CN101203329A - 高度多孔性的包覆细粒、组合物和制备方法 - Google Patents
高度多孔性的包覆细粒、组合物和制备方法 Download PDFInfo
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Abstract
高度多孔性的低密度材料的细粒,其中将孔腔至少部分抽空并且用具有低热导率的气体再充满,并且用保护性耐久的包覆层包封得到的粒子。所述粒子作为耐久的绝热材料是特别有用的。
Description
相关申请的交叉引用
本申请要求基于2005年3月22日提交的美国临时申请60/663,737和2005年3月29日提交的美国临时申请60/665,932的优先权,所述临时申请通过参考结合在此。
背景
本发明涉及一种由高度多孔性的低密度材料的粒子组成的材料,其中将孔腔至少部分抽空并且用具有低热导率的气体再充满,并且用保护性和耐久的包覆层包封得到的粒子。本发明还涉及这样的粒子、包含这样的粒子的组合物和制品,以及制备该粒子的方法。本发明的材料作为耐久的绝热材料是特别有用的。
一类已知的具有非常低的热导率的高度多孔性低密度材料包括通常称为“气凝胶”或“干凝胶”(该术语在本发明的说明书中交替使用)的材料。在其惯用含意中,术语“气凝胶”用于描述通过在高于临界温度的温度和高于临界压力的压力下干燥湿的溶胶-凝胶得到的材料。在这样的条件下,从溶胶-凝胶中除去凝胶液体如水导致多孔性结构,而不破坏凝胶的结构,所以得到高孔隙率。传统上,通过在低于超临界条件的条件下干燥得到的产物称为“干凝胶”,所述“干凝胶”由于至少一些孔结构在干燥处理过程中被破坏而具有较低的孔隙率。因为在超临界条件下的干燥处理非常耗能并且昂贵,所以已经尝试制备接近气凝胶性质的干凝胶。例如,美国专利5,565,142描述了:“一种极其多孔性的干凝胶,所述干凝胶是在真空-至-低于临界压力下干燥的,但是具有典型地在超临界压力下干燥的气凝胶的性质。这是通过使湿凝胶的内部孔表面与有机物质反应以在干燥过程中改变孔中的流体弯液面的接触角而完成的。”
二氧化硅气凝胶是第一种广泛研究的气凝胶。然而,可以制备具有各种化学组成的气凝胶和干凝胶。除不同于二氧化硅气凝胶的无机气凝胶以外,还有由有机聚合物制备并且有时称为“碳气凝胶”的有机气凝胶。
还可以表面处理气凝胶和干凝胶以改变它们的性质。例如,可以通过将表面-OH基团转变成-OR基团(其中R为脂族基团),使二氧化硅气凝胶较不亲水。美国专利6,806,299公开了疏水的有机气凝胶的制备,该专利的全部内容通过引用结合在此。
已知气凝胶具有优异的绝热性质,并且具有接近气凝胶的孔隙率和孔结构的干凝胶也是良好的绝热体。为了用作各种绝热层的绝热组分并且用于各种应用中,气凝胶和干凝胶已经成为科学和商业研究的主题。目前可商购的气凝胶体的实例包括在环境空气压力下的细粒、珠球或胶块(slabs)。然而,气凝胶的最佳耐热性值是在它们处于真空中时得到的。如美国专利6,132,837中所述,例如,将处于细粒、珠球、厚块、块料或胶块形式的气凝胶真空密封在塑料包装或容器中。与单独的粒子比较,这些气凝胶绝热材料的“收缩包装”或真空密封体较大。它们不像粒子一样通用,因为不能将它们以相同的方式混合或掺合到不同介质中。这些物件不容易用于建筑业、工业安装(industrial settings)或消费用安装。
上述气凝胶绝热材料的未包装体遭受耐久性的缺乏之苦,并且不能在恶劣环境中或在磨料的存在下使用。它们还遭受水分、油等在气凝胶孔中的吸收以及由增加的总密度和热导率所引起的相应的耐热性损失之苦。气凝胶绝热材料的收缩包装体随着时间的流逝经历真空度损失以及相应的耐热性损失。
发明概述
本发明克服了如现有技术中所知,在用于绝热的高度多孔性材料如气凝胶的应用中固有的缺点。
本发明的一个目的是提供处于分离体形式的绝热体(insulation),即高度多孔性的低密度材料的粒子,其中将孔腔中的空气至少部分抽空,并且将具有接近0的低热导率的气体引入到孔腔中,然后将所述粒子包封在本身具有固有的低热导率的材料的耐久、耐磨的极薄包覆层中。在高度多孔性的低密度材料为气凝胶或干凝胶的情况下,如此处理的气凝胶或干凝胶的包覆的分离体的特征在于,相对于充满空气的气凝胶或干凝胶在环境压力下的热导率,即约0.017W/mK,其热导率接近在理想真空中的气凝胶或干凝胶的热导率,即约0.008W/mK。所述包覆粒子的特征还在于对气凝胶或干凝胶的内部孔结构被降低气凝胶或干凝胶结构的耐热性的任何材料磨损、剪切或穿透的高抵抗力。
