf Corporation | Low-foaming latexes for use in printing ink formulations |
US5147841A (en) * | 1990-11-23 | 1992-09-15 | The United States Of America As Represented By The United States Department Of Energy | Method for the preparation of metal colloids in inverse micelles and product preferred by the method |
US5196199A (en) * | 1990-12-14 | 1993-03-23 | Fuisz Technologies Ltd. | Hydrophilic form of perfluoro compounds and method of manufacture |
US5416071A (en) | 1991-03-12 | 1995-05-16 | Takeda Chemical Industries, Ltd. | Water-soluble composition for sustained-release containing epo and hyaluronic acid |
JPH0679965B2 (ja) | 1991-04-12 | 1994-10-12 | 株式会社コロイドリサーチ | ジルコニアゾルの製造方法およびジルコニア成形体の製造方法 |
EP0510552B2 (en) | 1991-04-24 | 2000-11-15 | MITSUI TOATSU CHEMICALS, Inc. | Preparation process of alpha-aspartyl-L-phenylalanine methyl ester |
DK168738B1 (da) | 1991-04-30 | 1994-05-30 | Topsoe Haldor As | Keramisk binder, fremstilling og anvendelse deraf |
US5965194A (en) | 1992-01-10 | 1999-10-12 | Imation Corp. | Magnetic recording media prepared from magnetic particles having an extremely thin, continuous, amorphous, aluminum hydrous oxide coating |
US5268782A (en) | 1992-01-16 | 1993-12-07 | Minnesota Mining And Manufacturing Company | Micro-ridged, polymeric liquid crystal display substrate and display device |
US5344487A (en) | 1992-02-12 | 1994-09-06 | Whalen Shaw Michael | Layered composite pigments and method of making same |
DE4212768A1 (de) | 1992-04-16 | 1993-10-21 | Huels Chemische Werke Ag | Verfahren zur Herstellung von wäßrigen Polymerdispersionen |
FR2696185B1 (fr) | 1992-09-25 | 1994-12-02 | Inst Francais Du Petrole | Procédé amélioré de fabrication d'esters à partir de corps gras d'origine naturelle. |
ATE168497T1 (de) | 1993-01-21 | 1998-08-15 | Mayo Foundation | Mikropartikelschaltvorrichtung |
AT399340B (de) | 1993-02-01 | 1995-04-25 | Chemie Linz Gmbh | Copolymere auf basis von maleinsäurederivaten und vinylmonomeren, deren herstellung und verwendung |
FR2701471B1 (fr) | 1993-02-10 | 1995-05-24 | Rhone Poulenc Chimie | Procédé de synthèse de compositions à base d'oxydes mixtes de zirconium et de cérium, compositions ainsi obtenues et utilisations de ces dernières. |
US5753261A (en) | 1993-02-12 | 1998-05-19 | Access Pharmaceuticals, Inc. | Lipid-coated condensed-phase microparticle composition |
US5820879A (en) | 1993-02-12 | 1998-10-13 | Access Pharmaceuticals, Inc. | Method of delivering a lipid-coated condensed-phase microparticle composition |
US5654006A (en) | 1993-02-12 | 1997-08-05 | Mayo Foundation For Medical Education And Research | Condensed-phase microparticle composition and method |
US5424362A (en) | 1993-04-28 | 1995-06-13 | The Dow Chemical Company | Paintable olefinic interpolymer compositions |
US5424467A (en) | 1993-07-14 | 1995-06-13 | Idaho Research Foundation | Method for purifying alcohol esters |
US5393343A (en) | 1993-09-29 | 1995-02-28 | W. R. Grace & Co.-Conn. | Cement and cement composition having improved rheological properties |
US5891313A (en) | 1993-11-23 | 1999-04-06 | The Perkin-Elmer Corp. | Entrapment of nucleic acid sequencing template in sample mixtures by entangled polymer networks |
GB9407246D0 (en) | 1994-04-13 | 1994-06-08 | Sandoz Ltd | Improvements in or relating to organic compounds |
US5429761A (en) * | 1994-04-14 | 1995-07-04 | The Lubrizol Corporation | Carbonated electrorheological particles |
