CN103253989B - A kind of Method of selective metallization on ceramic surface and one pottery - Google Patents
A kind of Method of selective metallization on ceramic surface and one pottery Download PDFInfo
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Abstract
The invention provides a kind of Method of selective metallization on ceramic surface, comprise the following steps: A. by ceramic composition molding, fire and obtain ceramic base material；Described ceramic composition includes ceramic powder and the function powder being scattered in ceramic powder；One or more in the titanate compound of M of described function powder；One or more in the titanate compound of E of ceramic powder；B. use the selection area of energy beam radiation ceramic substrate surface, form chemical plating active center at selection area；C., ceramic substrate surface through step B carries out chemical plating, and selection area forms metal level.Present invention also offers a kind of pottery.The ceramic surface selective metal method of the present invention, the metal level formed by chemical plating is higher with the adhesive force of ceramic base material, and cost is relatively low.
Description
Technical field
The invention belongs to ceramic field, particularly relate to a kind of Method of selective metallization on ceramic surface and one pottery.
Background technology
Stereo circuit is formed, it is possible to form three-dimensional, to integrate dynamo-electric function circuit carrier at ceramic surface.With
Time, surface has the ceramic component of stereo circuit and has higher heat conductivity and mechanical strength, longer service life, stronger
Ageing-resistant performance etc., therefore will be used widely at electronic applications.At present, the technique forming stereo circuit at ceramic surface
It is: surface degreasing-mechanical coarsening-chemistry roughening-sensitization activation-chemical plating, technique is loaded down with trivial details, and the coat of metal obtained i.e. circuit
Relatively low with the adhesive force of ceramic base material.
Such as, CN101550546A discloses the chemically plating Preparation Method of a kind of ceramic substrate surface, by pottery
Surface coating semiconductor nano inorganic particle, is then directly immersed in containing the chemical plating fluid of the slaine of carried metal needed for surface
In, irradiate under the ultraviolet light that wavelength is 200-400nm and carry out chemical plating, thus at ceramic substrate surface carried metal, obtain
The ceramic material of surface metalation.Wherein semiconductor nano inorganic particle is nano titanium oxide, nano silicon oxide, nano oxidized
Zinc, nano tin dioxide or the semiconductor nano inorganic particle through doping vario-property, wherein doping vario-property is rear-earth-doped, rare earth oxygen
Compound doping, metal-doped or N doping.In the method, under laser irradiates, produce metal by semiconductor nano inorganic particle
Atom, thus realize chemical plating, but semiconductor nano inorganic particle is relatively costly, significantly limits its application.It addition, the method
In, semiconducting inorganic powder body is distributed in ceramic surface, it is difficult to ensure the adhesive force of remaining ceramic base material, it is also difficult to ensure chemical plating
Layer and the adhesive force of base material.
A kind of method disclosing pottery utilizing gamma-rays to prepare surface metalation in CN101684551A, by preparation
Containing the solution of metal ion, press required form distribution metal ion solution in ceramic workpiece surface presumptive area, then use γ
This region of x radiation x, finally carries out chemical plating and forms metal level in this region.In the method, by gamma-ray radiation, with
Time complete roughening and the formation in chemical plating active center of ceramic material surfaces, technique simplifies.But in the method, metal ion
Solution be distributed in ceramic surface, after radiation reduction formed metal active centres be present in ceramic surface, with ceramic base material
Adhesive force is the most weak so that chemical deposit is the most corresponding to the adhesive force of ceramic base material more weak.It addition, the method uses high-energy
Gamma-rays, cost is the highest.
Summary of the invention
The present invention solves that ceramic surface metal level present in prior art is low with base material adhesive force and ceramic surface
The technical problem that metallization cost is high.
The invention provides a kind of Method of selective metallization on ceramic surface, comprise the following steps:
A. by ceramic composition molding, fire and obtain ceramic base material；Described ceramic composition includes ceramic powder and dispersion
Function powder in ceramic powder；One or more in the titanate compound of M of described function powder, M is vanadium
(V), chromium (Cr), manganese (Mn), ferrum (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium
(Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold
(Au), indium (In), stannum (Sn), antimony (Sb), lead (Pb), bismuth (Bi), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium
(Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) or lutecium (Lu)；Ceramic powder is selected from E's
One or more in titanate compound, E is lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), beryllium (Be), magnesium
(Mg), calcium (Ca), strontium (Sr), barium (Ba), boron (B), aluminum (Al), gallium (Ga), silicon (Si), germanium (Ge), phosphorus (P), arsenic (As), scandium
(Sc), yttrium (Y), zirconium (Zr), hafnium (Hf) or lanthanum element；
B. use the selection area of energy beam radiation ceramic substrate surface, form chemical plating active center at selection area；
C., ceramic substrate surface through step B carries out chemical plating, and selection area forms metal level.
Present invention also offers a kind of pottery, described pottery includes ceramic base material and the gold of ceramic substrate surface selection area
Belong to layer；Described pottery method provided by the present invention obtains.