本发明的另一个目的是提供一种包含上述包覆和处理的多孔性粒子的组合物,以及用于制备这样的粒子和这样的组合物的方法。
附图简述
图1为描述用于制备根据本发明的包覆粒子的一个实例方案的原子层沉积用黏流反应器的示意图。
发明描述
本发明提供处于分离体形式的绝热材料或高度多孔性材料的粒子,其中将孔腔中的空气至少部分抽空,并且将具有接近0的低热导率的气体引入到孔腔中,然后将所述粒子包封在本身具有固有的低热导率的材料的耐久、耐磨的极薄包覆层中。在本申请中,得到的粒子称为“成品粒子”。
(i)高度多孔性材料的粒子
本发明中使用的高度多孔性粒子由通过干燥溶胶-凝胶得到的材料制成,并且具有至少80%的孔隙率和在1μm至5.0mm的范围内的粒径。在公开用于干燥溶胶-凝胶以及用于改变它的表面性质的各种方法的化学文献中,充分地证明了这些衍生自溶胶-凝胶的材料的化学性质和生产。这样的材料包括但不限于气凝胶和干凝胶。
气凝胶以及具有需要的接近气凝胶的孔隙率的高孔隙率的干凝胶适用于本发明。具体而言,可以使用无机气凝胶如二氧化硅气凝胶和其它无机气凝胶,以及由有机聚合物制备、有时称为“碳气凝胶”的气凝胶。无机干凝胶和有机干凝胶也适用于本发明,只要它们具有类似于气凝胶的性质即可。化学改性气凝胶以及具有类似于气凝胶的性质的化学改性干凝胶也适用于本发明。
适于本发明的高度多孔性粒子包括但不限于:通过其中在超临界压力下干燥湿溶胶-凝胶的方法制备的气凝胶粒子;以及通过其中在低于临界压力的压力下干燥湿溶胶-凝胶的方法制备的干凝胶粒子。可以使用无定形二氧化硅气凝胶或干凝胶的粒子,以及碳气凝胶或干凝胶的粒子。
适于本发明的高度多孔性粒子的尺寸在1μm至约5.0mm的范围内。在本发明的一个实施方案中,使用粒径在1μm至1,200μm,优选1μm至500μm,并且更优选1μm至15μm范围内的超细粒子。在本发明的另一个实施方案中,使用尺寸在约1.0mm至约5.0mm的范围内的粒子。
本发明中使用的高度多孔性粒子具有至少80%,并且优选至少90%的孔隙率,所述孔隙率为粒子的被空气占据的体积比例的量度。
粒子的形状不受特别限制,并且包括不规则形状以及平滑和对称的形状。
高度多孔性粒子典型地具有孔径不超过50nm的小孔。在本发明的一个实施方案中,粒子的特征在于约20nm的孔径。
由于具有高孔隙率以及小的粒径,适用于本发明的粒子具有例如在600至800m2/g的范围内的高表面积。
制备高度多孔性的粒子的气凝胶或干凝胶可以是疏水或亲水的。在本发明的一个实施方案中,气凝胶或干凝胶为非金属氧化物气凝胶或干凝胶,其中末端-OH基团中的氢原子被赋予气凝胶或干凝胶以疏水性(hydrophibicity)的非极性基团所取代。在另一个优选实施方案中,气凝胶或干凝胶为有机化合物的碳气凝胶或干凝胶,其中末端-CH基团中的氢原子被赋予气凝胶或干凝胶以疏水性的非极性基团所取代。
适用于本发明的气凝胶或干凝胶可以通过本领域中已知的方法制备,并且可以从商业供应商获得。
(ii)置换气体
可以使用具有接近0的低热导率的任何气体来置换孔腔中的空气。本领域普通技术人员可以鉴于具体应用,考虑成本、毒性、气体分子量对沉积在气凝胶上的特定包覆材料的厚度的影响等另外的因素进行气体的选择。氮气对于某些应用具有充分低的传导率(0.0002598W/cmK),并且具有通常可获得的优点。氙气对于一些应用是优选的,因为它具有0.0000569W/cmK的非常低的热导率,是化学惰性的,并且是价格经济的。具有比氙气略高的热导率但是价格更低的氪气也是适宜的。氡气具有比氙气和氪气甚至更低的热导率,并且可以在其中与人接触的危险最小的应用中使用。
(iii)保护性包覆层
保护性包覆层用材料的特征在于,在高度多孔性的粒子周围以在5nm-0.5mm的范围内的适宜厚度形成连续、坚固和不能渗透的保护壳层的能力。这种材料必须具有低的热导率。选择包覆层材料使其具有充分高于使用成品粒子的环境和应用的最高温度的熔点。从中可以选择包覆层材料的适宜化合物包括乙基纤维素、乙烯乙酸乙烯酯、羟丙基甲基纤维素邻苯二甲酸酯、蜡、丙烯酸类树脂、环氧树脂、其它的合成聚合物、金属氧化物,以及称为聚对二甲苯聚合物类(以类名帕利灵知名)、通常用作保形包覆层的聚合物类。
考虑到下列因素来选择保护性包覆层用材料:需要的低热导率水平、成品粒子所需的耐磨性和抗冲击性,以及将成品粒子混入其中作为主要组成材料的产品的性质。考虑到基材粒子的尺寸、包覆层材料的热导率以及需要的粒子的最终用途来确定包覆层的厚度。包覆层的总体积应当小于基材粒子的体积,优选不大于粒子体积的50%,并且更优选不大于粒子体积的20%。
