CN103805949B - Molybdenum bisuphide self-lubricating composite coating and be covered with the piston ring of this composite coating - Google Patents
Molybdenum bisuphide self-lubricating composite coating and be covered with the piston ring of this composite coating Download PDFInfo
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- CN103805949B CN103805949B CN201410052608.9A CN201410052608A CN103805949B CN 103805949 B CN103805949 B CN 103805949B CN 201410052608 A CN201410052608 A CN 201410052608A CN 103805949 B CN103805949 B CN 103805949B
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Abstract
The invention discloses a kind of molybdenum bisuphide self-lubricating composite coating and be covered with the piston ring of this composite coating, this molybdenum bisuphide self-lubricating composite coating includes the molybdenum nitride basis coating being overlying on piston ring substrate and the molybdenum bisuphide self-lubricating layer being overlying on the coating of molybdenum nitride basis, described molybdenum bisuphide self-lubricating layer is sulfur content through-thickness continuously varying gradient layer, and the sulfur content of gradient layer and molybdenum nitride basis coating contact surface is minimum.Molybdenum bisuphide self-lubricating composite coating of the present invention has suitable stiffness, low self-lubricating coefficient of friction and strong adhesive force, the piston ring applying this molybdenum bisuphide self-lubricating composite coating shows very big advantage in surface abrasion resistance self-lubricating, there is good wearability and self lubricity, can effectively solve the fretting wear problem between piston ring and cylinder.
Description
Technical field
The invention belongs to thin-film material technical field, relate to a kind of molybdenum bisuphide self-lubricating composite coating and be covered with the piston ring of this composite coating.
Background technology
Piston ring is as the key components and parts of fuel engines, and piston, cylinder collectively form friction system, and the friction of piston ring and cylinder wall is one of principal element affect engine friction loss, therefore that the wearability requirement of piston ring is higher.The wearability of piston ring is had higher requirement by particularly new Europe IV discharge standard.
At present typically via being coated with the method for wear-resisting figure layer on the piston ring to improve the wearability of piston ring.Conventional spray paint technique, Brush Plating etc. are not suitable for piston ring coating, and electrodeposited chromium processing method exists contaminated environment, chromium coating rubs performance and can not meet the problems such as New emission standard.Adopting physical gas-phase deposite method (PVD) coating chromium nitride wear-resistant coating can be effectively improved the anti-wear performance of piston ring on the piston ring, but PVD chromium nitride coating coefficient of friction is higher, coefficient of friction is more than 0.4.
Molybdenum based compound lubriation material is the lubriation material that a kind of tribological property is excellent, is widely used in the fields such as Aeronautics and Astronautics, navigation, machinery.Molybdenum bisuphide can be obviously improved bearing capacity and the abrasion resistance of grease, and anti-wear effect under high loads is particularly evident.Develop recently as coating technology, scientific research personnel develops molybdenum bisuphide self-lubricating coat in use, molybdenum bisuphide properties of solid self-lubricant coating has higher bearing capacity, is applicable to low speed, severe duty under DRY SLIDING, and its performance indications are better than the kollags such as graphite under the high temperature conditions.Molybdenum bisuphide self-lubricating coat in use is coated on piston ring surface and will be greatly improved the anti-wear performance of piston ring, thus improving Service Life of Piston Ring.
Summary of the invention
For the deficiency that prior art exists, the invention provides a kind of molybdenum bisuphide self-lubricating composite coating, the piston ring being covered with this composite coating and preparation method, to improve the anti-wear performance of piston ring further.
A kind of molybdenum bisuphide self-lubricating composite coating provided by the invention, including the molybdenum nitride basis coating being overlying on piston ring substrate and the molybdenum bisuphide self-lubricating layer being overlying on the coating of molybdenum nitride basis, described molybdenum bisuphide self-lubricating layer is sulfur content through-thickness continuously varying gradient layer, and the sulfur content of gradient layer and molybdenum nitride basis coating contact surface is minimum.
Above-mentioned molybdenum nitride basis thickness of coating is 3 ~ 6 microns.
Above-mentioned molybdenum bisuphide self-lubricating layer thickness is 0.3 ~ 4 micron.
Above-mentioned molybdenum bisuphide self-lubricating composite coating is coated on piston ring substrate, is remarkably improved the wearability of piston ring.Described piston ring substrate is steel substrate or cast iron matrix.