The Method of selective metallization on ceramic surface that the present invention provides, by first by containing ceramic powder and function powder
Ceramic composition molding firing ceramics base material, then uses the selection area of energy beam radiation ceramic substrate surface, radiation areas
The ceramic main body of ceramic substrate surface be etched, therefore the ceramic main body of radiation areas sink, the function ingredients exposed accordingly
Under energy beam effect, form chemical plating active center, then carry out chemical plating, form chemistry on surface, chemical plating active center
Coating.Before the present invention fires, function powder and ceramic powder Monodispersed, function powder and pottery after therefore firing
Base material has good adhesive force, and after energy beam radiation, the chemical plating active center of formation is embedded in ceramic base material, with
The adhesive force of ceramic base material is the highest, so that subsequent chemistry coating also has higher adhesive force with ceramic base material；It addition,
The ceramic main body of energy beam radiation areas is etched, surface depressions, and surface roughness increases, the chemical deposit being therefore subsequently formed
Higher with the adhesive force of ceramic base material.It addition, the present invention is by selecting the kind of function powder and ceramic powder, find
Function powder use M titanate compound in one or more, M is V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, Tc,
Ru、Rh、Pd、Ag、Cd、Ta、W、Re、Os、Ir、Pt、Au、In、Sn、Sb、Pb、Bi、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、
In Ho, Er, Tm, Yb or Lu, ceramic powder selected from E titanate compound in one or more, E is Li, Na, K, Rb, Cs,
Be, Mg, Ca, Sr, Ba, Sc, Y, Lu, Zr, Hf, B, Al, Ga, Si, Ge, P, As or lanthanum element, by function powder and pottery
The coupling of powder body so that in the ceramic base material of formation, ceramic main body is preferable with the function ingredients compatibility, is formed in sintering procedure
Eutectic liquid phase thus reduce ceramic base material sintering temperature, increase ceramic base material sintered density, it is ensured that ceramic base material has
Higher mechanical performance；And required energy when function additive is converted into chemical plating active center in subsequent power bundle radiative process
Without too high, i.e. relatively low to the energy requirement of energy beam, can effectively reduce cost.
Detailed description of the invention
The invention provides a kind of Method of selective metallization on ceramic surface, comprise the following steps:
A. by ceramic composition molding, fire and obtain ceramic base material；Described ceramic composition includes ceramic powder and dispersion
Function powder in ceramic powder；Described function powder selected from M titanate compound in one or more, M is V, Cr,
Mn、Fe、Co、Ni、Cu、Zn、Nb、Mo、Tc、Ru、Rh、Pd、Ag、Cd、Ta、W、Re、Os、Ir、Pt、Au、In、Sn、Sb、Pb、Bi、
Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu；Ceramic powder is selected from the titanate compound of E
Kind or multiple, E be Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Y, Lu, Zr, Hf, B, Al, Ga, Si, Ge, P, As or
Lanthanum element；
B. use the selection area of energy beam radiation ceramic substrate surface, form chemical plating active center at selection area；
C., ceramic substrate surface through step B carries out chemical plating, and selection area forms metal level.
In the present invention, by molding, firing ceramics base material ceramic composition in component select, specifically
Ground, described ceramic composition includes ceramic powder and is scattered in function powder in ceramic powder, and wherein function powder is selected from the titanium of M
One or more in phosphate compounds, M is V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd,
Ta, W, Re, Os, Ir, Pt, Au, In, Sn, Sb, Pb, Bi, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or
Lu；Ceramic powder selected from E titanate compound in one or more, E is Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba,
Sc, Y, Lu, Zr, Hf, B, Al, Ga, Si, Ge, P, As or lanthanum element so that molding fire after ceramic base material on the one hand surface
There is higher roughness, the adhesive force of subsequent chemistry coating and ceramic base material can be improved, simultaneously because radiation areas pottery master
Body sink, and exposes function ingredients and forms chemical plating active center under energy beam effect, this chemical plating active center and pottery
The adhesive force of base material is higher, can be further ensured that the high adhesion force of ceramic base material and chemical deposit；Simultaneously as ceramic powder with
The selection coupling of function powder so that in the ceramic base material being subsequently formed, ceramic main body is preferable with the function ingredients compatibility, is burning
Form eutectic liquid phase during system thus reduce the sintering temperature of ceramic base material, increase the sintered density of ceramic base material, it is ensured that
Ceramic base material has higher mechanical performance；And function additive is converted in chemical plating activity in subsequent power bundle radiative process
During the heart, aequum is without too high, can effectively reduce cost.
Under preferable case, inventor find M be V, Cr, Mn, Fe, Zn, Nb, Mo, Tc, Ru, Cd, Ta, W, Re, Os, In,
When Sn, Sb, Pb, Bi, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, the activity of function powder is higher,
Subsequent transformation when being chemical plating active center required energy requirement lower.In the case of more preferably, function powder is selected from FeTiO3、Mn
(TiO3)2、PbTiO3、V(TiO3)2、Cr2(TiO3)3、ZnTiO3、Nb2(TiO3)5Time better.
When in described ceramic powder, E is Mg, Ca, Ba, Al or Sr, it is preferable with the matching of function powder so that follow-up
Ceramic composition ceramic powder and function powder in sintering process have a preferable compatibility, thus merit in molding sintering procedure
Can be easier to dispersed with ceramic powder by powder body, the ceramic base material obtained has good each to concordance；Ceramic powder simultaneously
In molding, sintering procedure, required sintering temperature is relatively low, and sintered density is higher, and the ceramic main body formed has more preferable machine
Tool performance.In the case of more preferably, ceramic powder is selected from MgTiO3、CaTiO3、BaTiO3、Al2(TiO3)3Or Ba0. 45 Sr0. 55
TiO3In one or more.
In the present invention, function powder is converted into function ingredients, then with adjacent part ceramic body in sintering procedure
Function ingredients forms chemical plating active center when later stage energy beam radiates, for the carrying out of catalytic chemistry plating.But, function powder
The content of body is unsuitable too high, otherwise can reduce the mechanical performance of ceramic base material.Therefore, in the present invention, total with ceramic composition
On the basis of quality, the content of ceramic powder is 70-99.998wt%, and the content of function powder is 0.002-30wt%.Preferable case
Under, on the basis of the gross mass of ceramic composition, the content of ceramic powder is 90-99.998wt%, and the content of function powder is
0.002-10wt%.In the case of more preferably, on the basis of the gross mass of ceramic composition, the content of ceramic powder is 98-
99.995wt%, the content of function powder is 0.005-2wt%.
The method according to the invention, first by ceramic composition molding, fire formation ceramic base material, whole function powder
Body forms composite construction with adjacent part ceramic precursor reactant, i.e. forms aforementioned function ingredients；Remaining ceramic powder is fired
Ceramic main body it is converted into after completing.Described molding, the step fired are known to those skilled in the art, i.e. use prior art
Disclosed in molding, fire step, such as, molding can first use polyvinyl alcohol (PVA) that ceramic composition is carried out pelletize,
Then using manual moulding press that the powder composition after pelletize is pressed into the base substrate of a diameter of 15mm, pressure is 10MPa；Then will
Base substrate is put into and is carried out binder removal sintering in batch-type furnace, obtains pottery.Wherein binder removal sintering process can be controlled by temperature programming, rise
Temperature speed is 5 DEG C/min, and dump temperature is 400-800 DEG C.Sintering temperature is 1000-2300 DEG C, can be according in ceramic composition
Component select.Under preferable case, in order to promote the dense sintering of ceramic powder, sintering process also can apply extra
Mechanical pressure, force value is chosen as 20-200MPa.
In the present invention, described sintering procedure can be carried out the most in atmosphere, it is possible in vacuum, oxygen or inert atmosphere
Carry out.Described inert atmosphere is nitrogen atmosphere commonly used in the prior art or inert gas atmosphere, such as, can be argon gas atmosphere,
But it is not limited to this.
As a kind of preferred implementation of the present invention, be directly combined with ceramic base material for improving subsequent chemistry coating
Power, present invention additionally comprises the step that ceramic base material carried out before step B (i.e. energy beam radiation) chemistry roughening.By to pottery
Porcelain base material carries out chemistry roughening, can strengthen the mechanical snap between subsequent chemistry coating and ceramic base material, thus improve chemical plating
Layer and the adhesion of ceramic base material.In the present invention, described chemistry roughening is various methods commonly used in the prior art, the most permissible
Ceramic base material is put into 100ml/L H2SO4With 2.0mol/L CrO3Solution in 50 DEG C of roughening 120min, but be not limited to this.
The method according to the invention, after molding firing ceramics base material, then carries out energy to the selection area of ceramic base material
Bundle radiation, forms chemical plating active center at selection area, then carries out chemical plating, thus forms metal-plated at this selection area
Layer.
The method according to the invention, uses the selection area on energy beam radiation ceramic surface, and the pottery of this selection area is main
Body is etched so that the ceramic main body of selection area sink, and exposes the function ingredients being scattered in ceramic main body, then merit accordingly
Component can generate chemical plating active center under energy beam effect, then carry out chemical plating, can be at chemical plating active center table
Face forms chemical deposit.In the present invention, owing to function ingredients is scattered in ceramic main body, so the chemical plating active center formed
It is embedded in ceramic main body, the highest with the adhesive force of ceramic base material, so that chemical deposit also has relatively with ceramic base material
High adhesive force；It addition, the ceramic main body of selection area is roughened by energy beam radiative process simultaneously, improves this and select
The roughness of the ceramic base material in region, therefore can improve the adhesive force of subsequent chemistry coating and ceramic base material further.
In the present invention, the energy beam used during energy beam radiation can be laser, electron beam or ion beam.Under preferable case,
In the present invention, energy beam radiation uses laser.The condition of laser emission includes: optical maser wavelength is 200-3000nm, and power is 5-
3000W.Under preferable case, the condition of laser emission also includes: frequency is 0.1-200KHz, and laser Trace speed is 0.01-
50000mm/s, fills spacing 0.01mm-5mm.The laser equipment used during laser emission can use common in the art each
Plant laser equipment, such as, can use YAG laser.
The condition of described electron beam irradiation includes: power density: 101-1011W/cm2.The equipment that electron beam irradiation uses can
Use various electron beam equipments common in the art, such as, can use electron beam lithography machine.Described ion beam irradiation
Condition includes: ion beam energy is 101-106eV.The equipment used during ion beam irradiation can use common in the art each
Plant ion beam apparatus, such as, can use Ar ion beam apparatus.
Described selection area can be the whole surface of pottery；It is the part of ceramic surface also dependent on required circuitry shapes
Region, after energy beam has radiated thus forms required circuit in this subregion.
In the present invention, the method for described chemical plating is the chemical plating method that those skilled in the art commonly use, such as can be by
Ceramics sample through energy beam radiation contacts with chemical bronze plating liquid.Gold after contacting with chemical bronze plating liquid, in chemical plating fluid
Belong to ion generation reduction reaction, generate metallic particles, be wrapped in surface, chemical plating active center, and be interconnected to form one layer of cause
The close coat of metal.In the present invention, the plating solution that chemical plating is used can be various chemical bronze plating liquids common in the art, change
Learn nickel-plating liquid or gold plating liquid, the present invention is not particularly limited.Consisting of of such as chemical bronze plating liquid: CuSO4·5H2O
0.12mol/L, Na2EDTA·2H2O 0.14mol/L, potassium ferrocyanide 10mg/L, 2,2 '-bipyridyl 10mg/L, glyoxalic acid
(HCOCOOH) 0.10mol/L, and with NaOH and H2SO4The pH value of regulation plating solution is 12.5-13.
In the present invention, the time carrying out chemical plating on chemical plating catalyst surface is not particularly limited, according to forming coating
THICKNESS CONTROL.In the present invention, the activity of selected function additive is higher, and the activity in the chemical plating active center of formation is corresponding
Higher, therefore plating speed during subsequent chemistry plating is the highest.
The region that ceramic substrate surface is not radiated by energy beam, function ingredients will not be converted into chemical plating active center, because of
This this region in plating process does not have the deposition of metallic particles.It addition, this region surface can not show a candle to energy beam radiation
Selection area rough surface, even if so there being small part metal particles deposition, also can wipe out easily owing to adhesion is poor, from
And realize the direct purpose in selective metallization on ceramic surface of the present invention.
As a kind of preferred implementation of the present invention, also can be to concluding that region is formed with the ceramic base material entirety of metal level
Make annealing treatment.By annealing, can effectively eliminate diffusible hydrogen remaining in coating and consequent bubble
Compressive stress, thus improve the consistency of coating, improve the adhesion of coating and ceramic base material further.Described annealing
Step is annealing common in the art, such as, can be that the ceramic base material entirety that surface is formed metal level is carried out
Heat treated, was slowly cooled to room temperature with stove after insulation a period of time.The step of described annealing can be at vacuum or indifferent gas
Atmosphere is carried out, but is not limited to this.
Present invention also offers a kind of pottery, including ceramic base material and the metal level of ceramic substrate surface selection area；Institute
The method that stating the pottery present invention provides obtains.Specifically, described ceramic base material includes ceramic main body and is scattered in ceramic main body
Function ingredients.Described function ingredients is composited with adjacent part ceramic body by function powder in sintering procedure, pottery
Porcelain main body is transformed by remaining ceramic powder sintering procedure.
In the present invention, the selection area of the ceramic substrate surface of described pottery has metal level, the pottery of this selection area
The thickness of base material is less than the ceramic base material thickness in other regions.Under preferable case, the thickness ratio of ceramic base material selection area is not
The little 0.01-500um of thickness of selection area.In the present invention, the thickness for ceramic base material, metal level is not particularly limited, can
Select according to actual needs；The structure of the metal level of ceramic substrate surface selection area can be one-dimensional, two-dimentional or three-dimensional
's.
The pottery that the present invention provides, can be applied to as power model, mechanical structure parts, welding base material, decoration
Various fields.For example, it is possible to be applied to vehicle electronics and communication electronic device, power electronic semiconductor module, power electricity
Power quasiconductor module, DC motor speed-regulating module, LED encapsulating carrier plate, LED assemble wiring board, high frequency switch power, solid-state relay
Device, Laser industry electronics, intelligent power assembly, space flight, aviation and weaponry, DC motor speed-regulating module, automatic transmission,
High frequency switch power, computer industry signal generator, IT integrated memory, digital processing element circuit, data converter electricity
Road, consumer electronics product, sensor circuit, pre-amplification circuit, power amplification circuit, Mechanics of Machinery carry, decorate, weld
Connect, the technical field such as sealing.
Below in conjunction with embodiment, the present invention is further explained explanation.Raw materials used in embodiment and comparative example all pass through
It is commercially available.
The first kind: embodiment 1-8, ceramic powder is high-purity magnesium titanate (MgTiO3)
Embodiment 1
(1) ceramic composition:
Ceramic powder: particle diameter is less than high-purity magnesium titanate (MgTiO of 3um3) 9.95 grams of powder；Function powder: iron titanate
(FeTiO3) 0.05 gram.
(2) being sufficiently mixed uniformly by ceramic composition, being subsequently adding 1 gram of concentration is 6wt%PVA solution, grinds pelletize；So
Powder after pelletize is pressed into the base substrate of diameter 15mm by the manual moulding press of rear employing, and it is airtight that pressure is that 10MPa, just base substrate put into
Vacuum box type stove in binder removal, sintering, heating rate is 5 DEG C/min, dump temperature 575 DEG C, and sintering temperature 1450 DEG C is cold with stove
But ceramic base material is obtained.
(3) ceramic base material is first washed away with clear water the spot on surface, is then placed in 1.5mol/L, in the NaOH solution of 50 DEG C
Clean 15min, then be washed with deionized water clean；Put into 100ml/L H afterwards2SO4With 2.0mol/L CrO3Solution in 50 DEG C
Roughening 120min, is washed with deionized water clean afterwards.
(4) ceramic base material through step (3) be placed in the YAG laser that wavelength is 1064nm carry out laser emission,
Power is 50W, and frequency is 25KHz, and Trace speed is 100mm/s, and filling spacing is 0.1mm.
(5) sulfuric acid solution that the ceramic base material after laser emission is put into 5wt% cleans 1min, afterwards by ceramic base
Material is suspended in electroless copper, constantly blasts air with air agitator during plating, and temperature controls, at 50 DEG C, to change
Learn plating 1h.
(6) the chemical plating sample through step (5) is heated under vacuum 850 DEG C of insulation 15min, afterwards with stove
It is cooled to room temperature, obtains sample S1.
Embodiment 2
Use step same as in Example 1 to prepare ceramic base material, and ceramic surface is metallized, obtain sample note
For S2, difference is: in step (1), and function powder is manganese titanate (Mn (TiO3)2) 0.05 gram.
Embodiment 3
Use step same as in Example 1 to prepare ceramic base material, and ceramic surface is metallized, obtain sample note
For S3, difference is: in step (1), and function powder is lead titanates (PbTiO3) 0.05 gram.
Embodiment 4
Use step same as in Example 1 to prepare ceramic base material, and ceramic surface is metallized, obtain sample note
For S4, difference is: in step (1), and function powder is metatitanic acid vanadium (V (TiO3)2) 0.05 gram.
Embodiment 5
Use step same as in Example 1 to prepare ceramic base material, and ceramic surface is metallized, obtain sample note
For S5, difference is: in step (1), and function powder is metatitanic acid chromium (Cr2(TiO3)3) 0.05 gram.
Embodiment 6
Use step same as in Example 1 to prepare ceramic base material, and ceramic surface is metallized, obtain sample note
For S6, difference is: in step (1), and function powder is zinc titanate (ZnTiO3) 0.05 gram.
Embodiment 7
Use step same as in Example 1 to prepare ceramic base material, and ceramic surface is metallized, obtain sample note
For S7, difference is: in step (1), and function powder is niobium titanate (Nb2(TiO3)5) 0.05 gram；In step (3), use
Power density is 105W/cm2Electron beam substitute laser ceramic substrate surface is radiated.
Embodiment 8
Use step same as in Example 1 to prepare ceramic base material, and ceramic surface is metallized, obtain sample note
For S8, difference is: in step (1), and function powder is niobium titanate (Nb2(TiO3)5)0.05 gram；In step (3), use
Energy is that ceramic substrate surface is radiated by the ion beam replacement laser of 10keV.
Equations of The Second Kind: embodiment 9-15, ceramic powder is high-purity magnesium titanate (MgTiO that particle diameter is less than 3 μm3) powder and high purity titanium
Acid calcium (CaTiO3) uniform mixed powder
Embodiment 9
Use step same as in Example 1 to prepare ceramic base material, and ceramic surface is metallized, obtain sample note
For S9, difference is: in step (1), and ceramic powder is high-purity magnesium titanate (MgTiO that particle diameter is less than 3 μm3) powder and high-purity
Calcium titanate (CaTiO3) uniform mixed powder 9.95 grams, the mass ratio of magnesium titanate and calcium titanate is 0.95:0.05；In step (2),
Sintering temperature is 1360 DEG C.
Embodiment 10
Use step the same as in Example 9 to prepare ceramic base material, and ceramic surface is metallized, obtain sample note
For S10, difference is: in step (1), and function powder is manganese titanate (Mn (TiO3)2)0.05 gram.
Embodiment 11
Use step the same as in Example 9 to prepare ceramic base material, and ceramic surface is metallized, obtain sample note
For S11, difference is: in step (1), and function powder is lead titanates (PbTiO3) 0.05 gram.
Embodiment 12
Use step the same as in Example 9 to prepare ceramic base material, and ceramic surface is metallized, obtain sample note
For S12, difference is: in step (1), and function powder is metatitanic acid vanadium (V (TiO3)2) 0.05 gram；In step (2), batch-type furnace
In be oxygen atmosphere.
Embodiment 13
Use step the same as in Example 9 to prepare ceramic base material, and ceramic surface is metallized, obtain sample note
For S13, difference is: in step (1), and function powder is metatitanic acid chromium (Cr2(TiO3)3) 0.05 gram；In step (2), box
It stove is nitrogen atmosphere.
Embodiment 14
Use step the same as in Example 9 to prepare ceramic base material, and ceramic surface is metallized, obtain sample note
For S14, difference is: in step (1), and function powder is zinc titanate (ZnTiO3) 0.05 gram.
Embodiment 15
Use step the same as in Example 9 to prepare ceramic base material, and ceramic surface is metallized, obtain sample note
For S15, difference is: in step (1), and function powder is niobium titanate (Nb2(TiO3)5) 0.05 gram.
3rd class: embodiment 16-23, ceramic powder is that particle diameter is less than 3 μm Barium metatitanate. (BaTiO3)
Embodiment 16
Use step same as in Example 1 to prepare ceramic base material, and ceramic surface is metallized, obtain sample note
For S16, difference is: in step (1), and ceramic powder is that particle diameter is less than 3 μm Barium metatitanate. (BaTiO3) 9.95 grams；Step
(2), in, sintering temperature is 1400 DEG C.
Embodiment 17
Use the step identical with embodiment 16 to prepare ceramic base material, and ceramic surface is metallized, obtain sample
Being designated as S17, difference is: in step (1), and function powder is manganese titanate (Mn (TiO3)2) 0.05 gram.
Embodiment 18
Use the step identical with embodiment 16 to prepare ceramic base material, and ceramic surface is metallized, obtain sample
Being designated as S18, difference is: in step (1), and in step (1), function powder is lead titanates (PbTiO3) 0.05 gram.
Embodiment 19
Use the step identical with embodiment 16 to prepare ceramic base material, and ceramic surface is metallized, obtain sample
Being designated as S19, difference is: in step (1), and function powder is metatitanic acid vanadium (V (TiO3)2) 0.05 gram.
Embodiment 20
Use the step identical with embodiment 16 to prepare ceramic base material, and ceramic surface is metallized, obtain sample
Being designated as S20, difference is: in step (1), and function powder is metatitanic acid chromium (Cr2(TiO3)3) 0.05 gram.
Embodiment 21
Use the step identical with embodiment 16 to prepare ceramic base material, and ceramic surface is metallized, obtain sample
Being designated as S21, difference is: in step (1), and function powder is zinc titanate (ZnTiO3) 0.05 gram.
Embodiment 22
Use the step identical with embodiment 16 to prepare ceramic base material, and ceramic surface is metallized, obtain sample
Being designated as S22, difference is: in step (1), and function powder is niobium titanate (Nb2(TiO3)5)0.05 gram.
Embodiment 23
Use the step identical with embodiment 16 to prepare ceramic base material, and ceramic surface is metallized, obtain sample
Being designated as S23, difference is: in step (1), and function powder is lead titanates (PbTiO3) and cobalt titanate (CoTiO3) uniform
Mixed powder 0.05 gram, wherein the mass ratio of lead titanates and cobalt titanate is 1:1.
4th class: embodiment 24-30, ceramic powder is aluminium titanates (Al2(TiO3)3)
Embodiment 24
Use step same as in Example 1 to prepare ceramic base material, and ceramic surface is metallized, obtain sample note
For S24, difference is: in step (1), and ceramic powder is aluminium titanates (Al2(TiO3)3) 9.95 grams；In step (2), burn
Junction temperature is 1500 DEG C.
Embodiment 25
Use the step identical with embodiment 24 to prepare ceramic base material, and ceramic surface is metallized, obtain sample
Being designated as S25, difference is: in step (1), and function powder is manganese titanate (Mn (TiO3)2) 0.05 gram.
Embodiment 26
Use the step identical with embodiment 24 to prepare ceramic base material, and ceramic surface is metallized, obtain sample
Being designated as S26, difference is: in step (1), and function powder is lead titanates (PbTiO3)0.05 gram.
Embodiment 27
Use the step identical with embodiment 24 to prepare ceramic base material, and ceramic surface is metallized, obtain sample
Being designated as S27, difference is: in step (1), and function powder is metatitanic acid vanadium (V (TiO3)2)0.05 gram.
Embodiment 28:
Use the step identical with embodiment 24 to prepare ceramic base material, and ceramic surface is metallized, obtain sample
Being designated as S28, difference is: in step (1), and function powder is metatitanic acid chromium (Cr2(TiO3)3) 0.05 gram.
Embodiment 29
Use the step identical with embodiment 24 to prepare ceramic base material, and ceramic surface is metallized, obtain sample
Being designated as S29, difference is: in step (1), and function powder is zinc titanate (ZnTiO3) 0.05 gram.
Embodiment 30
Use the step identical with embodiment 24 to prepare ceramic base material, and ceramic surface is metallized, obtain sample
Being designated as S30, difference is: in step (1), and function powder is niobium titanate (Nb2(TiO3)5) 0.05 gram.
5th class: embodiment 31-37, ceramic powder is barium strontium titanate (Ba0. 45 Sr0. 55 TiO3)
Embodiment 31
Use step same as in Example 1 to prepare ceramic base material, and ceramic surface is metallized, obtain sample note
For S31, difference is: in step (1), and ceramic powder is that particle diameter is less than 3 μm barium strontium titanate (Ba0. 45 Sr0. 55 TiO3)
9.95 gram；In step (2), sintering temperature is 1380 DEG C
Embodiment 32:
Use the step identical with embodiment 31 to prepare ceramic base material, and ceramic surface is metallized, obtain sample
Being designated as S32, difference is: in step (1), and function powder is manganese titanate (Mn (TiO3)2) 0.05 gram.
Embodiment 33
Use the step identical with embodiment 31 to prepare ceramic base material, and ceramic surface is metallized, obtain sample
Being designated as S33, difference is: in step (1), and in step (1), function powder is lead titanates (PbTiO3) 0.05 gram.
Embodiment 34
Use the step identical with embodiment 31 to prepare ceramic base material, and ceramic surface is metallized, obtain sample
Being designated as S34, difference is: in step (1), and function powder is metatitanic acid vanadium (V (TiO3)2) 0.05 gram.
Embodiment 35
Use the step identical with embodiment 31 to prepare ceramic base material, and ceramic surface is metallized, obtain sample
Being designated as S35, difference is: in step (1), and function powder is metatitanic acid chromium (Cr2(TiO3)3) 0.05 gram.
Embodiment 36
Use the step identical with embodiment 31 to prepare ceramic base material, and ceramic surface is metallized, obtain sample
Being designated as S36, difference is: in step (1), and function powder is zinc titanate (ZnTiO3) 0.05 gram.
Embodiment 37
Use the step identical with embodiment 31 to prepare ceramic base material, and ceramic surface is metallized, obtain sample
Being designated as S37, difference is: in step (1), and function powder is niobium titanate (Nb2(TiO3)5)0.05 gram.
Comparative example 1
Carry out according to step disclosed in CN101550546A embodiment 4: nano-titanium dioxide powder is coated on glass multiple
Condensation material surface, is then immersed in 1.5L chemical nickel-plating liquid, temperature range 20-40 DEG C, does not stop stirring；It is 400nm's at wavelength
Irradiate 10-30min under ultraviolet light and carry out chemical plating, obtain glass sample DS1.
Comparative example 2
Carry out according to step disclosed in CN101684551A embodiment 3: the copper nitrate solution of preparation 0.01mol/L, solvent
For isopropanol, polyvinyl alcohol, water, add 12g polyacrylic resin after logical nitrogen deoxygenation, be then spin coated onto in ceramic surface, spin coating
Technological parameter: 800 turns/min, 5s；Then move under the gamma-rays (mobaltron of Shenzhen Chang Yuan company) of 60Gy/min
Irradiate 3min, finally carry out electroless copper, obtain ceramics sample and be designated as DS2.
Performance test:
1, adhesive force test: use method disclosed in ISO 2409 that each sample Y1-Y10 and DY1-DY2 are surveyed as follows
Examination: use the knife back of surgical knife or the intersection cutter specified at ceramic substrate surface metal level Shang Hua 12 road cut, two
Scratch is mutually the most at an angle of 90, in order to form grid from the teeth outwards, if cut be spaced apart the most standardized of 1mm(surface too I
Fork, i.e. 2 road cuts).Guarantee to be cut to ceramic substrate surface；Otherwise, the position of Ying Xin is cut again.Direction along cut
With brush brush 5 times.Viscous for 3M adhesive tape 600 from the teeth outwards, with finger tip, wiping belt is tight, it is ensured that with the good contact of metal level, 5
In minute, from the free end of adhesive tape, angle with 60 ° tore well-regulated for adhesive tape opening off adhesive tape in 0.5 second.As do not appointed
What comes off for 5B, and the amount of coming off is 4B between 0-5%, is 3B between 5-15%, is 2B between 15-35%, is 1B between 35-65%,
More than 65% is 0B.
2, coating cold-hot shock-testing: the knife back using surgical knife or the intersection cutter specified are at ceramic base material table
Metal level Shang Hua 12 road, face cut, two scratches are the most at an angle of 90, in order to form grid from the teeth outwards, cut be spaced apart 1mm
(if the most standardized fork of surface too I, i.e. 2 road cuts).Guarantee to be cut to ceramic substrate surface；Otherwise, the position of Ying Xin
Again cut.Direction brush brush 5 times along cut.Chilling in water is put into rapidly after sample is incubated at 300 DEG C 0.5h,
Observe the situation that warps, do not warp and be designated as OK, warp and be designated as NG.
Test result is as shown in table 1.
Table 1
。
From the test result of upper table 1 it can be seen that ceramic surface is metallized by the method using the present invention to provide, shape
The coat of metal become obtains bigger raising with the adhesive force of ceramic base material.
Claims (14)
1. a Method of selective metallization on ceramic surface, it is characterised in that comprise the following steps:
A. by ceramic composition molding, fire and obtain ceramic base material；Described ceramic composition includes ceramic powder and is scattered in pottery
Function powder in porcelain powder body；Described function powder selected from M titanate compound in one or more, M be vanadium, chromium, manganese,
Ferrum, cobalt, nickel, copper, zinc, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, indium, stannum, antimony, lead, bismuth,
Cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutecium element；Ceramic powder is in the titanate compound of E
One or more, E be lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, silicon, germanium, phosphorus, arsenic, scandium, yttrium, zirconium,
Hafnium or lanthanum element；
B. use the selection area of energy beam radiation ceramic substrate surface, form chemical plating active center at selection area；
C., ceramic substrate surface through step B carries out chemical plating, and selection area forms metal level.
Method the most according to claim 1, it is characterised in that M be vanadium, chromium, manganese, ferrum, zinc, niobium, molybdenum, technetium, ruthenium, cadmium, tantalum,
Tungsten, rhenium, osmium, indium, stannum, antimony, lead, bismuth, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutecium element.
Method the most according to claim 1 and 2, it is characterised in that function powder is selected from FeTiO3、Mn(TiO3)2、
PbTiO3、V(TiO3)2、Cr2(TiO3)3、ZnTiO3、Nb2(TiO3)5In one or more.
Method the most according to claim 1, it is characterised in that E is magnesium, calcium, barium, aluminum or strontium.
5. according to the method described in claim 1 or 4, it is characterised in that ceramic powder is selected from MgTiO3、CaTiO3、BaTiO3、
Al2(TiO3)3、Ba0. 45 Sr0. 55 TiO3In one or more.
Method the most according to claim 1, it is characterised in that on the basis of the gross mass of ceramic composition, ceramic powder
Content be 70-99.998wt%, the content of function powder is 0.002-30wt%.
Method the most according to claim 6, it is characterised in that on the basis of the gross mass of ceramic composition, ceramic powder
Content be 90-99.998wt%, the content of function powder is 0.002-10wt%.
Method the most according to claim 7, it is characterised in that on the basis of the gross mass of ceramic composition, ceramic powder
Content be 98-99.9 95wt%, the content of function powder is 0.005-2wt%.
Method the most according to claim 1, it is characterised in that firing at vacuum, air, oxygen atmosphere of ceramic composition
Or inert atmosphere is carried out.
Method the most according to claim 1, it is characterised in that before being additionally included in step B, ceramic base material is carried out chemistry
The step of roughening.
11. methods according to claim 1, it is characterised in that described energy beam is laser, electron beam or ion beam；Swash
The condition of light radiation includes: optical maser wavelength is 200-3000nm, and power is 5-3000W；The power density of electron beam irradiation is
101-1011W/cm2；The ion beam energy of ion beam irradiation is 101-106eV。
12. methods according to claim 11, it is characterised in that the condition of laser emission also includes: frequency is 0.1-
200KHz, laser Trace speed is 0.01-50000mm/s, fills spacing 0.01mm-5mm.
13. methods according to claim 1, it is characterised in that also include that selection area is formed with the ceramic base of metal level
Material entirety carries out the step made annealing treatment in vacuum or inert atmosphere.
14. 1 kinds of potteries, it is characterised in that described pottery includes ceramic base material and the metal of ceramic substrate surface selection area
Layer；Described pottery is obtained by the method described in any one of claim 1-13.
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| CN105057919B (en) * | 2015-09-16 | 2017-04-05 | 江苏科技大学 | For Si3N4The material and preparation method of ceramic surface metallization and soldering processes |
| CN106544654B (en) * | 2015-09-23 | 2019-04-19 | 比亚迪股份有限公司 | A kind for the treatment of fluid and its application and metallized product and method |
| CN106747287A (en) * | 2016-12-15 | 2017-05-31 | 苏州富艾姆工业设备有限公司 | A kind of production technology of ceramic packing |
| CN106512917A (en) * | 2016-12-15 | 2017-03-22 | 苏州富艾姆工业设备有限公司 | Particle filler production process |
| CN108054106B (en) * | 2018-01-11 | 2020-03-27 | 北京大学东莞光电研究院 | Method for preparing high-heat-dissipation ceramic packaging substrate |
| CN108558391B (en) * | 2018-06-26 | 2020-10-09 | 桂林电子科技大学 | Lead-free piezoelectric ceramic with giant piezoelectric response and preparation method thereof |
| DE102019109308A1 (en) | 2019-04-09 | 2020-10-15 | Tdk Electronics Ag | Ceramic component and method for producing the ceramic component |
| CN110950645A (en) * | 2019-12-10 | 2020-04-03 | 萍乡华鹏电瓷集团有限公司 | Preparation method of electric porcelain insulator for high-voltage transmission line |
| CN114163259B (en) * | 2021-12-14 | 2023-05-23 | 东莞智昊光电科技有限公司 | Method for metallizing ceramic surface and metallized ceramic |
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