CN103524148B - A kind of manufacture method of surface metallised ceramic - Google Patents
A kind of manufacture method of surface metallised ceramic Download PDFInfo
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- CN103524148B CN103524148B CN201310481491.1A CN201310481491A CN103524148B CN 103524148 B CN103524148 B CN 103524148B CN 201310481491 A CN201310481491 A CN 201310481491A CN 103524148 B CN103524148 B CN 103524148B
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Abstract
The invention discloses surface metallised ceramic and manufacture method thereof.The method comprises following operation steps: immersed in the metalized face of pottery in aluminum or aluminum alloy liquation, and make its relative liquation motion with the metalized face making described aluminum or aluminum alloy liquation soak pottery, again liquation is shifted out in the metalized face of pottery, the aluminium of surface adhesion or aluminium alloy liquid film are freely cooled, obtains the pottery that surface is connected with aluminum or aluminum alloy film.Compared with prior art, the interface in the present invention between pottery and aluminum or aluminum alloy film does not have amorphous oxide inclusion, and aluminum or aluminum alloy crystal grain is together with ceramic crystalline grain direct growth; The film dense internal organization formed, does not have oxide inclusion; The aluminum or aluminum alloy film thickness formed is several microns and arrives some tens of pm, and firm difficult drop-off, experiment proves that aluminum or aluminum alloy film is split stripping strength with ceramic chessboard and is more than or equal to 4.1N/cm.The present invention has broad application prospects in ceramic surface metallization field.
Description
The divisional application that the application is application number is 200910083280.6, the applying date is on April 30th, 2009, invention and created name is " a kind of surface metallised ceramic and manufacture method thereof ".
Technical field
The present invention relates to a kind of surface metallised ceramic and manufacture method thereof.
Background technology
Pottery has good heat conduction and insulating property, is a kind of good packaged material.Generally need during use to carry out surface metalation process to pottery, to make circuit or welding electronic component.Traditional method for surface metallation has Precious Metal sintering process, Mo-Mn method, DBC method and active metal brazing method.Wherein Precious Metal sintering process is that noble metal powder is added binding agent etc. again as silver powder and glass powder mixing, is mixed with slurry, is coated in ceramic surface, then form noble metal surface layer at about 900 DEG C sintering; Mo-Mn method is that molybdenum powder and oxidation manganese powder are hybridly prepared into slurry, is coated in ceramic surface, then forms surface metal molybdenum layer at 1500 DEG C of sintering; DBC method be by oxygen-bearing copper or surface oxidation after no-oxygen copper plate and ceramic plate lamination, be then heated to about 1070 DEG C in an inert atmosphere, copper material surface formed Cu-Cu
2o eutectic liquation, utilizes this liquation pottery and copper material to be linked together as solder; Active metal brazing method is that silver, copper, titanium valve etc. are mixed with slurry, is coated in ceramic surface, then superposes copper material, be heated to about 850 DEG C in a vacuum, makes silver-copper-titanium braze fusing, pottery and copper coin is brazed together.The metal level that Precious Metal sintering process and Mo-Mn method are formed is thinner, is mainly used in the light current device package such as CPU; And DBC method and active metal brazing method can form thicker copper conductive layer, be mainly used in power electronic devices, as the encapsulation of IGBT module.
Aluminium is a kind of good electro-conductive material, is widely used in integrated circuit wiring.In addition, the yield strength of aluminium is lower, substitutes the thermal stresses that copper can reduce surface metallised ceramic intralamellar part, improve its thermal shock resistance with aluminium.But because the chemical property of aluminium is very active, in the equilibrium partial pressure of itself and the oxygen temperature range below 1000 DEG C, be less than 10
-40pa, even if obtainable most high vacuum also cannot stop aluminum oxidation at present.By the impact of the primary oxide film in aluminium surface, the wettability of aluminium and pottery is poor; The interface of linker pottery and aluminium also exists amorphous oxide inclusion of aluminium, produce a large amount of macroscopic views and do not connect defect, large [the X.S.Ning of mechanical property variation of linker, T.Okamoto, Y.Miyamoto, A.Koreeda, K.Suganuma, and S.Goda, Bond strengthand interfacial structure of silicon nitride joints brazed withaluminium-silicon and aluminium-magnesium alloys, Journal of MaterialsScience, 26 volumes (1991) 2050-2054 page; E.Saiz; A.P.Tomsia; K.Sugamuma, Wetting and strength issues at Al/ α-alumina interfaces, J.European CeramicSociety 23 (2003) 2787-2796], affect its practical application.In order to eliminate the impact of aluminium surface film oxide, the human hairs such as Ning Xiaoshan understand interface non-oxidation method of attachment [X.S.Ning, C.Nagata, M.Sakuraba, T.Tanaka, K.Suganuma, M.Kimura; Chinese Patent No.68064, US Patent No.5965193, Korean Patent No.201887, Jpn Patent No.2918191, DE69529185T2, EU0676800B1].The feature of the method is inserted by ceramic plate in aluminum melt to move with the oxide film removing aluminium surface, and ceramic surface is soaked by aluminum melt, then aluminum melt casting is connected on ceramic plate by the method for casting.Adopt the method can realize pottery to be connected with the high-performance of aluminium, cover aluminium base with the pottery that this method is produced and there is excellent thermal shock resistance [X.S.Ning, M.Kimura, M.Sakuraba, C.Nagata, Jpn PatentNo.3430348; US Patent No.6183875], for the encapsulation of Hybrid Vehicle IGBT module.But aforesaid method is existing defects also, namely preparing film, particularly thickness, to be less than the film of 0.1mm more difficult.This be due to the method use casting mold, and casting mold must choose do not react with aluminium, non-wetted material, if casting mold gap is too small, then aluminium liquid cannot enter casting mold, so can not produce film.
Summary of the invention
As everyone knows, mobile can drive the liquid motion of periphery.According to interface non-slip amount of movement transmission theory, following relationship [D.R.Poirier and G.H.Geiger is there is between the thickness (δ) of the fluid (momentum boundary layer) that the object moved in a fluid drags and the viscosity (η) of speed of relative movement (V) and fluid, " TransportTransport Phenomena in Material Processing ", TMS, (1994): P62-67]:
Wherein ρ is the density of fluid, and L is solid characteristic length in the movement direction.
Fig. 1 is the liquid film of mobile and surface adhesion force analysis schematic diagram when departing from fluid surface.Assuming that the viscosity of liquid is enough large, liquid film is regarded as an entirety, then the reactive force that liquid film is subject to has: the bonding force of liquid and object interface; The gravity of liquid film self; Surface tension suffered during liquid film disengaging fluid surface.If the translational speed of object changes, liquid film also can be subject to the effect of the mass force that acceleration produces.Obviously, gravity, surface tension and mass force all hinder liquid film with object of which movement, and only have the bonding force of liquid and object interface to be greater than their sums, object could drag liquid film and move together.Therefore, adopt the method for dipping to form liquid film at solid surface, its key is to have enough large bonding force between liquid film and solid, ensures that interface does not produce slippage.Otherwise just there will be snowslide phenomenon once generation slippage, liquid film is all come off.
Due to the size of interface binding power and the bonding state of liquid and solid interface closely related, and the character of the bonding state at interface and liquid, the character of solid surface, temperature, liquid and solid contact time etc. are relevant; The surface tension liquid body composition of liquid, the impact of ambiance; And the weight of liquid film also has very big-difference because of the kind difference of liquid, therefore cannot predict and whether can form specific liquid film on particular solid surface.
Contriver is through large quantity research, find the metalized face of pottery to immerse in aluminum or aluminum alloy liquation to move, make the metalized face of the fully wetting pottery of aluminum or aluminum alloy liquation, and then it is shifted out aluminum or aluminum alloy liquation lentamente, cooling, one deck can be formed at ceramic surface to bond firmly aluminum or aluminum alloy film, thus complete the present invention.That is:
An object of the present invention is to provide the pottery that a kind of surface is connected with aluminum or aluminum alloy film.
Described aluminum or aluminum alloy film is solidified by the continuous liquid film of the aluminum or aluminum alloy sticked on pottery and forms, and its thickness is between several microns ~ some tens of pm.
The non-crystal oxide that the linkage interface of described pottery and aluminum or aluminum alloy film does not exist from aluminium surface native oxide is mingled with, and aluminum or aluminum alloy crystal grain is together with ceramic crystalline grain direct growth.
Described aluminum or aluminum alloy film is split stripping strength with the chessboard of pottery and is greater than 4.1N/cm.
Another object of the present invention is to provide a kind of method making ceramic surface connect aluminum or aluminum alloy film.
The method making ceramic surface connect aluminum or aluminum alloy film provided by the present invention, comprise following operation steps: immersed in the metalized face of pottery in aluminum or aluminum alloy liquation, and make its relative liquation motion with the metalized face making aluminum or aluminum alloy liquation soak pottery, and then liquation is shifted out in the metalized face of pottery, make aluminium or the aluminium alloy liquid film unfettered ground natural condensation of its surface adhesion, obtain surface and be connected with several microns ~ tens of microns thickness, fine and close aluminium or the pottery of aluminum alloy films.
Wherein, described pottery moves vertically upward by the described metalized face of the pottery method immersed in aluminum melt or molten aluminium alloy specifically being can be after the container bottom filling described aluminum or aluminum alloy liquation inserts liquation inside.
Described pottery can be oxide ceramics, nitride ceramics or carbide ceramics.
Described operation is best to be carried out in vacuum or inert gas atmosphere.
The pottery that the surface that aforesaid method obtains connects aluminum or aluminum alloy film also belongs to protection scope of the present invention.Described surface connects the pottery of aluminum or aluminum alloy film, and its pottery does not have non-crystal oxide with the linkage interface of aluminum or aluminum alloy.
Compared with prior art, the pottery of the present invention's aluminum or aluminum alloy film that surface adhesion can be provided to have several microns ~ tens of microns thickness.This film is that the microdefects such as inside does not have oxide film to be mingled with, pore, therefore have the good physical and mechanical properties that fine aluminium possesses by the continuous aluminum or aluminum alloy liquid film natural coagulation of uniform adhesion at ceramic surface.Figure 3 shows that the high resolution transmission electron microscope image of interface and the electron diffraction spot of each microcell of the linker of alumina-ceramic and the aluminium adopting the method that pottery is immersed movement in aluminium liquid to prepare.Therefrom can find out, this interface does not have common soldering interface non-crystal oxide that is ubiquitous, that be derived from the primary oxide film in aluminium surface to be mingled with, and [relevant common method for brazing interfacial oxide is mingled with can referring to following documents: X.S.Ning, K.Suganuma, M.Morita and T.Okamoto, Interfacial reaction betweensilicon nitride and aluminium, Philosophical Magazine letter, 55 volumes, (1987), 93-96 page; E.Saiz; A.P.Tomsia; K.Sugamuma, Wetting and strength issuesat Al/ α-alumina interfaces, Journal of European Ceramic Society, 23 volumes (2003) 2787-2796 page], illustrate that the present invention effectively removes the primary oxide film on aluminium surface.It can also be seen that from this figure, aluminium and aluminum oxide react, define coherent interface layer ((104) crystal face of the alumina layer of Interface debond and (104) face coherence of original alumina-ceramic crystal grain, (110) (111) face half coherence of face and aluminium), together with aluminium and pottery grow on an atomic scale.Theoretical Calculation shows: the coherent interface of aluminum oxide and aluminium has lower interfacial free energy and very high bonding force [W.Zhang; J.R.Smith; Nonsoichiometric Interfaces and Al
2o
3adhension with Al and Ag, PhysicalReview Letters, 85 volumes (2000) 3225-3228 page].These results of study show, adopt method of the present invention, can prevent interface from producing oxide inclusion, make aluminum or aluminum alloy film be grown directly upon ceramic surface, therefore firm difficult drop-off.The inventive method is simple to operate, time saving and energy saving, simple and practical.Therefore, the inventive method has broad application prospects in ceramic surface metallization field.
Accompanying drawing explanation
Fig. 1 is the applied external force schematic diagram that the liquid film of Solid Surface Adhesion is subject to.
Fig. 2 is the structural representation of ceramic surface metallization device.
Fig. 3 is the high resolution transmission electron microscope image microzone electron diffraction spot in the linkage interface region of alumina-ceramic and aluminium.
Embodiment
Inventive embodiments commercial-purity aluminium used, Al-20%Si aluminum silicon alloy, pure magnesium and all stupaliths obtain all from commercial channels.The Al-20%Si alloy that aluminium alloy adopts commercial sources to obtain, pure magnesium, fine aluminium melt formulated.
The ceramic surface metallization apparatus structure used in section Example of the present invention is as shown in Figure 2:
This device is made up of body of heater 1, bell 2, plumbago crucible 3, metallic resistance silk heating member 4, graphite guide rail 5, nitrogen inlet 6; Plumbago crucible is located in body of heater, and heating member is located at plumbago crucible surrounding; Bottom plumbago crucible, bottom of furnace body and bell are equipped with the opening matched with guide rail, three openings are coaxial; Guide rail is arranged in plumbago crucible by opening, between body of heater and bell, and to be fixedly connected with them; Guide rail is two parallel plates, and its inside is provided with the groove passed through for ceramic plate, and is provided with window 8 in the position that it is positioned at crucible inside, contacts with the ceramic plate 7 in guide rail to make the aluminium alloy solution 9 in crucible; In order to prevent graphite oxidation from burning, body of heater and bell junction silica gel sealing, pass into nitrogen protection in stove.
Gap between the guide rail of beneath window and ceramic plate is 0.1mm, and this gap can ensure that pottery moves freely in guide rail, and aluminium liquid can not flow out.Guide rail above window and the gap between ceramic plate are 1.3mm, can ensure that the aluminium liquid of ceramic plate surface adhesion does not contact with guide surface like this, can solidify by naturally cooling.
Embodiment 1, adopt above-mentioned ceramic surface metallization device, fine aluminium (99.9%) is put into plumbago crucible, by alumina ceramic plate (long 137mm, wide 35mm, thick 0.64mm, Guangdong section of Tsing-Hua University produces, and aluminum oxide purity is greater than 95%) be inserted through in the graphite guide rail of crucible, then (nitrogen flow rate is 20 liters/min) heating in nitrogen atmosphere, makes aluminium melt and is warmed up to 730 DEG C.Another block alumina ceramic plate is inserted guide rail from the guide rail entrance of device bottom with the speed of 68.5mm/min, promotes to insert in advance ceramic plate in guide rail with same speed upward vertical movement.In moving process, ceramic plate is contacted with the aluminum melt in crucible by the window on guide rail, then releases from guide upper together with the aluminum melt of surface adhesion, and cooling, respectively forms the aluminium film that thickness is about the densification of 6 microns on the two sides of ceramic plate.Metallurgical analysis shows, aluminium film inside does not have the defect such as oxide inclusion and pore.
With blade, aluminium film is cut into the checkerboard square of 1mm × 1mm.Be crimped on this checkerboard aluminium film with mightiness belt (Minnesota Mining and Manufacturing Company produces, and cohesive force is greater than 4.1N/cm), then tear fast, measure the cohesive strength of aluminium film.
3 repetitions are established in experiment, and result shows, the expulsion rate of aluminium film is 0, and aluminium film sticks on alumina ceramic plate securely.
Embodiment 2, except melt temperature is reduced to 700 DEG C, all the other are identical with embodiment 1.Form at ceramic surface the aluminium film that mean thickness is the densification of 7 microns by this method, its tape test expulsion rate is 0.3 repetitions are established in experiment, come to the same thing.
Embodiment 3, except melt temperature is brought up to 760 DEG C, all the other are identical with embodiment 1.Form at ceramic surface the aluminium film that mean thickness is the densification of 5 microns by this method, its adhesive tape test expulsion rate is 0.3 repetitions are established in experiment, come to the same thing.
Embodiment 4, the crucible filling fine aluminium is put into vacuum oven, be evacuated to 5 × 10
-3after Pa, electrified regulation to 850 DEG C.Then alumina ceramic plate is inserted aluminium liquid from upper vertical, and keep 10 minutes in aluminium liquid, then slowly mention with the speed of 10mm/min, close heating power supply naturally cooling.This method is adopted to be the aluminium film of 10 microns at the part surface bonding last layer mean thickness of alumina ceramic plate immersion aluminium liquid.
Adhesive tape described in embodiment 1 is adopted to tear method test aluminium film firmness.3 repetitions are established in experiment, and result shows, aluminium film expulsion rate is 0, and display aluminium film sticks on alumina ceramic plate securely.
Embodiment 5, adopt outside al nitride ceramic board (Fujian China is clear to produce, and aluminium nitride content is greater than 95%) except ceramic plate, other is all identical with embodiment 4.Test result shows, aluminium film mean thickness is 9 microns, and aluminium film expulsion rate is 0, and display aluminium film sticks on al nitride ceramic board securely.3 repetitions are established in experiment, come to the same thing.
Embodiment 6, outside ceramic plate adopts silicon nitride ceramic plate (normal pressure-sintered, silicon nitride content is greater than 92%), other condition is all identical with embodiment 4.Test result shows, aluminium film mean thickness is 9 microns, and aluminium film expulsion rate is 0, and display aluminium film sticks on silicon nitride ceramic plate securely.3 repetitions are established in experiment, come to the same thing.
Embodiment 7, except beyond ceramic plate adopts silicon carbide ceramics plate (reaction sintering, carborundum content is greater than 90%), other condition is identical with embodiment 4.Test result shows, aluminium film mean thickness is 10 microns, and aluminium film expulsion rate is 0, and display aluminium film sticks on silicon carbide ceramics plate securely.3 repetitions are established in experiment, come to the same thing.
Embodiment 8, except being changed into by fine aluminium except Al-8wt%Si alloy, all the other are all identical with embodiment 1.On ceramic plate, form by this method the aluminium alloy film that mean thickness is 8 microns, through the test of adhesive tape method, aluminium alloy film expulsion rate is 0, and display aluminium alloy film sticks on alumina-ceramic securely.3 repetitions are established in experiment, come to the same thing.
Embodiment 9, except being reduced to by nitrogen flow except 15 liters/min, other is all identical with embodiment 8.Form on ceramic plate surface the aluminium alloy film that mean thickness is 7 microns by this method, its adhesive tape test expulsion rate is 0.3 repetitions are established in experiment, come to the same thing.
Embodiment 10, except being brought up to by melt temperature except 780 DEG C, other is all identical with embodiment 9.On ceramic plate, define the aluminium film of mean thickness 6 microns like this, its adhesive tape test expulsion rate is 0.3 repetitions are established in experiment, come to the same thing.
Embodiment 11, except being changed into by aluminium except Al-12wt% aluminum silicon alloy, all the other are identical with embodiment 1.Form at alumina ceramic face the aluminium alloy layer that mean thickness is 5 microns by this method, its adhesive tape test expulsion rate is 0, and display aluminium alloy layer sticks on alumina-ceramic securely.3 repetitions are established in experiment, come to the same thing.
Embodiment 12, except being reduced to by melt temperature except 680 DEG C, all the other are identical with embodiment 11.Form the aluminium alloy layer of mean thickness 6 microns at alumina ceramic face by this method, its adhesive tape test expulsion rate is 0.3 repetitions are established in experiment, come to the same thing.
Embodiment 13, except being changed into by fine aluminium except Al-2wt%Si alloy, all the other are all identical with embodiment 1.On ceramic plate, form by this method the aluminium alloy film that mean thickness is 8 microns, through the test of adhesive tape method, aluminium alloy film expulsion rate is 0, and display aluminium alloy film sticks on alumina-ceramic securely.3 repetitions are established in experiment, come to the same thing.
Embodiment 14, except being changed into by fine aluminium except Al-1wt%Si alloy, all the other are all identical with embodiment 1.On ceramic plate, form by this method the aluminium alloy film that mean thickness is 17 microns, through the test of adhesive tape method, aluminium alloy film expulsion rate is 0, and display aluminium alloy film sticks on alumina-ceramic securely.3 repetitions are established in experiment, come to the same thing.
Embodiment 15, except being reduced to by temperature except 680 DEG C, all the other are all identical with embodiment 14.On ceramic plate, form by this method the aluminium alloy film that mean thickness is 51 microns, through the test of adhesive tape method, aluminium alloy film expulsion rate is 0, and display aluminium alloy film sticks on alumina-ceramic securely.3 repetitions are established in experiment, come to the same thing.
Embodiment 16, except being changed into by aluminium except Al-12wt%Si-1wt%Mg alsimag, all the other are identical with embodiment 12.Form the aluminium alloy layer of mean thickness 5 microns at alumina ceramic face by this method.3 repetitions are established in experiment, come to the same thing.
Embodiment 17, except nitrogen flow being reduced half (10 liters/min), all the other are identical with embodiment 16.Form the aluminium alloy layer of thickness 5 microns at alumina ceramic face by this method, there is slight oxidation on its surface.3 repetitions are established in experiment, come to the same thing.
Embodiment 18, except being brought up to by melt temperature except 730 DEG C, all the other are identical with embodiment 17.Form at ceramic surface the aluminium alloy film that mean thickness is 6 microns by this method, there is slight oxidation on its surface.3 repetitions are established in experiment, come to the same thing.
Embodiment 19, except being brought up to by melt temperature except 780 DEG C, all the other are identical with embodiment 17.Form at ceramic surface the aluminium alloy film that mean thickness is 4 microns by this method, there is slight oxidation on its surface.3 repetitions are established in experiment, come to the same thing.
Embodiment 20, except being reduced to by melt temperature except 630 DEG C, all the other are identical with embodiment 17.Form at ceramic surface the aluminium alloy film that thickness is 5 microns by this method, there is slight oxidation on its surface.3 repetitions are established in experiment, come to the same thing.
Control group experiment is as follows:
Comparative example 1, slowly insert in the aluminum melt being heated to 680 DEG C by the alumina ceramic plate after heating in an atmosphere, then slowly propose with the speed of 68.5mm/min, ceramic plate surface fails to adhere to aluminium liquid.3 repetitions are established in experiment, come to the same thing.Illustrate under oxide film existence, aluminium liquid can not soak with pottery, and ceramic surface can not adhere to aluminium liquid.
Comparative example 2, in an atmosphere the alumina ceramic plate after heating is inserted be heated to 680 DEG C aluminum melt in stir, then slowly mention with the speed of 27mm/min.With this method can on ceramic plate local adhesion aluminium film, aluminium film surface oxidation is serious.This aluminium film local can tear with hand simply, shows that it is failed and ceramic plate compact siro spinning technology.Through the test of adhesive tape method, aluminium alloy film expulsion rate is 34%.3 repetitions are established in experiment, and result is substantially identical, and expulsion rate is respectively 34%, and 27%, 45%.Illustrate if effectively all can not remove the primary oxide film on aluminium surface, remaining oxide film also can cause detrimentally affect to the connection of pottery and aluminium.
Claims (5)
1. one kind manufactures the method that surface is connected with the pottery of aluminum or aluminum alloy film, comprise following operation steps: immersed in the metalized face of pottery in aluminum or aluminum alloy liquation, and make its relative liquation motion with the metalized face making described aluminum or aluminum alloy liquation soak pottery, again the metalized face of pottery is moved up and shift out, make aluminium or the aluminium alloy liquid film unfettered ground naturally cooling of surface adhesion, obtain the pottery that surface is connected with aluminum or aluminum alloy film.
2. method according to claim 1, is characterized in that: described is moved the metalized face of the pottery method immersed in aluminum or aluminum alloy liquation vertically upward after the container bottom filling described aluminum or aluminum alloy liquation inserts liquation inside by described pottery.
3. method according to claim 1, is characterized in that: described pottery is oxide ceramics, nitride ceramics or carbide ceramics.
4., according to described method arbitrary in claim 1-3, it is characterized in that: described in operate in vacuum or inert gas atmosphere and carry out.
5. the surface that method described in claim 1 obtains connects the pottery of aluminum or aluminum alloy film, it is characterized in that: described pottery and described aluminum or aluminum alloy film interface do not have amorphous oxide inclusion of aluminium.
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| WO2010124532A1 (en) * | 2009-04-30 | 2010-11-04 | 清华大学 | Method for metallizing ceramic surface and method for connecting ceramic with aluminum |
| CN102452844B (en) * | 2010-10-30 | 2013-10-02 | 比亚迪股份有限公司 | Aluminum nitride aluminum-coated base plate and preparation method thereof |
| US10150184B2 (en) | 2015-10-21 | 2018-12-11 | Siemens Energy, Inc. | Method of forming a cladding layer having an integral channel |
| CN105418132A (en) * | 2016-01-07 | 2016-03-23 | 上海电机学院 | Method for adopting aluminum or aluminum alloy to directly braze aluminum nitride ceramics |
| CN107611104A (en) * | 2017-07-27 | 2018-01-19 | 比亚迪股份有限公司 | A kind of heat dissipation element and preparation method thereof and IGBT modules |
| CN109400206A (en) * | 2018-11-12 | 2019-03-01 | 苏州工业园区职业技术学院 | A kind of method of ceramic surface metallization |
| CN111302834B (en) * | 2020-04-15 | 2020-10-23 | 湖南省美程陶瓷科技有限公司 | Microwave magnetron insulating ceramic ring |
| CN114310997A (en) * | 2021-12-24 | 2022-04-12 | 宁波江丰电子材料股份有限公司 | Clamping device for ultra-high purity aluminum casting and clamping method thereof |
| CN115029653A (en) * | 2022-06-15 | 2022-09-09 | 宁波建锡新材料有限公司 | Preparation method, preparation device and application of aluminum-coated tungsten ball for ball mill |
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