Present invention also offers the method depositing above-mentioned molybdenum bisuphide self-lubricating composite coating on the piston ring, molybdenum bisuphide self-lubricating composite coating is deposited at vacuum moulding machine intracavity, including: arc evaporation molybdenum target in nitrogen environment, cvd nitride molybdenio plinth coating on piston ring substrate；Arc evaporation molybdenum target in hydrogen sulfide gas environment, deposits molybdenum bisuphide self-lubricating layer on the coating of molybdenum nitride basis.
As preferably, on piston ring substrate before cvd nitride molybdenio plinth coating, piston ring substrate being carried out plasma etching, to remove piston ring substrate surface contaminant.
A kind of detailed description of the invention of said method is:
Adopt arc evaporation on piston ring substrate cvd nitride molybdenio plinth coating and on the coating of molybdenum nitride basis deposit molybdenum bisuphide self-lubricating layer, wherein, on piston ring substrate in cvd nitride molybdenio plinth galvanization process, deposit cavity vacuum is 0.5 ~ 3.0Pa, deposit cavity temperature is 200 ~ 300 DEG C, and bias condition is-40 ~-400V；Depositing in molybdenum bisuphide self-lubricating layer process on the coating of molybdenum nitride basis, deposit cavity vacuum is 0.5 ~ 5.0Pa, and deposit cavity temperature is 200 ~ 400 DEG C, and bias condition is-40 ~-200V.
Molybdenum nitride basis coating deposits in molybdenum bisuphide self-lubricating layer process, makes hydrogen sulfide gas flow increase continuously, to obtain sulfur content through-thickness continually varying molybdenum bisuphide self-lubricating layer.
As preferably, depositing in molybdenum bisuphide self-lubricating layer process on the coating of molybdenum nitride basis, the hydrogen sulfide gas passed into is the hydrogen sulfide of ionization.Obtain the one of the hydrogen sulfide of ionization method particularly includes: pass into hydrogen sulfide by hollow cathode ion source to vacuum chamber, to improve the ionization level of hydrogen sulfide gas, it is thus achieved that the hydrogen sulfide of ionization.
The inventive method obtains metal molybdenum by arc evaporation molybdenum target, passes into N in deposit cavity2And to N2Ionization is to obtain nitrogen element；H is passed in deposit cavity2S to H2S ionizes to obtain element sulphur；And by being gradually increased hydrogen sulfide gas flow, molybdenum nitride basis coating deposits by the layer of molybdenum-disulfide of a lack of sulfur gradually excessively to the gradient layer of pure layer of molybdenum-disulfide, it is achieved there is the sulfur content through-thickness continually varying molybdenum bisuphide self-lubricating layer of gradient-structure.
The present invention has a characteristic that
Molybdenum nitride basis coating can be effectively improved piston ring substrate hardness, gives molybdenum bisuphide self-lubricating layer with good support simultaneously；The molybdenum bisuphide self-lubricating layer of gradient-structure solves molybdenum nitride basis coating to excessive lofty of molybdenum bisuphide self-lubricating layer, it is to avoid the excessive demoulding problem caused of stress, has good adhesive force, and effectively enhances the wearability of piston ring.
Compared with prior art, the present invention can bring following beneficial effect:
1, molybdenum bisuphide self-lubricating composite coating of the present invention has suitable hardness (hardness is about 2000Hv), cylinder will not cause unnecessary scraping damage because crossing high rigidity；There is low self-lubricating coefficient of friction (about 0.3), thus can rapidly adapt to and friction duty between cylinder.
2, the piston ring being coated with molybdenum bisuphide self-lubricating composite coating of the present invention shows very big advantage in surface abrasion resistance self-lubricating, there is good wearability and self lubricity, can effectively solve the fretting wear problem between piston ring and cylinder, it is remarkably improved Service Life of Piston Ring, reduce electromotor operation troubles incidence rate, improve electromotor runnability, thus bringing huge economic benefit and social benefit.
Accompanying drawing explanation
Fig. 1 is molybdenum bisuphide self-lubricating composite coating thickness measuring optical microscope picture of the present invention；
Fig. 2 is the change curve of molybdenum bisuphide self-lubricating composite coating typical case's the friction coefficient fraction time of the present invention；
Fig. 3 is the molybdenum bisuphide self-lubricating composite coating nano hardness of the present invention change curve with compression distance；
In figure, 1-piston ring substrate；2-molybdenum nitride basis coating；3-molybdenum bisuphide self-lubricating layer；4-molybdenum bisuphide self-lubricating composite coating surface.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further illustrated, but the protected content of the present invention is not limited to following example.
