CN101613854A - A kind of non-equilibrium magnetron-sputtering rare-earth multivariate graphite composite film and preparation method thereof - Google Patents
A kind of non-equilibrium magnetron-sputtering rare-earth multivariate graphite composite film and preparation method thereof Download PDFInfo
- Publication number
- CN101613854A CN101613854A CN200910304696A CN200910304696A CN101613854A CN 101613854 A CN101613854 A CN 101613854A CN 200910304696 A CN200910304696 A CN 200910304696A CN 200910304696 A CN200910304696 A CN 200910304696A CN 101613854 A CN101613854 A CN 101613854A
- Authority
- CN
- China
- Prior art keywords
- target
- transition
- rare earth
- bunch
- rare
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Physical Vapour Deposition (AREA)
Abstract
A kind of non-equilibrium magnetron-sputtering rare-earth multivariate graphite composite film disclosed by the invention, form by many first composite beds of compound plasma surface alloying layer, Cr/RE transition layer, C/Cr-RE gradient layer and C/Cr-RE successively, it consists of the Cr/RE transition layer according to mass percent: RE:0.1%～1%, surplus are Cr; It consists of the many first composite beds of C/Cr-RE according to mass percent: Cr:3%～15%, and RE:0.3%～10%, transition bunch metallic element: 0.3%～10%, surplus is C.The method for preparing non-equilibrium magnetron-sputtering rare-earth multivariate graphite composite film, at first determine the composite membrane composition, calculate a transition bunch metal of inlaying on quantity that the rare earth installed on high-purity chromium target and the high pure carbon target inserts and the high pure carbon target quantity of inserting, preparation is inserted accordingly and is installed, and magnetron sputtering obtains composite membrane.The invention solves existing non-balance magnetically controlled sputter solid lubrication composite film heat stability and electrochemically resistant and learn the problem of corrodibility difference.
Description
Technical field
The invention belongs to the physical gas phase deposition technology field of thin-film material and modern surface engineering technology, be specifically related to a kind of non-equilibrium magnetron-sputtering rare-earth multivariate graphite composite film, the invention still further relates to the preparation method of this rare-earth multivariate graphite composite film.
Background technology
The lubricated composite membrane of typical novel solid has the class graphite composite film of MOST, Graphit-ic, WC-DLC-WS2, Dymon-iC and WC/a-C nano composite membrane, particularly good environmental adaptability that boundless application prospect is arranged.The Graphit-ic class graphite composite film of Teer company preparation, the plasticity and toughness by compound certain content Cr element adjusting class graphite film reduce internal stress, improve composite membrane supporting capacity and wear resistance, have obtained good effect.
Because the thermostability of class graphite composite film is relatively poor, the composite membrane temperature surpasses 320 ℃ and just tangible oxidation occurs, seriously restricted the class graphite composite film in cutter, mould and mechanically operated application.In addition, in order to improve the consistency of class graphite composite film and metallic matrix, need carry out interface processing with intermediate metal and gradient cladding, improve the basement membrane bonding force of class graphite composite film, but the Cr transition layer is a column crystal, has hole between the crystal boundary, the part hole links to each other with the tissue defects of class graphite composite film, often run through the through matrix of whole rete, composite membrane itself just can not play the effect of isolating matrix and corrosive medium fully like this, has influenced the electrochemical corrosion performance of solid lubricant film.
In composite membrane, add trace rare-earth element and transition bunch metal, can improve over-all properties, particularly thermostability, corrosion stability and the wear resistance of composite membrane, so the rare earth multicomponent modification technology will be an important development direction of the lubricated composite membrane of novel solid.How rare earth element being introduced in the composite membrane is to realize a rare earth modified gordian technique.The researchist of Shenyang metal institute of the Chinese Academy of Sciences and Guangdong University of Technology once added Ce, Y when smelting the titanium alloy target, the titanium alloy target that has prepared Ti/Ce and Ti/Y, the negative electrode target that makes rare earth element is in the discharge process of arc ion plating, by plasma body rare earth is incorporated in the TiN coating, has obtained good modified effect.But the smelting cost of rare earth alloy target is big, rare earth composition relative fixed, and the solid solubility of rare earth in alloy is very low, and the content of rare earth regulation range is little, is difficult to reach the coating modified effect to nonmetal lubricant film; Patent text " the adding method of the rare earth modified coating middle-weight rare earths of ion plating " (application number: 200610123304.2, publication number: CN1966761, open day: 2007.05.23) rare earth halide is prepared into the organic RE additive, suck the ion plating vacuum chamber by negative pressure, method by nitrogen base mixed gas flow regulating and controlling content of rare earth, rare earth element is introduced the ion plating hard coat, also obtained good effect.But owing to introduced organic solvent and chlorion simultaneously, the performance of magnetron sputtering solid lubrication composite membrane there is serious counter productive.
Summary of the invention
The purpose of this invention is to provide a kind of non-equilibrium magnetron-sputtering rare-earth multivariate graphite composite film, solved the problem that existing non-balance magnetically controlled sputter solid lubrication composite film heat stability and electrochemically resistant are learned the corrodibility difference.
Another object of the present invention provides the preparation method of above-mentioned non-equilibrium magnetron-sputtering rare-earth multivariate graphite composite film.
The technical solution adopted in the present invention is that a kind of non-equilibrium magnetron-sputtering rare-earth multivariate graphite is multiple
Close film, form by many first composite beds of compound plasma surface alloying layer, Cr/RE transition layer, C/Cr-RE gradient layer and C/Cr-RE successively,
It consists of Cr/RE transition layer wherein according to mass percent: RE:0.1%～1%, surplus are Cr, and the mass percent sum of each component is 100%;
It consists of the many first composite beds of C/Cr-RE wherein according to mass percent: Cr:3%～15%, and RE:0.3%～10%, transition bunch metallic element: 0.3%～10%, surplus is C, the mass percent sum of each component is 100%.