SiO2是保护性包覆层的一个优选实施方案。通过原子层沉积,可以涂覆SiO2以形成厚度为至多40nm,优选20nm,并且更优选在12-14纳米的范围内的层,所以它固有的热导率对成品粒子的绝热性质具有可忽略的影响。用于本申请的SiO2的最重要的特性是SiO2在粒子周围提供气密;具有比包覆粒子的熔点更高的熔点(1830℃);具有优异的耐热冲击性、较高的抗张强度、较高的抗压强度;并且可以被表面改性为疏水、亲水或中性,这对于本申请是更重要的特性。
(iv)成品粒子的制备
用于将薄膜连续包覆层涂覆到小粒子上的已知方法可以用来制备成品粒子。实例为用于将药物粒子包封在特定和均匀的厚度的包覆层中以控制在摄取以后药物释放到身体中的速率的已知方法。这样的方法包括流化床包覆;掺混粉料;机械熔融加工;以及使用高速气流将粒子保持在悬浮或运动中以细雾的形式涂覆包覆层。在使用这些方法的任意一种来包覆本发明的粒子的过程中,包覆层材料与工业制药中使用的包覆层材料不同在于,它们并没有被设计成降解,而是被选择使得随着时间的流逝保持它们的结构完整性,并且在粒子周围提供永久、连续的保护性包覆层。其它适宜的包覆方法的实例为在电子工业中用于在半导体器件的制造中沉积薄层的那些方法,例如化学气相沉积。
特定的包覆方法是考虑到包覆层材料的性质来选择的,所述包覆层材料本身由粒子的最终应用以及该应用所需的粒状产品的体积来确定。
在用于制备成品粒子的方法的一个实施方案中,将高度多孔性的粒子放置在用于包覆处理的封闭室中。将该室抽空。然后将交换气体如氮气或氙气引入到该室中。然后在不引入空气或释放交换气体的情况下,将包覆层材料或用于包覆层材料的一种或多种前体引入到该封闭室中。在该封闭室中开始并且进行粒子的包覆,直至完成为止。在完成包覆处理时,从该室中抽空没有被包封在粒子中的交换气体、未使用的包覆层材料或前体,以及任何的反应产物。最后,将空气再引入到该室中直至压力在环境水平为止,开启该室,并且收集成品粒子。
用于包覆多孔性粒子的方法的一个优选实施方案是称为原子层外延或原子层沉积(ALD)的特殊化学气相沉积法。与其中使基材同时暴露于全部气态反应物中的常规化学气相沉积相比,在ALD法中,使基材依次暴露于两种或更多种气态反应物的每一种中。通过限制使基材暴露于在基材的表面经历自限制反应的单一气态反应物中,可以控制各个沉积层和依次暴露于全部气态反应物中所产生的最终包覆层的特性。已经进一步开发ALD来专用于包覆粒子。在其全部结合在此的美国专利6,613,383和6,713,177中描述了这种通过ALD的粒子包覆的实例。
在本发明的一个优选实施方案中,高度多孔性的粒子包覆有薄的SiO2层。如在Hausman等,“Rapid Vapor Deposition of Highly Conformal SilicaNanolaminates”,Science,2002,298,402-406中所述,可以使用SiO2沉积用前体,例如与三(叔丁氧基)硅烷醇结合的三乙基铝,通过ALD将SiO2沉积在多孔性粒子上。在此优选实施方案中,将多孔性粒子的孔的开口密封,并且同时用约10-12纳米厚的SiO2层包覆多孔性粒子的外部表面。与三甲基铝的初始表面反应在多孔性粒子的表面上沉积了Al,从而提供用于随后来自硅前体的SiO2的原子层沉积的催化表面。硅前体的实例为三(叔丁氧基)硅烷醇、三(叔戊氧基)硅烷醇和三(异丙氧基)硅烷醇。ALD是在由交换气体组成的惰性气体气氛中进行的。成品粒子的孔包含低压,优选约O.01个大气压的交换气体。
成品粒子为高度多孔性的粒子,其中用还覆盖粒子表面的薄包覆层密封在粒子表面的孔开口,并且孔腔充满低压惰性气体。在本发明的其它实施方案中,当特定的应用需要时,可以通过例如已知的化学改性方法进行随后的成品粒子的表面化学改性,以对粒子的表面赋予疏水或亲水的性质。
下列实施例进一步说明了本发明的各方面。应当理解所述实施例不意在限制本发明,并且本领域技术人员可以在不改变本发明的必要特征和基本概念的情况下进行各种改变。除非另外指出,否则在实施例和本说明书的其余部分中的所有份、百分数、比率等都是按重量计的。
实施例
使用抛光的不锈钢模具和手压机,将获自Cabot Corporation的二氧化硅气凝胶细粒(NANOGEL Product Number TLD 201)压制到钨栅网(grid)中,所述二氧化硅气凝胶细粒具有在5至15μm的范围内的粒径和约20nm的孔径。该栅网具有约2cm×3cm的尺寸以及0.002英寸的厚度和100线/英寸。
