CN102388158B - 阻止热喷涂中金属氧化的方法 - Google Patents
阻止热喷涂中金属氧化的方法 Download PDFInfo
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- CN102388158B CN102388158B CN201080010476.3A CN201080010476A CN102388158B CN 102388158 B CN102388158 B CN 102388158B CN 201080010476 A CN201080010476 A CN 201080010476A CN 102388158 B CN102388158 B CN 102388158B
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 16
- 239000002184 metal Substances 0.000 title claims abstract description 16
- 230000003647 oxidation Effects 0.000 title abstract description 5
- 238000007254 oxidation reaction Methods 0.000 title abstract description 5
- 238000007751 thermal spraying Methods 0.000 title abstract 3
- 150000002739 metals Chemical class 0.000 title abstract 2
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 20
- 238000005507 spraying Methods 0.000 claims description 15
- 238000006722 reduction reaction Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000012720 thermal barrier coating Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000000242 pagocytic effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Coating By Spraying Or Casting (AREA)
Abstract
本发明涉及一种通过将待使用的金属粉末涂覆纳米碳化物来阻止热喷涂中金属氧化的方法，涉及采用所述方法所制备的涂层，还涉及一种用纳米碳化物处理金属粉末的方法。依据本发明所述方法适用于所有在热喷涂中应用的金属粉末，而且，由于本发明可采用较廉价的材料，它们在经济上尤其有优势。
Description
本发明涉及阻止热喷涂中金属氧化的方法以及涂覆金属粉末的方法。
之前，人们通过将待喷涂材料合金化，由此使混合物的氧亲和力降低，来努力将氧化程度减到最少。但是，采用昂贵的合金化剂却不能完全阻止涂层上氧化物层的产生。
另外一种解决方法是真空等离子体喷涂(VPS)，凭借该方法可获得完全无氧的涂层，但是由于其制备成本相当高，只有绝对有必要时该方法才使用。例如，由于高制备成本，涂覆燃气轮机时就积极地倾向于避免采用VPS涂覆。
公开号为6376103的美国专利申请描述了金属粉末的制备，其可用在通过热喷涂产生的涂层。该申请的金属粉末被制备成金属碳化物复合材料烧结体，从而粉末粒子本身中包含有碳化物。
因此，针对不同金属和合金优化碳化物的量是本发明的最大挑战。该量应该足以使热喷涂涂层不被氧化，但也不能太高以致在涂层中留下太多未反应的碳化物。喷涂中碳的释放速度取决于所采用是何种碳化物。当碳从碳化物中释放出来时，碳化物的金属成分留存于涂层中，借此碳化物还应当根据其适用性进行选择。
大体上，热喷涂金属涂层中最大的问题之一是其脆性，以及一般地，其弱耐腐蚀性。所不变的是，在所有的热喷涂金属涂层的应用中，例如导电/导热层、防腐蚀涂层或燃气轮机热障涂层(TBC)，其趋势都是想获得尽可能被氧化得少的涂层。为了使喷涂中氧化的程度最小，就必须在这些应用中采用相当复杂和昂贵的金属合金。
依据本发明所述方法有能力排除之前已知方案中出现的问题。由于本发明能采用较便宜的材料，依据本发明所述方法在经济上具有相当的优势。
在权利要求1的特征部分对本发明这种阻止热喷涂中金属氧化的方法的特征进行了描述。
接着，权利要求4对依据本发明的热喷涂涂层的特征也进行了描述，而权利要求8对依据本发明涂覆金属粉末的方法的特征进行了描述。
结合附图1对本发明的一个实施方式进行具体阐述，图1表示了依据本实施方式发生的反应。
本发明涉及一种阻止热喷涂中金属氧化的方法，其中纳米碳化物附着在金属粉末表面，然后，被包裹的金属粉末经过热喷涂法喷涂，在物体(即，可被热喷涂法喷涂的基体)表面上形成金属涂层，由此纳米碳化物在喷涂的熔融状态下在金属粉末粒子表面上提供碳化物的还原反应，使得熔融金属液滴的表面无法被氧化。
本发明还涉及采用所述方法所制备的热喷涂涂层，还涉及一种涂覆用于热喷涂中的所述金属粉末的方法。
当熔融液滴在物体表面固化时，形成热喷涂涂层。在常规方法中，在喷涂过程中熔融金属液滴可以与周围的氧发生反应，从而在涂层中形成氧化物层。附着于用于热喷涂涂覆的金属粉末表面的纳米碳化物(例如碳化钨或WC)，在喷涂过程中防止金属的氧化。该碳化物按照受控方式释放碳，碳与周围的氧反应，形成气态化合物(CO，CO2)，从而熔融金属液滴表面不能被氧化。按照这种方法，涂层中就没有氧化物层形成。纯碳与周围氧的反应过于迅速，从而保护功能不能得以实现。
热喷涂金属涂层最大的问题涉及脆性和弱耐腐蚀性，这是氧化物层所带来的。
图1中，叫做“氧吞噬性”碳化物的材料的作用是在金属粒子表面上提供还原反应来抵消在熔融状态下所产生的氧化作用。由于碳化物被破坏，当检验碳化物金属基体复合材料涂层时可观察到该现象，其目的在于避免涂层中的碳损失。例如，WC在涂布过程中分解为碳和金属钨。根据本发明，同样的现象可被用来提供受控的还原反应，其中释放中的碳与氧反应，形成二氧化碳，同时保护金属不被氧化。
本发明中采用的是通过水基合成法(一种经济有效的制备纳米碳化物的方法)制备纳米碳化物的技术。可改变该方法使纳米碳化物从含水浆料直接生成至金属粒子表面。这几乎不会增加粉末的制备成本。另外，还可以在这些应用中利用较为廉价的金属，从而总成本将有相当程度的降低。无氧涂层也将打开一个广阔的新应用空间，其中现有的金属涂层的性能将不再足够。
本发明适用于所有热喷涂金属粉末，而且其会对热喷涂金属粉末的制造产生变革，并且能实现在越来越多的应用中利用金属涂层。
Claims (5)
1.一种阻止热喷涂中金属氧化的方法，其特征在于：
-附着纳米碳化物至待用于热喷涂的金属粉末粒子表面，然后
-在物体表面上通过热喷涂方法喷涂该经涂覆过的金属粉末而形成金属涂层，从而所述纳米碳化物在该喷涂的熔融状态下在所述金属粉末粒子表面上提供所述碳化物的还原反应，由此使所述熔融金属液滴的表面不会被氧化。
2.权利要求1所述的方法，其特征在于，所述纳米碳化物直接从含水浆料生成至所述金属粒子的所述表面上。
3.权利要求1或2所述的方法，其特征在于，采用碳化钨作为所述纳米碳化物。
4.通过权利要求1-3任一项所述的方法制造的热喷涂涂层，其特征在于，所述涂层由涂覆有纳米碳化物的金属粉末形成。
5.权利要求4所述的热喷涂涂层，其特征在于，所述涂层不含氧化物层。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI20095212 | 2009-03-03 | ||
| FI20095212A FI20095212A0 (fi) | 2009-03-03 | 2009-03-03 | Menetelmä metallien hapettumisen estämiseksi termisessä ruiskutuksessa |
| PCT/FI2010/050164 WO2010100336A1 (en) | 2009-03-03 | 2010-03-03 | Method of preventing oxidation of metals in thermal spraying |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102388158A CN102388158A (zh) | 2012-03-21 |
| CN102388158B true CN102388158B (zh) | 2014-08-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080010476.3A Expired - Fee Related CN102388158B (zh) | 2009-03-03 | 2010-03-03 | 阻止热喷涂中金属氧化的方法 |
Country Status (6)
| Country | Link |
|---|---|
| US (2) | US20120020828A1 (zh) |
| EP (1) | EP2403971A4 (zh) |
| JP (1) | JP5487221B2 (zh) |
| CN (1) | CN102388158B (zh) |
| FI (1) | FI20095212A0 (zh) |
| WO (1) | WO2010100336A1 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI123710B (fi) * | 2011-03-28 | 2013-09-30 | Teknologian Tutkimuskeskus Vtt | Termisesti ruiskutettu pinnoite |
| EP3875630B1 (en) * | 2018-11-02 | 2023-03-15 | Nissan Motor Co., Ltd. | Thermally sprayed coating for sliding member and sliding device provided with said thermally sprayed coating for sliding member |
| WO2020089666A1 (ja) * | 2018-11-02 | 2020-05-07 | 日産自動車株式会社 | 摺動部材用溶射被膜及び該摺動部材用溶射被膜を備える摺動装置 |
| JP2023517279A (ja) * | 2020-02-04 | 2023-04-25 | １１８８５１１ カナダ エルティーディー． | 電磁力を使用した被加工物に対する操作の実行 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073217A (zh) * | 1991-12-12 | 1993-06-16 | 通用电气公司 | 用于热喷涂熔敷物的合金粉末的选择性预氧化 |
| US5690716A (en) * | 1994-09-09 | 1997-11-25 | Osram Sylvania Inc. | Thermal spray powder |
| US6513728B1 (en) * | 2000-11-13 | 2003-02-04 | Concept Alloys, L.L.C. | Thermal spray apparatus and method having a wire electrode with core of multiplex composite powder its method of manufacture and use |
| CN101134193A (zh) * | 2006-04-20 | 2008-03-05 | 朱马国际公司 | 通过热喷涂形成的涂层及其形成方法 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3655425A (en) * | 1969-07-01 | 1972-04-11 | Metco Inc | Ceramic clad flame spray powder |
| US3725017A (en) * | 1970-01-07 | 1973-04-03 | Ramsey Corp | Coated nervous substrate |
| US5746803A (en) * | 1996-06-04 | 1998-05-05 | The Dow Chemical Company | Metallic-carbide group VIII metal powder and preparation methods thereof |
| WO1999010121A1 (en) * | 1997-08-22 | 1999-03-04 | Inframat Corporation | Grain growth inhibitor for superfine materials |
| US7141110B2 (en) * | 2003-11-21 | 2006-11-28 | General Electric Company | Erosion resistant coatings and methods thereof |
| EP1797212A4 (en) * | 2004-09-16 | 2012-04-04 | Vladimir Belashchenko | DEPOSIT SYSTEM, METHODS AND MATERIALS FOR COMPOSITE COATINGS |
| US20100035746A1 (en) * | 2006-06-20 | 2010-02-11 | University Of Utah Research Foundation | Methods for Making Carbide-Metal Nanocomposite Powders |
| WO2008049080A1 (en) * | 2006-10-18 | 2008-04-24 | Inframat Corporation | Superfine/nanostructured cored wires for thermal spray applications and methods of making |
-
2009
- 2009-03-03 FI FI20095212A patent/FI20095212A0/fi not_active Application Discontinuation
-
2010
- 2010-03-03 WO PCT/FI2010/050164 patent/WO2010100336A1/en active Application Filing
- 2010-03-03 JP JP2011552482A patent/JP5487221B2/ja not_active Expired - Fee Related
- 2010-03-03 EP EP10748390A patent/EP2403971A4/en not_active Withdrawn
- 2010-03-03 US US13/254,471 patent/US20120020828A1/en not_active Abandoned
- 2010-03-03 CN CN201080010476.3A patent/CN102388158B/zh not_active Expired - Fee Related
-
2016
- 2016-07-05 US US15/202,284 patent/US20160312349A1/en not_active Abandoned
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073217A (zh) * | 1991-12-12 | 1993-06-16 | 通用电气公司 | 用于热喷涂熔敷物的合金粉末的选择性预氧化 |
| US5690716A (en) * | 1994-09-09 | 1997-11-25 | Osram Sylvania Inc. | Thermal spray powder |
| US6513728B1 (en) * | 2000-11-13 | 2003-02-04 | Concept Alloys, L.L.C. | Thermal spray apparatus and method having a wire electrode with core of multiplex composite powder its method of manufacture and use |
| CN101134193A (zh) * | 2006-04-20 | 2008-03-05 | 朱马国际公司 | 通过热喷涂形成的涂层及其形成方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2403971A1 (en) | 2012-01-11 |
| US20120020828A1 (en) | 2012-01-26 |
| EP2403971A4 (en) | 2012-09-26 |
| WO2010100336A1 (en) | 2010-09-10 |
| JP5487221B2 (ja) | 2014-05-07 |
| US20160312349A1 (en) | 2016-10-27 |
| JP2012519775A (ja) | 2012-08-30 |
| CN102388158A (zh) | 2012-03-21 |
| FI20095212A0 (fi) | 2009-03-03 |
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