US5424364A (en) | 1994-05-17 | 1995-06-13 | E. I. Du Pont De Nemours & Company | Comb pigment dispersants |
GB9412579D0 (en) * | 1994-06-22 | 1994-08-10 | Tioxide Specialties Ltd | Compositions containing zirconium compounds |
US5626862A (en) | 1994-08-02 | 1997-05-06 | Massachusetts Institute Of Technology | Controlled local delivery of chemotherapeutic agents for treating solid tumors |
DE4431302A1 (de) | 1994-09-02 | 1996-03-07 | Roehm Gmbh | Kammpolymere |
US6228217B1 (en) * | 1995-01-13 | 2001-05-08 | Hercules Incorporated | Strength of paper made from pulp containing surface active, carboxyl compounds |
DE19519042A1 (de) | 1995-05-24 | 1996-11-28 | Basf Ag | Herstellung von Polyalkenylbernsteinsäure-Derivaten und ihre Verwendung als Kraft- und Schmierstoffadditive |
US5681658A (en) | 1995-05-30 | 1997-10-28 | Aluminum Company Of America | Gelation-resistant alumina |
US5665158A (en) | 1995-07-24 | 1997-09-09 | W. R. Grace & Co.-Conn. | Cement admixture product |
US5556460A (en) | 1995-09-18 | 1996-09-17 | W.R. Grace & Co.-Conn. | Drying shrinkage cement admixture |
SE505386C2 (sv) * | 1995-11-29 | 1997-08-18 | Akzo Nobel Surface Chem | Polyelektrolytkomposition |
MA24137A1 (fr) | 1996-04-16 | 1997-12-31 | Procter & Gamble | Fabrication d'agents de surface ramifies . |
EG22088A (en) | 1996-04-16 | 2002-07-31 | Procter & Gamble | Alkoxylated sulfates |
EG21623A (en) | 1996-04-16 | 2001-12-31 | Procter & Gamble | Mid-chain branced surfactants |
PH11997056158B1 (en) | 1996-04-16 | 2001-10-15 | Procter & Gamble | Mid-chain branched primary alkyl sulphates as surfactants |
US6436167B1 (en) * | 1996-05-13 | 2002-08-20 | The United States Of America As Represented By The Secretary Of The Navy | Synthesis of nanostructured composite particles using a polyol process |
MA25183A1 (fr) | 1996-05-17 | 2001-07-02 | Arthur Jacques Kami Christiaan | Compositions detergentes |
US5958858A (en) | 1996-06-28 | 1999-09-28 | The Procter & Gamble Company | Low anionic surfactant detergent compositions |
US5711958A (en) | 1996-07-11 | 1998-01-27 | Life Medical Sciences, Inc. | Methods for reducing or eliminating post-surgical adhesion formation |
JP3429958B2 (ja) * | 1996-08-28 | 2003-07-28 | 三井金属鉱業株式会社 | 銀コロイド液の製造方法 |
US5783136A (en) * | 1996-09-09 | 1998-07-21 | Ford Global Technologies, Inc. | Method of preparing a stereolithographically produced prototype for experimental stress analysis |
US6447727B1 (en) | 1996-11-19 | 2002-09-10 | Caliper Technologies Corp. | Microfluidic systems |
US6465257B1 (en) | 1996-11-19 | 2002-10-15 | Caliper Technologies Corp. | Microfluidic systems |
US6093856A (en) | 1996-11-26 | 2000-07-25 | The Procter & Gamble Company | Polyoxyalkylene surfactants |
US6989115B2 (en) * | 1996-12-20 | 2006-01-24 | Z Corporation | Method and apparatus for prototyping a three-dimensional object |
US6103868A (en) * | 1996-12-27 | 2000-08-15 | The Regents Of The University Of California | Organically-functionalized monodisperse nanocrystals of metals |
US6139623A (en) | 1997-01-21 | 2000-10-31 | W. R. Grace & Co.-Conn. | Emulsified comb polymer and defoaming agent composition and method of making same |
US5780525A (en) * | 1997-02-14 | 1998-07-14 | Reliance Electric Industrial Company | Photocurable composition for electrical insulation |
US6133227A (en) | 1997-06-23 | 2000-10-17 | The Procter & Gamble Company | Enzymatic detergent compositions |
NZ502141A (en) | 1997-06-25 | 2001-12-21 | W | Admixture and method for optimizing addition of EO/PO superplasticizer to concrete containing smectite clay-containing aggregates |
US6211249B1 (en) | 1997-07-11 | 2001-04-03 | Life Medical Sciences, Inc. | Polyester polyether block copolymers |
US6127094A (en) | 1997-10-02 | 2000-10-03 | Napp Systems Inc. | Acrylate copolymer-containing water-developable photosensitive resins and printing plates prepared therefrom |
US6242406B1 (en) | 1997-10-10 | 2001-06-05 | The Procter & Gamble Company | Mid-chain branched surfactants with cellulose derivatives |
JP2001520261A (ja) | 1997-10-14 | 2001-10-30 | ザ、プロクター、エンド、ギャンブル、カンパニー | 中鎖分岐界面活性剤を含む顆粒洗剤組成物 |
US6027326A (en) | 1997-10-28 | 2000-02-22 | Sandia Corporation | Freeforming objects with low-binder slurry |
US6342298B1 (en) * | 1997-11-19 | 2002-01-29 | Basf Aktiengesellschaft | Multicomponent superabsorbent fibers |
US6167910B1 (en) | 1998-01-20 | 2001-01-02 | Caliper Technologies Corp. | Multi-layer microfluidic devices |
DE19909757A1 (de) | 1998-03-07 | 1999-09-16 | Beiersdorf Ag | Sulfonierte Kammpolymere und Zubereitungen, insbesondere haarkosmetische Zubereitungen auf der Grundlage von solchen sulfonierten Kammpolymeren |
US6613234B2 (en) | 1998-04-06 | 2003-09-02 | Ciphergen Biosystems, Inc. | Large pore volume composite mineral oxide beads, their preparation and their applications for adsorption and chromatography |
ATE275977T1 (de) | 1998-04-13 | 2004-10-15 | Massachusetts Inst Technology | Kamm-polymere zur regelung der zelloberflächenwechselwirkung |
US6080216A (en) | 1998-04-22 | 2000-06-27 | 3M Innovative Properties Company | Layered alumina-based abrasive grit, abrasive products, and methods |
US6107409A (en) | 1998-05-06 | 2000-08-22 | Bridgestone Corporation | Gels derived from extending grafted comb polymers and polypropylene via a solution synthesis |
EP1094994A4 (en) | 1998-06-18 | 2003-01-02 | Grace W R & Co | AIR TRAINING USING POLYOXYALKYLENE COPOLYMERS FOR CONCRETE TREATED WITH OXYALKYLENE SHRINK-REDUCING MIXTURES |
US6576478B1 (en) | 1998-07-14 | 2003-06-10 | Zyomyx, Inc. | Microdevices for high-throughput screening of biomolecules |
US6262129B1 (en) * | 1998-07-31 | 2001-07-17 | International Business Machines Corporation | Method for producing nanoparticles of transition metals |
MY125159A (en) * | 1998-09-14 | 2006-07-31 | Mitsubishi Materials Corp | Fine metal particle-dispersion solution and conductive film using the same |
US6258161B1 (en) | 1998-11-04 | 2001-07-10 | W. R. Grace & Co.-Conn. | Masonry blocks and masonry concrete admixture for improved freeze-thaw durability |
US6395804B1 (en) | 1998-12-18 | 2002-05-28 | 3M Innovative Properties Company | Polyelectrolyte dispersants for hydrophobic particles in water-based systems |
US6602994B1 (en) | 1999-02-10 | 2003-08-05 | Hercules Incorporated | Derivatized microfibrillar polysaccharide |
US6165406A (en) | 1999-05-27 | 2000-12-26 | Nanotek Instruments, Inc. | 3-D color model making apparatus and process |
US6517199B1 (en) * | 1999-11-12 | 2003-02-11 | Canon Kabushiki Kaisha | Liquid composition, ink set, colored area formation on recording medium, and ink-jet recording apparatus |
DE10003397A1 (de) * | 2000-01-27 | 2001-08-09 | Hartmann Paul Ag | Polyelektrolyt-Feststoffsystem, Verfahren zur Herstellung desselben sowie Wundverband |
US6441054B1 (en) | 2000-03-02 | 2002-08-27 | W.R. Grace & Co.-Conn | Air management in cementitious mixtures having plasticizer and a clay-activity modifying agent |
JP2001269859A (ja) | 2000-03-27 | 2001-10-02 | Jsr Corp | 化学機械研磨用水系分散体 |
DE10018987A1 (de) * | 2000-04-17 | 2001-10-31 | Envision Technologies Gmbh | Vorrichtung und Verfahren zum Herstellen von dreidimensionalen Objekten |
AU2001257121A1 (en) | 2000-04-21 | 2001-11-07 | Science & Technology Corporation @ Unm | Prototyping of patterned functional nanostructures |
WO2001087575A2 (en) | 2000-05-12 | 2001-11-22 | The Regents Of The University Of Michigan | Reverse fabrication of porous materials |
US6645432B1 (en) | 2000-05-25 | 2003-11-11 | President & Fellows Of Harvard College | Microfluidic systems including three-dimensionally arrayed channel networks |
DE10026955A1 (de) * | 2000-05-30 | 2001-12-13 | Daimler Chrysler Ag | Materialsystem zur Verwendung beim 3D-Drucken |
DE10044164A1 (de) * | 2000-09-07 | 2002-03-21 | Basf Ag | Vinylamin-Verbindungen |
JP2004509192A (ja) | 2000-09-11 | 2004-03-25 | マサチューセッツ・インスティチュート・オブ・テクノロジー | グラフトコポリマー、親水性鎖を疎水性ポリマー上にグラフトするための方法、およびそれらの物品 |
JP3880838B2 (ja) | 2000-12-27 | 2007-02-14 | 日本碍子株式会社 | 碍子 |
GB0103754D0 (en) * | 2001-02-15 | 2001-04-04 | Vantico Ltd | Three-dimensional structured printing |
US6746510B2 (en) * | 2001-04-02 | 2004-06-08 | The United States Of America As Represented By The Secretary Of The Navy | Processing of nanocrystalline metallic powders and coatings using the polyol process |
US6418968B1 (en) | 2001-04-20 | 2002-07-16 | Nanostream, Inc. | Porous microfluidic valves |
US6572673B2 (en) * | 2001-06-08 | 2003-06-03 | Chang Chun Petrochemical Co., Ltd. | Process for preparing noble metal nanoparticles |
US6656410B2 (en) | 2001-06-22 | 2003-12-02 | 3D Systems, Inc. | Recoating system for using high viscosity build materials in solid freeform fabrication |
US6645444B2 (en) | 2001-06-29 | 2003-11-11 | Nanospin Solutions | Metal nanocrystals and synthesis thereof |
US20030032727A1 (en) | 2001-07-09 | 2003-02-13 | Sridevi Narayan-Sarathy | Comb-shaped polymers having anionic functionality |
FR2830206B1 (fr) | 2001-09-28 | 2004-07-23 | Corning Inc | Dispositif microfluidique et sa fabrication |
JP4301763B2 (ja) * | 2001-10-31 | 2009-07-22 | 藤倉化成株式会社 | 銀化合物ペースト |
US20030091647A1 (en) * | 2001-11-15 | 2003-05-15 | Lewis Jennifer A. | Controlled dispersion of colloidal suspensions via nanoparticle additions |
DE60231252D1 (de) * | 2001-12-17 | 2009-04-02 | Univ Northwestern | Strukturierung von solid-state-merkmalen durch nanolithographisches direktschreibedrucken |
US6861205B2 (en) | 2002-02-06 | 2005-03-01 | Battelle Memorial Institute | Three dimensional microstructures and method of making |
EP1507834A1 (en) * | 2002-05-29 | 2005-02-23 | E.I. Du Pont De Nemours And Company | Fibrillar microstructure for conformal contact and adhesion |
US6878184B1 (en) * | 2002-08-09 | 2005-04-12 | Kovio, Inc. | Nanoparticle synthesis and the formation of inks therefrom |
US20040226620A1 (en) * | 2002-09-26 | 2004-11-18 | Daniel Therriault | Microcapillary networks |
US7909929B2 (en) | 2002-11-13 | 2011-03-22 | Nippon Soda Co., Ltd. | Dispersoid having metal-oxygen bonds, metal oxide film, and monomolecular film |
US7053125B2 (en) * | 2002-11-14 | 2006-05-30 | The Board Of Trustees Of The University Of Illinois | Controlled dispersion of colloidal suspension by comb polymers |
US6974493B2 (en) | 2002-11-26 | 2005-12-13 | Honda Motor Co., Ltd. | Method for synthesis of metal nanoparticles |
US7309728B2 (en) * | 2003-01-09 | 2007-12-18 | Hewlett-Packard Development Company, L.P. | Freeform fabrication low density material systems |
US7081322B2 (en) * | 2003-03-27 | 2006-07-25 | Kodak Graphics Communications Canada Company | Nanopastes as ink-jet compositions for printing plates |
JP4899289B2 (ja) * | 2003-04-07 | 2012-03-21 | セイコーエプソン株式会社 | 水性インク組成物およびその製造方法 |
US6929675B1 (en) * | 2003-04-24 | 2005-08-16 | Sandia Corporation | Synthesis metal nanoparticle |
US7141617B2 (en) | 2003-06-17 | 2006-11-28 | The Board Of Trustees Of The University Of Illinois | Directed assembly of three-dimensional structures with micron-scale features |
KR100539392B1 (ko) * | 2003-08-12 | 2005-12-27 | (주)해은켐텍 | 습도센서 감습막용 전해질 고분자 조성물, 그로부터제조되는 전해질 고분자 잉크 및 잉크젯 인쇄방식을이용하여 감습막을 형성하는 습도센서 제조방법 |
US7160525B1 (en) * | 2003-10-14 | 2007-01-09 | The Board Of Trustees Of The University Of Arkansas | Monodisperse noble metal nanocrystals |
TWI318173B (en) * | 2004-03-01 | 2009-12-11 | Sumitomo Electric Industries | Metallic colloidal solution and inkjet-use metallic ink |
JP3858902B2 (ja) * | 2004-03-03 | 2006-12-20 | 住友電気工業株式会社 | 導電性銀ペーストおよびその製造方法 |
CA2558425A1 (en) * | 2004-03-08 | 2005-09-22 | Ecology Coating, Inc. | Environmentally friendly coating compositions for coating metal objects, coated objects therefrom, and methods, processes and assemblages for coating thereof |
US7956102B2 (en) | 2007-04-09 | 2011-06-07 | The Board Of Trustees Of The University Of Illinois | Sol-gel inks |
-
2003
- 2003-06-17 US US10/463,834 patent/US7141617B2/en not_active Expired - Fee Related
-
2004
- 2004-06-08 WO PCT/US2004/018353 patent/WO2005000977A2/en active Application Filing
- 2004-06-08 DE DE112004001096.9T patent/DE112004001096B4/de not_active Expired - Fee Related
- 2004-06-08 GB GB0525788A patent/GB2418918B/en not_active Expired - Fee Related
- 2004-06-08 CN CNA2004800208428A patent/CN1826393A/zh active Pending
-
2006
- 2006-11-16 US US11/560,610 patent/US7790061B2/en not_active Expired - Fee Related
-
2010
- 2010-09-03 US US12/875,821 patent/US20100330220A1/en not_active Abandoned
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105315792A (zh) * | 2015-11-18 | 2016-02-10 | Tcl集团股份有限公司 | 量子点油墨及其制备方法、量子点发光二极管 |
WO2019075866A1 (zh) * | 2017-10-16 | 2019-04-25 | 深圳市华星光电半导体显示技术有限公司 | 电子传输层喷墨打印墨水及其制备方法 |
US10781326B2 (en) | 2017-10-16 | 2020-09-22 | Shenzhen China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Ink-jet printing ink of an electron transport layer and its manufacturing method |
CN107974131A (zh) * | 2017-11-16 | 2018-05-01 | 华南师范大学 | 一种碳点墨水及其制备方法和应用 |
CN107974131B (zh) * | 2017-11-16 | 2021-01-12 | 华南师范大学 | 一种碳点墨水及其制备方法和应用 |
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US20070228335A1 (en) | 2007-10-04 |
WO2005000977A3 (en) | 2005-03-31 |
US7790061B2 (en) | 2010-09-07 |
DE112004001096T5 (de) | 2006-10-26 |
DE112004001096B4 (de) | 2017-11-02 |
WO2005000977A2 (en) | 2005-01-06 |
US7141617B2 (en) | 2006-11-28 |
US20100330220A1 (en) | 2010-12-30 |
GB0525788D0 (en) | 2006-01-25 |
US20060235105A1 (en) | 2006-10-19 |
GB2418918B (en) | 2008-07-09 |
GB2418918A (en) | 2006-04-12 |
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