CN1833055A - 在降低的反应温度下以高产率和高选择性制备纳米碳材料的改进的催化剂和方法 - Google Patents
在降低的反应温度下以高产率和高选择性制备纳米碳材料的改进的催化剂和方法 Download PDFInfo
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- 229910002651 NO3 Inorganic materials 0.000 description 1
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- RIVXQHNOKLXDBP-UHFFFAOYSA-K aluminum;hydrogen carbonate Chemical compound [Al+3].OC([O-])=O.OC([O-])=O.OC([O-])=O RIVXQHNOKLXDBP-UHFFFAOYSA-K 0.000 description 1
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/40—
-
- B01J35/613—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
以非常高的纯度(大于95%)、碳形态选择性和格外高的产率合成碳纳米纤维***。粒度<10nm和高表面积(>50m2/g)的定制催化剂提供了更高的形态选择性和更高的产率。即使在反应24小时后,这些催化剂颗粒保持了活性,使得产率超过200g碳/g催化剂。通过美国专利6,132,653教导的火焰合成法将作为所得产品和产率的关键的催化剂制备成规定的特定参数(粒度分布、组成和结晶度)。
Description
发明人:PRADHAN,Bhabendra,360 Bloombridge Way N.W.,Marietta,GA 30066,India公民。
受让人:COLUMBIAN CHEMICALS COMPANY(Delaware Corporation),1800 West Oak Commons Court,Marietta,Georgia 30062
相关申请的交叉引用
在美国,本申请是2003年7月28日提交的美国申请10/628,842的部分继续申请。
由此要求2003年7月28日提交的美国申请10/628,842的优先权。
在此将2003年7月28日提交的美国申请10/628,842引入作为参考。
关于联邦资助研究或开发的声明
不适用
参考“微缩胶片附录”
不适用
发明背景
1.技术领域
本发明涉及纳米碳材料的制备,更具体地,本发明涉及在降低的反应温度下高产率和高选择性地制备纳米碳材料的改进的催化剂和方法。
2.一般背景
纳米结构材料,更具体地,碳纳米结构材料对于各种商业应用日益重要。该应用包括将它们用于存储分子氢、担当催化剂载体、作为聚合物复合体的增强组分、用于电磁屏蔽以及用于各种类型的电池和其它储能装置中。通常在约500℃至约1200℃的温度下,在选择的催化金属表面上分解含碳气体而制备碳纳米结构材料。
例如,碳纳米纤维可以用于锂离子电池,其中阳极将由石墨纳米纤维组成。石墨片基本上垂直于或平行于碳纳米纤维的纵轴。这种应用的实例见于美国专利6,503,660。此外,美国专利5,879,836教导了使用原纤作为锂离子电池的原料。原纤被描述为由平行的碳层组成,所述碳层是围绕纵轴布置的一系列同心管的形式,而不是多层平面石墨片。
此外,在美国专利6,485,858中,石墨纳米纤维具有以下结构,其中石墨片以与纤维轴基本垂直或基本平行的方向对直,并分别定义为板和带。此外,纳米纤维的暴露面由至少95%的边缘区域(edge regions)构成,与几乎完全由基本面区域和极少量的边缘位点构成的常规石墨相反。
