CN101871086A - Preparation method for catalytic plasma nitrocarburized and diamond-like carbon composite film - Google Patents
Preparation method for catalytic plasma nitrocarburized and diamond-like carbon composite film Download PDFInfo
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- CN101871086A CN101871086A CN 201010187500 CN201010187500A CN101871086A CN 101871086 A CN101871086 A CN 101871086A CN 201010187500 CN201010187500 CN 201010187500 CN 201010187500 A CN201010187500 A CN 201010187500A CN 101871086 A CN101871086 A CN 101871086A
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Abstract
The invention relates to a preparation method for a catalytic plasma nitrocarburized and diamond-like carbon composite film. The method includes the following steps: (1) catalytic plasma nitrocarburization: a substrate is placed in an ion-nitriding furnace, the gas mixture of nitrogen, hydrogen and saturated C1 to C3 alkyl alcohol solution steam containing rare-earth oxide are charged under 50 Pa, and the ratio of nitrogen to hydrogen is 2:1 to 10:1; (2) DLC film deposition: C2H2 or CH4 is adopted as a carbon source, the gas flow is 50sccm to 150sccm, the Ar gas flow is 100sccm to 150sccm, the ion source is 0.2kW to 2.0kW, the bias voltage is 50V to 200V, the pressure is 0.2Pa to 1.0Pa, or graphite target is adopted as the carbon source, the Ar pressure is 0.2Pa to 1.0Pa, the magnetron sputtering power is 0.5W/cm<2> to 10W/cm<2>, the ion source is 0.2kW to 1.0kW, and the bias voltage is 50V to 200V. The prepared catalytic plasma nitrocarburized and diamond-like carbon composite film is characterized by high rigidity, minor difference from the rigidity of the substrate and high film/substrate bonding force. The method has the advantages of cleanliness, environment-friendliness and simple technique, and is suitable for mass industrial production.
Description
Technical field
The present invention relates to the preparation method of a kind of metallic surface composite film, particularly a kind of preparation method of oozing plasma carbonitriding and quasi-diamond composite film that urges.
Background technology
Quasi-diamond (DLC) have high rigidity (10～80GPa), low-friction coefficient (0.07～0.3), high Young's modulus, high acoustic propagation velocity, high heat conductance, good unreactiveness and biocompatibility etc. are widely used in wear resistant friction reducing occasion, biological field and ornament etc.Because the structure and the performance difference of DLC rete and matrix (as steel, titanium alloy etc.) are big, cause film/basic bonding force poor, directly on matrix, peel off easily during deposition and cause the rete inefficacy.In order to reduce the mutagenicity of rete and base material, reduce interfacial stress, improve DLC rete and high base strength, adopt the structure of gradient transition usually.Ion nitriding and PVD recombining process are the composite film coating methods that development in recent years is got up.Ion nitriding can form thick tens nitrided cases to the hundreds of micron that reach at matrix surface, has obtained the surface layer of higher surface hardness and gradient hardness.The follow-up DLC of the being coated with rete that rises to of substrate material surface hardness provides the good supporting effect, reduces the hardness sudden change between DLC rete and the matrix, obtains the interface structure of continuous transition, can increase substantially the performance and the work-ing life of DLC rete.Compare with single quasi-diamond rete, adopt ion nitriding and diamond-film-like compound coating performance to significantly improve.
CN 101665940A adopts the method for plasma nitriding and magnetic filtering cathode arc-magnetron sputtering composite deposition quasi-diamond rete to handle the piston ring surface, hardness and the bonding strength of comparing rete with single DLC film or hard chrome plating all are improved, film/basic bonding force has only 35～40N then, still remains further to be improved.
Summary of the invention
The objective of the invention is big at the DLC rete of prior art and matrix hardness difference, film/basic bonding force is poor, propose a kind of rare-earth oxide and urge the preparation method of oozing plasma carbonitriding and ion plating DLC composite film.
