CA1070142A - Superalloy composite structure - Google Patents
Superalloy composite structureInfo
- Publication number
- CA1070142A CA1070142A CA228,901A CA228901A CA1070142A CA 1070142 A CA1070142 A CA 1070142A CA 228901 A CA228901 A CA 228901A CA 1070142 A CA1070142 A CA 1070142A
- Authority
- CA
- Canada
- Prior art keywords
- filaments
- matrix
- composite member
- tungsten
- nitride
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/02—Pretreatment of the fibres or filaments
- C22C47/04—Pretreatment of the fibres or filaments by coating, e.g. with a protective or activated covering
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Physical Vapour Deposition (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
- Powder Metallurgy (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
ABSTRACT
Superalloys such as those with a nickel or cobalt-base reach their maximum practical operating temperature in the neigh-bourhood of 1000°C. Efforts have been made to raise this oper-ating temperature by using reinforcing materials such as filaments of tungsten or other strong refractory materials. Migration of alloy constituents into these filaments may have a detrimental effect on their strength. Coatings are proposed which prevent this migration. Such coatings may consist of materials such as hafnium carbide, hafnium nitride, titanium nitride, zirconium carbide or zirconium nitride.
Superalloys such as those with a nickel or cobalt-base reach their maximum practical operating temperature in the neigh-bourhood of 1000°C. Efforts have been made to raise this oper-ating temperature by using reinforcing materials such as filaments of tungsten or other strong refractory materials. Migration of alloy constituents into these filaments may have a detrimental effect on their strength. Coatings are proposed which prevent this migration. Such coatings may consist of materials such as hafnium carbide, hafnium nitride, titanium nitride, zirconium carbide or zirconium nitride.
Description
~ ~7al~4~
~ O~ lD 07 ]IIVE~_O~
is invention relates to structures for operation at elevated temperatures, for example, temperatures in excess of 1000C and in particular composite structures which are made up of superalloys with suitable reinforcement.
In the past, it has been known certain alloys generally re~erred to as superalloys having nickel or cobalt base and con-- taining alloying agents such as carbon, tungsten~ molybdenum, cobalt, chromium, aluminum, titanium, zirconium, hafnium and boron and having an iron base and containing alloying agents including at least chromium, aluminum~ yttrium and carbon, may be operated at temperatures in the neighbourhood of 750C to 1000C.
Apparatus such as gas turbines~ may desirably operate in this temperature range and the blade structures in particular, must continue to retain substantial strength at their maximum operating temperatures. It would be desirable if the maximum ; operating temperatures could be raised to at least 1100C and ` even higher temperatures such as 1200C might find application.
; Unfortunately, superalloys of the type referred to begin to lose their mechanical strength about 1000C and indeed may be relatively useless at temperatures in the neighbourhood of 1100C.
It has been proposed to reinforce such alloys by the i` introduction o~ filaments in particular, tungsten and tungsten ; alloy filaments. Such filaments may contain in addition to their tungsten base, potassium, silicon, rhenium, thoria or hafnium - carbide and the filaments may vary in size depending upon the particu~ar application. Alternatively~ the filaments may consist of graphi-te, silicon carbide or molybdenumO All such ` 30 reinforcements contribute to the strength of the composite structure because they themselves are stronger than the matrix alloy at the elevated temperatures.
Unfortunately9 in operation, at elevated temperatures over a long period of time, materials wi-thin the alloy migrate in-to the rein~orcing material and in general, i~ the nickel or
~ O~ lD 07 ]IIVE~_O~
is invention relates to structures for operation at elevated temperatures, for example, temperatures in excess of 1000C and in particular composite structures which are made up of superalloys with suitable reinforcement.
In the past, it has been known certain alloys generally re~erred to as superalloys having nickel or cobalt base and con-- taining alloying agents such as carbon, tungsten~ molybdenum, cobalt, chromium, aluminum, titanium, zirconium, hafnium and boron and having an iron base and containing alloying agents including at least chromium, aluminum~ yttrium and carbon, may be operated at temperatures in the neighbourhood of 750C to 1000C.
Apparatus such as gas turbines~ may desirably operate in this temperature range and the blade structures in particular, must continue to retain substantial strength at their maximum operating temperatures. It would be desirable if the maximum ; operating temperatures could be raised to at least 1100C and ` even higher temperatures such as 1200C might find application.