Another technical scheme of the present invention is, a kind of method for preparing non-equilibrium magnetron-sputtering rare-earth multivariate graphite composite film is implemented according to following steps,
Step 1: determine the rare-earth multivariate graphite composite film composition, wherein, it consists of the Cr/RE transition layer according to mass percent: RE:0.1%～1%, surplus are Cr, and the mass percent sum of each component is 100%; It consists of the many first composite beds of C/Cr-RE according to mass percent: Cr:3%～15%, and RE:0.3%～10%, transition bunch metallic element: 0.3%～10%, surplus is C, the mass percent sum of each component is 100%;
Step 2: calculate the high-purity rare-earth of inlaying on high-purity chromium target and the high pure carbon target quantity of inserting, and a transition bunch metal of inlaying on the high pure carbon target quantity of inserting:
(a) calculate the high-purity rare-earth of inlaying on high-purity chromium target and the high pure carbon target quantity of inserting
A＝α
*β
*γ
*S
1/S
n＝S
1/S
2
In the formula,
A: content or rare earth elements RE the content in C/Cr-RE many first composite beds of rare earth elements RE in the Cr/RE transition layer of determining in the step 1;
α: the ratio of rare earth element and carbon or chromium target element sputtering yield;
β: the ratio of rare earth element and carbon or chromium target element density;
γ: the insert content of middle-weight rare earths element of rare earth;
S
1: the total area that the etched area rare earth is inserted;
S
2: the face area that single rare earth is inserted;
S: the target etched area total area;
N: the rare earth that target the is inlayed quantity of inserting;
The ratio α of the content A of rare earth element in the Cr/RE transition layer, rare earth element and high-purity chromium target element sputtering yield, rare earth element and ratio β, the rare earth of chromium density insert the content γ of middle-weight rare earths element, the total area S that the etched area rare earth is inserted
1, the face area S that inserts of single rare earth
2, in the above-mentioned formula of target etched area total area S substitution, the rare earth that obtains inlaying on the high-purity chromium target quantity n that inserts;
The ratio α of the content A of rare earth element in the many first composite beds of C/Cr-RE, rare earth element and high pure carbon target element sputtering yield, rare earth element and ratio β, the rare earth of carbon density insert the content γ of middle-weight rare earths element, the total area S that the etched area rare earth is inserted
1, the face area S that inserts of single rare earth
2, in the above-mentioned formula of target etched area total area S substitution, the rare earth that obtains inlaying on the high pure carbon target quantity n that inserts;
(b) calculate a transition bunch metal of inlaying on the high pure carbon target quantity of inserting
C＝ε
*δ
*λ
*S
3/S
n
1＝S
3/S
4
In the formula,
C: the content of transition bunch metallic element in the many first composite beds of C/Cr-RE of determining in the step 1;
ε: the ratio of transition bunch metallic element and carbon sputtering yield;
δ: the ratio of transition bunch metallic element and carbon density;
λ: the content of transition bunch metallic element during transition bunch metal is inserted;
S
3: the total area that etched area transition bunch metal is inserted;
S
4: the face area that single transition bunch metal is inserted;
S: the target etched area total area;
n
1: the transition that target the is inlayed bunch metal quantity of inserting;
Content λ, the total area S that etched area transition bunch metal is inserted of transition bunch metallic element during the content C of transition bunch metallic element in the many first composite beds of Cr/RE, transition bunch metallic element inserted with ratio δ, the transition bunch metal of carbon density with ratio ε, the transition bunch metallic element of high pure carbon target element sputtering yield
3, the face area S that inserts of single transition bunch metal
4, in the above-mentioned formula of target etched area total area S substitution, a transition bunch metal that obtains inlaying on the high pure carbon target quantity n that inserts
1
Step 3: at the open holes of inserting of the high-purity chromium target of non-balance magnetically controlled sputter and high pure carbon target upper edge magnetron processing some amount and specification, preparation is inserted with high-purity chromium of high-purity chromium target, the identical material of high pure carbon target and high pure carbon is inserted respectively, and the specification that high-purity chromium is inserted insert with high pure carbon is identical, prepares simultaneously that the high-purity rare-earth of purity more than 3N inserted and a transition bunch metal is inserted;
Step 4: the rare earth of inlaying on the high-purity chromium target that calculates according to step 2 quantity of inserting, inlay rare earth in the open holes of inserting on high-purity chromium target that step 3 obtains and insert, inlay inserting with high-purity chromium of material that step 3 obtains in the unnecessary open holes of inserting with high-purity chromium target; The rare earth of inlaying on the high pure carbon target that calculates according to step 2 quantity of inserting, inlaying rare earth in the open holes of inserting on the high pure carbon target that step 3 obtains inserts, a transition bunch metal that calculates according to step 2 quantity of inserting, inlay a transition bunch metal in the open holes of inserting on the high pure carbon target that step 3 obtains and insert, inlay inserting with the high pure carbon of material that step 3 obtains in the unnecessary open holes of inserting with high pure carbon target;
Step 5: sputtered substrate metallic surface, vacuum tightness: E-3～E-4Pa, bias voltage: 500～1000V is infused in base metal surface with static backflushing technique by plasma sputtering before frock speed of rotation: the 2～10r/min, plated film and obtains 10～50nm plasma surface alloying layer;
Step 6: the sputtering current of heightening the Cr/RE target gradually is 2.0～6.0A, and the adjusting time is 5～10 minutes, obtains the Cr/RE transition layer of 0.2～0.5um on the plasma surface alloying layer that step 5 obtains;
Step 7: the sputtering current that improves the C/RE target gradually is 2.0～8.0A, and the sputtering current that reduces the Cr/RE target is 0.15～0.6A, and the adjusting time is 5～10 minutes, obtains the C/Cr-RE gradient layer of 0.2～0.5um on the Cr/RE transition layer that step 6 obtains;
Step 8: control sputtering current parameter, the sputtering current of C/RE target is 2.0～8.0A, the sputtering current of Cr/RE target is 0.15～0.6A, bias voltage: 50～100V, hold-time: 60～480 minutes, on the C/Cr-RE gradient layer that step 7 obtains, obtain the many first composite beds of C/Cr-RE of 1.0～3.0um.