其它参考文献包括″Catalytic Growth of Carbon Filaments,″其来自1989年Chemical Engineering Department of Auburn University的文章,在该文章中讨论了纤维状碳的形成。另一信息来源是题目为″A Review of CatalyticGrown Carbon Nanofibers,″,由Material Research Society在1993年出版的。在该文章中,讨论的碳纳米纤维是通过在小金属颗粒上催化分解特定烃而以相对较大的规模制备的。
在所有上述情况中,合成纯碳纳米材料都是具有挑战性的。这些材料的大部分应用都需要纯碳纳米材料***。因此,提供制备纯碳纳米材料的***是有利的,其中可以以非常高的纯度(大于95%)、高结晶度、碳形态选择性和格外高的产率合成碳***。另外,具有特定粒度和高表面积的定制催化剂(custom made catalyst)会产生更高选择性和更高活性。
发明简述
在本发明中,以非常高的纯度(大于95%)、高结晶度、碳形态选择性和格外高的产率合成碳纳米纤维***。与迄今为止可获得的催化剂相比,平均单晶粒度≤10nm和高表面积(>50m2/g)的定制催化剂提供了更高的形态选择性和更高的活性。即使在反应24小时后,这些催化剂颗粒的活性仍得以保持,使得产率超过200g碳/g催化剂。通过美国专利6,132,653教导的火焰合成法将作为获得产品和产率的关键的催化剂制备成规定的特定参数(粒度分布、组成和结晶度)。在此引入美国专利6,132,653的内容作为参考。
为了本申请的目的,本文中使用的术语将具有下面的定义:
″纯度″定义为碳含量,具有认为包含催化剂的杂质。
″选择性″定义为具有预计形态(石墨层(graphene layer)的取向)的含碳产物的分数;和
″产率″定义为生产的碳重量除以催化剂重量;在该催化工艺中,有时也可以表示为利用率(turnover)。
因此,本发明的主要目的是以极其高的纯度、碳形态的高选择性和格外高的产率合成碳纳米材料。
本发明的另一目的是在具有特定粒度、表面积和化学组成的定制催化剂存在下,合成碳纳米材料,以得到高的形态选择性、产率和纯度。
本发明的又一目的是在定制催化剂存在下制备碳纳米材料,以便在给定量的时间内,产率超过200g碳/g催化剂。
附图简述
为了进一步了解本发明的本质、目的和优势,参考下面的详细描述并结合附图,其中相同的标记表示相同的元件,且其中:
图1为在铁氧化物催化剂存在下,24小时期间内时间对碳纳米纤维生长的影响图;
图2为在铁:镍催化剂存在下,在24小时期间内,时间对碳纳米纤维生长的影响图;
图3为在如图1所述的铁氧化物催化剂存在下制备的碳纳米纤维碳微观结构的具体形态;
图4为在如图1所述的铁氧化物催化剂存在下制备的碳纳米纤维碳微观结构的具体形态的高分辨图。
图5为在如图2所述的铁:镍催化剂存在下制备的碳纳米纤维的碳微观结构的具体形态;
图6为在如图2所述的铁:镍催化剂存在下制备的碳纳米纤维碳微观结构的具体形态的高分辨图;
图7为与常规催化剂相比,用铁氧化物催化剂制备的具有片晶形态(platelet morphology)的碳纳米纤维的制备图;和
图8为与常规催化剂相比,具有用铁:镍催化剂制备的管状形态(tubularmorphology)的碳纳米纤维的制备图。
优选实施方式
制造催化剂的方法
在生产本文披露的纳米纤维中所使用的催化剂的制备和美国专利6,132,653中披露的相似,本文中在前面参考并引入了该专利。
可以作为催化剂的部分的金属列举如下:
铁(Fe)、镍(Ni)、钴(Co)、钼(Mo)、铜(Cu)、镧(La)、银(Ag)、金(Au)和合金。
用所述催化剂制备的纳米材料
现在参考下表和以下信息,其讨论了用上述新型催化剂(火焰合成)和常规催化剂(共沉淀)制备的材料的性质。
表1
性质 | 新型催化剂(火焰合成) | 常规或市售催化剂(共沉淀) |
化学形式 | 金属氧化物 | 预还原的金属,具有氧化物薄层 |
尺寸(nm) | ~10 | 500-2000 |
形态 | 单晶 | 多晶 |
表面积(m2/g) | ~130 | <20 |
