CN100371496C - Self-lubricated composite plating in multiple layers and preparation method - Google Patents

Abstract

The present invention relates to a self-lubricating multi-layer composite coating which is a multi-layer Mo/IF-MoS2 composite coating formed by alternating metal Mo layers with the thickness of 10 to nm 50 nm and IF-MoS2 layers with the thickness of 20 nm to 100 nm. the total thickness of the composite coating is from 1 m um to 5 m um. the composite coating is prepared by that MoS2 powder which is in a layer-shaped structure, pure S powder and a metal Mo sheet are used as basic raw material, and the metal Mo layers and the IF-MoS2 layers are repeatedly and crosswise sputtered and deposited by magnetron sputtering and multi-arc ion plating. The self-lubricating multi-layer composite coating has the advantages of good environmental stability, low friction coefficient, high abrasion resistance and good bonding strength with a metal substrate. The self-lubricating multi-layer composite coating can be used for preparing self-lubricating abrasion-resistant protective coatings for the surfaces of bearings, gyroscopes, gears, etc. which are universally used in the environment of vacuum, atmosphere, etc.

Description

A kind of self-lubricated composite plating in multiple layers and preparation method thereof

Technical field

The present invention relates to from moistening sliding compound coating of multilayer and preparation method thereof.

Background technology

As traditional solid lubricant or antifriction constituent element, the transient metal sulfide of laminate structure is (as 2H-MoS ₂) because the undersaturated dangling bonds of crystal edge have chemically reactive, in the friction process of damp atmosphere and oxygen-enriched environment, be adhered to metallic surface and oxidized and sharply reduced its frictional behaviour easily.The noticeable change of frictional coefficient to harsh temperatures circulation time between transformation, low temperature and the normal temperature of humid atmosphere, can take place, as the 2H-MoS of laminate structure at high vacuum environment in this class solid lubricant ₂Coating frictional coefficient in a vacuum is 0.02-0.05, and can sharply increase to 0.20-0.40 at damp atmosphere (relative humidity 50-80%).Because the use of liquid lubricant is restricted under envrionment conditionss such as high vacuum and low temperature, the friction and wear behavior in the various component of machine runnings is to the safe reliability and the work-ing life of mechanical system producing significant effects.

Material or surface engineering technology with low friction and high-wear resistance can reduce the energy consumption of system, the work-ing life of elongated component.Inorganic fullerene MoS with spherical nested stratiform enclosed construction ₂Nano particle (is called for short IF-MoS ₂) have excellent self-lubricating property, for the bigger frictional fit of surfaceness, IF-MoS ₂Nano material disperse equably distributes or is filled in the body material, therefore can not influence the surfaceness or the smooth finish of body material.Chhowalla M. etc. adopt the IF-MoS of arc-over preparation ₂Film has excellent tribological property, even be that its frictional coefficient also has only 0.005 in 45% nitrogen atmosphere in humidity, shows excellent environmental stability (Chhowalla, M.; Amaratunga, G.A.J.Nature.2000,407,164).

Summary of the invention

The objective of the invention is to provide a kind of have fine environment stability, excellent self-lubricating property, good abrasion resistance, and with good sliding compound coating of the multilayer of profit certainly of metallic matrix bonding strength and preparation method thereof.

Self-lubricated composite plating in multiple layers of the present invention is to be that metal M o layer and the thickness of 10-50nm is the IF-MoS of 20-100nm by thickness ₂The multilayer Mo/IF-MoS that layer alternately forms ₂Compound coating, the total thickness of compound coating are 1-5 μ m.

The preparation of self-lubricated composite plating in multiple layers is the MoS with laminate structure ₂Powder, pure S powder and metal M o sheet are basic raw material, adopt magnetron sputtering and multi-arc ion coating to intersect sputtering sedimentation metal M o layer and IF-MoS repeatedly ₂The layer and make, specifically may further comprise the steps:

1) with the MoS of laminate structure ₂Powder mixes by mass ratio with pure S powder at 4: 1, and ball milling under argon shield is made the non-crystalline state MoS that particle size is 60-100nm ₃Powder, and cold pressing and make target;

2) adopt magnetron sputtering and multi-arc ion coating to intersect sputter repeatedly and prepare multilayer Mo/IF-MoS ₂Compound coating: in reaction chamber, be the metal M o layer of 10-50nm with magnetically controlled sputter method sputtering sedimentation thickness on the Ti alloy substrates earlier, Ti alloy substrates temperature remains on 200 ℃, and sputtering bias-voltage is 150V, and vacuum tightness is 1.2 * 10 in the reaction chamber ^-3Pa, feeding air pressure in magnetron sputtering process is the Ar gas of 1Pa, behind magnetron sputtering deposition metal M o layer, bombards non-crystalline state MoS with multi-arc ion coating again at same reaction chamber ₃Target, deposit thickness is the IF-MoS of 50-100nm on metal M o layer ₂The particle rete is at multi-arc ion coating bombardment non-crystalline state MoS ₃Target sputtering sedimentation IF-MoS ₂In the layer process, feeding total gas pressure in vacuum chamber is Ar and the H of 1Pa ₂Mixed gas, Ar and H ₂Throughput ratio is 9: 1, repeats above-mentioned magnetron sputtering and multi-arc ion coating sputter procedure, makes the multilayer Mo/IF-MoS that total thickness is 1-5 μ m ₂Compound coating.

In the multi-layer composite coatings of the present invention because the IF-MoS that the nano particle of spherical nested stratiform enclosed construction constitutes ₂The self-lubricating function of rete makes compound coating have excellent antifriction performance; Simultaneously because IF-MoS ₂There are not the undersaturated dangling bonds of crystal edge in spherical nested stratiform enclosed construction, has excellent chemical stability, is difficult for having an effect with ambiance, shows excellent friction stability under varying environment.Metal M o layer in the multi-layer composite coatings has obviously reduced the internal stress of compound coating, has improved the interface bond strength of compound coating and metallic matrix, and metal M o layer also has good environmental stability simultaneously.Multilayer Mo/IF-MoS of the present invention ₂Compound coating can be used to be manufactured on surperficial self-lubricating abrasion-resistant protective coating such as bearing general in the environment such as vacuum and atmosphere, gyrostat and gear.

Embodiment

Further specify the present invention below in conjunction with embodiment.

Embodiment

MoS with common laminate structure ₂Powder, pure S powder and metal M o sheet are basic raw material.MoS with laminate structure ₂Powder mixes by mass ratio with pure S powder at 4: 1, and high-energy ball milling is 120 hours under argon shield, makes the non-crystalline state MoS that average particle size particle size is 90nm ₃Powder.The non-crystalline state MoS that mechanical alloying is made ₃Powder is colded pressing and is made the target of thickness 6mm, and mechanical workout metal M o sheet is made the Mo target.Adopt magnetron sputtering and multi-arc ion coating to intersect the method for sputter coupling repeatedly and prepare multilayer Mo/IF-MoS ₂Compound coating.At first use the magnetically controlled sputter method metal M o layer that sputtering sedimentation 30nm is thick on the Ti alloy substrates, temperature remains on 200 ℃ on the Ti alloy substrates, and sputtering bias-voltage is 150V, and vacuum tightness is 1.2 * 10 in the reaction chamber ^-3Pa, feeding air pressure in magnetron sputtering process is the Ar gas of 1Pa, behind magnetron sputtering deposition metal M o layer, bombards non-crystalline state MoS with multi-arc ion coating again at same reaction chamber ₃Target, the thick IF-MoS of deposition 70nm on metal M o layer ₂Layer.At multi-arc ion coating bombardment non-crystalline state MoS ₃Target sputtering sedimentation IF-MoS ₂In the process, feeding total gas pressure in the reaction chamber is Ar and the H of 1Pa ₂Mixed gas, Ar and H ₂Throughput ratio is 9: 1.Repeat above-mentioned magnetron sputtering and multi-arc ion coating sputter procedure, make the multilayer Mo/IF-MoS that total thickness is 3 μ m ₂Compound coating.

Adopt ball-disc type frictional wear machine to estimate multilayer Mo/IF-MoS down in varying environment (vacuum, damp atmosphere, oxygen-enriched atmosphere) ₂The friction and wear behavior of compound coating.The ball sample is the GCr15 steel of hardness 60HRC, and diameter is 3mm, and the dish sample is multilayer Mo/IF-MoS ₂Compound coating.Test conditions is: load 15N, sliding velocity 0.11m/s, metal to-metal contact (oil-free lubricatoin) state, room temperature, frictional distance 15000m.Automatically write down frictional coefficient, weighing multilayer Mo/IF-MoS after wearing test in the test process ₂The wear weight loss of compound coating is scaled wear rate.With the interface binding power of scratch test according to mensuration compound coating and metal base.Table 1 is multilayer Mo/IF-MoS ₂The frictional coefficient that compound coating is measured in varying environment and the comparison of wear rate.

Table 1

Ambient condition	Kinetic friction coefficient (μ)	Wear rate (mg/km)
			Vacuum (10 -2Pa)	0.013-0.056	1.43
Damp atmosphere (relative humidity 60%)	0.017-0.067	1.55
			Oxygen-enriched atmosphere (60%O 2，40％N 2)	0.015-0.063	1.49

Multilayer Mo/IF-MoS of the present invention₂Composite coating has following features:

1, the environment friction stability is high. Because multilayer Mo/IF-MoS of the present invention₂Metal M o layer has good environmental stability in the composite coating, the IF-MoS that is made of the nested stratiform enclosed construction of sphere simultaneously₂Nano-particular film also has good chemical stability, is difficult for having an effect multilayer Mo/IF-MoS in the friction 15000m process under above-mentioned varying environment condition with humid air and oxygen atmosphere₂The coefficient of friction fluctuation of composite coating is little, also shows excellent friction stability under humid air and oxygen-enriched atmosphere environment. Multilayer Mo/IF-MoS of the present invention₂Composite coating coefficient of friction and wear rate in a vacuum is all substantially suitable with wear rate with the coefficient of friction in humid air and oxygen-enriched atmosphere environment.

2, extremely low coefficient of friction, higher anti-wear performance. Multilayer Mo/IF-MoS of the present invention₂The mean coefficient of kinetic sliding friction of composite coating in vacuum, humid air and oxygen-enriched atmosphere environment is respectively 0.034,0.042 and 0.039, shows excellent self-lubricating property. Multilayer Mo/IF-MoS₂The hardness of composite coating is HV1120, and the average wear rate in vacuum, humid air and oxygen-enriched atmosphere environment is respectively 1.43,1.55 and 1.49, with respect to 2H-MoS₂Average wear rate 1.54 in Coatings in Vacuum, humid air and the oxygen-enriched atmosphere environment, 4.47 and 3.09 has preferably anti-wear performance.

3, good with the metallic substrates interface bond strength. Multilayer Mo/IF-MoS of the present invention₂The metal M o layer and the IF-MoS that are the nanoscale yardstick in the composite coating₂Layer makes has very low internal stress in the composite coating, the multilayer Mo/IF-MoS that adopts scratch test to measure₂The critical load at composite coating and metallic substrates interface (Lc) is 86N, and composite coating and metallic substrates interface bond strength are high, and composite coating can cracking and peeled off in process of friction and wear.

Claims (3)

1. self-lubricated composite plating in multiple layers is characterized in that by thickness being that metal M o layer and the thickness of 10-50nm is the IF-MoS of 20-100nm ₂The multilayer Mo/IF-MoS that layer alternately forms ₂Compound coating, the total thickness of compound coating are 1-5 μ m.

2. self-lubricated composite plating in multiple layers according to claim 1, the thickness that it is characterized in that metal M o layer is 30nm, IF-MoS ₂The thickness of layer is 70nm, and the total thickness of compound coating is 3 μ m.

3. the preparation method of claim 1 or 2 described self-lubricated composite plating in multiple layers is characterized in that may further comprise the steps:

1) with the MoS of laminate structure ₂Powder mixes by mass ratio with pure S powder at 4: 1, and ball milling under argon shield is made the non-crystalline state MoS that particle size is 60-100nm ₃Powder, and cold pressing and make target;

2) adopt magnetron sputtering and multi-arc ion coating to intersect sputter repeatedly and prepare multilayer Mo/IF-MoS ₂Compound coating: in reaction chamber, be the metal M o layer of 10-50nm with magnetically controlled sputter method sputtering sedimentation thickness on the Ti alloy substrates earlier, Ti alloy substrates temperature remains on 200 ℃, and sputtering bias-voltage is 150V, and vacuum tightness is 1.2 * 10 in the reaction chamber ^-3Pa, feeding air pressure in magnetron sputtering process is the Ar gas of 1Pa, behind magnetron sputtering deposition metal M o layer, bombards non-crystalline state MoS with multi-arc ion coating again at same reaction chamber ₃Target, deposit thickness is the IF-MoS of 50-100nm on metal M o layer ₂The particle rete is at multi-arc ion coating bombardment non-crystalline state MoS ₃Target sputtering sedimentation IF-MoS ₂In the layer process, feeding total gas pressure in vacuum chamber is Ar and the H of 1Pa ₂Mixed gas, Ar and H ₂Throughput ratio is 9: 1, repeats above-mentioned magnetron sputtering and multi-arc ion coating sputter procedure, makes the multilayer Mo/IF-MoS that total thickness is 1-5 μ m ₂Compound coating.