; Unfortunately, superalloys of the type referred to begin to lose their mechanical strength about 1000C and indeed may be relatively useless at temperatures in the neighbourhood of 1100C.
It has been proposed to reinforce such alloys by the i` introduction o~ filaments in particular, tungsten and tungsten ; alloy filaments. Such filaments may contain in addition to their tungsten base, potassium, silicon, rhenium, thoria or hafnium - carbide and the filaments may vary in size depending upon the particu~ar application. Alternatively~ the filaments may consist of graphi-te, silicon carbide or molybdenumO All such ` 30 reinforcements contribute to the strength of the composite structure because they themselves are stronger than the matrix alloy at the elevated temperatures.
Unfortunately9 in operation, at elevated temperatures over a long period of time, materials wi-thin the alloy migrate in-to the rein~orcing material and in general, i~ the nickel or
- 2 -cobalt migrates into the reinforcing material, it will weaken the filaments.
In the case of tungsten filaments immersed in a cobalt base alloy, there is a detrimental interaction due to the migrat-lon of cobalt into khe tungsten filaments producing intermetallic compounds which weaken the filament. In the case o~ tungsten fllaments immersed in a nickel base alloy there is a detrimental interaction due to the migration of nickel into the tungsten causing recrystallization of the tungsten alloy which reduced the strength of the filaments rendering them unsuitable as reinforce-ment.
It has been proposed to coat such filaments with a pro-jfl~1 ;bi f tective coating to ~4_}~ migration of the materials from the alloy into the filament. One example o~ the prior art was the ~ coating of tungsten filaments with tantalum carbide for use as reinforcements in cobalt base superalloys as disclosed in Septem-` ber 1973 Technical Report AD756867, Ahmad, I., et al, National ` Technical Information Service, U.S.-3-Department of Commerce, Springfield, Va. 22151. This coating, however, proved to be in-effecti~e in nickel base alloys.
SUMMARY OF THE INVENTION
~: It is an ob~ect of this invention to overcome the prior problems and weakening of the reinforcing material due to migration of alloy constituents into the reinforcing material. To this end, it has been found that hafnium carbide, hafnium nitride, titanium nitride, zirconium carbide and zirconium nitride form barriers ^ which protect the reinforcing material and inhibit migration of the undesirable components of the alloys into the reinforcing ~ibres.
It has been found, for example, that tungsten alloy ' :
filaments for use as reinforcing material in nickel base super-alloys and cobalt base superalloys may be protected from migration 0~0~4~
o~ alloy constituents, particularly of nickel from the super-alloy by coating the filament with a layer of hafnium carbide or nitride. The composite material so formed, that is, tungsten alloy filaments coated with hafnium carbide or ni-tride embedded in superalloy materials, has been found to have a useful operating temperature as high as 1176C. Titanium nitride has also been found to provide a suitable barrier layer over tungsten alloy ~ilament immersed in cobalt superalloys up to about 1095C.
In accordance with this invention, the reinforcing materials are coated with suitable protective barrier layers in accordance with the desired operating temperature and the consti-; tuents of the superalloy. A protective layer may be considered to be suitable and inhibit migration of the matrix components into the filament if, when exposed to the maximum operating temperature~
the composite article shows no evidence of detrimental migration in a 200 hour test and may therefore be predicted to have a reasonable operating life at its operating temperature. Various methods can be used to deposit these barrier layers such as '` sputtering, electron beam evaporation ion plating or chemical vapour deposition.
EXAMPLE "A"
Wires of tungsten plus 2% thoria having a diameter of 02 inches were coated with a layer of hafnium carbide about 8microns thick by means of R.F. sputtering~ The coated wires were incorporated into a nickel base superalloy Mar-M-200 by surround-ing the wires with powdered superalloy within an evacuated metal container and subjecting the filled container to hot isostatic pressure. The isostatic press provided a pressure of 12 Ksi of argon while heating -the con-tainer to 1120C. The composite struc-ture was removed from the press and cut into samplesa Each samplewas enclosed in a silica glass evacuated tube and subjected to prolonged heating~ Samples were subjected to 1065C, 1121C
:'~
~ - 4 ~
~- ` ' ,' . .
~ - ~Q7~ 2 and 1176C for 10, 30, 100, 1,000 and 27000 hours. The samples were then subjected to metallographic examination by optical and stereoscan electron microscopyO At all temperatures, samples exposed up to -100 hours showed no signs of recrystallization.
Samples exposed to 1176C for 2,000 hours showed a recrystallization zone of` only about 15 microns thickness.
The single figure of drawings illustrates an apparatus `
:' ~' , ' :~ , - 4a ~ ~i ',~
1)7a~ Z
for chemical vapour deposition of such barrier materials. The tungsten filament 3 passes through a chamber 4, preferably formed of glass, entering and exiting through mercury seals 5 and 6 which are arranged to permit the tungsten filament to pass through the seal but prevent gases from entering or leaving the chamber 4.
The wire 3 pas~es centrally down the chamber through a coaxial tube 7 which is supported and sealed to the outer wall of the chamber 4 by means of an annular member 8~ A metallic chloride generator 9 may consist simply of a chamber for retaining metall~c particles of a suitable material such as hafnium and having an open end into which hydrogen chloride gas or chlorine gas may be intro-duced. The reaction products consist of chlorides of hafnium which flow out through a tube at the bottom o~ the chamber desig-nated 11. A further inlet in the tube 12 at 13 permits the intro-duction of a suitable reactive gas and hydrogen, for example ; methane and hydrogen. The two outputs mixed at the end of tube 11 will flow into the chamber 4, down the chamber 4 to its right hand end and into the coaxial tube 7, back through the chamber 4 to its ~ar end and out through outlet 1~ which is connected to a suit-able trap, an arrangement for venting the gases. In traversing the chamber 4~ the gas flows over the filament 3.
Heating and insulating members cover the reactive areas to maintain suitable temperatures. The wire is maintained at a higher temperature by means of current passing through the wire between electrodes 15 and 16 which are immersed in the mercury seals. This current is ad~usted to maintain the wire at the des-ired temperature usually between 900 and 1300C.
To produce a nitride coating, nitrogen is substituted for the methane at inlet 13. Titanium can be added to the process by the direct introduction o~ titanium chloride which is commer-cially available.
` In order that the coatJng produced may be su~iciently . .
adherent, it will be necessary that wire be carefully cleaned, for example by treatment with triclorethylene followed by exposure to hydrogen at about 900C.
The result of -this whole process is an adherent coating two/ten microns thick of titanium nitride, hafnium nitride~ haf-nium carbide, zirconium nitride or zirconium carbide as desired.
me finished wire coated with the selected material may now be assembled together with the superalloy to produce the des-ired composite memberO me fabrication of the composite member can be accomplished by several techniques including hot isostatic ; pressing, diffusion bonding, or hot die bonding~ By proper selec-tion of the superalloy and the coating for the fibres, the com-posite structure may be designed to withstand much higher temper-atures than the matrix material. By proper selection of the coatings, the filaments may be protected from the deleterious effect of the matrix and may maintain strength even in the pres-ence of prolonged exposure to high temperatures.
- EXAMPLE "B'' Tungsten 2% thoria alloy wires .020" in diameter were coated with hafnium nitride by chemical vapour deposition to pro-duce a layer about 5 microns thicko The coated wires were sur rounded with powdered cobalt base superalloy Y~S~w~ within an evacuated metal containerO The container was subjected to hot isostatic pressing at a temperature of 1200C a~d an argon pres-sure of 10 Ksi. The composite structure was removed from the press and cut into samples each of which was placed in an evac-- uated silica glass container and subjected to prolonged heating.
Samples were heatsd to temperatures of 1186C and 1095~C for ~ periods o~ 100 and 170 hours.
- 30 The samples were then subjected to metallographic exam-ination by optical and stereoscan electron microscopyO No inter~
:
action layer was observed in any of the samples. The protective layer was therefore considered to inhibit migration of the cobalt into the tungsten fibres~
` ~ - 6 -.:
711~
E~MPLE ''C'' : The experiment of Example B was repeated substituting titanium nitride for hafnium nitride. When subjected to metal-lographic examination, the sample subjected to 1186C for 170 hours showed only a very thin inter action layer, less than 1 micron thick~ Here again the titanium nitride layer was considered to effectively inhibit the migration of cobalt into the tungsten at this temperature.
While the invention has been described primarily in association with tungsten alloys, it is noted that other fila-: ments as indicated earlier in the specification such as graphite and silicon carbide and molybedenum may be used which may require coating with suitable barriers as selected for the particular , combinations of filament material and alloy constituents and while the superalloys described were those having nickel or cobalt base, other alloys may be encountered, including those having an iron base as previously identified which require filament reinforcing.
` - 7 -,,,"' ~1 .``'.
.
. ~, . . . .
In the case of tungsten filaments immersed in a cobalt base alloy, there is a detrimental interaction due to the migrat-lon of cobalt into khe tungsten filaments producing intermetallic compounds which weaken the filament. In the case o~ tungsten fllaments immersed in a nickel base alloy there is a detrimental interaction due to the migration of nickel into the tungsten causing recrystallization of the tungsten alloy which reduced the strength of the filaments rendering them unsuitable as reinforce-ment.
It has been proposed to coat such filaments with a pro-jfl~1 ;bi f tective coating to ~4_}~ migration of the materials from the alloy into the filament. One example o~ the prior art was the ~ coating of tungsten filaments with tantalum carbide for use as reinforcements in cobalt base superalloys as disclosed in Septem-` ber 1973 Technical Report AD756867, Ahmad, I., et al, National ` Technical Information Service, U.S.-3-Department of Commerce, Springfield, Va. 22151. This coating, however, proved to be in-effecti~e in nickel base alloys.
SUMMARY OF THE INVENTION
~: It is an ob~ect of this invention to overcome the prior problems and weakening of the reinforcing material due to migration of alloy constituents into the reinforcing material. To this end, it has been found that hafnium carbide, hafnium nitride, titanium nitride, zirconium carbide and zirconium nitride form barriers ^ which protect the reinforcing material and inhibit migration of the undesirable components of the alloys into the reinforcing ~ibres.
It has been found, for example, that tungsten alloy ' :
filaments for use as reinforcing material in nickel base super-alloys and cobalt base superalloys may be protected from migration 0~0~4~
o~ alloy constituents, particularly of nickel from the super-alloy by coating the filament with a layer of hafnium carbide or nitride. The composite material so formed, that is, tungsten alloy filaments coated with hafnium carbide or ni-tride embedded in superalloy materials, has been found to have a useful operating temperature as high as 1176C. Titanium nitride has also been found to provide a suitable barrier layer over tungsten alloy ~ilament immersed in cobalt superalloys up to about 1095C.
In accordance with this invention, the reinforcing materials are coated with suitable protective barrier layers in accordance with the desired operating temperature and the consti-; tuents of the superalloy. A protective layer may be considered to be suitable and inhibit migration of the matrix components into the filament if, when exposed to the maximum operating temperature~
the composite article shows no evidence of detrimental migration in a 200 hour test and may therefore be predicted to have a reasonable operating life at its operating temperature. Various methods can be used to deposit these barrier layers such as '` sputtering, electron beam evaporation ion plating or chemical vapour deposition.
EXAMPLE "A"
Wires of tungsten plus 2% thoria having a diameter of 02 inches were coated with a layer of hafnium carbide about 8microns thick by means of R.F. sputtering~ The coated wires were incorporated into a nickel base superalloy Mar-M-200 by surround-ing the wires with powdered superalloy within an evacuated metal container and subjecting the filled container to hot isostatic pressure. The isostatic press provided a pressure of 12 Ksi of argon while heating -the con-tainer to 1120C. The composite struc-ture was removed from the press and cut into samplesa Each samplewas enclosed in a silica glass evacuated tube and subjected to prolonged heating~ Samples were subjected to 1065C, 1121C
:'~
~ - 4 ~
~- ` ' ,' . .
~ - ~Q7~ 2 and 1176C for 10, 30, 100, 1,000 and 27000 hours. The samples were then subjected to metallographic examination by optical and stereoscan electron microscopyO At all temperatures, samples exposed up to -100 hours showed no signs of recrystallization.
Samples exposed to 1176C for 2,000 hours showed a recrystallization zone of` only about 15 microns thickness.
The single figure of drawings illustrates an apparatus `
:' ~' , ' :~ , - 4a ~ ~i ',~
1)7a~ Z
for chemical vapour deposition of such barrier materials. The tungsten filament 3 passes through a chamber 4, preferably formed of glass, entering and exiting through mercury seals 5 and 6 which are arranged to permit the tungsten filament to pass through the seal but prevent gases from entering or leaving the chamber 4.
The wire 3 pas~es centrally down the chamber through a coaxial tube 7 which is supported and sealed to the outer wall of the chamber 4 by means of an annular member 8~ A metallic chloride generator 9 may consist simply of a chamber for retaining metall~c particles of a suitable material such as hafnium and having an open end into which hydrogen chloride gas or chlorine gas may be intro-duced. The reaction products consist of chlorides of hafnium which flow out through a tube at the bottom o~ the chamber desig-nated 11. A further inlet in the tube 12 at 13 permits the intro-duction of a suitable reactive gas and hydrogen, for example ; methane and hydrogen. The two outputs mixed at the end of tube 11 will flow into the chamber 4, down the chamber 4 to its right hand end and into the coaxial tube 7, back through the chamber 4 to its ~ar end and out through outlet 1~ which is connected to a suit-able trap, an arrangement for venting the gases. In traversing the chamber 4~ the gas flows over the filament 3.
Heating and insulating members cover the reactive areas to maintain suitable temperatures. The wire is maintained at a higher temperature by means of current passing through the wire between electrodes 15 and 16 which are immersed in the mercury seals. This current is ad~usted to maintain the wire at the des-ired temperature usually between 900 and 1300C.
To produce a nitride coating, nitrogen is substituted for the methane at inlet 13. Titanium can be added to the process by the direct introduction o~ titanium chloride which is commer-cially available.
` In order that the coatJng produced may be su~iciently . .
adherent, it will be necessary that wire be carefully cleaned, for example by treatment with triclorethylene followed by exposure to hydrogen at about 900C.
The result of -this whole process is an adherent coating two/ten microns thick of titanium nitride, hafnium nitride~ haf-nium carbide, zirconium nitride or zirconium carbide as desired.
me finished wire coated with the selected material may now be assembled together with the superalloy to produce the des-ired composite memberO me fabrication of the composite member can be accomplished by several techniques including hot isostatic ; pressing, diffusion bonding, or hot die bonding~ By proper selec-tion of the superalloy and the coating for the fibres, the com-posite structure may be designed to withstand much higher temper-atures than the matrix material. By proper selection of the coatings, the filaments may be protected from the deleterious effect of the matrix and may maintain strength even in the pres-ence of prolonged exposure to high temperatures.
- EXAMPLE "B'' Tungsten 2% thoria alloy wires .020" in diameter were coated with hafnium nitride by chemical vapour deposition to pro-duce a layer about 5 microns thicko The coated wires were sur rounded with powdered cobalt base superalloy Y~S~w~ within an evacuated metal containerO The container was subjected to hot isostatic pressing at a temperature of 1200C a~d an argon pres-sure of 10 Ksi. The composite structure was removed from the press and cut into samples each of which was placed in an evac-- uated silica glass container and subjected to prolonged heating.
Samples were heatsd to temperatures of 1186C and 1095~C for ~ periods o~ 100 and 170 hours.
- 30 The samples were then subjected to metallographic exam-ination by optical and stereoscan electron microscopyO No inter~
:
action layer was observed in any of the samples. The protective layer was therefore considered to inhibit migration of the cobalt into the tungsten fibres~
` ~ - 6 -.:
711~
E~MPLE ''C'' : The experiment of Example B was repeated substituting titanium nitride for hafnium nitride. When subjected to metal-lographic examination, the sample subjected to 1186C for 170 hours showed only a very thin inter action layer, less than 1 micron thick~ Here again the titanium nitride layer was considered to effectively inhibit the migration of cobalt into the tungsten at this temperature.
While the invention has been described primarily in association with tungsten alloys, it is noted that other fila-: ments as indicated earlier in the specification such as graphite and silicon carbide and molybedenum may be used which may require coating with suitable barriers as selected for the particular , combinations of filament material and alloy constituents and while the superalloys described were those having nickel or cobalt base, other alloys may be encountered, including those having an iron base as previously identified which require filament reinforcing.
` - 7 -,,,"' ~1 .``'.
.
. ~, . . . .
Claims (8)
1. A composite member comprising a high temperature metal alloy matrix and a plurality of reinforcing filaments, a layer constituting a barrier for inhibiting migration of constituents into said filaments from said matrix at temperatures above 1000°C, said layer material surrounding said filaments selected in the group consisting of hafnium nitride, titanium nitride and zirconium nitride.
2. A composite member as claimed in claim 1 wherein said filaments consist primarily of tungsten.
3. A composite member as claimed in claim 1 wherein said matrix is a nickel base superalloy.
4. A composite member as claimed in claim 1 wherein said matrix is a cobalt base superalloy.
5. A composite member as claimed in claim 1 wherein said matrix is an iron base superalloy.
6. A composite member as claimed in claim 2 wherein said matrix is a nickel base superalloy.
7. A composite member as claimed in claim 2 wherein said matrix is a cobalt base superalloy.
8. A composite member as claimed in claim 2 wherein said matrix is an iron base superalloy.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA228,901A CA1070142A (en) | 1975-06-09 | 1975-06-09 | Superalloy composite structure |
| DE19762619394 DE2619394A1 (en) | 1975-06-09 | 1976-04-30 | COMPOSITE OBJECTS FOR USE IN HIGH TEMPERATURES |
| IT2327676A IT1063254B (en) | 1975-06-09 | 1976-05-14 | STRUCTURE SUITABLE FOR OPERATION AT HIGH TEMPERATURES CONSTITUTED BY SUPERLEGHE |
| FR7616328A FR2314257A1 (en) | 1975-06-09 | 1976-05-31 | ARMED SUPERALLIES |
| GB2358876A GB1518416A (en) | 1975-06-09 | 1976-06-08 | Reinforced superalloy member |
| JP6667076A JPS51149118A (en) | 1975-06-09 | 1976-06-09 | Composite body structures |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA228,901A CA1070142A (en) | 1975-06-09 | 1975-06-09 | Superalloy composite structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1070142A true CA1070142A (en) | 1980-01-22 |
Family
ID=4103291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA228,901A Expired CA1070142A (en) | 1975-06-09 | 1975-06-09 | Superalloy composite structure |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS51149118A (en) |
| CA (1) | CA1070142A (en) |
| DE (1) | DE2619394A1 (en) |
| FR (1) | FR2314257A1 (en) |
| GB (1) | GB1518416A (en) |
| IT (1) | IT1063254B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015533A (en) * | 1988-03-10 | 1991-05-14 | Texas Instruments Incorporated | Member of a refractory metal material of selected shape and method of making |
| GB2219006A (en) * | 1988-05-26 | 1989-11-29 | Rolls Royce Plc | Coated fibre for use in a metal matrix |
| DE29519066U1 (en) * | 1995-12-01 | 1996-01-25 | Schunk Kohlenstofftechnik GmbH, 35452 Heuchelheim | Device for guiding molten glass, in particular a drop of glass |
| CN109207786B (en) * | 2018-11-01 | 2020-08-07 | 西北工业大学 | Zr3Al3C5-ZrAlxSiyMethod for preparing composite material |
| CN115354279B (en) * | 2022-08-24 | 2023-11-17 | 西安电子科技大学 | Diffusion shielding layer applied between monocrystal nickel-based alloy and surface thermal barrier coating and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3437511A (en) * | 1966-04-07 | 1969-04-08 | Us Air Force | Metal surfaced with boron and coating of silicon,silicon carbide or titanium nitride |
| CH528596A (en) * | 1970-07-03 | 1972-09-30 | Bbc Brown Boveri & Cie | Process for the production of metal reinforced with carbon fibers |
| DE2136405A1 (en) * | 1970-07-31 | 1972-02-03 | Gen Electric | Process for protecting interfaces |
| GB1472479A (en) * | 1973-05-23 | 1977-05-04 |
-
1975
- 1975-06-09 CA CA228,901A patent/CA1070142A/en not_active Expired
-
1976
- 1976-04-30 DE DE19762619394 patent/DE2619394A1/en not_active Withdrawn
- 1976-05-14 IT IT2327676A patent/IT1063254B/en active
- 1976-05-31 FR FR7616328A patent/FR2314257A1/en active Granted
- 1976-06-08 GB GB2358876A patent/GB1518416A/en not_active Expired
- 1976-06-09 JP JP6667076A patent/JPS51149118A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE2619394A1 (en) | 1976-12-23 |
| GB1518416A (en) | 1978-07-19 |
| IT1063254B (en) | 1985-02-11 |
| JPS5646547B2 (en) | 1981-11-04 |
| FR2314257B1 (en) | 1980-12-12 |
| JPS51149118A (en) | 1976-12-21 |
| FR2314257A1 (en) | 1977-01-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |