CN100432281C - Iridium coating layer for carbon material anti oxidation and its preparation method - Google Patents
Iridium coating layer for carbon material anti oxidation and its preparation method Download PDFInfo
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- CN100432281C CN100432281C CNB2006100411199A CN200610041119A CN100432281C CN 100432281 C CN100432281 C CN 100432281C CN B2006100411199 A CNB2006100411199 A CN B2006100411199A CN 200610041119 A CN200610041119 A CN 200610041119A CN 100432281 C CN100432281 C CN 100432281C
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Abstract
This invention relates to a type of carbon material iridium smear layer used for antioxygen. The feature is it has two iridium smear layer: one permeates under carbon material; one deposit on the surface. The depth of infiltrated layer is 10-50um, surface layer is 50-300um. Iridium and carbon material has combined, and the ingredient forms gradient transition from infiltrated layer to surface layer and has no catastrophe of ingredient and mechanical property. The preparation of this smear layer includes follow steps: use iridium board and carbon material as cathode, vacuum chamber shell as joint using anode in the vacuum glow discharge installation; draw vacuum to ultimate vacuum, post in argon gas, light aura, and then alloy elementary particle of source electrode iridium target is sputtered and deposit on the surface of carbon material; the last step is high temperature diffusion.
Description
Technical field
The present invention relates to a kind of iridium coating layer and preparation method thereof, particularly relate to a kind of iridium coating layer for carbon material anti oxidation and preparation method thereof.
Background technology
Carbon material comprises graphite simple substance material and carbon/carbon composite, density is little, specific tenacity is big, anti-thermal shock, creep resistance, intensity raises with temperature between 1000 ℃～2200 ℃, is applied in multiple empty day aircraft such as strategic missile bullet, airship return capsule, the space shuttle leading edge of a wing.Yet,, therefore solve the bottleneck that the carbon material anti oxidation problem is the carbon material widespread use because carbon material generates carbon monoxide or carbonic acid gas volatilization promptly reacting with oxidizing atmosphere more than 400 ℃.At present, develop multiple ceramic oxidation resistant coating both at home and abroad, satisfied application demand between the carbon material high temperature, short time.But, because therefore ceramic taking off of oxidation resistant coating high temperature since the invention sixties in last century carbon/carbon composite, still do not had a kind of oxidation resistant coating that carbon material is worked long hours in high-temperature oxidation environment.
2443 ℃ of precious metal iridium fusing points have an excellent high temperature oxidation resistance because of saturation steam forces down, oxygen permeability is low, are unique metals that still has good mechanical properties in the air more than 1600 ℃, and are not reacting with carbon below 2280 ℃.Because the excellent antioxidant performance that has of iridium and and carbon do not react, so the carbon-based material surface is applied with iridium coating layer and is become an important channel of improving its antioxidant property.As far back as the sixties in 20th century, the United States Air Force material laboratory is a precursor with iridium halogenide, adopt chemical Vapor deposition process to prepare iridium coating layer at graphite surface, but halogenide precursor volatility is relatively poor, and deposition is low, to equipment and substrate seriously corroded.
In " Journal of Materials Science Letters " the 12nd volume the 18th phase magazine of publishing on September 15th, 1993 " Iridium coatings on carbon-carbon composites produced by two different sputteringmethods:a comparative study " (P1411-1412) literary composition disclose with the method for physical vaporous deposition at carbon/carbon composite surface preparation iridium coating layer.This method is a target plate with the iridium plate, makes the iridium volatilization form steam by electron-bombardment, deposits to the carbon/carbon composite surface, forms iridium coating layer through 1700 ℃ of thermal treatments again.The advantage of this method is that cost is low, and technology is simple; The shortcoming of this method is that iridium coating layer and carbon/carbon composite bonding force are low, and scour resistance is poor, and coatingsurface has crackle, and antioxidant property is also poor.