Technical scheme of the present invention is made up of following steps:
1) rare-earth oxide is urged and is oozed the plasma carbonitriding: the base material oil removing that eliminates rust is placed in the ion-nitriding furnace, below the pressure 50Pa, feeds nitrogen: hydrogen=2: 1～10: 1 and contain the saturated C of rare-earth oxide
1～3The mixed gas of alkyl alcohol solution vapor, furnace pressure are 200～1500Pa, and 450～600 ℃ of furnace temperature are incubated 1～10 hour, reduce to room temperature with furnace temperature then;
2) DLC films deposited layer: 1. above-mentioned rare-earth oxide is urged the workpiece that oozes after the plasma carbonitriding is handled, put into vacuum chamber after the oven dry, base vacuum degree 5.0 * 10
-3Pa, 100～200 ℃ of temperature, workpiece rotational frequency 2～10rpm; 2. at pressure 0.2～1.0Pa, under ion source 0.2～2kW and the bias voltage 50～1000V, with Ar icon bombardment cleaning 10～30min; 3. DLC films deposited layer: adopt C
2H
2Or CH
4Be carbon source, airshed 50～150sccm, Ar airshed 100～150sccm, ion source 0.2～2.0kW, bias voltage 50～200V, pressure 0.2～1.0Pa or employing graphite target are carbon source, Ar pressure 0.2～1.0Pa, magnetron sputtering power 0.5～10W/cm
2, ion source 0.2～1.0kW, bias voltage 50～200V.
Described rare-earth oxide is yttrium oxide, lanthanum trioxide or cerium oxide.
Described C
1～3Alkyl alcohol is methyl alcohol, ethanol or Virahol.
C in the described mixed gas
1～3It is 10～22% that the alkyl alcohol solution vapor accounts for the volume percentage.
Urge the steel surface of oozing the processing of plasma carbonitriding can obtain higher nitrided layer hardness and milder hardness gradient surface through rare-earth oxide, improve the supporting role of matrix.Rare earth metal can promote the formation of toughness phase γ ' simultaneously, thereby increases the plasticity and toughness of infiltration layer, improves rete and high base strength.Matrix with excellent support effect can be brought into play the performance advantage of DLC rete, reduces the internal stress of DLC film, improves membranous layer stability.The method of this Combined Processing can increase substantially the work-ing life of workpiece.With not through rare-earth oxide urge ooze that the plasma carbonitriding is handled and directly the DLC films deposited layer compare, rare-earth oxide urges the performance of oozing ionitrocarburizing and DLC composite film to significantly improve, and shows that mainly surface hardness, film/basic bonding force, wear resisting property etc. are improved significantly.Urge the film/basic bonding force of oozing the plasma carbonitriding and directly plating the DLC rete to have only about 25N through rare-earth oxide on H13 die steel, hardness is at HV
0.025,151380, urge the film/basic bonding force of oozing after the processing of plasma carbonitriding and DLC rete to reach more than the 60N through rare-earth oxide, hardness has reached HV
0.025,152175.Method clean environment firendly of the present invention, technology is simple, can realize the big area suitability for industrialized production.
But utilize rare earth catalytic cementation plasma carbonitriding technology and DLC film Combined Processing not to appear in the newspapers with the research of the use properties that improves diamond-film-like.
Description of drawings
Fig. 1 urges the hardness gradient curve that oozes the plasma carbonitriding for adding yttrium oxide, lanthanum trioxide and not adding rare-earth oxide;
Fig. 2 does not urge the XRD spectra of oozing the plasma carbonitriding for the H13 steel adds rare-earth oxide;
Fig. 3 urges the XRD spectra of oozing the plasma carbonitriding for the H13 steel through yttrium oxide.
Embodiment
Adopt the H13 steel, carry out oil removing before shove charge, rust cleaning is cleaned, and dehydrates.
Embodiment 1
1) base material is placed ion-nitriding furnace, reach below the 50Pa in vacuum tightness, feed nitrogen: the mixed gas of hydrogen=3: 1 and the saturated ethanolic soln steam of yttrium oxide, it is 10% that yttrium oxide ethanolic soln steam accounts for the mixed gas volume content, furnace pressure 1200Pa, 540 ℃ of temperature are incubated 4 hours, then furnace cooling.Alloying layer thickness: 180～210 μ m.
2) DLC films deposited layer:
1. with after the polishing of the substrate surface after the above-mentioned processing, the ultrasonic wave oil removing is cleaned, and puts into vacuum chamber after the oven dry, base vacuum degree 5.0 * 10
-3Pa, 150 ℃ of temperature, workpiece rotational frequency 4rpm.