The invention has the beneficial effects as follows,
(1) the polynary element introducing method of non-equilibrium magnetron-sputtering rare-earth and transition bunch metal has been realized the rare earth modified of solid lubrication composite membrane, is suitable for MoS
2, relevant solid lubrication nano composite membrane magnetron sputtering technology of preparing such as diamond, DLC, class graphite.This rare earth modified method is simple to operate, can be according to the composition of working condition requirement and performance characteristics flexible design composite membrane, and rare earth and transition bunch metal element content can be regulated in more wide in range scope.
(2) thermostability of rare earth multicomponent graphite composite film improves more than 30%; the basement membrane bonding force improves more than 20%; the electrochemically resistant of composite membrane corrosive power and wear resistance also are significantly improved simultaneously, and the class graphite composite film is had very positive pushing effect in the application aspect cutter, mould and the mechanical transmission.
Description of drawings
Fig. 1 is the structural representation of non-equilibrium magnetron-sputtering rare-earth multivariate graphite composite film of the present invention;
Fig. 2 is the structural representation of the non-balance magnetically controlled sputter target of the present invention's employing;
Fig. 3 is the work synoptic diagram of the non-balance magnetically controlled sputter target of the present invention's employing.
Among the figure, 1. matrix metal, 2. plasma surface alloying layer, 3.Cr/RE transition layer, 4.C/Cr-RE gradient layer, the many first composite beds of 5.C/Cr-RE, 6. plane sputtering target, 7. magnetron, the open holes of 8. inserting.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
A kind of non-equilibrium magnetron-sputtering rare-earth multivariate graphite composite film of the present invention, form by many first composite beds 5 of compound plasma surface alloying layer 2, Cr/RE transition layer 3, C/Cr-RE gradient layer 4 and C/Cr-RE successively, it consists of Cr/RE transition layer 3 wherein according to mass percent: RE:0.1%～1%, surplus is Cr, and the mass percent sum of each component is 100%; It consists of the many first composite beds 5 of C/Cr-RE wherein according to mass percent: Cr:3%～15%, RE:0.3%～10%, transition bunch metallic element: 0.3%～10%, surplus is C, the mass percent sum of each component is 100%, and bunch metallic element of transition is wherein selected one or more the mixture among Zr, Ta or the Nb for use.Plasma surface alloying layer 2, C/Cr-RE gradient layer 4 be those skilled in the art adopt in the class graphite composite film that ordinary method prepares general rete.
The present invention prepares the method for non-equilibrium magnetron-sputtering rare-earth multivariate graphite composite film, specifically implements according to following steps:
Step 1: determine the rare-earth multivariate graphite composite film composition, wherein, it consists of Cr/RE transition layer 3 according to mass percent: RE:0.1%～1%, surplus are Cr, and the mass percent sum of each component is 100%; It consists of the many first composite beds 5 of C/Cr-RE according to mass percent: Cr:3%～15%, RE:0.3%～10%, transition bunch metallic element: 0.3%～10%, surplus is C, the mass percent sum of each component is 100%, and bunch metallic element of transition is wherein selected one or more the mixture among Zr, Ta or the Nb for use.
Step 2: calculate the high-purity rare-earth of inlaying on high-purity chromium target and the high pure carbon target quantity of inserting, and a transition bunch metal of inlaying on the high pure carbon target quantity of inserting:
(a) calculate the high-purity rare-earth of inlaying on high-purity chromium target and the high pure carbon target quantity of inserting
A＝α
*β
*γ
*S
1/S????????????(1)
n＝S
1/S
2????????????????????(2)
In the formula,
A: content or rare earth elements RE the content (wt%) in C/Cr-RE many first composite beds 5 of rare earth elements RE in Cr/RE transition layer 3 of determining in the step 1;
α: the ratio of rare earth element and (carbon or chromium) target elements sputtering yield;
β: the ratio of rare earth element and (carbon or chromium) target elements density;
γ: the insert content (wt%) of middle-weight rare earths element of rare earth;
S
1: the total area that the etched area rare earth is inserted;
S
2: the face area that single rare earth is inserted;
S: the target etched area total area;
N: the rare earth that target the is inlayed quantity of inserting.
The ratio α of the content A of rare earth element in Cr/RE transition layer 3, rare earth element and high-purity chromium target element sputtering yield, rare earth element and ratio β, the rare earth of chromium density insert the content γ of middle-weight rare earths element, the total area S that the etched area rare earth is inserted
1, the face area S that inserts of single rare earth
2, in target etched area total area S substitution formula 1 and the formula 2, the rare earth that obtains inlaying on the high-purity chromium target quantity n that inserts;
The ratio α of the content A of rare earth element in the many first composite beds 5 of C/Cr-RE, rare earth element and high pure carbon target element sputtering yield, rare earth element and ratio β, the rare earth of carbon density insert the content γ of middle-weight rare earths element, the total area S that the etched area rare earth is inserted
1, the face area S that inserts of single rare earth
2, in target etched area total area S substitution formula 1 and the formula 2, the rare earth that obtains inlaying on the high pure carbon target quantity n that inserts;
(b) calculate a transition bunch metal of inlaying on the high pure carbon target quantity of inserting
C＝ε
*δ
*λ
*S
3/S????????????(3)
n
1＝S
3/S
4???????????????????(4)
In the formula,
C: the content (wt%) of transition bunch metallic element in the many first composite beds 5 of C/Cr-RE of determining in the step 1;
ε: the ratio of transition bunch metallic element and carbon sputtering yield;
δ: the ratio of transition bunch metallic element and carbon density;
λ: the content (wt%) of transition bunch metallic element during transition bunch metal is inserted;
S
3: the total area that etched area transition bunch metal is inserted;
S
4: the face area that single transition bunch metal is inserted;
S: the target etched area total area;
n
1: the transition that target the is inlayed bunch metal quantity of inserting.