压实密度 | 小于松密度 | 与松密度相同 |
获得上述结果的实验细节:
a:常规或市售催化剂
将已知量的预还原催化剂(0.1g)放入陶瓷皿或石英量筒中。然后将该皿转移到石英反应器(_=47mm)中。用氮气,以200sccm的流量吹扫反应器30分钟。以5℃/分钟的加热速率,在10-20%H2(其余的为N2)下将反应器加热到450℃。在该温度下保持1小时。然后在30分钟内在N2流下将温度升高到反应温度600℃(铁)或650℃(铁-镍氧化物催化剂)。当设定的温度稳定后,在不同的时间段(1、2、4、6、8和24小时)内将反应气体(CO/H2或C2H4/H2)引入到反应器中。
b:新型催化剂
将已知量的氧化物催化剂(0.1g)放入陶瓷皿或石英量筒中。然后将该皿转移到石英反应器(_=47mm)中。用氮气以200sccm的流量吹扫反应器30分钟。以5℃/分钟的加热速率,在10-20%H2(其余的为N2)下将反应器加热到450℃。在该温度下保持1小时。然后在30分钟内在N2流下将温度升高到反应温度550℃(铁氧化物和铁-镍氧化物催化剂)。当设定的温度稳定后,在不同的时间段内(1、2、4、6、8和24小时)将反应气体(CO/H2或C2H4/H2)引入到反应器中。
在550℃以CO∶H2∷4∷1的比例使用铁氧化物催化剂产生特定形态的碳微观结构,其中石墨平面垂直于碳生长轴,如图3和4所示。与常规催化剂比较,该试验显示了更好的碳产率(高2至3倍)和低50℃的合成温度(550℃相对于600℃)。在***中得到大于99.6%纯度的碳产物。形态选择性为100%。
在第二实施例中,使用铁∶镍催化剂以C2H2∶H2∷1∶4的比例在550℃下产生特定形态的碳微观结构,即其中石墨平面与碳生长轴平行和/或呈现一定角度,如图5和6所示。与其它常规或市售催化剂相比,该试验显示了更好的碳产率(高2至3倍)和低100℃的合成温度(550℃相对于650℃)。在该***中可以得到大于99.2%纯度的碳产物。形态选择性为大于95%。在上述使用的两实施例中,催化剂可以是选自以下金属的金属氧化物催化剂,所述金属包括铁、镍、钴、镧、金、银、钼、铁-镍、铁-铜及其合金。
c.流化床工艺方案:
已知量的氧化物催化剂(0.1-1.2g)放入具有Al2O3(14.9-13.8g)的沸腾流化床反应器中。以1000sccm的流量,用氮气吹扫反应器30分钟。以5℃/分钟的加热速率,在10-20%H2(其余的为N2)下将反应器加热到450℃。在该温度下保持1小时。然后在30分钟内在N2流下将温度升高到反应温度550℃(铁-镍氧化物催化剂)。当设定的温度稳定后,将反应气体(C2H4/H2)在已知的时间段(2小时)内引入反应器中。产率可以达到140g碳/g催化剂。
现在参考图1,图1显示了时间对于利用铁氧化物催化剂以CO∶H2∷4∶1的比例在550℃下生长的碳纳米纤维的影响。在该图中,制造的碳纳米纤维包括碳片晶形态,如图3和4中所示。曲线10记录(track)了g碳/g催化剂。曲线20记录了金属含量(重量%)。参考图1,当过程持续大约24小时,金属含量以产物的重量%计下降到0.3%,产率(碳/g催化剂)为>300g/g。还显示了催化颗粒即使在反应24小时后仍然有活性。在这一具体实施例中,铁氧化物催化剂以CO∶H2∷4∶1的比例在550℃下产生了特定形态的碳微观结构,即其中石墨平面垂直于碳生长轴,再次如图3和4所示。另外,与市售催化剂相比,如前面所描述的,该试验显示了更好的碳产率(高2至3倍)和低50℃的合成温度。得到了99.7%的纯碳产物,形态选择性为100%。如图3和4所示,特定形态的碳微观结构显示石墨平面垂直于碳生长轴。
现在参考图2,该图描述了时间对于利用铁-镍催化剂以C2H2∶H2∷1∶4的比例在550℃下生长的碳纳米纤维的影响。曲线30记录了g碳/g催化剂。曲线40记录了金属含量(重量%)。如该图所示制造的碳纳米纤维产生了特定形态的碳微观结构,即石墨平面与生长轴平行或呈现一定角度,如图5和6所示。与常规催化剂比较,这显示了更好的碳产率和低100℃的合成温度。还得到具有99.6%纯度的碳产物,形态选择性为大于95%。在24小时反应期间的最后,产物的金属含量为0.4%,而碳产率为200-250g/g催化剂。