2. Ar icon bombardment cleaning, pressure is 0.5Pa, ion source 1kW, bias voltage 1000V, the time is 30min;
3. pressure 0.5Pa, Ar airshed 100sccm, C
2H
2Flow 60sccm, bias voltage 100V, ion source 1kW deposits 3 hours DLC retes, and the DLC thicknesses of layers is 2.5 μ m, and film/basic bonding force is 60N.
Embodiment 2
1) workpiece is placed ion-nitriding furnace, reach below the 50Pa in vacuum tightness, feed nitrogen: the mixed gas of hydrogen=5: 1 and the saturated methanol solution steam of lanthanum trioxide, it is 15% that lanthanum trioxide methanol solution steam accounts for the mixed gas volume content, furnace pressure 300Pa, 580 ℃ of temperature are incubated 8 hours, then furnace cooling.Alloying layer thickness: 300～320 μ m.
2) DLC films deposited layer:
1. with after the polishing of the substrate surface after the above-mentioned processing, the ultrasonic wave oil removing is cleaned, and puts into vacuum chamber after the oven dry, base vacuum degree 5.0 * 10
-3Pa, 150 ℃ of temperature, workpiece rotational frequency 4rpm.
2. Ar icon bombardment cleaning: pressure is 0.8Pa, ion source 0.4kW, and bias voltage 1000V, the time is 30min;
3. adopt graphite target, pressure 0.4Pa, Ar airshed: 150sccm, magnetron sputtering power 8W/cm
2, bias voltage 100V, ion source 0.5kW deposits 2 hours DLC films, DLC thicknesses of layers 1.5 μ m, film/basic bonding force is 62N.
Claims (4)
1. urge the preparation method of oozing plasma carbonitriding and quasi-diamond composite film for one kind, it is characterized in that forming by following steps:
1) rare-earth oxide is urged and is oozed the plasma carbonitriding: the base material oil removing that eliminates rust is placed in the ion-nitriding furnace, below the pressure 50Pa, feeds nitrogen: hydrogen=2: 1～10: 1 and contain the saturated C of rare-earth oxide
1～3The mixed gas of alkyl alcohol solution vapor, furnace pressure are 200～1500Pa, and 450～600 ℃ of furnace temperature are incubated 1～10 hour, reduce to room temperature with furnace temperature then;
2) DLC films deposited layer: 1. above-mentioned rare-earth oxide is urged the workpiece that oozes after the plasma carbonitriding is handled, put into vacuum chamber after the oven dry, base vacuum degree 5.0 * 10
-3Pa, 100～200 ℃ of temperature, workpiece rotational frequency 2～10rpm; 2. at pressure 0.2～1.0Pa, under ion source 0.2～2kW and the bias voltage 50～1000V, with Ar icon bombardment cleaning 10～30min; 3. DLC films deposited layer: adopt C
2H
2Or CH
4Be carbon source, airshed 50～150sccm, Ar airshed 100～150sccm, ion source 0.2～2.0kW, bias voltage 50～200V, pressure 0.2～1.0Pa or employing graphite target are carbon source, Ar pressure 0.2～1.0Pa, magnetron sputtering power 0.5～10W/cm
2, ion source 0.2～1.0kW, bias voltage 50～200V.
2. the preparation method of oozing plasma carbonitriding and quasi-diamond composite film that urges according to claim 1 is characterized in that described rare-earth oxide is yttrium oxide, lanthanum trioxide or cerium oxide.
3. the preparation method of oozing plasma carbonitriding and quasi-diamond composite film that urges according to claim 1 is characterized in that described C
1～3Alkyl alcohol is methyl alcohol, ethanol or Virahol.