Content λ, the total area S that etched area transition bunch metal is inserted of transition bunch metallic element during the content C of transition bunch metallic element in the many first composite beds 5 of Cr/RE, transition bunch metallic element inserted with ratio δ, the transition bunch metal of carbon density with ratio ε, the transition bunch metallic element of high pure carbon target element sputtering yield
3, the face area S that inserts of single transition bunch metal
4, in target etched area total area S substitution formula 3 and the formula 4, a transition bunch metal that obtains inlaying on the high pure carbon target quantity n that inserts
1
Step 4: the rare earth of inlaying on the high-purity chromium target that calculates according to step 2 quantity of inserting, inlay rare earth in the open holes 8 of inserting on high-purity chromium target that step 3 obtains and insert, inlay inserting with high-purity chromium of material that step 3 obtains in the unnecessary open holes 8 of inserting with high-purity chromium target; The rare earth of inlaying on the high pure carbon target that calculates according to step 2 quantity of inserting, inlaying rare earth in the open holes 8 of inserting on the high pure carbon target that step 3 obtains inserts, a transition bunch metal that calculates according to step 2 quantity of inserting, inlay a transition bunch metal in the open holes 8 of inserting on the high pure carbon target that step 3 obtains and insert, inlay inserting with the high pure carbon of material that step 3 obtains in the unnecessary open holes 8 of inserting with high pure carbon target;
Step 5: Fig. 3 is seen in the chromium target of non-equilibrium closed magnetron sputtering film device and the distribution of carbon target, two chromium targets and two carbon targets are symmetrically distributed, sputtered substrate metal 1 surface at first, vacuum tightness: E-3～E-4Pa, bias voltage: 500～1000V, be infused in matrix metal 1 surface with static backflushing technique by plasma sputtering before frock speed of rotation: the 2～10r/min, plated film and obtain 10～50nm plasma surface alloying layer 2;
Step 6: the sputtering current of heightening the Cr/RE target gradually is 2.0～6.0A, and the adjusting time is 5～10 minutes, prepares the Cr/RE transition layer 3 of 0.2～0.5um on the plasma surface alloying layer 2 that step 5 obtains;
Step 7: the sputtering current that improves the C/RE target gradually is 2.0～8.0A, the sputtering current that reduces the Cr/RE target is 0.15～0.6A, the adjusting time is 5～10 minutes, prepares the C/Cr-RE gradient layer 4 of 0.2～0.5um on the Cr/RE transition layer 3 that step 6 obtains;
Step 8: control sputtering current parameter, the sputtering current of C/RE target is 2.0～8.0A, the sputtering current of Cr/RE target is 0.15～0.6A, bias voltage: 50～100V, hold-time: 60～480 minutes, on the C/Cr-RE gradient layer 4 that step 7 obtains, prepare the many first composite beds 5 of C/Cr-RE of 1.0～3.0um.
Determine the composite membrane composition, wherein, it consists of Cr/RE transition layer 3 according to mass percent: Ce:0.1%, and Cr:99.9%, it consists of the many first composite beds 5 of C/Cr-RE according to mass percent, Cr:3%, Ce:0.3%, Zr:0.3%, C:96.4%.
Calculate the Rare-Earth Ce of inlaying on the high-purity chromium target quantity of inserting, known S=650cm
2, α
Ce/Cr=0.51, β
Ce/Cr=0.95, γ
Ce=99.9%, A=0.1% gets S by formula (1)
1=1.34cm
2, when the diameter of inserting is Φ 10mm, S
2=0.785cm
2, get n by formula (2)
1=S
1/ S
2=1.7, rounding is that 2 Ce insert;
Calculate the Rare-Earth Ce of inlaying on the high pure carbon target quantity of inserting, known S=650cm
2, α
Ce/C=5, β
Ce/C=2.99, γ
Ce=99.9%, A=0.3% gets S by formula (1)
1=0.13cm
2, S when the diameter of inserting is Φ 4mm
2=0.126cm
2, get n by formula (2)
2=S
1/ S
2=1.03, rounding is that 1 Ce inserts;
Calculate the metallic Z r that inlays on the high pure carbon target quantity of inserting, known S=650cm
2, ε
Zr/C=5.42, δ
Zr/Cr=2.88, λ
Zr=99.9%, C=0.3% gets S by formula (3)
3=0.125cm
2, when the diameter of inserting is Φ 4mm, S
4=0.126cm
2, by formula (4) n
3=S
3/ S
4=0.99, rounding is that 1 Zr inserts;
At 6 Φ 10mm inlaid holes of high-purity chromium target upper edge magnetron processing, process 6 Φ 4mm inlaid holes respectively at two high pure carbon target upper edge magnetrons, the Ce of preparation purity more than 3N inserts and Zr inserts; Preparation is inserted with high-purity chromium of chromium target, the identical material of carbon target and specification and high pure carbon is inserted respectively.
Inlay 2 blocks of high-purity Ce rare earths on high-purity chromium target, all the other holes are inlayed with high-purity chromium of chromium target homogeneity and are inserted; Inlay 1 Ce high-purity rare-earth and 1 Zr inserts on high pure carbon target, remaining hole is inlayed with the high pure carbon of carbon target homogeneity and is inserted.Sputter clean piece surface at first, vacuum tightness E-3Pa, bias voltage 500V, frock speed of rotation 2r/min.Go into the plasma surface alloying layer of 10nm earlier by the plasma sputtering injection with static backflushing technique; The sputtering current of heightening the Cr/RE target gradually is to 2.0A, and sputtering time 5 minutes prepares the Cr/RE transition layer of 0.2um; The sputtering current that improves the C/RE target gradually is to 2.0A again, and the sputtering current that reduces the Cr/RE target is to 0.15A, and sputtering time is 5 minutes, prepares the C/Cr-RE gradient cladding of 0.2um; The sputtering current of controlling the C/RE target at last is 2.0A, and the sputtering current of Cr/RE target is 0.15A, and bias voltage 50V, prepares the many first composite beds of C/Cr-RE of 1.0um at 60 minutes time.
Embodiment 2
Determine the composite membrane composition, wherein, it consists of Cr/RE transition layer 3 according to mass percent: Ce:0.5%, and Cr:99.5%, it consists of the many first composite beds 5 of C/Cr-Ce according to mass percent: Cr:15%, Ce:5%: Ta:5%, C:75%.
Calculate the Rare-Earth Ce of inlaying on the high-purity chromium target quantity of inserting, known S=650cm
2, α
Ce/Cr=0.51, β
Ce/Cr=0.95, γ
Ce=99.9%, A=0.5% gets S by formula (1)
1=6.72cm
2, when the diameter of inserting is Φ 17mm, S
2=2.27cm
2, get n by formula (2)
1=S
1/ S
2=2.96, rounding is that 3 Ce insert;
Calculate the Rare-Earth Ce of inlaying on the high pure carbon target quantity of inserting, known S=650cm
2, α
Ce/C=5, β
Ce/C=2.99, γ
Ce=99.9%, A=5% gets S by formula (1)
1=2.18cm
2, when the diameter of inserting is Φ 8mm, S
2=0.50cm
2, get n by formula (2)
2=S
1/ S
2=4.36, rounding is that 4 Ce insert;
Calculate the metallic Z r that inlays on the high pure carbon target quantity of inserting, known S=650cm
2, λ
Ta=99.9%, ε
Ta/C=5.42, δ
Ta/Cr=2.88, A=5% gets S by formula (3)
3=2.08cm
2, when the diameter of inserting is Φ 8mm, S
4=0.50cm
2, get n by formula (4)
3=S
3/ S
4=4.16, rounding is that 4 Ta insert;
At 6 Φ 17mm inlaid holes of high-purity chromium target upper edge magnetron processing, process 8 Φ 8mm inlaid holes respectively at two high pure carbon target upper edge magnetrons, the Ce of preparation purity more than 3N inserts and Zr inserts, and preparation is inserted with high-purity C of chromium target, the identical material of carbon target and specification and high-purity Cr inserts.
Inlay 3 Φ 17mmCe high-purity rare-earths and insert on high-purity chromium target, all the other holes are inlayed with high-purity chromium of chromium target homogeneity and are inserted; Inlay 4 Φ 8mmCe high-purity rare-earths and insert on high pure carbon target, inlay 4 blocks of Φ 8mmTa metals and insert on high pure carbon target, the high pure carbon with carbon target homogeneity is inlayed in unnecessary hole.Sputter clean piece surface at first, vacuum tightness E-4Pa, bias voltage 700V, frock speed of rotation 5r/min.Go into the Cr/RE plasma surface alloying layer of 30nm earlier by the plasma sputtering injection with static backflushing technique; The sputtering current of heightening the Cr/RE target gradually is to 4.0A, and the adjusting time is 8 minutes, prepares the Cr/RE transition layer of 0.35um; The sputtering current that improves the C/RE target gradually is to 5.0A again, and the sputtering current that reduces the Cr/RE target is to 0.40A, and the adjusting time is 8 minutes, prepares the C/Cr-RE gradient layer of 0.35u m; The sputtering current of controlling the C/RE target at last is 5.0A, and the sputtering current of Cr/RE target is 0.35A, and bias voltage 75V, prepares the many first composite beds of C/Cr-RE of 2.0um at 240 minutes hold-times.
Embodiment 3
Determine the composite membrane composition, wherein, it consists of Cr/RE transition layer 3 according to mass percent: Ce:1%, and Cr:99%, it consists of the many first composite beds 5 of C/Cr-Ce according to mass percent: Cr:10%, Ce:10%, Zr:10%, C:70%.
Calculate the Rare-Earth Ce of inlaying on the high-purity chromium target quantity of inserting, known S=650cm
2, γ
Ce=99.9%, α
Ce/Cr=0.51, β
Ce/Cr=0.95, A=0.5% gets S by formula (1)
1=13.43cm
2, when the diameter of inserting is Φ 17mm, S
2=2.27cm
2, get n by formula (2)
1=S
1/ S
2=5.92, rounding is that 6 Ce insert;
Calculate the Rare-Earth Ce of inlaying on the high pure carbon target quantity of inserting, known S=650cm
2, γ
Ce=99.9%, α
Ce/C=5, β
Ce/C=2.99, A=10% gets S by formula (1)
1=4.35cm
2, when the diameter of inserting is Φ 8mm, S
2=0.50cm
2, get n by formula (2)
2=S
1/ S
2=8.70, rounding is that 8 Ce insert;
Calculate the metallic Z r that inlays on the high pure carbon target quantity of inserting, known S=650cm
2, λ
Zr=99.9%, ε
Zr/C=5.42, δ
Zr/Cr=2.88, A=5% gets S by formula (3)
3=4.17cm
2, when the diameter of inserting is Φ 8mm, S
4=0.50cm
2, get n by formula (4)
3=S
3/ S
4=8.34, rounding is that 8 blocks of Zr metals are inserted;
Add 6 Φ 17mm inlaid holes at high-purity chromium target upper edge magnetron, process 8 Φ 8mm inlaid holes respectively at two high pure carbon target upper edge magnetrons, the Ce of preparation purity more than 3N inserts and Zr inserts, and preparation is inserted with high-purity C of chromium target, the identical material of carbon target and specification and high-purity Cr inserts.
On high pure carbon target, inlay 6 Φ 17mmCe high-purity rare-earths and insert, on high pure carbon target, inlay respectively 8 blocks of Φ 8mmZr metals insert and 8 blocks of Φ 8mmCe rare earths insert.Sputter clean piece surface at first, vacuum tightness E-4Pa, bias voltage 1000V, frock speed of rotation 10r/min.Inject the Cr/RE plasma surface alloying layer of 50nm earlier by plasma sputtering with static backflushing technique; The sputtering current of heightening the Cr/RE target gradually is to 6.0A, and the adjusting time is 10 minutes, prepares the Cr/RE transition layer of 0.5um; The sputtering current that improves the many first targets of C/RE gradually is to 8.0A again, and the sputtering current that reduces the Cr/RE sputtering target is to 0.6A, and the adjusting time is 10 minutes, prepares the C/Cr-RE gradient layer of 0.50um; The sputtering current of controlling the C/RE target at last is 8.0A, and the sputtering current of Cr/RE target is 0.6A, and bias voltage 100V, prepares the many first composite beds of C/Cr-RE of 3.0um at 480 minutes time.
Table 1 is the rare-earth multivariate graphite composite film of embodiment 1, embodiment 2 and embodiment 3 preparations and the performance comparison table of the class graphite composite film that ordinary method prepares,
The performance comparison table of table 1 rare-earth multivariate graphite composite film and class graphite composite film
| Composite membrane | Critical basement membrane bonding force (scratch method) | Beginning oxidizing temperature (unprotect heating) | Frictional coefficient | Wear rate |
| The class graphite composite film | ??60N | ??300℃ | ??0.1～0.12 | ??E-16m
3/ |
| Embodiment | ||||
| 1 | ??73N | ??380℃ | ??0.09～0.10 | ??E-17m 3/N.m |
| Embodiment 2 | ??77N | ??395℃ | ??0.085～0.10 | ??E-18m 3/N.m |
| Embodiment 3 | ??80N | ??405℃ | ??0.075～0.09 | ??E-18m 3/N.m |
Remarks: 1. adopt the variable load scratch method to detect critical basement membrane bonding force, ultimate load 100N, stroke 10mm;
2. POD pin dish friabilator load 60N, linear velocity 0.2m/s, metal to-metal contact are used in wear test.
As can be seen from Table 1, the rare-earth multivariate graphite composite film that the inventive method is prepared, its critical basement membrane bonding force and thermostability are than the class graphite composite film height of ordinary method preparation, and its frictional coefficient is lower than the class graphite composite film of ordinary method preparation.
At the plated film sputter clean and the transition layer deposition initial stage in early stage, there is certain rare earth to inject metallic matrix, the solid solution rare earth mainly is enriched in crystal boundary or other lattice defect (as dislocation, room etc.) is located, cause the change of physics, chemical environment or the interfacial energy of crystal boundary, cause the variation of modified layer microstructure and property.The rare earth element activity is higher, in film-Ji near interface enrichment, participates in film forming and surface reaction takes place, and has slowed down stress distribution gradient at the interface, helps significantly improving of film-film-substrate binding strength.
In containing the modified layer of rare earth, the interpolation of rare earth has changed the kinetics of diffusion of alloy oxidation process, to metallic cation played restraining effect to external diffusion, promoted negatively charged ion O comparatively speaking
2-Inwardly transmit, changed the formation and the growth mechanism of oxide film, generate densification and the protective oxide film of very strong bonding strength is arranged, thereby the resistance of oxidation of alloy is improved greatly with coating itself.The active element effect (REE) of rare earth also reduces oxide growth speed, improves the antistripping of oxide film, promotes oxidn film selective oxidation.The interpolation of trace rare-earth can make composite membrane structure refinement and densification, and the surface topography defective of solid lubricant film is reduced, and improves the density of coating, and this is one of major reason of improving thermostability.
High-melting-point refractory metals such as Zr, the Nb of compound certain content, Ti in rare earth modified multicomponent class graphite composite bed at the distribute carbide of these refractory metals of carbon composite layer disperse, can further improve the oxidation-resistance property of class graphite composite film.
Claims (4)
1. a non-equilibrium magnetron-sputtering rare-earth multivariate graphite composite film is characterized in that, by multiple successively
The plasma surface alloying layer (2) that closes, Cr/RE transition layer (3), C/Cr-RE gradient layer (4) and the many first composite beds of C/Cr-RE (5) are formed,
It consists of Cr/RE transition layer (3) wherein according to mass percent: RE:0.1%～1%, surplus are Cr, and the mass percent sum of each component is 100%;
It consists of the many first composite beds of C/Cr-RE wherein (5) according to mass percent: Cr:3%～15%, and RE:0.3%～10%, transition bunch metallic element: 0.3%～10%, surplus is C, the mass percent sum of each component is 100%.
2. according to the described composite membrane of claim 1, it is characterized in that described transition bunch metallic element is selected one or more the mixture among Zr, Ta or the Nb for use.
3. a method for preparing the described non-equilibrium magnetron-sputtering rare-earth multivariate graphite composite film of claim 1 is characterized in that, implement according to following steps,
Step 1: determine the rare-earth multivariate graphite composite film composition, wherein, it consists of Cr/RE transition layer (3) according to mass percent: RE:0.1%～1%, surplus are Cr, and the mass percent sum of each component is 100%; It consists of the many first composite beds of C/Cr-RE (5) according to mass percent: Cr:3%～15%, and RE:0.3%～10%, transition bunch metallic element: 0.3%～10%, surplus is C, the mass percent sum of each component is 100%;
Step 2: calculate the high-purity rare-earth of inlaying on high-purity chromium target and the high pure carbon target quantity of inserting, and a transition bunch metal of inlaying on the high pure carbon target quantity of inserting:
(a) calculate the high-purity rare-earth of inlaying on high-purity chromium target and the high pure carbon target quantity of inserting
A＝α*β*γ*S1/S
n＝S1/S2
In the formula,
A: content or rare earth elements RE the content in C/Cr-RE many first composite beds (5) of rare earth elements RE in Cr/RE transition layer (3) of determining in the step 1;
α: the ratio of rare earth element and carbon or chromium target element sputtering yield;
β: the ratio of rare earth element and carbon or chromium target element density;
γ: the insert content of middle-weight rare earths element of rare earth;
S1: the total area that the etched area rare earth is inserted;
S2: the face area that single rare earth is inserted;
S: the target etched area total area;
N: the rare earth that target the is inlayed quantity of inserting;
The ratio α of the content A of rare earth element in Cr/RE transition layer (3), rare earth element and high-purity chromium target element sputtering yield, rare earth element and ratio β, the rare earth of chromium density are inserted in face area S2 that the content γ of middle-weight rare earths element, the total area S1 that the etched area rare earth is inserted, single rare earth insert, the above-mentioned formula of the target etched area total area S substitution rare earth that obtains inlaying on the high-purity chromium target quantity n that inserts;
The ratio α of the content A of rare earth element in the many first composite beds of C/Cr-RE (5), rare earth element and high pure carbon target element sputtering yield, rare earth element and ratio β, the rare earth of carbon density are inserted in face area S2 that the content γ of middle-weight rare earths element, the total area S1 that the etched area rare earth is inserted, single rare earth insert, the above-mentioned formula of the target etched area total area S substitution rare earth that obtains inlaying on the high pure carbon target quantity n that inserts;
(b) calculate a transition bunch metal of inlaying on the high pure carbon target quantity of inserting
C＝ε*δ*λ*S3/S
n1＝S3/S4
In the formula,
C: the content of transition bunch metallic element in the many first composite beds of C/Cr-RE (5) of determining in the step 1;
ε: the ratio of transition bunch metallic element and carbon sputtering yield;
δ: the ratio of transition bunch metallic element and carbon density;
λ: the content of transition bunch metallic element during transition bunch metal is inserted;
S3: the total area that etched area transition bunch metal is inserted;
S4: the face area that single transition bunch metal is inserted;
S: the target etched area total area;
N1: the transition that target the is inlayed bunch metal quantity of inserting;
In the content λ of transition bunch metallic element during the content C of transition bunch metallic element in the many first composite beds of Cr/RE (5), transition bunch metallic element inserted with ratio δ, the transition bunch metal of carbon density with ratio ε, the transition bunch metallic element of high pure carbon target element sputtering yield, total area S3 that etched area transition bunch metal is inserted, face area S4 that single transition bunch metal is inserted, the above-mentioned formula of target etched area total area S substitution, a transition bunch metal that obtains inlaying on the high pure carbon target quantity n1 that inserts;
Step 3: at the open holes of inserting (8) of the high-purity chromium target of non-balance magnetically controlled sputter and high pure carbon target upper edge magnetron (7) processing some amount and specification, preparation is inserted with high-purity chromium of high-purity chromium target, the identical material of high pure carbon target and high pure carbon is inserted respectively, and the specification that high-purity chromium is inserted insert with high pure carbon is identical, prepares simultaneously that the high-purity rare-earth of purity more than 3N inserted and a transition bunch metal is inserted;
Step 4: the rare earth of inlaying on the high-purity chromium target that calculates according to step 2 quantity of inserting, inlay rare earth in the open holes of inserting (8) on high-purity chromium target that step 3 obtains and insert, inlay inserting with high-purity chromium of material that step 3 obtains in the unnecessary open holes of inserting (8) with high-purity chromium target; The rare earth of inlaying on the high pure carbon target that calculates according to step 2 quantity of inserting, inlaying rare earth in the open holes of inserting (8) on the high pure carbon target that step 3 obtains inserts, a transition bunch metal that calculates according to step 2 quantity of inserting, inlay a transition bunch metal in the open holes of inserting (8) on the high pure carbon target that step 3 obtains and insert, inlay inserting with the high pure carbon of material that step 3 obtains in the unnecessary open holes of inserting (8) with high pure carbon target;
Step 5: sputtered substrate metal (1) surface, vacuum tightness: E-3～E-4Pa, bias voltage: 500～1000V is infused in matrix metal (1) surface with static backflushing technique by plasma sputtering before frock speed of rotation: the 2～10r/min, plated film and obtains 10～50nm plasma surface alloying layer (2);
Step 6: the sputtering current of heightening the Cr/RE target gradually is 2.0～6.0A, and the adjusting time is 5～10 minutes, obtains the Cr/RE transition layer (3) of 0.2～0.5um on the plasma surface alloying layer (2) that step 5 obtains;
Step 7: the sputtering current that improves the C/RE target gradually is 2.0～8.0A, the sputtering current that reduces the Cr/RE target is 0.15～0.6A, the adjusting time is 5～10 minutes, obtains the C/Cr-RE gradient layer (4) of 0.2～0.5um on the Cr/RE transition layer (3) that step 6 obtains;
Step 8: control sputtering current parameter, the sputtering current of C/RE target is 2.0～8.0A, the sputtering current of Cr/RE target is 0.15～0.6A, bias voltage: 50～100V, hold-time: 60～480 minutes, on the C/Cr-RE gradient layer (4) that step 7 obtains, obtain the many first composite beds of C/Cr-RE (5) of 1.0～3.0um.
4. according to the described preparation method of claim 3, it is characterized in that described transition bunch metallic element is selected one or more the mixture among Zr, Ta or the Nb for use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009103046966A CN101613854B (en) | 2009-07-23 | 2009-07-23 | Non-equilibrium magnetron-sputtering rare-earth multivariate graphite composite film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009103046966A CN101613854B (en) | 2009-07-23 | 2009-07-23 | Non-equilibrium magnetron-sputtering rare-earth multivariate graphite composite film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101613854A true CN101613854A (en) | 2009-12-30 |
| CN101613854B CN101613854B (en) | 2011-06-15 |
Family
ID=41493738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009103046966A Active CN101613854B (en) | 2009-07-23 | 2009-07-23 | Non-equilibrium magnetron-sputtering rare-earth multivariate graphite composite film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101613854B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103469217A (en) * | 2013-09-24 | 2013-12-25 | 中国船舶重工集团公司第十二研究所 | Super-lubricated surface strengthening method of graphite-like carbon film for high-speed gear |
| CN104818483A (en) * | 2015-04-13 | 2015-08-05 | 南京理工大学 | Medium carbon CrNiMo steel surface chromium-tantalum gradient coating and preparation method thereof |
| CN110578115A (en) * | 2019-10-15 | 2019-12-17 | 河南科技大学 | Doped sulfide composite film, preparation method thereof and workpiece containing doped sulfide composite film |