在这两种***中,如图1和2所示,可以在8小时的反应时间内得到99%的碳。这些结果示于表2和3中。
在这些表的每个表中以及如图7和图8分别描述的,与市售或常规催化剂相比,铁催化剂和铁∶镍催化剂分别在较低温度下,以高于95%的形态选择性、较高产率和较低金属杂质得到碳纳米材料片晶或管状形态。曲线50记录了550℃下g碳/gMCT催化剂。曲线60记录了金属含量(重量%)。曲线70记录了600℃下g碳/gJT Baker催化剂。曲线80记录了金属含量(重量%)。曲线90记录了550℃下g碳/gMCT催化剂。曲线100记录了金属含量(重量%)。曲线110记录了600℃下g碳/g CCC。曲线120记录了金属含量(重量%)。
对于片晶形态,催化剂铁,CO∶H2∷4∶1。
表2
催化剂 | 温度(℃) | 选择性(目测) | 产率(g/6h) | 杂质(金属) |
火焰 | 550 | 100 | 77 | 1.3 |
市售(J.T.Baker) | 600 | 90 | 50 | 2 |
对于管状形态,催化剂铁∶镍∷8∶2,C2H2∶H2∷1∶4
表3
催化剂 | 温度(℃) | 选择性(目测) | 产率(g/6h) | 杂质(金属) |
火焰 | 550 | >95 | 81 | 1.25 |
常规制备的CCC | 650 | 60 | 26.33 | 3.8 |
“常规制备的CCC”催化剂是利用液态沉淀法制备的。使用铁、镍和铜金属硝酸盐。金属硝酸盐和水以化学计量混合,并在室温下快速搅拌。添加碳酸氢铝,得到大约9的pH,并搅拌大约5分钟。一夜后形成沉淀物,洗涤并干燥沉淀物。在110℃干燥金属碳酸盐24小时,然后在空气中在400℃煅烧4小时。球磨金属氧化物6小时,并在500℃在200sscm氮气中的10%氢气中还原20小时。金属粉末在氮气中的2%氧气中钝化1小时。如下所述,参考R.J.Best和W.W.Russel的J.Am.Chem.Soc.76,8383(1954)进行上述方法和反应。
通过火焰/等离子体法合成粉末催化剂:
制备金属(铁、镍和铜)的硝酸盐/硫酸盐混合物的乙醇溶液,并蒸发/雾化为火焰或等离子体火舌(torch),并且通过该工艺,使用在美国专利6,123,653中描述的方法获得纯氧化物或混合金属氧化物的粉末。
通常,制备纳米碳材料的方法是通过提供平均粒度≤10nm、表面积大于50m2/g的催化剂进行的,但是可以改变。接着,在催化剂存在下,在给定的时间内反应含碳反应物,得到纯度大于99%和形态选择性为100%以及具有更高活性的碳纳米纤维。
通过美国专利6123653描述的方法制备的催化剂是选自以下金属的金属氧化物催化剂,所述金属包括:铁、镍、钴、镧、金、银、钼、铁-镍、铁-铜及其合金。随着试验进一步进行,可以发现其它合适的金属氧化物。通过火焰合成法,将催化剂本身制备成规定的特定参数(粒度、组成和结晶度);其具有单晶形态。通过利用选自上述的催化剂,所得碳纳米材料的产率为≥140g碳/g催化剂,但是产率可以更大,而碳微观结构的形态包括可控定向垂直或平行于碳生长轴的石墨平面(取决于催化剂组成和含碳原料),得到99.6%纯度的碳产物。
仅仅以实施例的方式给出前述实施方式,本发明的范围只受到权利要求限定。
Claims (19)
1.制造纳米碳材料的方法,包括下列步骤:
a.提供粒度≤10nm和表面积大于50m2/g的催化剂;
b.在所述催化剂存在下,反应含碳原料给定时间,以制造碳纳米纤维,该碳纳米纤维具有大于99%的纯度且形态选择性接近100%,产率≥140g碳/g催化剂,并具有更高活性。
2.权利要求1的方法,其中催化剂是选自以下金属的金属氧化物催化剂,所述金属包括铁、镍、钴、镧、金、银、钼、铁-镍、铁-铜及其合金。
3.权利要求1的方法,其中通过火焰合成法将催化剂制成规定的特定参数(粒度分布、组成和结晶度)。
4.权利要求1的方法,其中催化剂具有单晶形态。
5.权利要求1的方法,其中得到的碳纳米材料的产率≥140g碳/g催化剂。
6.权利要求1的方法,其中能够选择性地控制碳微观结构的形态,以≥90%的选择性获得各种所需取向。
7.制备纳米碳材料的方法,包括以下步骤:
a.提供粒度为约≤10nm和表面积大于50m2/g的金属氧化物催化剂;
b.在所述催化剂存在下,反应含碳原料给定时间,以制造碳纳米纤维,该碳纳米纤维具有大于99%的纯度和接近100%的形态选择性,产率为≥140g碳/g催化剂。
8.权利要求7的方法,其中在不超过550℃的温度下进行反应。
9.权利要求7的方法,其中反应8小时后,碳纳米纤维的纯度为≥99%。
10.权利要求7的方法,其中金属氧化物催化剂选自以下金属,所述金属包括铁、镍、钴、镧、金、银、钼、铁-镍、铁-铜及其合金。
11.高纯度和高活性的碳纳米纤维,其通过以下步骤制造:
a.提供粒度≤10nm和表面积大于50m2/g的金属氧化物催化剂;
b.在所述催化剂存在下,反应含碳原料给定时间,以制造碳纳米纤维,该碳纳米纤维具有大于99%的纯度且选择性接近100%,并具有更高活性。
12.通过权利要求11的方法制造的碳纳米纤维,其中金属氧化物催化剂选自以下金属,所述金属包括铁、镍、钴、镧、金、银、钼、铁-镍、铁-铜及其合金。
13.通过权利要求11的方法制造的碳纳米纤维,其中反应8小时后,碳纳米纤维的纯度为≥99%。
14.一种在金属氧化物催化剂存在下制备的碳纳米纤维,该碳纳米纤维包括至少99%的纯碳,并以高产率和>90%的形态选择性制造。
15.权利要求14的碳纳米纤维,其中金属氧化物催化剂选自以下金属,所述金属包括铁、镍、钴、镧、金、银、钼、铁-镍、铁-铜及其合金。
16.碳纳米纤维组合物,其对单一形态显示出90%的选择性。
17.权利要求16的组合物,其中所述形态包括与纤维轴平行定向的石墨层。
18.权利要求16的组合物,其中所述形态包括与纤维轴垂直定向的石墨层。
19.权利要求16的组合物,其中所述形态包括与纤维轴以特定的和相同的(±10°)角度定向的石墨层。
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- 2004-04-20 WO PCT/US2004/012136 patent/WO2005016853A2/en active Application Filing
- 2004-05-03 TW TW093112404A patent/TW200505788A/zh unknown
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CN107124875A (zh) * | 2014-11-06 | 2017-09-01 | 贝克休斯公司 | 制备抗摩擦涂层的方法 |
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JP2007500121A (ja) | 2007-01-11 |
KR20060052923A (ko) | 2006-05-19 |
EP1654406A2 (en) | 2006-05-10 |
AR044387A1 (es) | 2005-09-07 |
BRPI0413069A (pt) | 2006-10-17 |
TW200505788A (en) | 2005-02-16 |
US20050025695A1 (en) | 2005-02-03 |
EP1654406A4 (en) | 2007-08-22 |
WO2005016853A2 (en) | 2005-02-24 |
WO2005016853A3 (en) | 2005-09-29 |
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