CN103951468A - Metallization sintering powder for 95 alumina ceramic middle temperate metallization paste and preparation method thereof - Google Patents
Metallization sintering powder for 95 alumina ceramic middle temperate metallization paste and preparation method thereof Download PDFInfo
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Abstract
The invention discloses metallization sintering powder for 95 alumina ceramic middle temperate metallization paste and a preparation method thereof, and the metallization sintering powder comprises the following components by weight: 60-80 parts of molybdenum powder; a glass phase component comprising 10-20 parts of MnO, 0.5-4 parts of Al2O3, 7-12 parts of SiO2, 0.5-1 part of CaO and 1-5 parts of Mg; and a sintering additive component comprising at least one substance of 0-1.2 parts of TiO2, 0-1.2 parts of BaO, 0-1.2 parts of Y2O3, 0-1.2 parts of La2O3 and 0-1.2 parts of P2O5. The sintering additive is added into the metallization paste, so that the metallization sintering temperature is reduced, Al2O3 ceramic surface metallization can be realized at 1370-1420 DEG C by the metallization paste using the sintering additive, and a ceramic metallization layer with high sintered density, good air tightness and high sealing tensile strength can be obtained. The tensile strength of a sample sealed with the metallization paste is over 120MPa, and at the same temperature, the metallization paste is much better than metallization paste without adding of a sintering additive in performance, and the preparation method has the advantages of simple process and convenient operation, and can ensure the stability of the paste and the requirements for mass production.
Description
Technical field
The invention belongs to ceramic metal formed material applied technical field, relate to warm Metal slurry metallization sintering powder and preparation method thereof in a kind of 95 alumina-ceramic.
Background technology
At present, the sealing-in of 95 alumina-ceramic and metal, be widely used in the vacuum device in the electric fields such as vacuum switch tube, discharge tube, magnetron, X-ray tube, microwave tube, and the committed step of sealing-in is the surface metalation of 95 alumina-ceramic.When 95 porcelain are metallized, generally adopt Mo-Mn metallization, take molybdenum as main body, the oxide raw materials such as manganese-aluminium-silicon-calcium-magnesium form glassy phase, are mixed with Metal slurry, are coated in alumina-ceramic surface, through high temperature sintering, on alumina-ceramic surface, make metal layer.Be activation Mo-Mn method ceramic-metal sealing process flow process below.
Porcelain piece is ground------cleans------biscuiting, prepares metal powder,-----joins cream to prepare oxidate powder simultaneously
With joining cream be coated with cream in the porcelain piece of biscuiting---sintering metal-----nickel plating------sintering.
Each factory of China is to 95%Al
2o
3molybdenum manganese method formula in the conventional metallizing formula of porcelain is shown in the form in Fig. 1: simultaneously also can be referring to ceramic-to-metal seal guide P76 page table 3-9.
But these are filled a prescription for 95% alumina-ceramic, temperature drift, minimum is 1470 ℃.For some, need glazing shell, the melt temperature of glaze is wished higher, is greater than 1450 ℃, and metallized temperature is wished again lower, is less than 1400 ℃, and the two is contradiction.On the other hand, metallization sintering temperature is high, and energy consumption is increased, and refractory wear increases, and more seriously aluminium oxide ceramic products easily deforms, and causes conforming product rate to reduce.Therefore guaranteeing under the prerequisite that metal layer quality does not reduce, reducing metallization sintering temperature significant.And temperature metallization at present more existing often can run into Metallization strength on the low side, the problems such as slow gas leakage.This just need a kind of preferably in warm metallizing formula adapt to the needs of scale operation.
Summary of the invention
The present invention is in order to solve the problems of the technologies described above, a kind of sintering aid component of adding in metallizing paste is provided, under proof strength and bubble-tight prerequisite, reduce metallized temperature, can in 1370-1420 ℃ of temperature, realize in 95 alumina-ceramic of ceramic metallization metallization sintering powder and preparation method thereof for warm Metal slurry.
The present invention is achieved through the following technical solutions:
A metallization sintering powder for warm Metal slurry in 95 alumina-ceramic, calculates and comprises following component by weight:
Molybdenum powder, 60-80 part;
Glassy phase component:
MnO, 10-20 part;
Al
2o
3, 0.5-4 part;
SiO
2, 7-12 part;
CaO, 0.5-1 part;
Mg, 1-5 part;
Sintering aid component:
TiO
2, 0-1.2 part;
BaO, 0-1.2 part;
Y
2o
3, 0-1.2 part;
La
2o
3, 0-1.2 part;
P
2o
5, 0-1.2 part.
In 95 alumina-ceramic, a preparation method for metallization sintering powder for warm Metal slurry, is characterized in that, comprises the following steps:
A) calculate by weight configuration metallization sintering powder formula, described formula comprises following component:
Molybdenum powder, 60-80 part;
Glassy phase component:
MnO, 10-20 part;
Al
2o
3, 0.5-4 part;
SiO
2, 7-12 part;
CaO, 0.5-1 part;
Mg, 1-5 part;
Sintering aid component:
TiO
2, 0-1.2 part;
BaO, 0-1.2 part;
Y
2o
3, 0-1.2 part;
La
2o
3, 0-1.2 part;
P
2o
5, 0-1.2 part.
B) prepare glass auxiliary agent powder:
By above-mentioned formula, meter, takes each glassy phase component and sintering aid component 20-40 part by weight, and each oxide compound purity in described glassy phase component and sintering aid component is greater than 99%; Granularity is 1-5 μ m, after mixing, is placed in platinum crucible, with Si-Mo rod cabinet-type electric furnace, founds, and through 1500-1550 ℃ of melting, the glass metal after dissolving is poured in cold water fast, and shrend obtains glass dregs;
Pack glass dregs into agate jar, with planetary ball mill, carry out ball milling, take dehydrated alcohol as ball-milling medium, pressing glass dregs is 3-1:1 with dehydrated alcohol ratio, the rotating speed ball milling 10-20 hour of 400-450r/min, after ball milling completes, obtains the elementary glass auxiliary agent powder after ball milling;
To elementary glass auxiliary agent powder, at bath temperature, be to carry out heating in water bath at the temperature of 80-95 ℃, carry out solid-liquid separation, solid glass auxiliary agent powder after separation is continued to dry, cross after 200-400 mesh sieve, be placed in baking oven and dry, bake out temperature is 70-85 ℃, time 2-3 hour, obtain glass auxiliary agent powder, bottle stand-by;
C) molybdenum powder and glass auxiliary agent powder are pressed to proportioning ball mill mixing, drying is ground and is sieved, and makes metallization sintering powder.
The method is further comprising the steps of:
By the weight ratio of metallization sintering powder and binding agent, be that 100:20-23 adds binding agent in metallization sintering powder, through three-roll grinder rolling, mix and make Metal slurry;
By Metal slurry through silk-screen sintering, the condition of sintering is that above to control its dew points be 15 ± 5 ℃ for 1370-1420 ℃, insulation 60min, 1000 ℃, sintering atmosphere is the hydrogen-nitrogen mixture gas that pure hydrogen or volume ratio are 3:1.5, after insulation finishes, dew point is controlled at-20 ± 5 ℃ of metallization that complete 95 alumina-ceramic.
Described binding agent is comprised of following weight ratio:
Terpineol 350: dibutyl phthalate: nonyl phenol polyglycol ether: polyvinyl butyral acetal=160:20:5:25.
Compared with prior art, the present invention has following useful technique effect:
The present invention be take molybdenum as main body, and manganese-aluminium-silicon-calcium-magnesium is five yuan of glassy phase components, by giving in the glassy phase component of filling a prescription, suitably adds the oxidesintering auxiliary agent that can promote silicate reaction, warm metallizing formula in formation, in the metal layer sintering process of lesser temps, sintering aid BaO, P
2o
5, TiO
2, Y
2o
3add high temperature viscosity and the fusing point that has reduced glassy phase, increased activity and the mobility of glassy phase, accelerated Ca, Ba, Mn ion is to 95%Al
2o
3the diffusion of ceramic surface crystal boundary.And consistent with the Changing Pattern of glass structure, can crystal grain thinning, grain-size is consistent, and density is higher.The migration of furtherance glassy phase and Mo powder sintering.
Add a small amount of La
2o
3(0.1%-1.2%), CaO and La
2o
3between two components, exist interaction, be conducive to the formation of Active sites, and can demonstrate good low-temperature catalyzed performance, and do not have new thing to produce mutually; At 1300-1400 ℃ of sintering, can effectively improve the stability of its High-Temperature Mo;
The present invention compared with prior art, by add sintering aid in Metal slurry, under proof strength and bubble-tight prerequisite, has reduced metallization sintering temperature, uses the Metal slurry of sintering aid of the present invention between 1370-1420 ℃, to realize Al
2o
3ceramic surface metallization, obtains the ceramic metallized layer that sintered density is high, resistance to air loss good and sealing-in tensile strength is high.The tensile strength of sealing-in sample surpasses 120MPa. at same temperature, and its performance will obviously be better than not adding the Metal slurry of sintering aid.The tensile strength of the sample of this Metal slurry sealing-in surpasses 120MPa.
The method technique is simple, easy to operate, can guarantee stability and the volume production requirement of slurry.
Accompanying drawing explanation
Fig. 1 is that domestic each factory is to 95%Al
2o
3molybdenum manganese method formula in the conventional metallizing formula of porcelain.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, and the explanation of the invention is not limited.
The purity of the present embodiment pulvis used is all greater than 99.9%, 3 microns of mean particle sizes.
Sealing strength of the present invention detects according to SJ3226-199 standard.
Leak rate of the present invention detects according to SJ20600-1996 standard.
Embodiment 1:
A) take 65 parts, Mo powder (mass ratio); 35 parts of glass auxiliary powders (mass ratio), preparing metal slurry.
Molybdenum powder, 65 parts,
Glassy phase component:
MnO, 16 parts;
Al
2o
3, 3 parts;
SiO
2, 11 parts;
CaO, 0.7 part;
Mg, 3 parts.
Sintering aid component:
TiO
2, 0 part;
BaO, 0.3 part;
Y
2o
3, 0 part;
La
2o
3, 0 part;
P
2o
5, 1 part.
B) prepare the glass auxiliary agent powder that melt temperature is lower.By above-mentioned formula, by weight, take 35 parts of each glassy phase component and sintering aid components, after mixing, be placed in platinum crucible, with Si-Mo rod cabinet-type electric furnace, found.Through 1500 ℃ of meltings, the glass metal after dissolving to be poured in cold water fast, shrend obtains glass dregs.Pack glass dregs into agate jar, with planetary ball mill, carry out ball milling, take dehydrated alcohol as ball-milling medium, ratio of grinding media to material is 3:1, the rotating speed ball milling of 400r/min 10 hours.After ball milling completes, heating in water bath, bath temperature is 80 ℃, and solid-liquid separation continues to dry, and crosses after 200 mesh sieves, is placed in baking oven and dries, and bake out temperature is 70 ℃, 3 hours time, obtain glass auxiliary agent powder, bottle stand-by.
C) Mo powder and glass auxiliary agent powder are pressed to proportioning wet ball grinding batch mixing, drying is ground and is sieved, and makes metallization sintered powder; Then add binding agent to mix and make Metal slurry through three-roll grinder rolling, the weight ratio of mixed powder and binding agent is 100:20; Binding agent proportioning forms: Terpineol 350: dibutyl phthalate: nonyl phenol polyglycol ether: polyvinyl butyral acetal=160:20:5:25 (weight ratio)
Through silk screen printing, at alumina surface, apply.Thickness is 30 microns.The aluminum oxide porcelain piece having applied is placed in to hydrogen furnace and carries out sintering.The condition of sintering is 1385 ℃. and insulation 60min, 1000 ℃ of above its dew points of control are 15 ± 5 ℃. and sintering atmosphere is pure hydrogen, and after insulation finishes, dew point is controlled at-20 ± 5 ℃. complete metallization.
Embodiment 2:
A) take 70 parts, Mo powder (mass ratio); 30 parts of glass auxiliary powders (mass ratio), preparing metal slurry.
Molybdenum powder, 70 parts,
Glassy phase component:
MnO, 14 parts;
Al
2o
3, 2 parts;
SiO
2, 8 parts;
CaO, 1 part;
Mg, 2 parts.
Sintering aid component:
TiO
2, 1 part;
BaO, 0.5 part;
Y
2o
3, 0 part;
La
2o
3, 1 part;
P
2O
5，0.5
B) prepare the glass auxiliary agent powder that melt temperature is lower.By above-mentioned formula, by weight, take 30 parts of each glassy phase component and sintering aid components, after mixing, be placed in platinum crucible, with Si-Mo rod cabinet-type electric furnace, found.Through 1530 ℃ of meltings, the glass metal after dissolving to be poured in cold water fast, shrend obtains glass dregs.Pack glass dregs into agate jar, with planetary ball mill, carry out ball milling, take dehydrated alcohol as ball-milling medium, ratio of grinding media to material is 2:1, the rotating speed ball milling of 450r/min 12 hours.After ball milling completes, heating in water bath, bath temperature is 90 degree, and solid-liquid separation continues to dry, and crosses after 300 mesh sieves, is placed in baking oven and dries, and bake out temperature is 80 ℃, 2.5 hours time, obtain glass auxiliary agent powder, bottle stand-by.
C) Mo powder and glass auxiliary agent powder are pressed to proportioning wet ball grinding batch mixing, drying is ground and is sieved, and makes metallization sintered powder; Then add binding agent to mix and make Metal slurry through three-roll grinder rolling, the weight ratio of mixed powder and binding agent is 100:22.5; Binding agent proportioning forms: Terpineol 350: dibutyl phthalate: nonyl phenol polyglycol ether: polyvinyl butyral acetal=160:20:5:25 (weight ratio)
Through silk screen printing, at alumina surface, apply.Thickness is 35 microns.The aluminum oxide porcelain piece having applied is placed in to hydrogen furnace and carries out sintering.The condition of sintering is 1400 ℃. and being incubated 60min.1000 ℃ of above its dew point of control is 15 ± 5 ℃. and sintering atmosphere is hydrogen-nitrogen mixture gas (its volume ratio is 3:1.5), and after insulation finishes, dew point is controlled at-20 ± 5 ℃. complete metallization.
Embodiment 3:
A) take 75 parts, Mo powder (mass ratio); 25 parts of glass auxiliary powders (mass ratio), preparing metal slurry.
Molybdenum powder, 75 parts,
Glassy phase component:
MnO, 10 parts;
Al
2o
3, 2 parts;
SiO
2, 9 parts;
CaO, 0.5 part;
Mg, 1 part.
Sintering aid component:
TiO
2, 0.5 part;
BaO, 1 part;
Y
2o
3, 0.5 part;
La
2o
3, 0 part;
P
2o
5, 0.5 part.
B) prepare the glass auxiliary agent powder that melt temperature is lower.By above-mentioned formula, by weight, take 25 parts of each glassy phase component and sintering aid components, after mixing, be placed in platinum crucible, with Si-Mo rod cabinet-type electric furnace, found.Through 1550 ℃ of meltings, the glass metal after dissolving to be poured in cold water fast, shrend obtains glass dregs.Pack glass dregs into agate jar, with planetary ball mill, carry out ball milling, take dehydrated alcohol as ball-milling medium, ratio of grinding media to material is 1:1, the rotating speed ball milling of 430r/min 15 hours.After ball milling completes, heating in water bath, bath temperature is 95 ℃, and solid-liquid separation continues to dry, and crosses after 400 mesh sieves, is placed in baking oven and dries, and bake out temperature is 85 ℃, and time 2 h obtains glass auxiliary agent powder, bottles stand-by.
C) Mo powder and glass auxiliary agent powder are pressed to proportioning wet ball grinding batch mixing, drying is ground and is sieved, and makes metallization sintered powder; Then add binding agent to mix and make Metal slurry through three-roll grinder rolling, the weight ratio of mixed powder and binding agent is 100:25; Binding agent proportioning forms: Terpineol 350: dibutyl phthalate: nonyl phenol polyglycol ether: polyvinyl butyral acetal=160:20:5:25 (weight ratio)
Through silk screen printing, at alumina surface, apply.Thickness is 32 microns.The aluminum oxide porcelain piece having applied is placed in to hydrogen furnace and carries out sintering.The condition of sintering is 1415 ℃. and being incubated 60min.1000 ℃ of above its dew point of control is 15 ± 5 ℃. and sintering atmosphere is pure hydrogen or hydrogen-nitrogen mixture gas (its volume ratio is 3:1.5), and after insulation finishes, dew point is controlled at-20 ± 5 ℃. complete metallization.
Embodiment 4:
A) take 60 parts, Mo powder (mass ratio); 40 parts of glass auxiliary powders (mass ratio), preparing metal slurry.
Molybdenum powder, 60 parts,
Glassy phase component:
MnO, 18 parts;
Al
2o
3, 4 parts;
SiO
2, 11 parts;
CaO, 1 part;
Mg, 3 parts.
Sintering aid component:
TiO
2, 1 part;
BaO, 1 part;
Y
2o
3, 0 part;
La
2o
3, 0 part;
P
2o
5, 1 part.
B) prepare the glass auxiliary agent powder that melt temperature is lower.By above-mentioned formula, by weight, take 40 parts of each glassy phase component and sintering aid components, after mixing, be placed in platinum crucible, with Si-Mo rod cabinet-type electric furnace, found.Through 1500 ℃ of meltings, the glass metal after dissolving to be poured in cold water fast, shrend obtains glass dregs.Pack glass dregs into agate jar, with planetary ball mill, carry out ball milling, take dehydrated alcohol as ball-milling medium, ratio of grinding media to material is 3:1, the rotating speed ball milling of 400r/min 10 hours.After ball milling completes, heating in water bath, bath temperature is 80 ℃, and solid-liquid separation continues to dry, and crosses after 200 mesh sieves, is placed in baking oven and dries, and bake out temperature is 70 ℃, 3 hours time, obtain glass auxiliary agent powder, bottle stand-by.
C) Mo powder and glass auxiliary agent powder are pressed to proportioning wet ball grinding batch mixing, drying is ground and is sieved, and makes metallization sintered powder; Then add binding agent to mix and make Metal slurry through three-roll grinder rolling, the weight ratio of mixed powder and binding agent is 100:20; Binding agent proportioning forms: Terpineol 350: dibutyl phthalate: nonyl phenol polyglycol ether: polyvinyl butyral acetal=160:20:5:25 (weight ratio).
Through silk screen printing, at alumina surface, apply.Thickness is 30 microns.The aluminum oxide porcelain piece having applied is placed in to hydrogen furnace and carries out sintering.The condition of sintering is 1370 ℃. and insulation 60min, 1000 ℃ of above its dew points of control are 15 ± 5 ℃. and sintering atmosphere is pure hydrogen or hydrogen-nitrogen mixture gas (its volume ratio is 3:1.5), and after insulation finishes, dew point is controlled at-20 ± 5 ℃. complete metallization.
Embodiment 5:
A) take 80 parts, Mo powder (mass ratio); 20 parts of glass auxiliary powders (mass ratio), preparing metal slurry.
Molybdenum powder, 80 parts,
Glassy phase component:
MnO, 10 parts;
Al
2o
3, 0.5 part;
SiO
2, 7 parts;
CaO, 0.5 part;
Mg, 1 part.
Sintering aid component:
TiO
2, 0.5 part;
BaO, 0.2 part;
Y
2o
3, 0 part;
La
2o
3, 0 part;
P
2o
5, 0.3 part.
B) prepare the glass auxiliary agent powder that melt temperature is lower.By above-mentioned formula, by weight, take 20 parts of each glassy phase component and sintering aid components, after mixing, be placed in platinum crucible, with Si-Mo rod cabinet-type electric furnace, found.Through 1550 ℃ of meltings, the glass metal after dissolving to be poured in cold water fast, shrend obtains glass dregs.Pack glass dregs into agate jar, with planetary ball mill, carry out ball milling, take dehydrated alcohol as ball-milling medium, ratio of grinding media to material is 1:1, the rotating speed ball milling of 430r/min 15 hours.After ball milling completes, heating in water bath, bath temperature is 95 ℃, and solid-liquid separation continues to dry, and crosses after 400 mesh sieves, is placed in baking oven and dries, and bake out temperature is 85 ℃, and time 2 h obtains glass auxiliary agent powder, bottles stand-by.
C) Mo powder and glass auxiliary agent powder are pressed to proportioning wet ball grinding batch mixing, drying is ground and is sieved, and makes metallization sintered powder; Then add binding agent to mix and make Metal slurry through three-roll grinder rolling, the weight ratio of mixed powder and binding agent is 100:25; Binding agent proportioning forms: Terpineol 350: dibutyl phthalate: nonyl phenol polyglycol ether: polyvinyl butyral acetal=160:20:5:25 (weight ratio)
Through silk screen printing, at alumina surface, apply.Thickness is 32 microns.The aluminum oxide porcelain piece having applied is placed in to hydrogen furnace and carries out sintering.The condition of sintering is 1420 ℃. and being incubated 60min.1000 ℃ of above its dew point of control is 15 ± 5 ℃. and sintering atmosphere is pure hydrogen, and after insulation finishes, dew point is controlled at-20 ± 5 ℃. complete metallization.
The made metallization sealing strength of embodiment 1,2,3,4,5 (MPa) is as follows:
No. 1 128.86MPa;
No. 2 130.50MPa;
No. 3 125.65MPa;
No. 4 123.10MPa;
No. 5 120.28MPa.
● (tensile strength numerical value is the mean value of 3 samples, and sealing-in area is 1.15cm
2.) this product
Tensile strength surpasses 120MPa.
Embodiment 6
A) take 65 parts, Mo powder (mass ratio); 35 parts of glass auxiliary powders (mass ratio), preparing metal slurry.
Molybdenum powder, 65 parts,
Glassy phase component:
MnO, 20 parts;
Al
2o
3, 2.25 parts;
SiO
2, 9.5 parts;
CaO, 0.75 part;
Mg, 1 part.
Sintering aid component:
TiO
2, 0.6 part;
BaO, 0.6 part;
Y
2o
3, 0.3 part;
La
2o
3, 0 part;
P
2o
5, 0 part.
B) prepare the glass auxiliary agent powder that melt temperature is lower.By above-mentioned formula, by weight, take 35 parts of each glassy phase component and sintering aid components, after mixing, be placed in platinum crucible, with Si-Mo rod cabinet-type electric furnace, found.Through 1500 ℃ of meltings, the glass metal after dissolving to be poured in cold water fast, shrend obtains glass dregs.Pack glass dregs into agate jar, with planetary ball mill, carry out ball milling, take dehydrated alcohol as ball-milling medium, ratio of grinding media to material is 3:1, the rotating speed ball milling of 400r/min 10 hours.After ball milling completes, heating in water bath, bath temperature is 80 ℃, and solid-liquid separation continues to dry, and crosses after 200 mesh sieves, is placed in baking oven and dries, and bake out temperature is 70 ℃, 3 hours time, obtain glass auxiliary agent powder, bottle stand-by.
C) Mo powder and glass auxiliary agent powder are pressed to proportioning wet ball grinding batch mixing, drying is ground and is sieved, and makes metallization sintered powder; Then add binding agent to mix and make Metal slurry through three-roll grinder rolling, the weight ratio of mixed powder and binding agent is 100:20; Binding agent proportioning forms: Terpineol 350: dibutyl phthalate: nonyl phenol polyglycol ether: polyvinyl butyral acetal=160:20:5:25 (weight ratio)
Through silk screen printing, at alumina surface, apply.Thickness is 30 microns.The aluminum oxide porcelain piece having applied is placed in to hydrogen furnace and carries out sintering.The condition of sintering is 1385 ℃. and insulation 60min, 1000 ℃ of above its dew points of control are 15 ± 5 ℃. and sintering atmosphere is pure hydrogen, and after insulation finishes, dew point is controlled at-20 ± 5 ℃. complete metallization.
Embodiment 7
A) take 65 parts, Mo powder (mass ratio); 35 parts of glass auxiliary powders (mass ratio), preparing metal slurry.
Molybdenum powder, 65 parts,
Glassy phase component:
MnO, 15 parts;
Al
2o
3, 0.5 part;
SiO
2, 12 parts;
CaO, 0.5 part;
Mg, 5 parts.
Sintering aid component:
TiO
2, 1.2 parts;
BaO, 0 part;
Y
2o
3, 0.6 part;
La
2o
3, 0.1 part;
P
2o
5, 0.1 part.
B) prepare the glass auxiliary agent powder that melt temperature is lower.By above-mentioned formula, by weight, take 35 parts of each glassy phase component and sintering aid components, after mixing, be placed in platinum crucible, with Si-Mo rod cabinet-type electric furnace, found.Through 1500 ℃ of meltings, the glass metal after dissolving to be poured in cold water fast, shrend obtains glass dregs.Pack glass dregs into agate jar, with planetary ball mill, carry out ball milling, take dehydrated alcohol as ball-milling medium, ratio of grinding media to material is 3:1, the rotating speed ball milling of 400r/min 10 hours.After ball milling completes, heating in water bath, bath temperature is 80 ℃, and solid-liquid separation continues to dry, and crosses after 200 mesh sieves, is placed in baking oven and dries, and bake out temperature is 70 ℃, 3 hours time, obtain glass auxiliary agent powder, bottle stand-by.
C) Mo powder and glass auxiliary agent powder are pressed to proportioning wet ball grinding batch mixing, drying is ground and is sieved, and makes metallization sintered powder; Then add binding agent to mix and make Metal slurry through three-roll grinder rolling, the weight ratio of mixed powder and binding agent is 100:20; Binding agent proportioning forms: Terpineol 350: dibutyl phthalate: nonyl phenol polyglycol ether: polyvinyl butyral acetal=160:20:5:25 (weight ratio)
Through silk screen printing, at alumina surface, apply.Thickness is 30 microns.The aluminum oxide porcelain piece having applied is placed in to hydrogen furnace and carries out sintering.The condition of sintering is 1385 ℃. and insulation 60min, 1000 ℃ of above its dew points of control are 15 ± 5 ℃. and sintering atmosphere is pure hydrogen, and after insulation finishes, dew point is controlled at-20 ± 5 ℃. complete metallization.
It should be noted that, the material in described sintering aid component is at least containing more than one.
Invention Analysis on Mechanism:
By doping vario-property technology, can improve intensity and resistance to air loss, be a kind of effectively in warm method for metallising.Its mechanism of action is to make material powder generation particle bonding by sintering, and through material, migration makes powder produce intensity and cause densification and the process of recrystallize.On the one hand by doping, destroy stable crystalline network, make to produce in crystal defect or cause that lattice distortion realizes, activate lattice, reduction sintering intensity of activation; On the other hand, accelerate expansion process, mainly by produce liquid phase in system, it is bonding and fill pore that liquid phase produces particle by surface tension, by mass transfer in liquid phase effect, makes the little crystal grain that dissolves gradually at crystal grain surface deposition greatly, reaches the effect of acceleration of sintering.
Metallization of alumina ceramic surface is liquid phase sintering, therefore metallization process temperature depends primarily on the melt temperature of glassy phase, why traditional technology must realize under higher temperature, and each oxide raw material powder silicate reaction temperature that essential reason is to be dispersed between molybdenum powder is higher.Practice shows, temperature reaches 1500 ℃ of left and right conventionally.In metal layer, amount of glassy phase and condition are the important factor in order of metallization of alumina ceramic surface character in addition.Glass state material in metal layer is on the one hand from pottery itself, on the one hand from the vitreum in metallizing formula itself, when the glassiness is too much or composition not at that time, the sintered density of Mo declines on the contrary.The viscosity of glassy phase is also to being sealed with considerable influence, too high when viscosity, just needs higher metallizing temperature or extends soaking time.
Effect of the present invention:
Ceramic metallization slurry sintering aid reasonable ratio provided by the invention, adding of sintering aid, can soften in the lower melting of lesser temps (1340-1390 ℃) glassy phase, and viscosity significantly reduces, and has formed liquid phase flow, fills Mo hole, with Al
2o
3in glassy phase mutually move and interpenetrate fusion, with Al
2o
3between there is silicate reaction, connection metal layer and Al
2o
3matrix, realizes the chemical bonding of metal layer and alumina-ceramic matrix.In melting process of cooling, also there is stronger crystallization ability.Formed densification and continuous Mo metal level.Metallization like this, at a lower temperature also can obtain higher bonding strength.
It is low that the present invention has cost, effective, and the advantage of simple process has strengthened the stability of metallizing paste technique, the consistence of improving the quality of products simultaneously.Along with industrial expansion, more and more higher to the requirement of ceramic-metal sealing technology.As developing rapidly of power electronic devices, increasing to the demand of high-power silicon controlled rectifier shell, the requirement of quality is also improved day by day.From considering with quality economically, the present invention can adapt to the needs of glazing shell scale operation.
More than show and described ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and specification sheets, describes just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (4)
1. a warm Metal slurry metallization sintering powder in 95 alumina-ceramic, is characterized in that, calculates and comprises following component by weight:
Molybdenum powder, 60-80 part;
Glassy phase component:
MnO, 10-20 part;
Al
2o
3, 0.5-4 part;
SiO
2, 7-12 part;
CaO, 0.5-1 part;
Mg, 1-5 part;
Sintering aid component:
TiO
2, 0-1.2 part;
BaO, 0-1.2 part;
Y
2o
3, 0-1.2 part;
La
2o
3, 0-1.2 part;
P
2o
5, 0-1.2 part.
2. a preparation method for warm Metal slurry use metallization sintering powder in 95 alumina-ceramic based on claim 1, is characterized in that, comprises the following steps:
A) prepare glass auxiliary agent powder:
By above-mentioned formula, meter, takes each glassy phase component and sintering aid component 20-40 part by weight, and each oxide compound purity in described glassy phase component and sintering aid component is greater than 99%; Granularity is 1-5 μ m., after mixing, is placed in platinum crucible, with Si-Mo rod cabinet-type electric furnace, founds, and through 1500-1550 ℃ of melting, the glass metal after dissolving is poured in cold water fast, and shrend obtains glass dregs;
Pack glass dregs into agate jar, with planetary ball mill, carry out ball milling, take dehydrated alcohol as ball-milling medium, pressing glass dregs is 3-1:1 with dehydrated alcohol ratio, the rotating speed ball milling 10-20 hour of 400-450r/min, after ball milling completes, obtains the elementary glass auxiliary agent powder after ball milling;
To elementary glass auxiliary agent powder, at bath temperature, be to carry out heating in water bath at the temperature of 80-95 ℃, carry out solid-liquid separation, solid glass auxiliary agent powder after separation is continued to dry, cross after 200-400 mesh sieve, be placed in baking oven and dry, bake out temperature is 70-85 ℃, time 2-3 hour, obtain glass auxiliary agent powder, bottle stand-by;
B) molybdenum powder, glass auxiliary agent powder are pressed to proportioning ball mill mixing, drying is ground and is sieved, and makes metallization sintering powder.
3. the preparation method of warm Metal slurry use metallization sintering powder in 95 alumina-ceramic according to claim 2, is characterized in that, the method is further comprising the steps of:
By the weight ratio of metallization sintering powder and binding agent, be that 100:20-23 adds binding agent in metallization sintering powder, through three-roll grinder rolling, mix the Metal slurry of system;
By Metal slurry through silk-screen sintering, the condition of sintering is that above to control its dew points be 15 ± 5 ℃ for 1370-1420 ℃, insulation 60min, 1000 ℃, sintering atmosphere is the hydrogen-nitrogen mixture gas that pure hydrogen or volume ratio are 3:1.5, after insulation finishes, dew point is controlled at-20 ± 5 ℃ of metallization that complete 95 alumina-ceramic.
4. the preparation method of warm Metal slurry use metallization sintering powder in 95 alumina-ceramic according to claim 2, is characterized in that, described binding agent is comprised of following weight ratio:
Terpineol 350: dibutyl phthalate: nonyl phenol polyglycol ether: polyvinyl butyral acetal=160:20:5:25.
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| CN106631166A (en) * | 2016-12-12 | 2017-05-10 | 湖南省新化县林海陶瓷有限公司 | Preparation technology of novel metallized paste |
| CN106636827A (en) * | 2016-12-08 | 2017-05-10 | 苏州长风航空电子有限公司 | Ceramic metallization powder and manufacturing method thereof |
| CN107082652A (en) * | 2017-05-25 | 2017-08-22 | 山东大学 | A kind of manganese oxide silica alumina system activator metalization layer and its preparation technology |
| CN107814560A (en) * | 2017-09-30 | 2018-03-20 | 江苏金石研磨有限公司 | A kind of ceramic grinding ball rolls shaping composite fortifier and preparation method thereof and its application method |
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| CN111548193A (en) * | 2020-05-18 | 2020-08-18 | 宜宾红星电子有限公司 | Metallization method for ultra-high purity alumina ceramic |
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