In " Carbon " the 39th volume the 7th phase magazine of publishing June calendar year 2001 " A novel laser technique foroxidation-resistant coating of carbon-carbon composite " (P991-999) literary composition method for preparing iridium coating layer with the induced with laser chemical thermal decomposition is disclosed.This method is raw material with the iridium chloride, makes its distillation become gaseous state under the high temperature, carries out chemical heat then and decompose under induced with laser, generates iridium and chlorine, and iridium is deposited on the carbon/carbon composite surface and forms iridium coating layer, and the chlorine volatilization is overflowed.The advantage of this method is the iridium coating layer densification, and antioxidant effect is good; The shortcoming of this method is that iridium coating layer and carbon/carbon composite bonding strength are low, and scour resistance is low.
In " solid-rocket technology " the 29th volume the 1st phase magazine of publishing in February, 2006 " mocvd method prepares the microstructure of multilayer iridium coating layer " (P56-59) literary composition method that the organic alkoxide chemical Vapor deposition process of metal prepares iridium coating layer is disclosed.This method is to be raw material with praseodynium iridium, will send into the constant temperature chemical vapor deposition chamber after its distillation, and the thermolysis of praseodynium iridium forms iridium coating layer at charcoal material surface.The advantage of this method is that iridium coating layer is even, can obtain fine and close iridium coating layer by chemical vapour deposition repeatedly; The shortcoming of this method is the cost height, praseodynium iridium price up to 1100 yuan/gram, and iridium coating layer and charcoal are nonwetting, a large amount of cracking of generation after the pyroprocessing, anti-oxidant scour resistance is low.
Above-mentioned present Research shows, although iridium coating layer is considered to very ideal carbon material anti oxidation coating, yet does not have a kind of method can prepare high-quality iridium coating layer, and this is the problem to be solved in the present invention just.
Summary of the invention
Problem to be solved by this invention provides a kind of iridium coating layer for carbon material anti oxidation, and it is two-layer up and down to it is characterized in that iridium coating layer is divided into, and penetrates into the penetrating layer that is below the carbon material surface, is deposited on the upper layer that is of carbon material surface.The penetrating layer degree of depth is 10～50 μ m, and surface layer thickness is 50～300 μ m.Iridium and carbon material metallurgical binding, its composition to the upper layer gradient transition, are thrown the sudden change that composition and mechanical property are arranged from penetrating layer.
Another technical problem to be solved by this invention provides a kind of preparation method of above-mentioned iridium coating layer, it is characterized in that being target plate with the iridium target earlier, prepares iridium coating layer by the double-deck glow plasma surface alloying at carbon material surface.Be negative electrode with iridium plate and carbon material in the vacuum glow discharge device, vacuum chamber housing is public anode, between anode and two negative electrodes tunable voltage dc power supply is set respectively.Be evacuated to final vacuum, send into argon gas, light aura, the alloying element particle of source electrode iridium target is sputtered out, and is deposited on workpiece utmost point carbon material surface, forms surface alloying layer by High temperature diffusion.
The source electrode and the workpiece utmost point are equipped with a cover direct supply respectively, and voltage output range is 0～2000V, and adjustable continuously, and two cover power supplys are public anode with the vacuum chamber housing of ground connection.
Discharge air pressure is 13.3～133Pa, and final vacuum is not less than 0.1Pa, source potential-800V～-2000V, the workpiece current potential-200V～-1000V.
In the vacuum glow discharge device, the spacing between two negative electrodes of iridium plate and carbon material is 5～40mm.
A kind of preparation method of iridium coating layer for carbon material anti oxidation is characterized in that comprising following sequential steps:
(1) with carbon material 1800～2000 ℃ of pyroprocessing, make in the carbon material impurity volatilization, avoid in the coating preparation process iridium target to poison;
(2) iridium plate and carbon material being packed in the vacuum glow discharge device, is negative electrode with iridium plate and carbon material, and vacuum chamber housing is public anode, between anode and two negative electrodes tunable voltage dc power supply is set respectively;
(3) adjust iridium plate and two cathode spacings of carbon material;
(4) be evacuated to final vacuum, send into argon gas, light aura, the alloying element particle of source electrode iridium target is sputtered out, and is deposited on carbon material surface;
(5) behind the certain hour, outage, the vacuum glow discharge device is opened in inflation, takes out carbon material, finishes coating preparation.
Major advantage of the present invention is: (1) iridium coating layer can penetrate into carbon material inside, and the penetrating layer of formation and carbon material bonding strength height have improved the anti-ablation ability of iridium coating layer; (2) the iridium coating layer free of pinholes of the present invention's preparation, finer and close more than the iridium coating layer of physical vapor deposition and chemical vapour deposition, resistance of oxidation is strong; (3) the inventive method preparation temperature height, iridium coating layer does not shrink in the thermal cycling process, does not crack; (4) iridium coating layer of the present invention does not have the sudden change at interface from the inner outwards gradient transition of carbon material, does not have stress mutation, and the iridium coating layer thermal shock resistance is good; (5) the present invention is that target plate excites iridium atom directly to the carbon material internal penetration by the plasma bombardment target surface with the iridium plate, the technology simple controllable; (6) the present invention is starting material with the iridium plate, 300～500 yuan of every grams, the iridium coating layer output efficiency is 50%, and the metal alkoxide chemical vapour deposition is a raw material with praseodynium iridium, 1500～2000 yuan of every grams, the iridium coating layer output efficiency only is 15%, thereby the present invention prepares iridium coating layer method cost and reduces greatly.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1 prepares iridium coating layer at graphite surface
(1) with graphite piece 2000 ℃ of pyroprocessing;
(2) iridium plate and graphite are packed into vacuum glow discharge device is a negative electrode with iridium plate and graphite, and vacuum chamber housing is public anode;
(3) iridium plate and graphite spacing are 25mm;
(4) be evacuated to final vacuum, send into argon gas, light aura;
(5) carry out 10 hours, outage, the vacuum glow discharge device is opened in inflation, takes out carbon material, finishes coating preparation.
Embodiment 2 is at carbon/carbon composite surface preparation iridium coating layer
(1) with carbon/carbon composite 2100 ℃ of pyroprocessing;
(2) iridium plate and carbon/carbon composite are packed into vacuum glow discharge device is a negative electrode with iridium plate and carbon/carbon composite, and vacuum chamber housing is public anode;
(3) iridium plate and carbon/carbon composite spacing are 15mm;
(4) be evacuated to final vacuum, send into argon gas, light aura;
(5) carry out 5 hours, outage, the vacuum glow discharge device is opened in inflation, takes out carbon material, finishes coating preparation.
Claims (9)
1. an iridium coating layer for carbon material anti oxidation is characterized in that iridium coating layer is two-layer about being divided into, and penetrates into the penetrating layer that is below the carbon material surface, is deposited on the upper layer that is of carbon material surface.
2. according to the described coating of claim 1, it is characterized in that the penetrating layer degree of depth is 10～50 μ m, surface layer thickness is 50～300 μ m.
3. according to the described coating of claim 1, it is characterized in that iridium and carbon material metallurgical binding, its composition to the upper layer gradient transition, does not have the sudden change of composition and mechanical property from penetrating layer.
4. according to the preparation method of the described a kind of iridium coating layer for carbon material anti oxidation of claim 1, it is characterized in that the iridium plate is that target plate prepares iridium coating layer by the double-deck glow plasma surface alloying at carbon material surface.
5. according to the described preparation method of claim 4, it is characterized in that source electrode iridium plate and workpiece utmost point carbon material are negative electrode in the vacuum glow discharge device, vacuum chamber housing is public anode, between anode and two negative electrodes tunable voltage dc power supply is set respectively.
6. according to the described preparation method of claim 5, it is characterized in that the source electrode and the workpiece utmost point are equipped with a cover direct supply respectively, voltage output range is 0～2000V, and adjustable continuously, and two cover power supplys are public anode with the vacuum chamber housing of ground connection.
7. according to the described preparation method of claim 5, the air pressure that it is characterized in that discharging is 13.3～133Pa, and final vacuum is not less than 0.1Pa, source potential-800V～-2000V, the workpiece current potential-200V～-1000V.
8. according to the described preparation method of claim 4, it is characterized in that the spacing between the iridium plate and two negative electrodes of carbon material is 5～40mm in the vacuum glow discharge device.
9. according to the described preparation method of claim 4, it is characterized in that comprising following sequential steps:
(1) with carbon material 1800～2000 ℃ of pyroprocessing;
(2) iridium plate and carbon material being packed in the vacuum glow discharge device, is negative electrode with iridium plate and carbon material, and vacuum chamber housing is public anode;
(3) adjust iridium plate and two cathode spacings of carbon material;
(4) be evacuated to final vacuum, send into argon gas, light aura;
(5) behind the certain hour, outage, the vacuum glow discharge device is opened in inflation, takes out carbon material, finishes coating preparation.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100411199A CN100432281C (en) | 2006-08-04 | 2006-08-04 | Iridium coating layer for carbon material anti oxidation and its preparation method |
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| CNB2006100411199A CN100432281C (en) | 2006-08-04 | 2006-08-04 | Iridium coating layer for carbon material anti oxidation and its preparation method |
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| CN1904126A CN1904126A (en) | 2007-01-31 |
| CN100432281C true CN100432281C (en) | 2008-11-12 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105669254B (en) * | 2016-01-18 | 2018-03-06 | 太原理工大学 | A kind of method for improving carbon/carbon composite pyro-oxidation resistance |
| CN108866502A (en) * | 2018-06-21 | 2018-11-23 | 太原理工大学 | A kind of titanium alloy surface high temperature coatings and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04149082A (en) * | 1990-10-09 | 1992-05-22 | Mitsubishi Heavy Ind Ltd | Carbon material having oxidation resistance at high temperature |
| JPH08295583A (en) * | 1995-04-25 | 1996-11-12 | Mitsubishi Heavy Ind Ltd | Carbonaceous material with oxidation resistant coating for use at high temperature |
| CN1227276A (en) * | 1999-02-11 | 1999-09-01 | 太原理工大学 | Pulse glow discharge plasma surface metallurgical technology |
| CN1455016A (en) * | 2002-05-01 | 2003-11-12 | 田中贵金属工业株式会社 | Raw-material compound for CVD and chemical gas-phase steam-plating method for iridium and iridium compound film |
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2006
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04149082A (en) * | 1990-10-09 | 1992-05-22 | Mitsubishi Heavy Ind Ltd | Carbon material having oxidation resistance at high temperature |
| JPH08295583A (en) * | 1995-04-25 | 1996-11-12 | Mitsubishi Heavy Ind Ltd | Carbonaceous material with oxidation resistant coating for use at high temperature |
| CN1227276A (en) * | 1999-02-11 | 1999-09-01 | 太原理工大学 | Pulse glow discharge plasma surface metallurgical technology |
| CN1455016A (en) * | 2002-05-01 | 2003-11-12 | 田中贵金属工业株式会社 | Raw-material compound for CVD and chemical gas-phase steam-plating method for iridium and iridium compound film |
Non-Patent Citations (4)
| Title |
|---|
| A novel laser technique for oxidation-resistant coatingofcarbon-carbon composite. Lloyd Snell, Avery Nelson, Pal Molian.CARBON,Vol.39 . 2001 |
| A novel laser technique for oxidation-resistant coatingofcarbon-carbon composite. Lloyd Snell, Avery Nelson, Pal Molian.CARBON,Vol.39 . 2001 * |
| Iridium coatings on carbon-carbon composites producedby two different sputtering methods:a comparative study. K.Mumtaz, J.Echigoya, T.Hirai, Y.Shindo.JOURNAL OF MATERIALS SCIENCE LETTERS,Vol.12 . 1993 |
| Iridium coatings on carbon-carbon composites producedby two different sputtering methods:a comparative study. K.Mumtaz, J.Echigoya, T.Hirai, Y.Shindo.JOURNAL OF MATERIALS SCIENCE LETTERS,Vol.12 . 1993 * |
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