In following embodiment, with arc ion plating apparatus for depositing device, and being aided with hollow cathode ion source ionization hydrogen sulfide gas, target is the vacuum moulding machine intracavity that molybdenum target, target and work rest are arranged at arc ion plating apparatus.
Embodiment 1
It is clamped on work rest after cleaning piston ring, to vacuum cavity evacuation, when vacuum is higher than 5 × 10-3During Pa, beginning to warm up degasification, temperature is controlled in 200 DEG C.When vacuum 5 × 10-3During Pa, passing into Ar gas, temperature controls, at 200 DEG C, to open grid bias power supply, and piston ring substrate is carried out plasma etching.
After plasma etching terminates, it is-40V by bias adjustment, closes Ar gas passage, pass into N2Gas, and deposit cavity vacuum is adjusted to 0.5Pa, temperature 200 DEG C, arc evaporation molybdenum target, on piston ring substrate, deposit thickness is the molybdenum nitride basis coating of 3 microns.
Molybdenum nitride basis coating deposition closes N after terminating2Passage, passes into H by hollow cathode ion source2S, is adjusted to 0.5Pa gradually by deposit cavity vacuum, keeps bias-40V, temperature 200 DEG C, increases continuously and pass into H2The flow of S, the molybdenum bisuphide self-lubricating layer of the gradient-structure of deposit thickness 0.3 micron on the coating of molybdenum nitride basis.After molybdenum bisuphide self-lubricating layer deposition terminates, take out piston ring after naturally cooling to room temperature, namely obtain depositing the piston ring of molybdenum bisuphide self-lubricating composite coating.
Embodiment 2
It is clamped on work rest after cleaning piston ring, to vacuum cavity evacuation, when vacuum is higher than 5 × 10-3During Pa, beginning to warm up degasification, temperature is controlled in 300 DEG C.When vacuum 5 × 10-3During Pa, passing into Ar gas, temperature controls, at 300 DEG C, to open grid bias power supply, and piston ring substrate is carried out plasma etching.
After plasma etching terminates, it is-400V by bias adjustment, closes Ar gas passage, pass into N2Gas, and deposit cavity vacuum is adjusted to 3.0Pa, temperature 300 DEG C, arc evaporation molybdenum target, on piston ring substrate, deposit thickness is the molybdenum nitride basis coating of 6 microns.
Molybdenum nitride basis coating deposition closes N after terminating2Passage, passes into H by hollow cathode ion source2S, is adjusted to 5Pa gradually by deposit cavity vacuum, keeps bias-200V, temperature 300 DEG C, increases continuously and pass into H2The flow of S, the molybdenum bisuphide self-lubricating layer of the gradient-structure of deposit thickness 4 microns on the coating of molybdenum nitride basis.After molybdenum bisuphide self-lubricating layer deposition terminates, take out piston ring after naturally cooling to room temperature, namely obtain depositing the piston ring of molybdenum bisuphide self-lubricating composite coating.
Embodiment 3
It is clamped on work rest after cleaning piston ring, to vacuum cavity evacuation, when vacuum is higher than 5 × 10-3During Pa, beginning to warm up degasification, temperature is controlled in 250 DEG C.When vacuum 5 × 10-3During Pa, passing into Ar gas, temperature controls, at 250 DEG C, to open grid bias power supply, and piston ring substrate is carried out plasma etching.
After plasma etching terminates, it is-200V by bias adjustment, closes Ar gas passage, pass into N2Gas, and deposit cavity vacuum is adjusted to 2Pa, temperature 250 DEG C, arc evaporation molybdenum target, on piston ring substrate, deposit thickness is the molybdenum nitride basis coating of 3 microns.
Molybdenum nitride basis coating deposition closes N after terminating2Passage, passes into H by hollow cathode ion source2S, is adjusted to 2.0Pa gradually by deposit cavity vacuum, keeps bias-200V, temperature 250 DEG C, increases continuously and pass into H2The flow of S, the molybdenum bisuphide self-lubricating layer of the gradient-structure of deposit thickness 2 microns on the coating of molybdenum nitride basis.After molybdenum bisuphide self-lubricating layer deposition terminates, take out piston ring after naturally cooling to room temperature, namely obtain depositing the piston ring of molybdenum bisuphide self-lubricating composite coating.