| CN110578114A (en) * | 2019-10-15 | 2019-12-17 | 河南科技大学 | Doped graphite-like composite film, preparation method thereof and part containing doped graphite-like composite film |
| CN110578110A (en) * | 2019-10-15 | 2019-12-17 | 河南科技大学 | Sulfide-based composite film layer, preparation method thereof and wear-resistant workpiece |
| CN110643943A (en) * | 2019-10-15 | 2020-01-03 | 河南科技大学 | Graphite-like carbon doped film, preparation method thereof and workpiece |
| CN111254395A (en) * | 2020-03-23 | 2020-06-09 | 中国船舶重工集团公司第十二研究所 | High-temperature-resistant corrosion-resistant multilayer composite film and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1130214A (en) * | 1995-02-28 | 1996-09-04 | 中国航空工业总公司第633研究所 | Technology and equipment for vacuum continuous permeating plating poly alloy and compound thin film for blind hole |
| US5718811A (en) * | 1996-02-28 | 1998-02-17 | Seagate Technology, Inc. | Sputter textured magnetic recording medium |
| CN101209606B (en) * | 2007-12-25 | 2011-05-04 | 浙江大学 | Self-lubricating abrasion-proof graphite//TiC gradient composite thin film |
-
2009
- 2009-07-23 CN CN2009103046966A patent/CN101613854B/en active Active
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103469217A (en) * | 2013-09-24 | 2013-12-25 | 中国船舶重工集团公司第十二研究所 | Super-lubricated surface strengthening method of graphite-like carbon film for high-speed gear |
| CN103469217B (en) * | 2013-09-24 | 2015-09-16 | 中国船舶重工集团公司第十二研究所 | A kind of high-speed gear amorphous carbon coating surpasses lubricated surface enhancement method |
| CN104818483A (en) * | 2015-04-13 | 2015-08-05 | 南京理工大学 | Medium carbon CrNiMo steel surface chromium-tantalum gradient coating and preparation method thereof |
| CN110578115A (en) * | 2019-10-15 | 2019-12-17 | 河南科技大学 | Doped sulfide composite film, preparation method thereof and workpiece containing doped sulfide composite film |
| CN110578114A (en) * | 2019-10-15 | 2019-12-17 | 河南科技大学 | Doped graphite-like composite film, preparation method thereof and part containing doped graphite-like composite film |
| CN110578110A (en) * | 2019-10-15 | 2019-12-17 | 河南科技大学 | Sulfide-based composite film layer, preparation method thereof and wear-resistant workpiece |
| CN110643943A (en) * | 2019-10-15 | 2020-01-03 | 河南科技大学 | Graphite-like carbon doped film, preparation method thereof and workpiece |
| CN110578115B (en) * | 2019-10-15 | 2021-08-20 | 河南科技大学 | Doped sulfide composite film, preparation method thereof and workpiece containing doped sulfide composite film |
| CN110578110B (en) * | 2019-10-15 | 2021-08-27 | 河南科技大学 | Sulfide-based composite film layer, preparation method thereof and wear-resistant workpiece |
| CN110643943B (en) * | 2019-10-15 | 2022-09-09 | 河南科技大学 | Graphite-like carbon doped film, preparation method thereof and workpiece |
| CN111254395A (en) * | 2020-03-23 | 2020-06-09 | 中国船舶重工集团公司第十二研究所 | High-temperature-resistant corrosion-resistant multilayer composite film and preparation method thereof |
| CN111254395B (en) * | 2020-03-23 | 2021-11-26 | 中国船舶重工集团公司第十二研究所 | High-temperature-resistant corrosion-resistant multilayer composite film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101613854B (en) | 2011-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101613854B (en) | Non-equilibrium magnetron-sputtering rare-earth multivariate graphite composite film and preparation method thereof | |
| CN101613855B (en) | Non-equilibrium magnetron-sputtering rare-earth graphite composite film and preparation method thereof | |
| CN109234690B (en) | A kind of high-entropy alloy target and its preparation process containing aluminium and boron element | |
| CN108642449A (en) | Superhard tough high-entropy alloy nitride nano composite coating hard alloy blade and preparation method thereof | |
| CN103084600B (en) | Superhard TiN-TiSiN-CN multilayer alternate composite gradient coating carbide blade and preparation method thereof | |
| CN109346743A (en) | A kind of conductive anti-corrosion coating of fuel battery metal double polar plate | |
| CN103132026B (en) | The apparatus and method of AlCrN coating are prepared in cathode arc ion plating | |
| CN108330459A (en) | A kind of application of symmetrical magnetron sputtering technique and its diamond-like coating | |
| CN101395294A (en) | System and method for sputtering a tensile silicon nitride film | |
| CN101323946A (en) | Preparation of nanocrystalline metal Ta film having out phase structure | |
| TW200718797A (en) | SnO2 sputtering target and process for producing the same | |
| CN108149198B (en) | A kind of WC hard alloy film and its gradient layer technology room temperature preparation method | |
| CN104213088A (en) | Method for manufacturing wear-resisting amorphous carbon and nitrogen double-layer thin film on surface of titanium alloy material | |
| CN109898056B (en) | PVD (physical vapor deposition) technology-based bulk metal/metal ceramic nanometer gradient material as well as preparation method and application thereof | |
| CN106567047A (en) | Method of preparing high-purity microstructure-controllable Mo-Nb alloy target material through hot-pressing process | |
| CN103045998A (en) | Product containing CrNiTiAlN quinary coating and preparation method thereof | |
| CN104532189A (en) | Fine Sn phase AlSn20Cu coating for bearing bush and preparation method thereof | |
| CN110643943B (en) | Graphite-like carbon doped film, preparation method thereof and workpiece | |
| CN109576662A (en) | A kind of two-way nanometer gradient material of bulk metal ceramic/metal/cermet and preparation method thereof based on PVD technique | |
| CN104630725A (en) | TiN/Ti/Si/Ti multi-layer wear-resistant corrosion-resistant thin film material and preparation method thereof | |
| Hu et al. | Improving the porosity of the alloy Ni-Cr-WC by coating CeO2: First principles calculation combined with experiment | |
| CN116121700A (en) | Refractory element doped wear-resistant gradient HfMSiCN ceramic layer and preparation method thereof | |
| CN101818330A (en) | Unbalanced magnetron sputtering C/Ta graphite-like carbon film and preparation method thereof | |
| CN107313007B (en) | A kind of charging connector, electronic equipment and charging connector intensifying method | |
| CN110306153A (en) | A kind of preparation method for the DLC coating adulterating Cr |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |