CN1300064C - Surface alloying ceramic and its preparing process - Google Patents
Surface alloying ceramic and its preparing process Download PDFInfo
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- CN1300064C CN1300064C CNB2004100125751A CN200410012575A CN1300064C CN 1300064 C CN1300064 C CN 1300064C CN B2004100125751 A CNB2004100125751 A CN B2004100125751A CN 200410012575 A CN200410012575 A CN 200410012575A CN 1300064 C CN1300064 C CN 1300064C
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Abstract
The present invention relates to surface alloying ceramics and a preparation method thereof, which relates to the technology of ceramics surface modification and the preparation field of composite materials. By using a composite target designed by the method of the present invention, common ceramics is carried out with surface alloying in an arc glowing furnace. The composite target is in a mechanical combination by active metal titanium (or zirconium, hafnium) and one or several kinds of other required metal materials (such as iron, chromium, nickel, manganese, molybdenum, copper, aluminum, silver, etc.) according to certain proportions. The composite target is evaporated or melted under the action of arc heat, and metal ions impact a ceramics surface at high speed under the action of a high electric field. The present invention has the advantages of quick cementation speed and high bond strength, and the thickness of an alloy layer can reach more than 100 mu m. the method can realize the preparation of surface alloying ceramics with different types and laminar composite materials.
Description
One, technical field
Surface alloying ceramic of the present invention and preparation method relate to ceramic surface modification technology and Composite Preparation
Technical field.
Two, background technology
Stupalith has many advantages, and good etc. as high temperature resistant, corrosion-resistant, high rigidity, wear-resistant and electrical insulating property, therefore, stupalith has obtained widespread use.But because pottery has inevitable shortcoming,, intensity crisp as property is disperseed and poor processability etc., has limited the further use of pottery.With the ceramic surface alloying, forming surface alloying ceramic is to maximize favourable factors and minimize unfavourable ones to enlarge the main path of ceramic applications.Thereby surface alloying ceramic has broad application prospects.
The greatest difficulty of ceramic surface metallization is because stupalith is different with the bonding mechanism of metallic substance, and stupalith is a covalent linkage, and metallic substance is a metallic bond, so metal is difficult in the ceramic material surfaces wetting and spreading.Therefore also just produced the method for many ceramic surface metallizations, wherein Mn-Mo method and vapour deposition process are the most frequently used methods.The Mn-Mo method is in the sintering process process of complexity, and at ceramic surface, such metallization processes descends ceramic surface smooth finish with Mn and Mo powdered material sintering, and performance reduces; The characteristics of vapor deposited metal method are that pottery is without undergoing high temperature, can guarantee the dimensional precision of part, metalized film is fine and close continuously, thermal conductivity is good, high-frequency loss is little, the intensity height, but only can deposit single metallic element, so can only be called the ceramic surface metallization method, owing to there is not the effect of active element, metal level is lower with the bonding strength of pottery in addition.
Advantageous effect based on active element titanium and ceramic chemical reaction, the arc-added glow that applicant was once carried out ceramic surface oozes titanium, but such method only makes ceramic surface realize titanium metalization, metallic element is single, conformability is relatively poor, and because the oxyphie ability of titanium is stronger, layer of titanium metal forms oxide film and is unfavorable for follow-up application process easily by atmospheric oxidn.As being connected of on this basis pottery and metal, because the titanium layer of ceramic surface plating is difficult to all react with solder and mix in brazing process, ceramic side at pottery and metal jointing has kept one deck titanium layer, solder and the wetting of pottery and reaction have been influenced, directly influenced the strength of joint of pottery with metal, the existence of a large amount of intermetallic compound of ceramic side increases joint fragility in the joint, occurs cracking under the unrelieved stress effect easily.
Therefore in order further to enlarge the range of application of pottery, finding out a kind of conveniently surface alloying ceramic preparation method, is imperative.
Three, summary of the invention
Surface alloying ceramic of the present invention and preparation method's purpose is to utilize existing conventional ceramic to prepare surface alloying ceramic, conventional ceramic by the present invention designed composition target and processing method after, make conventional ceramic surface plating one deck contain one or more the alloy layer with required composition performance in reactive metal titanium, zirconium or hafnium and required metallic substance iron, chromium, nickel, manganese, molybdenum, copper, aluminium or the silver, surface alloying ceramic has metallicities such as conduction, thermal conductivity on its surface.Further utilize surface alloying ceramic on this basis, realize that pottery is connected with the high quality soldering of metal.
Surface alloying ceramic of the present invention, it is characterized in that it being that a kind of composition target that utilizes carries out Alloying Treatment to the conventional ceramic surface in the arc-added glow stove, make conventional ceramic surface plating one deck contain one or more alloy layer in reactive metal titanium, zirconium or hafnium and required metallic substance iron, chromium, nickel, manganese, molybdenum, copper, aluminium or the silver, its surface has the surface alloying ceramic of conduction, conductive metal performance.
The preparation method of above-mentioned surface alloying ceramic, it is characterized in that the composition target that utilizes the present invention to design, in the arc-added glow stove, conventional ceramic is carried out surface alloying, composition target evaporates under the effect of arc heat or melts, metal ion under high effect of electric field high-speed impact at ceramic surface, and process spreads and chemical metallurgy reacts plating at ceramic surface, the alloy layer that the ceramic surface acquisition is made up of these metallic elements, preparation technology parameter is: final vacuum is less than 6Pa, operating air pressure 10～20Pa, the working medium argon gas, glow voltage 300～900V, flame current 40～100A, plating time 10～50min, this method can realize the preparation of broad variety surface alloying ceramic and laminated composite materials.
The preparation method of above-mentioned surface alloying ceramic, it is characterized in that described composition target is by one or more machinery combinations in proportion in reactive metal titanium, zirconium or hafnium and other required metallic substance iron, chromium, nickel, manganese, molybdenum, copper, aluminium or the silver, calculate from usable floor area, the shared ratio of metal titanium, zirconium or hafnium is 10～40%, and other metallic element proportion is different different because of alloying constituent respectively.
The preparation method of above-mentioned surface alloying ceramic, it is characterized in that in the arc-added glow stove, conventional ceramic being carried out surface alloying, use common Ag-Cu solder, do not need brazing flux, its glow soldering processing parameter is: final vacuum is less than 6Pa, operating air pressure 10～20Pa, glow voltage 300～900V, 750～900 ℃ of brazing temperatures, soaking time 5～15min, working medium argon gas.
The preparation method of above-mentioned surface alloying ceramic is characterized in that described stupalith is Si
3N
4, ZrO
2, Al
2O
3, a kind of among the SiC.
The purpose of preparation surface alloying ceramic is exactly in order to be connected with the metallic substance soldering, in the selection of composition target, also can consider especially, as select Cu and Ti binary composition target or Ag, Cu and Ti ternary composition target, form Cu-Ti binary alloy or Ag-Cu-Ti ternary alloy at ceramic surface, these two kinds of materials itself are exactly good solder, thereby help the soldering connection of surface alloying ceramic/metal.So not only save solder, and can carry out soldering to it in (under the atmospheric condition) under the multiple envrionment conditions.
Adopt this preparation method also can carry out surface alloying, can form two-sided alloying ceramic the flaky pottery two sides.Also can and weld together, form laminated composite materials two-sided alloying ceramic stack, shown in Figure 5 as accompanying drawing.
This preparation method compares and has the following advantages with existing ceramic metallization method, ceramic/metal method for welding:
1. the metallization and the alloying that help ceramic surface form surface alloying ceramic, have further widened ceramic range of application.
2. avoid single ooze titanium layer obstruction and embrittlement influence, helped alloy layer and ceramic chemical reaction, improved interface bond strength, reduced the interfacial stress intensity;
3. the composite impregnation-plating alloy layer is difficult for by atmospheric oxidn.
4. surface alloying ceramic can be under lower vacuum degree condition, even can realize in atmospheric environment that soldering connects; Utilize normal solder to carry out soldering, can obtain good welding joint.
5. preparation speed is fast, the efficient height.
Four, description of drawings
Fig. 1 is surface alloying ceramic of the present invention and the used arc-added glow vacuum oven of preparation method equipment synoptic diagram.1 is cooling circulating water; 2 for plate target be composition target; The 3rd, the furnace wall is the chuck form, inner logical water coolant 1; 4 is additional cathode, plays the heat tracing effect; 5 is the negative electrode pedestal; 6 is seal washer; 7 ceramic workpieces; 8 are the striking hook, are used to light electric arc and pilot arc; 9 is arc power; 10 is the aura power supply.
Fig. 2 is the section of structure of the composition metal target that adopts among surface alloying ceramic of the present invention and the preparation method.
Fig. 3 is the upward view of the composition metal target that adopts among surface alloying ceramic of the present invention and the preparation method.Component difference according to required alloying, material 11,12,13,14 can be in titanium, zirconium or hafnium active element material and iron, copper, nickel, chromium, manganese, aluminium, molybdenum etc. one or more, generally speaking, consider from economic angle, outmost turns is more cheap material, and inner ring is precious materials.For stupalith, active element is indispensable, because they can carry out certain chemical reaction with pottery.11,12,13,14 material proportions are pressed area and are calculated, because of stupalith different different and different with required alloy layer component.
Fig. 4 is a method for welding synoptic diagram of the present invention.15 is surface alloying ceramic, and 16 is alloy layer, and 17 is solder, and 18 is metal (or surface alloying ceramic).Surface alloying ceramic 15, solder 17 and metal 18 are assembled, put into glow soldering stove or vacuum oven, the processing parameter according to afore mentioned rules carries out the soldering connection then.
Fig. 5 is the ceramic/metal laminated composite materials.19 is pottery; 20 is metallic substance;
Five, embodiment
Surface alloying Al
2O
3The preparation of pottery, purpose is used for surface conduction.
Pottery is Al
2O
3, composition target adopts titanium, copper, three kinds of components of aluminium, is arranged as copper, aluminium, titanium material from outside to inside, and area ratio is 30～40%, 30～40%, 20～40%.The processing parameter of ceramic surface alloying is:
Final vacuum 6Pa glow voltage 600V
Flame current 60A plating time 30min
The working medium argon gas
Al
2O
3The ceramic surface alloy layer thickness is 20 μ m, has excellent conducting performance.
Surface alloying ceramic is used for little connection
Stupalith is Al
2O
3, metal is the aluminium foil behind the 15 μ m, and composition target adopts aluminium, two kinds of compositions of titanium, and employing aluminium is the outer ring, and titanium is an inner ring, the area ratio of aluminium, titanium is 60～80%, 20～40% in the composition target.Surface alloying ceramic is put into vacuum oven with metal and solder and is connected.
Ceramic surface alloying and be with the processing parameter of the soldering of metal:
Final vacuum 6Pa operating air pressure 20Pa
Glow voltage 700V flame current 60A
500 ℃ of plating time 50min brazing temperatures
Soaking time 10min working medium argon gas
Al
2O
3Ceramic surface cemented alloy layer thickness is 10～20 μ m, and the soldering result shows Al
2O
3Ceramic/metal aluminium foil joint flawless, entire joint face is the junction invariably, and the brazed joint slip resistance is 100MPa.
The rough vacuum soldering of surface alloying ceramic and metal is used for ceramic/metal and connects
Stupalith is Si
3N
4, metallic substance is carbon steel Q235, composition target adopts copper, titanium, three kinds of compositions of iron, employing copper is the outer ring, titanium copper is an inner ring, and the area ratio of copper, titanium, iron is 40～60%, 20～40%, 10～40%, and surface alloying ceramic and metal and Ag-Cu solder are put into vacuum oven and carried out soldering.
Ceramic surface alloying and be with the processing parameter of the soldering of metal:
Final vacuum 6Pa operating air pressure 20Pa
Glow voltage 700V flame current 60A
850 ℃ of plating time 50min brazing temperatures
Soldering vacuum tightness 5 * 10
-2Pa soaking time 10min
The working medium argon gas
The ceramic surface alloy layer thickness is 30 μ m, and the brazed joint quality is good, Si
3N
4The pottery flawless, entire joint face is the junction invariably, and the brazed joint slip resistance is 300MPa.
Si
3N
4With ZrO
2Rough vacuum soldering after the ceramic surface alloying
Pottery is Si
3N
4And ZrO
2, Si
3N
4Composition target adopts copper, titanium, three kinds of elements of nickel during the ceramic surface alloying, and employing copper is the outer ring, and nickel is inner ring, and copper, titanium, nickel ratio are respectively 40～60%, 20～40%, 10～40%, ZrO
2Composition target is selected zirconium, chromium, three kinds of elements of nickel for use during the ceramic surface alloying, and the ratio that zirconium, chromium, nickel account for respectively is 20～40%, 40～60%, 15～30%, and the ceramic solder behind the surface alloying is put into vacuum oven and carried out soldering.Its processing parameter is:
Final vacuum 6Pa operating air pressure 20Pa
Glow voltage 800V flame current 60A
930 ℃ of plating time 40min brazing temperatures
Soldering vacuum tightness 0.5Pa soaking time 10min
The working medium argon gas
The ceramic surface alloy layer thickness is 30 μ m, and soldering is the good joint of obtained performance as a result, Si
3N
4And ZrO
2The ceramic joint flawless, entire joint face is the junction invariably, and the brazed joint slip resistance is 230MPa.
Al
2O
3After the ceramic surface alloying with the arc-added glow soldering of metal
Pottery is Al
2O
3Metal is carbon steel Q235B, and composition target adopts titanium, nickel, three kinds of compositions of aluminium, and the employing titanium is the outer ring, the ratio that titanium, nickel, aluminium account for respectively is 20～40%, 20～40%, 30～50%, and pottery after the alloying and metal and solder are put into the aura stove and carried out glow soldering.Ceramic surface alloying and be with the processing parameter of the glow soldering of metal:
Final vacuum 6Pa operating air pressure 20Pa
Glow voltage 600V flame current 60A
900 ℃ of plating time 40min brazing temperatures
Soaking time 10min working medium argon gas
The ceramic surface alloying layer thickness is about 35 μ m, and soldering is the good joint of obtained performance as a result, Al
2O
3The pottery flawless, entire joint face is the junction invariably, and the brazed joint slip resistance is 210MPa.
ZrO
2After the ceramic surface alloying with metal soldering under atmospheric condition
Pottery is ZrO
2Metal is carbon steel Q235B, and composition target adopts zirconium, iron, three kinds of compositions of nickel, adopts nickel, is the outer ring, the ratio that zirconium, iron, nickel account for respectively is 20～40%, 40～60%, 15～20%, and pottery behind the surface alloying and metal carry out soldering under atmospheric condition.Ceramic surface alloying and be with the brazing process parameter of metal:
Final vacuum 6Pa operating air pressure 20Pa
Glow voltage 700V flame current 60A
920 ℃ of plating time 20min brazing temperatures
Soaking time 10min working medium argon gas
The ceramic surface alloying layer thickness is about 30 μ m, and soldering is the good joint of obtained performance as a result, ZrO
2The pottery flawless, entire joint face is the junction invariably, and the brazed joint slip resistance is 180MPa.
Al
2O
3Ceramic laminated material preparation
Pottery is sheet Al
2O
3, composition target adopts titanium, copper, aluminium, four kinds of compositions of silver, and employing copper is the outer ring, and the ratio that titanium, copper, aluminium, silver account for respectively is 20～40%, 40～60%, 15～20%, 5～10% couples of sheet Al
2O
3Two-sided surface alloying is stacked together 3 two-sided alloying ceramics then, carries out soldering in vacuum oven.
Ceramic surface alloying and be with the brazing process parameter of metal:
Final vacuum 6Pa operating air pressure 20Pa
Glow voltage 700V flame current 60A
920 ℃ of plating time 20min brazing temperatures
Soaking time 10min working medium argon gas
Soldering vacuum tightness 0.5Pa
The ceramic surface alloying layer thickness is that bonding surface is the junction invariably about 40 μ m.
Claims (2)
1, a kind of preparation method of surface alloying ceramic is characterized in that: utilize composition target in the arc-added glow stove to Si
3N
4, ZrO
2, Al
2O
3Or SiC carries out the surface alloying processing, composition target evaporates under the effect of arc heat or melts, metal ion under high effect of electric field high-speed impact in ceramic material surfaces, and process spreads and chemical metallurgy reacts plating at described ceramic surface, processing parameter is: final vacuum is less than 6Pa, operating air pressure 10～20Pa, the working medium argon gas, glow voltage 300～900V, flame current 40～100A, plating time 10～50min, wherein composition target is by titanium, zirconium or hafnium and iron, chromium, nickel, manganese, molybdenum, copper, one or more compositions in aluminium and the silver, by usable floor area, titanium, zirconium or hafnium proportion are 10～40%.
2, the Si that makes according to the described surface alloying ceramic preparation method of claim 1
3N
4, ZrO
2, Al
2O
3Or SiC surface alloying ceramic.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100125751A CN1300064C (en) | 2004-09-30 | 2004-09-30 | Surface alloying ceramic and its preparing process |
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| CNB2004100125751A CN1300064C (en) | 2004-09-30 | 2004-09-30 | Surface alloying ceramic and its preparing process |
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| CNB2006101258482A Division CN100434218C (en) | 2004-09-30 | 2004-09-30 | Application method of surface alloying ceramic |
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| CN1300064C true CN1300064C (en) | 2007-02-14 |
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| CN104372231B (en) * | 2014-10-23 | 2016-08-24 | 苏州莱特复合材料有限公司 | A kind of corrosion resistant cermet material and preparation method thereof |
| CN109317810B (en) * | 2018-09-11 | 2019-11-12 | 南京航空航天大学 | A kind of raising Si3N4The surface treatment method of ceramics and titanium alloy welding performance |
| CN113857606B (en) * | 2021-11-01 | 2022-09-30 | 哈尔滨工业大学 | Low-temperature sealing method and sealing joint for sapphire optical window |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6437482A (en) * | 1987-08-04 | 1989-02-08 | Nippon Steel Corp | Metallizing of ceramic |
| JPH05148067A (en) * | 1991-11-26 | 1993-06-15 | Tokin Corp | Ceramic substrate and its production |
| JPH0637482A (en) * | 1992-04-23 | 1994-02-10 | Toutan Seimitsu Kk | Jig for assembling electronic parts and its manufacture |
| CN1364748A (en) * | 2002-01-31 | 2002-08-21 | 中国科学院上海硅酸盐研究所 | Combining method for aluminium nitride and copper |
-
2004
- 2004-09-30 CN CNB2004100125751A patent/CN1300064C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6437482A (en) * | 1987-08-04 | 1989-02-08 | Nippon Steel Corp | Metallizing of ceramic |
| JPH05148067A (en) * | 1991-11-26 | 1993-06-15 | Tokin Corp | Ceramic substrate and its production |
| JPH0637482A (en) * | 1992-04-23 | 1994-02-10 | Toutan Seimitsu Kk | Jig for assembling electronic parts and its manufacture |
| CN1364748A (en) * | 2002-01-31 | 2002-08-21 | 中国科学院上海硅酸盐研究所 | Combining method for aluminium nitride and copper |
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