将如此装载有粒子的栅网放置在ALD用黏流反应器(在图1中用示意图表示)的流动管(3)中的基材支架(2)上,在所述黏流反应器中(4)为加热器,(5)为节流阀,(6)为抽吸穿过流动管的气流的机械泵,所述流动管具有3.5cm的内径并且长约60cm。将超高纯度的氮气(7)供给至在水(8)、三甲基铝(TMA)(9)和三(叔戊氧基)硅烷醇(10)的反应物管线上的最大通过量为500sccm的质量流量控制器。通过气体开关阀装置(11)将去离子水、半导体级(高纯度)TMA和高纯度三(叔戊氧基)硅烷醇的脉冲流(pulse)交替注入到氮气载体气流中。通过配备有模拟和数字输入/输出板的个人电脑控制该反应器。可以在下列文献中找到这种反应器的进一步描述:Elam等,“Viscous flow reactor with quartz crystal microbalance for thin film growth byatomic layer deposition”,Review of Scientific Instruments,2004,73(8),2981-87。
在上述反应器中,将SiO2在以下说明的条件下沉积在气凝胶粒子上:
温度:175℃
氮气流速:100sccm
基准压力:0.65 Torr
前体:被加热至130℃
通过包括下列连续阶段的黏流法沉积:
1.每次10剂量/1秒(每次400mTorr)的水,随后吹扫45秒。
2.每次15剂量/2秒(每次500mTorr)的TMA,随后吹扫45秒。
3.每次10剂量/1秒(每次400mTorr)的水,随后吹扫45秒。
4.每次15剂量/2秒(每次500mTorr)的TMA,随后吹扫45秒。
5.每次15剂量/1秒(每次500mTorr)的三(叔戊氧基)硅烷醇,随后吹扫120秒。
在沉积过程结束时,与未包覆的气凝胶粒子的半透明的白色外观相比,从栅网回收的包覆的气凝胶粒子的外观为不透明的白色。
相对于未处理和未包覆的粒子,根据本发明的成品粒子表现出许多优点。由于它们不易碎,但耐久并且耐磨,因此它们在苛刻的使用环境中是特别有用的。它们的保护性包覆层还防止液体、油或其它物质吸收到孔腔中,从而防止作为结果而发生的绝热能力的损失。
根据本发明的成品粒子的另一个优点是可以使它们的包覆层非常薄,薄至10-30nm,因此几乎不增加多孔性材料的热导率,尤其是当包覆层材料本身具有固有的低热导率的时候。
可以将根据本发明的成品粒子混入绝热组合物和组分中,或者单独用作绝热材料。
考虑在此公开的本发明的说明书和实践,本发明的其它实施方案对于本领域技术人员是显而易见的。其意图在于在本发明的真正范围和精神由后附权利要求指出的情况下,说明书和实施例被认为只是说明性的。
Claims (20)
1.一种孔隙率为至少80%并且孔腔充满具有低热导率的气体的材料的粒子,其中所述粒子被包封在厚度为至多0.5mm的保护性耐久包覆层中。
2.如权利要求1的粒子,所述粒子具有至少90%的孔隙率。
3.如权利要求1的粒子,所述粒子具有1μm至5mm的粒径。
4.如权利要求1的粒子,所述粒子具有1μm至1,200μm的粒径。
5.如权利要求1的粒子,所述粒子具有1μm至500μm的粒径。
6.如权利要求1的粒子,所述粒子具有1μm至15μm的粒径。
7.如权利要求1的粒子,所述粒子具有1mm至5.0mm的粒径。
8.如权利要求1的粒子,所述粒子为无定形二氧化硅气凝胶粒子。
9.如权利要求1的粒子,所述粒子为无定形二氧化硅干凝胶粒子。
10.如权利要求1的粒子,所述粒子为碳气凝胶粒子。
11.如权利要求1的粒子,所述粒子为碳干凝胶粒子。
12.如权利要求1的粒子,其中所述包覆层具有至多40nm的厚度。
13.如权利要求1的粒子,其中所述包覆层具有至多20nm的厚度。
14.如权利要求1的粒子,其中所述包覆层为SiO2。
15.如权利要求1的粒子,其中所述包覆层为通过原子层沉积而沉积的SiO2。
16.如权利要求1的粒子,其中所述具有低热导率的气体为氮气。
17.如权利要求1的粒子,其中所述具有低热导率的气体为氙气。
18.一种包含如权利要求1的粒子的材料。
19.一种包含如权利要求1的粒子的制品。
20.一种包含如权利要求1的粒子的组合物。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114833733A (zh) * | 2022-04-25 | 2022-08-02 | 亳州市鑫磊超硬材料有限责任公司 | 一种金刚石树脂砂轮及其制备方法 |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20140022440A (ko) * | 2005-10-21 | 2014-02-24 | 캐보트 코포레이션 | 에어로겔 기재 복합체 |
US7794805B2 (en) * | 2007-06-29 | 2010-09-14 | Schlumberger Technology Corporation | Thermal insulation barriers |
GB0723841D0 (en) * | 2007-12-06 | 2008-01-16 | Univ Leuven Kath | Enhancing catalytic activity of nanoprous materials |
US8629076B2 (en) * | 2010-01-27 | 2014-01-14 | Lawrence Livermore National Security, Llc | High surface area silicon carbide-coated carbon aerogel |
US9284643B2 (en) | 2010-03-23 | 2016-03-15 | Pneumaticoat Technologies Llc | Semi-continuous vapor deposition process for the manufacture of coated particles |
DE102010015470A1 (de) * | 2010-04-16 | 2011-10-20 | Forschungszentrum Jülich GmbH | Verfahren zur Innenbeschichtung von Funktionsschichten mit einem Vergütungsmaterial |
DE102010034194B9 (de) | 2010-08-12 | 2018-12-27 | Kulzer Gmbh | Verwendung von Kleselsäure(n) zur Eigenschaftsverbesserung von Dentalmaterial und entsprechende Verfahren |
US20120263876A1 (en) * | 2011-02-14 | 2012-10-18 | Asm Ip Holding B.V. | Deposition of silicon dioxide on hydrophobic surfaces |
DE102013215400A1 (de) * | 2013-08-06 | 2015-02-12 | Robert Bosch Gmbh | Silicat-Aerogel und Verfahren zu seiner Herstellung |
EP3409695A4 (en) * | 2016-01-26 | 2019-10-16 | Kyoto University | LOW DENSITY GEL ARTICLES AND METHOD FOR PRODUCING A LOW DENSITY GEL ARTICLE |
CN112999988B (zh) * | 2019-12-18 | 2022-09-20 | 航天特种材料及工艺技术研究所 | 一种防掉粉透波气凝胶及其制备方法和应用 |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2093454A (en) * | 1934-10-01 | 1937-09-21 | Samuel S Kistler | Method of producing aerogels |
US2870109A (en) * | 1954-05-06 | 1959-01-20 | Monsanto Chemicals | Coated silica aerogel, silicone rubber reinforced therewith and method of making |
US3769770A (en) * | 1969-01-23 | 1973-11-06 | Sanders Nuclear Corp | Thermal super insulation |
US5409683A (en) * | 1990-08-23 | 1995-04-25 | Regents Of The University Of California | Method for producing metal oxide aerogels |
IT1251937B (it) * | 1991-10-17 | 1995-05-27 | Donegani Guido Ist | Xerogels di silice ad alta porosita` e processo per la loro preparazione. |
US5565142A (en) * | 1992-04-01 | 1996-10-15 | Deshpande; Ravindra | Preparation of high porosity xerogels by chemical surface modification. |
US5313485A (en) * | 1992-10-26 | 1994-05-17 | Sandia Corporation | Luminescent light source for laser pumping and laser system containing same |
US5478867A (en) * | 1993-07-07 | 1995-12-26 | The Dow Chemical Company | Microporous isocyanate-based polymer compositions and method of preparation |
DE4407026A1 (de) * | 1994-03-04 | 1995-09-07 | Heraeus Industrietechnik Gmbh | Thermische Isolierung, Verfahren zur thermischen Isolierung, thermisch isolierendes Gehäuse und dessen Verwendung |
DE4409309A1 (de) * | 1994-03-18 | 1995-09-21 | Basf Ag | Formkörper, enthaltend Silica-Aerogel-Partikel sowie Verfahren zu ihrer Herstellung |
FR2736342B1 (fr) * | 1995-07-07 | 1999-01-29 | Univ Claude Bernard Lyon | Procede pour la fabrication d'aerogels de silice monolithiques et aerogels de silice ainsi obtenus |
US6132837A (en) * | 1998-09-30 | 2000-10-17 | Cabot Corporation | Vacuum insulation panel and method of preparing the same |
US6613383B1 (en) * | 1999-06-21 | 2003-09-02 | Regents Of The University Of Colorado | Atomic layer controlled deposition on particle surfaces |
DE19938822A1 (de) * | 1999-08-19 | 2001-02-22 | Zae Bayern | Verfahren zur Herstellung einer offenporigen monolithischen Elektrode aus Kohlenstoff für den Einsatz in einer reversiblen Lithium-Ionen-Batterie |
US7005181B2 (en) * | 2000-04-06 | 2006-02-28 | American Aerogel Corporation | Organic, open cell foam materials, their carbonized derivatives, and methods for producing same |
US6713177B2 (en) * | 2000-06-21 | 2004-03-30 | Regents Of The University Of Colorado | Insulating and functionalizing fine metal-containing particles with conformal ultra-thin films |
US6806299B2 (en) * | 2001-05-18 | 2004-10-19 | The Regents Of The University Of California | Preparation of hydrophobic organic aeorgels |
GB0200259D0 (en) * | 2002-01-07 | 2002-02-20 | Univ Reading The | Encapsulated radioactive nuclide microparticles and methods for their production |
JP4369239B2 (ja) * | 2002-01-29 | 2009-11-18 | キャボット コーポレイション | 耐熱性エーロゲル絶縁複合材料およびその製造方法、エーロゲルバインダー組成物およびその製造方法 |
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2006
- 2006-03-22 EP EP06748621.7A patent/EP1863596A4/en not_active Withdrawn
- 2006-03-22 KR KR1020077024210A patent/KR20080012843A/ko active IP Right Grant
- 2006-03-22 US US11/909,441 patent/US8383238B2/en not_active Expired - Fee Related
- 2006-03-22 RU RU2007138728/12A patent/RU2399432C2/ru not_active IP Right Cessation
- 2006-03-22 AU AU2006226872A patent/AU2006226872B2/en not_active Ceased
- 2006-03-22 CN CN200680017035XA patent/CN101203329B/zh not_active Expired - Fee Related
- 2006-03-22 WO PCT/US2006/010698 patent/WO2006102568A2/en active Application Filing
- 2006-03-22 CA CA002605905A patent/CA2605905A1/en not_active Abandoned
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114833733A (zh) * | 2022-04-25 | 2022-08-02 | 亳州市鑫磊超硬材料有限责任公司 | 一种金刚石树脂砂轮及其制备方法 |
CN114833733B (zh) * | 2022-04-25 | 2024-03-08 | 亳州市鑫磊超硬材料有限责任公司 | 一种金刚石树脂砂轮及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
RU2399432C2 (ru) | 2010-09-20 |
AU2006226872A1 (en) | 2006-09-28 |
KR20080012843A (ko) | 2008-02-12 |
WO2006102568A2 (en) | 2006-09-28 |
HK1121987A1 (en) | 2009-05-08 |
RU2007138728A (ru) | 2009-04-27 |
US8383238B2 (en) | 2013-02-26 |
AU2006226872B2 (en) | 2011-03-24 |
EP1863596A2 (en) | 2007-12-12 |
WO2006102568A3 (en) | 2007-01-11 |
CN101203329B (zh) | 2012-07-25 |
US20100140532A1 (en) | 2010-06-10 |
EP1863596A4 (en) | 2013-12-11 |
CA2605905A1 (en) | 2006-09-28 |
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