Adopt pin dish friction wear testing machine test molybdenum bisuphide self-lubricating composite coating coefficient of friction and the change curve with fraction time thereof, see Fig. 2, as can be seen from the figure molybdenum bisuphide self-lubricating composite coating coefficient of friction about 0.3.Adopting nanoindenter to measure the nano hardness of molybdenum bisuphide self-lubricating composite coating and with the change curve of compression distance, see Fig. 3, molybdenum bisuphide self-lubricating composite coating nano hardness is about 22GPa as can be seen from Figure.
Claims (4)
1. the method depositing molybdenum bisuphide self-lubricating composite coating on the piston ring, it is characterised in that deposit molybdenum bisuphide self-lubricating composite coating at vacuum moulding machine intracavity, including:
Arc evaporation molybdenum target in nitrogen environment, cvd nitride molybdenio plinth coating on piston ring substrate；Arc evaporation molybdenum target in hydrogen sulfide gas environment, deposits molybdenum bisuphide self-lubricating layer on the coating of molybdenum nitride basis；
Molybdenum nitride basis coating deposits in molybdenum bisuphide self-lubricating layer process, makes hydrogen sulfide gas flow increase continuously.
2. the method for claim 1, it is characterised in that:
On piston ring substrate before cvd nitride molybdenio plinth coating, piston ring substrate is carried out plasma etching.
3. the method for claim 1, it is characterised in that:
Adopt arc evaporation on piston ring substrate cvd nitride molybdenio plinth coating and on the coating of molybdenum nitride basis deposit molybdenum bisuphide self-lubricating layer, wherein, on piston ring substrate in cvd nitride molybdenio plinth galvanization process, deposit cavity vacuum is 0.5～3.0Pa, deposit cavity temperature is 200～300 DEG C, and bias condition is-40～-400V；Depositing in molybdenum bisuphide self-lubricating layer process on the coating of molybdenum nitride basis, deposit cavity vacuum is 0.5～5.0Pa, and deposit cavity temperature is 200～400 DEG C, and bias condition is-40～-200V.
4. the method for claim 1, it is characterised in that:
In vacuum deposit chamber body, hydrogen sulfide is passed into by hollow cathode ion source.
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| CN201410052608.9A CN103805949B (en) | 2014-02-17 | 2014-02-17 | Molybdenum bisuphide self-lubricating composite coating and be covered with the piston ring of this composite coating |
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| CN201410052608.9A CN103805949B (en) | 2014-02-17 | 2014-02-17 | Molybdenum bisuphide self-lubricating composite coating and be covered with the piston ring of this composite coating |
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| CN103805949B true CN103805949B (en) | 2016-07-27 |
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| CN104988453A (en) * | 2015-06-30 | 2015-10-21 | 苏州华日金菱机械有限公司 | Composite coating thermal spraying method |
| CN104988450A (en) * | 2015-06-30 | 2015-10-21 | 苏州华日金菱机械有限公司 | Composite coating |
| CN107160117A (en) * | 2017-07-21 | 2017-09-15 | 上海宇盛压缩机械有限公司 | One kind is without oily piston and its processing technology and piston compressor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS61159568A (en) * | 1985-01-07 | 1986-07-19 | Mitsubishi Heavy Ind Ltd | Method for plating molybdenum bisulfide |
| GB9514773D0 (en) * | 1995-07-19 | 1995-09-20 | Teer Coatings Ltd | Methods for improving the sputter deposition of metal-sulphur coatings e.g.molybdenum disulphide(MoS2) coatings |
| JP4771202B2 (en) * | 2005-04-13 | 2011-09-14 | 日立金属株式会社 | Composite film having excellent adhesion and sliding properties and method for producing the same |
| CN101270700A (en) * | 2007-03-21 | 2008-09-24 | 江苏省仪征活塞环厂 | High abrasion-proof steel piston ring and its production technique |
| CN101315100A (en) * | 2007-05-30 | 2008-12-03 | 襄阳鹰牌荣华轴承有限公司 | Plated film bearing |
| CN101698362B (en) * | 2009-10-30 | 2013-07-10 | 华南理工大学 | Self-lubricating hard nanocomposite laminated coating and preparation method thereof |
| CN103143761B (en) * | 2013-03-22 | 2015-06-24 | 武汉大学 | AlTiN-MoN nano multi-layer composite coating milling cutter and preparation method thereof |
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