4. the preparation method of oozing plasma carbonitriding and quasi-diamond composite film that urges according to claim 1 is characterized in that C in the described mixed gas
1～3It is 10～22% that the alkyl alcohol solution vapor accounts for the volume percentage.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102168269A (en) * | 2011-03-16 | 2011-08-31 | 广州有色金属研究院 | Method for preparing accelerated carburizing plasma nitrocarburizing and titanium carbonitride composite membrane layer |
| CN102423270A (en) * | 2011-09-28 | 2012-04-25 | 尹路 | Method for sputtering protective film on surface of denture stent |
| CN103219226A (en) * | 2013-04-09 | 2013-07-24 | 上海华力微电子有限公司 | Method for reducing metal pollution on back of wafer during sedimentation of amorphous carbon film |
| CN103849830A (en) * | 2014-03-29 | 2014-06-11 | 蚌埠铁路五金建材总厂 | Catalytic penetrating agent applied to nitriding treatment of railway public-work fittings |
| CN104726873A (en) * | 2015-03-19 | 2015-06-24 | 陕西天元智能再制造有限公司 | Anti-corrosive insulated wear-resistant treatment method for petroleum pipeline surface |
| CN107217228A (en) * | 2017-05-18 | 2017-09-29 | 清华大学 | Improve the method and bearing of bearing anti-wear performance |
| CN108546869A (en) * | 2018-05-14 | 2018-09-18 | 合肥东方节能科技股份有限公司 | A kind of energetic ion slitting wheel alloy material |
| CN109267000A (en) * | 2018-12-06 | 2019-01-25 | 哈尔滨工业大学 | A method of diamond/graphite composite structure wear resistant friction reducing layer is prepared based on plasma heat balance method of |
| CN113430485A (en) * | 2021-06-28 | 2021-09-24 | 哈尔滨工业大学 | Method for preparing antifriction self-lubricating composite layer based on plasma composite thermal diffusion |
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| US20030106617A1 (en) * | 2001-12-10 | 2003-06-12 | Caterpillar Inc. | Surface treatment for ferrous components |
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| US20030106617A1 (en) * | 2001-12-10 | 2003-06-12 | Caterpillar Inc. | Surface treatment for ferrous components |
| CN101210310A (en) * | 2007-12-21 | 2008-07-02 | 广州有色金属研究院 | Multi-component multi-layer hard thin film material for minitype drill bit surface modification and preparation method thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102168269A (en) * | 2011-03-16 | 2011-08-31 | 广州有色金属研究院 | Method for preparing accelerated carburizing plasma nitrocarburizing and titanium carbonitride composite membrane layer |
| CN102423270B (en) * | 2011-09-28 | 2013-12-25 | 尹路 | Method for sputtering protective film on surface of denture stent |
| CN102423270A (en) * | 2011-09-28 | 2012-04-25 | 尹路 | Method for sputtering protective film on surface of denture stent |
| CN103219226B (en) * | 2013-04-09 | 2015-12-02 | 上海华力微电子有限公司 | The method of wafer rear metallic pollution when being reduced in deposited amorphous carbon film |
| CN103219226A (en) * | 2013-04-09 | 2013-07-24 | 上海华力微电子有限公司 | Method for reducing metal pollution on back of wafer during sedimentation of amorphous carbon film |
| CN103849830A (en) * | 2014-03-29 | 2014-06-11 | 蚌埠铁路五金建材总厂 | Catalytic penetrating agent applied to nitriding treatment of railway public-work fittings |
| CN104726873A (en) * | 2015-03-19 | 2015-06-24 | 陕西天元智能再制造有限公司 | Anti-corrosive insulated wear-resistant treatment method for petroleum pipeline surface |
| CN107217228A (en) * | 2017-05-18 | 2017-09-29 | 清华大学 | Improve the method and bearing of bearing anti-wear performance |
| CN107217228B (en) * | 2017-05-18 | 2019-11-22 | 清华大学 | Improve the method and bearing of bearing wear-resisting property |
| CN108546869A (en) * | 2018-05-14 | 2018-09-18 | 合肥东方节能科技股份有限公司 | A kind of energetic ion slitting wheel alloy material |
| CN109267000A (en) * | 2018-12-06 | 2019-01-25 | 哈尔滨工业大学 | A method of diamond/graphite composite structure wear resistant friction reducing layer is prepared based on plasma heat balance method of |
| CN109267000B (en) * | 2018-12-06 | 2020-12-01 | 哈尔滨工业大学 | Method for preparing diamond/graphite composite structure wear-resistant antifriction layer based on plasma thermal equilibrium method |
| CN113430485A (en) * | 2021-06-28 | 2021-09-24 | 哈尔滨工业大学 | Method for preparing antifriction self-lubricating composite layer based on plasma composite thermal diffusion |
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Application publication date: 20101027 |