CN109650871A - A kind of ZnAl2O4Ceramic systems material and preparation method thereof - Google Patents
A kind of ZnAl2O4Ceramic systems material and preparation method thereof Download PDFInfo
- Publication number
- CN109650871A CN109650871A CN201910084152.7A CN201910084152A CN109650871A CN 109650871 A CN109650871 A CN 109650871A CN 201910084152 A CN201910084152 A CN 201910084152A CN 109650871 A CN109650871 A CN 109650871A
- Authority
- CN
- China
- Prior art keywords
- glass
- silicate glass
- znal
- zinc
- borated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/36—Glass starting materials for making ceramics, e.g. silica glass
- C04B2235/365—Borosilicate glass
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
Abstract
A kind of ZnAl2O4Ceramic systems material and preparation method thereof belongs to ceramic material and preparation technical field.Material of the present invention includes the glass of mass fraction 60%~70% and the aluminium oxide that mass fraction is 30%~40%；The glass is the mixture of potassium aluminium borated silicate glass and zinc borated silicate glass, and wherein the mass fraction of potassium aluminium borated silicate glass is 30%~56%, and the mass fraction of zinc borated silicate glass is 12%~35%；Glass and aluminium oxide are made for (810 DEG C~850 DEG C) of low-temperature sintering after mixing, drying, molding.ZnAl is made in the present invention2O4The dielectric constant of ceramic systems material is that 4.65~4.98, Q × f value is 4746~7360GHz, and thermal expansion coefficient is 4.7~5.6ppm/ DEG C, and bending strength is 150~202Mpa.The present invention compares existing ZnAl2O4Base ceramic material significantly reduces sintering temperature, LTCC technology can be compatible with for circuit integration, and dielectric properties and mechanical performance are excellent, while preparation method is simple, cost of material is low, it is essentially identical with the preparation process of traditional glass ceramics, there is good technology stability.
Description
Technical field
The invention belongs to ceramic material and preparation technical fields, and in particular to a kind of ZnAl2O4Ceramic systems material and its system
Preparation Method.
Background technique
Microwave-medium ceramics are one of the novel information ceramic materials that recent decades grow up, and are current information function
The research emphasis of energy material.With the rapid growth in the consumer electronics market of wireless telecommunication system and microwave device, it is desirable that electricity
Sub- component develops towards high frequency, highly integrated, micromation, lighting, multifunction, cost effective direction.This is simultaneously
Also the microwave electron component for requiring microwave dielectric ceramic materials to make has more preferably dielectric properties.
Low-temperature co-fired ceramics (Low Temperature Co-fired ceramics, LTCC) technology can effectively exist
Multilayered structure circuit is designed on three-dimensional space, is a kind of good solution in face of current numerous demands.LTCC technology group
It closes many ceramics and conductor thin layer forms multilayer module, while integrating Passive components such as strip transmission line, antenna, filtering
The entire module realization of the Joint Designings such as device, resonator, capacitor, inductance, frequency divider is more multi-functional, can be used for manufacturing chip multilayer member
Part and multilayer module obtain the microwave electron element for meeting application request, meet the micro- of all kinds of microwave devices in circuit
Type, integrated, modular requirement.Wherein, largely used when designing three dimensional wiring advanced low-k materials (ε be 4~
9), it follows that the ceramic material of low-k is the continuous pursuit of the current and following LTCC technology.On the other hand, with
The working frequency of communication equipment is further expanded to high-frequency range, and material polarization loss problem and signal delay phenomenon are more bright
Aobvious, system loss and calorific value can also increase with it, and when material dielectric constant reduction, the signal transmission rate and quality of material
Factor can be significantly improved, at this point, with the continuous improvement of running frequency, after millimere-wave band, communicator
Part size is about millimeter magnitude, is deteriorated compared to system stability, and the miniaturization of device has become relatively inessential.So
In order to overcome frequency to widen bring great number of issues, the dielectric that microwave device must be reduced while guaranteeing high quality factor is normal
Number.Meanwhile LTCC technology requires to carry out multilayer wiring cofiring, these metal materials with the metal of the high conductivities low costs such as silver or copper
Material has lower conductor losses and low resistance in frequency applications, but since the fusing point of metal Ag and Cu electrode is lower, this is just
It is required that the sintering temperature of LTCC microwave dielectric ceramic materials can be lower than the melting temperature of electrode.It is situated between for this purpose, research and development have
Electric constant and high quality factor and can low sintering microwave dielectric ceramic materials, to realize the further of modern communication technology
Development is the necessary trend and requirement of future communications career development, is also to provide the important guarantee of communication quality and service.
The LTCC material of Current commercial generally has the relative dielectric constant higher than 5, as Dupont951 (ε=7.85,
δ=0.0063 tan), Dupont943 (δ=0.002 ε=7.5, tan), Heraeus CT800 (ε=7.68, tan δ=
0.0039) etc..There is the dielectric constant of part business LTCC material lower than 5, such as Kyocera GL530 (ε=4.9, Q × f=
3330GHz), NEC glass MLS 25M (ε=4.7, Q × f=720GHz).However, being lower than 5 and Q × f about dielectric constant
The research of LTCC material higher than 5000 is deficienter.
LTCC material includes glass ceramics system and devitrified glass system.Wherein, with Ferro A6 in devitrified glass system
To represent, its dielectric constant is 5.7 ± 0.2, tan δ < 0.1% under 10GHz frequency.And for glass ceramics system, it is most of
Research be all to ultimately form the glass ceramic material using aluminium oxide as principal crystalline phase using aluminium oxide as ceramic fillers.Oxidation
The dielectric constant of aluminium is 9.8, therefore to be generally higher than 5 and Q × f lower for obtained glass ceramic material dielectric constant.Such as
In the research of Xingyu Chen, with SiO2–B2O3Sintering aid of-CaO-MgO the glass as aluminium oxide, acquisition are with aluminium oxide
It is 0.0015 that the glass ceramic material of principal crystalline phase dielectric constant at 1MHz, which is 7.3, tan δ,.And in the research of I.J.Induja
In, using K-Ba-Si glass as the sintering aid of aluminium oxide, obtaining using aluminium oxide is the glass ceramic material of principal crystalline phase in 1MHz
Lower dielectric constant is 4.8, but glass ceramic material loss is bigger than normal, and tan δ is 0.007.
ZnAl2O4Base ceramic material is a kind of novel high quality factor microwave dielectric ceramic materials of Recent study report,
It has lower dielectric constant and higher quality factor, is a kind of Novel microwave dielectric ceramic with wide Research Prospects
Material.However, ZnAl2O4The comprehensive performance of base microwave dielectric ceramics is ideal not enough, and ZnAl2O4The sintering of microwave ceramics
Temperature is more than 1400 DEG C.And in actual augmentation work, when one of or two kinds of performances, which obtain, to be improved, other performances are past
Toward by large effect, this just gives ZnAl2O4The research of ceramic systems brings challenge.In the research of K.P.Surendran
In, ZnAl that they prepare under 1425 DEG C of sintering temperature2O4The dielectric constant of microwave ceramics is 8.5 (than the dielectric of aluminium oxide
Constant is low) and its Q × f be 56319GHz.K.P.Surendran's research shows that with ZnAl2O4To facilitate glass when principal crystalline phase
Ceramics obtain lower dielectric constant and higher Q × f.In the research of Sang Ok Yoon, by adding Zn-B-Si glass
As the sintering aid of aluminium oxide, obtain with ZnAl2O4For the glass ceramic material of principal crystalline phase, which has 5.72~
6.61 dielectric constant, Q × f value are 17757GHz, and densification sintering temperature is 900 degree, however, Sang Ok Yoon is obtained
Glass ceramics there are the second crystal phase aluminium oxide, dielectric constant is 6 or so.In addition, in the research of summer qin, by individually adding
Sintering aid of the KABS glass as aluminium oxide, it is 0.002 that the material of acquisition dielectric constant at 1MHz, which is 6.1, tan δ,.
To sum up, one kind is studied with ZnAl2O4Have for principal crystalline phase, dielectric constant lower than 5, the higher glass ceramics of Q × f value
Wide market application prospect.
Summary of the invention
In view of the demand of the prior art, and loss larger problem higher for current glass ceramic material dielectric constant,
The present invention provides a kind of ZnAl with low-k, high quality factor and sintering temperature and low2O4Ceramic systems material and its system
Preparation Method.
Technical scheme is as follows:
The one side present invention provides a kind of ZnAl2O4Ceramic systems material, which is characterized in that including mass fraction 60%~
The aluminium oxide that 70% glass and mass fraction is 30%~40%；The glass is potassium aluminium borated silicate glass and zinc borosilicate system glass
The mixture of glass, wherein the mass fraction of potassium aluminium borated silicate glass is 30%~56%, and the mass fraction of zinc borated silicate glass is
12%~35%；Glass and aluminium oxide are made through mixing, drying, molding, sintering.
It is preferred that the mass fraction of the potassium aluminium borated silicate glass is 30%~36%, zinc borated silicate glass
Mass fraction is 24%~35%, and with this condition, the crystalline phase of the microwave dielectric ceramic materials is single ZnAl2O4Phase.
Further, the raw material of the potassium aluminium borated silicate glass includes K2O, Al2O3, B2O3And SiO2。
It is preferred that the raw material of the potassium aluminium borated silicate glass further includes Na2O, Na2The addition of O in system itself
Existing K2O forms double alkali effects, and then reduces dielectric loss.
It is preferred that the raw material of the potassium aluminium borated silicate glass further includes Y2O3, Y2O3Addition facilitate enhance glass
The chemical stability of glass system.
Further, the group of the potassium aluminium borated silicate glass becomes 2%~4% K2O, 1%~4% Al2O3, 10%
~16% B2O3, 70%~80% SiO2, 0.5%~2% Na2O, 0.2%~0.8% Y2O3。
Further, the raw material of the potassium aluminium borated silicate glass includes ZnO, B2O3And SiO2。
It is preferred that the raw material of the zinc borated silicate glass further includes Al2O3, Al2O3Addition contribute to form
[AlO4] structure, and then improve glass bending strength.
Further, the group of the zinc borated silicate glass becomes 70%~80% ZnO, 10%~18% B2O3, 10%
~15% SiO2, 1%~2% Al2O3。
Further, the ZnAl2O4The dielectric constant of ceramic systems material be 4.65~4.98, Q × f value be 4746~
7360GHz, thermal expansion coefficient are 4.7~5.6ppm/ DEG C, and bending strength is 150~202Mpa.
On the other hand.The present invention provides a kind of ZnAl2O4The preparation method of ceramic systems material, which is characterized in that including such as
Lower step:
Step 1: ingredient；
By K2O, Al2O3, B2O3, SiO2Raw material as potassium aluminium borated silicate glass carries out ingredient, by ZnO, B2O3, SiO2Make
Ingredient is carried out for the raw material of zinc borated silicate glass；
Step 2: a ball milling；
The raw material of potassium aluminium borated silicate glass and the raw material of zinc borated silicate glass prepare to step 1 carries out a ball respectively
Mill, two bulb abrasive material of gained after the completion of ball milling, dried and be sieved, obtain potassium aluminium borosilicate system's powder and zinc borosilicate system powder；
Step 3: melten glass；
Potassium aluminium borosilicate system's powder made from heating stepses 2 and zinc borosilicate system powder are melted respectively, and in molten condition
Obtained glass melt is quenched rapidly down, thus respectively obtains potassium aluminium borated silicate glass and zinc borated silicate glass；
Step 4: secondary ball milling；
Secondary ball milling is carried out to aluminium oxide is added in the mixture of potassium aluminium borated silicate glass and zinc borated silicate glass powder,
In, the mass fraction that the quality sum of potassium aluminium borated silicate glass and zinc borated silicate glass powder accounts for gross mass is 60%~70%,
The mass fraction that the quality of aluminium oxide accounts for gross mass is 30%~40%；After the completion of ball milling, by the drying of gained ball milling material and mistake
Sieve, obtains the mixed powder of glass and alumina filler；
Step 5: being granulated, molding, dumping；
It is granulated to granulating agent is added in the mixed powder of the glass and alumina filler, is given birth to through molding
Base, and the green compact are subjected to dumping；
Step 6: sintering；
It is sintered obtained green compact are handled through step 5 1~3 hour under 810 DEG C~850 DEG C of atmospheric atmosphere, it is naturally cold
But low sintering ZnAl is obtained afterwards2O4Ceramic systems material.
Further, the raw material of potassium aluminium borated silicate glass further includes Na in the step 12O, Na2The addition of O is the same as in system
Existing K itself2O forms double alkali effects, and then reduces dielectric loss.
Further, the raw material of potassium aluminium borated silicate glass further includes Y in the step 12O3, Y2O3Addition help to increase
The chemical stability of strong glass system.
Further, in the step 1 potassium aluminium borated silicate glass group become 2%~4% K2O, 1%~4%
Al2O3, 10%~16% B2O3, 70%~80% SiO2, 0.5%~2% Na2O, 0.2%~0.8% Y2O3。
Further, the raw material of zinc borated silicate glass further includes Al in the step 12O3, Al2O3Addition facilitate shape
At [AlO4] structure, and then improve glass bending strength.
Further, in the step 1 group of zinc borated silicate glass become 70%~80% ZnO, 10%~18%
B2O3, 10%~15% SiO2, 1%~2% Al2O3。
Further, the operation of a ball milling is specific as follows in the step 2: using deionized water as solvent, using dioxy
Change zirconium ball is ball-milling medium, and by raw material ball milling mixing in planet-shaped ball mill, the mass ratio of solvent, ball-milling medium and material is
(0.6~1):, (4~6): (0.5~1.5), Ball-milling Time be 3~6 hours.
Further, the heating temperature of potassium aluminium borosilicate system powder is 1300~1500 DEG C in the step 3.
Further, the heating temperature of zinc borosilicate system powder is 1350~1500 DEG C in the step 3.
Further, the heating rate heated in the step 3 is 2~4 DEG C/min.
Further, the mass fraction of potassium aluminium borated silicate glass is preferably 30%~36% in the step 4, zinc borosilicate system
The mass fraction of glass is preferably 24%~35%, and with this condition, the microwave dielectric ceramic materials are single ZnAl2O4
Crystalline phase.
Further, the operation of secondary ball milling is specific as follows in the step 5: using deionized water as solvent, using dioxy
Change zirconium ball is ball-milling medium, and by raw material ball milling mixing in planet-shaped ball mill, the mass ratio of solvent, ball-milling medium and material is
(0.6~1):, (4~6): (0.5~1.5), Ball-milling Time be 3~6 hours.
Further, ZnAl is made in the present invention2O4The dielectric constant of ceramic systems material is that 4.65~4.98, Q × f value is
4746~7360GHz, thermal expansion coefficient are 4.7~5.6ppm/ DEG C, and bending strength is 150~202Mpa.
Compared with prior art, beneficial effects of the present invention are as follows:
The present invention can be obtained with ZnAl2O4For the microwave dielectric ceramic materials of single crystalline phase, and gained ceramic systems
The excellent combination property of material.The dielectric constant of material has reached the level (ε is 4.65~4.98) lower than 5, this is highly beneficial
In the transmission rate for improving electric signal and reduce material and the loss of interelectrode coupling interaction, while Q × f value is higher, microwave
The dielectric loss of signal is smaller, and the frequency range especially suitable for component improves, and densification can be carried out at 810 DEG C~850 DEG C
Existing ZnAl is compared in sintering2O4Base ceramic material significantly reduces sintering temperature, can be compatible with LTCC technology and be used for circuit integration,
Its excellent electric property, thermal property, mechanical performance and operational characteristic is played, promotes electronic component to micromation, integrate
Change the developing direction with multifunction；Ceramic systems material of the present invention has preferable bending strength maximum (up to 202Mpa),
Compact structure meets the needs of base application；Ceramic systems material of the present invention also has the thermal expansion system with GaAs match materials
Number (thermal expansion coefficient of GaAs be 5.5ppm/ DEG C), when use material package GaAs of the present invention for the integrated electricity of semiconductor material
The problem of road chip is avoided that package failure.In addition, the preparation method of ceramic systems material of the present invention is simple, cost of material is low,
It is essentially identical with the preparation process of traditional glass ceramics, there is good technology stability.
Detailed description of the invention
Fig. 1 is the obtained ZnAl of the embodiment of the present invention 1 to 42O4The XRD spectrum of ceramic systems material.
Fig. 2 is the obtained ZnAl of the embodiment of the present invention 1 to 42O4SEM figure of the ceramic systems material under 10 microns.
Fig. 3 is that ZnAl is made in the embodiment of the present invention 42O4SEM figure of the ceramic systems material under 20 microns.
Specific embodiment
In order to enable one of ordinary skill in the art can more understand the present invention program and principle, with reference to the accompanying drawing and have
Body embodiment is described in detail.The contents of the present invention are not limited to any specific embodiment, and also not representing is most preferred embodiment,
General substitution well-known to those skilled in the art is also encompassed within the scope of the invention.
Embodiment 1；
The present embodiment provides a kind of ZnAl2O4The preparation method of ceramic systems material, which comprises the steps of:
Step 1: ingredient
By 3.5% K2O, 4% Al2O3, 13% B2O3, 78% SiO2, 1% Na2O, 0.5% Y2O3As
The raw material (hereinafter referred to as KABS glass) of potassium aluminium borated silicate glass carries out ingredient；By 73% ZnO, 14% B2O3, 12%
SiO2, 1% Al2O3Raw material (hereinafter referred to as ZBS glass) as zinc borated silicate glass carries out ingredient；Specifically it is detailed in following table
1；
Step 2: ball milling
According to quality described in step 1 than after ingredient, using deionized water as ball-milling medium, zirconia ball being added, passes through planet-shaped
Ball mill ball milling 4 hours, drum's speed of rotation 280r/min.The slurry of acquisition is dried 24 hours at 100 DEG C and crosses 60 mesh
Sieve obtains K-Al-B-Si powder and Zn-B-Si powder；
Step 3: melten glass
The powder obtained after step 2 sieving is heated in sintering furnace with the heating rate of 2 DEG C/min, wherein K-
Al-B-Si powder is heated to 1450 DEG C, and Zn-B-Si powder is heated to 1400 DEG C；When reaching institute's heating temperature, by glass melt
Deionization quenching-in water chilling is poured into, KABS glass and ZBS glass are obtained；
Step 4: alumina filler is added
KABS glass and ZBS glass are crushed, two kinds of glass powders are obtained, then according to KABS glass and ZBS glass powder
Mass ratio be to be mixed at 8: 2, Al then is added into the mixture of KABS glass powder and ZBS glass powder2O3, Al2O3
Quality account for the total amount including glass percentage be 30%, complete ingredient after is added deionized water ball milling 4 hours, acquisition two kinds
The mixed slurry of glass and aluminium oxide, the mixed slurry is dry, sieving, obtains the mixed powder of glass and alumina filler
Body；
Step 5: being granulated, molding, dumping
To granulating agent is added in the mixed powder of glass and alumina filler, polyvinyl alcohol is selected in the present embodiment, so
It is dry-pressing formed afterwards to obtain green compact and carry out dumping；
Step 6: sintering；
The green compact for completing dumping are sintered 2 hours in 810 DEG C~850 DEG C of air, ceramic material is obtained after natural cooling
Material.
Embodiment 2；
The step of the present embodiment, is substantially same as Example 1, and difference is: the mass ratio of KABS glass and ZBS glass powder
It is 7: 3, data that see Table 2 for details.
Embodiment 3；
The step of the present embodiment, is substantially same as Example 1, and difference is: the mass ratio of KABS glass and ZBS glass powder
It is 6: 4, data that see Table 2 for details.
Embodiment 4；
The step of the present embodiment, is substantially same as Example 1, and difference is: the mass ratio of KABS glass and ZBS glass powder
It is 5: 5, data that see Table 2 for details.
Table 1: the formula of glass in embodiment
Table 2: the formula of glass and aluminium oxide in embodiment
The XRD diffraction pattern of glass ceramic material provided by the present embodiment 1 to 4 is as shown in Figure 1.Pass through XRD diffraction analysis
It can obviously observe the change formed with glass, aluminium oxide is mutually constantly reduced and faded away, and final sample S3 and S4 is obvious
Single ZnAl is obtained2O4There is not the second crystalline phase in spinel crystal phase.Meanwhile from S1 to S4, it can be observed that
ZnAl when 2theta is about 36 degree2O4Crystalline phase highest peak gradually increases.
The SEM of glass ceramic material provided by the present embodiment 1 to 4 scheme as shown in Fig. 2, wherein Fig. 2 a, Fig. 2 b, Fig. 2 c and
Fig. 2 d respectively corresponds embodiment 1 to 4.By observation SEM result it is found that the increase of KABS glass powder facilitates the shape of liquid phase
At this will be helpful to reduce sintering temperature；With the increase of ZBS glass powder, can gradually be observed in figure (c) and figure (d)
To the crystal grain obviously occurred, this demonstrate ZnAl2O4The formation of crystalline phase.Wherein glass ceramic material provided by embodiment 4 exists
As shown in figure 3, can be seen that by scanning electron microscope analysis, crystal grain is embedded in glass liquid phase SEM figure under 20 microns, is almost observed
Less than stomata.
It can be seen that in conjunction with electron-microscope scanning figure and XRD diffraction pattern, the increase of KABS glass powder facilitates the formation of liquid phase, glass
The sintering of glass ceramic densifying is namely based on liquid-phase sintering, and liquid phase may advantageously facilitate more ZnO and more oxidations in ZBS glass
The reaction of aluminium.Therefore to guarantee that the content of KABS glass powder is suitable, it is unsuitable very few, ZBS glass in system could be made in this way
It is sufficiently reacted with aluminium oxide and obtains the ZnAl of single-phase2O4Crystalline phase.
The performance parameter of ceramics is made as shown in the following table 3 to 6 in embodiment 1 to 4:
Table 3: performance of the embodiment 1 under different sintering temperatures
Table 4: performance of the embodiment 2 under different sintering temperatures
Table 5: performance of the embodiment 3 under different sintering temperatures
Table 6: performance of the embodiment 4 under different sintering temperatures
Can intuitively it find out from table 3 to 6, sintering temperature can be significantly reduced in the increase of KABS glass, dielectric constant is reduced,
But it will increase dielectric loss, reduce bending strength；The increase of ZBS glass can remarkably promote ZnAl2O4Enhancing, and improve anti-
Curved intensity improves dielectric constant and Q × f value, while can also improve thermal expansion coefficient.
Comparative example 1:
The step of the present embodiment, is substantially same as Example 1, and difference is: the mass ratio of KABS glass and ZBS glass powder
It is 10: 0, that is, is not added with ZBS glass, data that see Table 7 for details.
Comparative example 2:
The step of the present embodiment, is substantially same as Example 1, and difference is: the mass ratio of KABS glass and ZBS glass powder
It is 0: 10, that is, is not added with KABS glass, data that see Table 7 for details.
Table 7: the formula of glass and aluminium oxide in comparative example
Experiment discovery comparative example 1 and 2 does not obtain the ceramics of compact structure, is sintered when individually adding KABS glass
Product glass is excessive, and bending strength is smaller, and there are many product air holes being sintered when individually adding ZBS glass, bending strength
Smaller, the bending strength and shrinking percentage data of the two are detailed in the following table 3.
Table 8: bending strength and shrinking percentage of the comparative example 1 under different sintering temperatures
Table 9: bending strength and shrinking percentage of the comparative example 2 under different sintering temperatures
Along with the exclusion of stomata, it is bright in tri- directions generations of XYZ that this is embodied in sample green compact for the densification of ceramic material
Aobvious Shrinkage behavior.It can intuitively find out from table 8 and 9, be sintered when individually adding KABS glass or independent plus ZBS glass
Contractibility is less than normal.This shows that there are many interiors of products stomata when individually adding glass, causes bending strength smaller.According to
Existing literature reports the strength range of commercial glass ceramic substrate material in 120~320MPa, it can thus be seen that individually addition
The product being sintered when KABS glass or independent plus ZBS glass is difficult to apply.
The embodiment of the present invention is elaborated in conjunction with attached drawing above, but the invention is not limited to above-mentioned
Specific embodiment, above-mentioned specific embodiment is only schematical, rather than restrictive, the ordinary skill people of this field
Member under the inspiration of the present invention, can also make many in the case where not departing from present inventive concept and claimed range
Deformation, these belong to protection of the invention.
Claims (10)
1. a kind of ZnAl2O4Ceramic systems material, which is characterized in that glass and quality including mass fraction 60%~70% point
The aluminium oxide that number is 30%~40%；The glass is the mixture of potassium aluminium borated silicate glass and zinc borated silicate glass, wherein potassium
The mass fraction of aluminium borated silicate glass is 30%~56%, and the mass fraction of zinc borated silicate glass is 12%~35%；Glass and
Aluminium oxide is made through mixing, drying, molding, sintering.
2. a kind of ZnAl according to claim 12O4Ceramic systems material, which is characterized in that the potassium aluminium borated silicate glass
Raw material include K2O, Al2O3, B2O3And SiO2；The raw material of the potassium aluminium borated silicate glass includes ZnO, B2O3And SiO2。
3. a kind of ZnAl according to claim 22O4Ceramic systems material, which is characterized in that the potassium aluminium borated silicate glass
Raw material further include Na2O and/or Y2O3；The raw material of the zinc borated silicate glass further includes Al2O3。
4. a kind of ZnAl according to claim 32O4Ceramic systems material, which is characterized in that the potassium aluminium borated silicate glass
Group become 2%~4% K2O, 1%~4% Al2O3, 10%~16% B2O3, 70%~80% SiO2, 0.5%~
2% Na2O, 0.2%~0.8% Y2O3；The group of the zinc borated silicate glass become 70%~80% ZnO, 10%~
18% B2O3, 10%~15% SiO2, 1%~2% Al2O3。
5. a kind of ZnAl according to claim 12O4Ceramic systems material, which is characterized in that the ZnAl2O4Ceramic systems
The dielectric constant of material is that 4.65~4.98, Q × f value is 4746~7360GHz, and thermal expansion coefficient is 4.7~5.6ppm/ DEG C,
Bending strength is 150~202Mpa.
6. a kind of ZnAl2O4The preparation method of ceramic systems material, which comprises the steps of:
Step 1: ingredient；
By K2O, Al2O3, B2O3, SiO2Raw material as potassium aluminium borated silicate glass carries out ingredient, by ZnO, B2O3, SiO2As zinc
The raw material of borated silicate glass carries out ingredient；
Step 2: a ball milling；
The raw material of potassium aluminium borated silicate glass and the raw material of zinc borated silicate glass prepare to step 1 carries out a ball milling respectively, to
After the completion of ball milling, two bulb abrasive material of gained is dried and is sieved, potassium aluminium borosilicate system's powder and zinc borosilicate system powder are obtained；
Step 3: melten glass；
Potassium aluminium borosilicate system's powder made from heating stepses 2 and zinc borosilicate system powder are melted respectively, and fast in the molten state
Speed quenches obtained glass melt, thus respectively obtains potassium aluminium borated silicate glass and zinc borated silicate glass；
Step 4: secondary ball milling；
Secondary ball milling is carried out to aluminium oxide is added in the mixture of potassium aluminium borated silicate glass and zinc borated silicate glass powder, wherein
The mass fraction that the quality sum of potassium aluminium borated silicate glass and zinc borated silicate glass powder accounts for gross mass is 60%~70%, oxidation
The mass fraction that the quality of aluminium accounts for gross mass is 30%~40%；After the completion of ball milling, gained ball milling material is dried and is sieved, is obtained
To the mixed powder of glass and alumina filler；
Step 5: being granulated, molding, dumping；
It is granulated to granulating agent is added in the mixed powder of the glass and alumina filler, obtains green compact through molding, and
The green compact are subjected to dumping；
Step 6: sintering；
It is sintered 1~3 under 810 DEG C~850 DEG C of atmospheric atmosphere by obtained green compact are handled through step 5, is obtained after natural cooling
Low sintering ZnAl2O4Ceramic systems material.
7. a kind of ZnAl according to claim 62O4The preparation method of ceramic systems material, which is characterized in that the step
The group of potassium aluminium borated silicate glass becomes 2%~4% K in 12O, 1%~4% Al2O3, 10%~16% B2O3, 70%~
80% SiO2, 0.5%~2% Na2O, 0.2%~0.8% Y2O3；The group of zinc borated silicate glass becomes 70%~80%
ZnO, 10%~18% B2O3, 10%~15% SiO2, 1%~2% Al2O3。
8. a kind of ZnAl according to claim 62O4The preparation method of ceramic systems material, which is characterized in that the step
The operation of a ball milling is specific as follows in 2: using deionized water as solvent, using zirconia balls for ball-milling medium, in planet-shaped
By raw material ball milling mixing in ball mill, the mass ratio of solvent, ball-milling medium and material is (0.6~1):, (4~6): (0.5~
1.5), Ball-milling Time is 3~6 hours.
9. a kind of ZnAl according to claim 62O4The preparation method of ceramic systems material, which is characterized in that the step
The heating temperature of potassium aluminium borosilicate system powder is 1300~1500 DEG C 1450 DEG C in 3；The heating of zinc borosilicate system powder in the step 3
Temperature is 1350~1500 DEG C 1400 DEG C.
10. a kind of ZnAl according to claim 62O4The preparation method of ceramic systems material, which is characterized in that the step
The operation of secondary ball milling is specific as follows in rapid 5: using deionized water as solvent, using zirconia balls for ball-milling medium, in planet
By raw material ball milling mixing in type ball mill, the mass ratio of solvent, ball-milling medium and material is (0.6~1):, (4~6): (0.5~
1.5), Ball-milling Time is 3~6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910084152.7A CN109650871B (en) | 2019-01-29 | 2019-01-29 | ZnAl2O4Ceramic matrix material and method for producing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910084152.7A CN109650871B (en) | 2019-01-29 | 2019-01-29 | ZnAl2O4Ceramic matrix material and method for producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109650871A true CN109650871A (en) | 2019-04-19 |
| CN109650871B CN109650871B (en) | 2021-11-23 |
Family
ID=66121972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910084152.7A Active CN109650871B (en) | 2019-01-29 | 2019-01-29 | ZnAl2O4Ceramic matrix material and method for producing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109650871B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256060A (en) * | 2019-07-09 | 2019-09-20 | 嘉兴佳利电子有限公司 | A kind of high frequency low-k low-temperature co-burning ceramic material and preparation method |
| CN110357419A (en) * | 2019-07-18 | 2019-10-22 | 成都宏科电子科技有限公司 | A kind of glass composition and millimeter wave low-temperature co-burning ceramic material and preparation method thereof |
| CN112441830A (en) * | 2019-08-30 | 2021-03-05 | 中国科学院上海硅酸盐研究所 | High-quality-factor yttrium-doped zirconia microwave dielectric ceramic material and preparation method thereof |
| CN113943147A (en) * | 2021-12-07 | 2022-01-18 | 无锡市惠丰电子有限公司 | Preparation method of dielectric ceramic material |
| CN115432933A (en) * | 2022-08-30 | 2022-12-06 | 电子科技大学 | High bending strength glass ceramic material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101136261A (en) * | 2007-07-06 | 2008-03-05 | 广东风华高新科技股份有限公司 | Copper electrode slurry material and manufacturing method thereof |
| CN101609849A (en) * | 2009-07-13 | 2009-12-23 | 中南大学 | Silver conductive paste used for positive electrode of solar battery and preparation technology thereof |
| CN104891952A (en) * | 2015-05-19 | 2015-09-09 | 电子科技大学 | A low-temperature-sintered low-dielectric-constant glass ceramic composite substrate material and a preparing method thereof |
| CN105130418A (en) * | 2015-04-07 | 2015-12-09 | 电子科技大学 | Li-Nb-Ti-based microwave dielectric ceramic material |
-
2019
- 2019-01-29 CN CN201910084152.7A patent/CN109650871B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101136261A (en) * | 2007-07-06 | 2008-03-05 | 广东风华高新科技股份有限公司 | Copper electrode slurry material and manufacturing method thereof |
| CN101609849A (en) * | 2009-07-13 | 2009-12-23 | 中南大学 | Silver conductive paste used for positive electrode of solar battery and preparation technology thereof |
| CN105130418A (en) * | 2015-04-07 | 2015-12-09 | 电子科技大学 | Li-Nb-Ti-based microwave dielectric ceramic material |
| CN104891952A (en) * | 2015-05-19 | 2015-09-09 | 电子科技大学 | A low-temperature-sintered low-dielectric-constant glass ceramic composite substrate material and a preparing method thereof |
Non-Patent Citations (2)
| Title |
|---|
| QIN XIA ET AL: "low temperature sintering and characteristics of K2O-B2O3-SiO2-Al2O3 glass/ceramic composites for LTCC applications", 《JOURNAL OF MATERIALS SCIENCE:MATERIALS IN ELECTRONICS》 * |
| SANG OK YOON ET AL: "low temperature preparation and microwave dielectric properties of ZBS glass-Al2O3 composites", 《CERAMICS INTERNATIONAL》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256060A (en) * | 2019-07-09 | 2019-09-20 | 嘉兴佳利电子有限公司 | A kind of high frequency low-k low-temperature co-burning ceramic material and preparation method |
| CN110256060B (en) * | 2019-07-09 | 2021-10-08 | 嘉兴佳利电子有限公司 | High-frequency low-dielectric-constant low-temperature co-fired ceramic material and preparation method thereof |
| CN110357419A (en) * | 2019-07-18 | 2019-10-22 | 成都宏科电子科技有限公司 | A kind of glass composition and millimeter wave low-temperature co-burning ceramic material and preparation method thereof |
| CN112441830A (en) * | 2019-08-30 | 2021-03-05 | 中国科学院上海硅酸盐研究所 | High-quality-factor yttrium-doped zirconia microwave dielectric ceramic material and preparation method thereof |
| CN112441830B (en) * | 2019-08-30 | 2021-12-07 | 中国科学院上海硅酸盐研究所 | High-quality-factor yttrium-doped zirconia microwave dielectric ceramic material and preparation method thereof |
| CN113943147A (en) * | 2021-12-07 | 2022-01-18 | 无锡市惠丰电子有限公司 | Preparation method of dielectric ceramic material |
| CN115432933A (en) * | 2022-08-30 | 2022-12-06 | 电子科技大学 | High bending strength glass ceramic material and preparation method thereof |
| CN115432933B (en) * | 2022-08-30 | 2023-08-04 | 电子科技大学 | Glass ceramic material with high bending strength and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109650871B (en) | 2021-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109650871A (en) | A kind of ZnAl2O4Ceramic systems material and preparation method thereof | |
| CN107602088B (en) | Low-temperature co-fired ceramic material highly matched with high-temperature conductive silver paste and preparation method thereof | |
| CN101870584B (en) | Preparation method of molybdenum-based ultralow-temperature sintering microwave medium ceramic materials | |
| CN101613200B (en) | Low-temperature sintered microwave medium ceramic material and preparation method thereof | |
| CN101823880B (en) | Phenacite type molybdenum-based and tungsten-based ultralow temperature sintered microwave dielectric ceramic materials and preparation method thereof | |
| CN104230329A (en) | Low-temperature sintered microwave ceramic material and preparation method thereof | |
| WO2001083395A1 (en) | Low temperature sinterable and low loss dielectric ceramic compositions and method thereof | |
| CN108358632B (en) | Ultralow-temperature sintered high-Q x f-value microwave dielectric material and preparation method thereof | |
| CN101362647A (en) | Low temperature sintering lithium-base microwave dielectric ceramic material and preparation thereof | |
| CN114409389B (en) | Low-dielectric low-loss Ba-Si-B-M-based LTCC material and preparation method thereof | |
| WO2023159896A1 (en) | Silicate-based low-temperature sintered microwave dielectric ceramic material and preparation method therefor | |
| CN107986774A (en) | Low temperature sintering high-dielectric constant microwave-medium ceramics material and preparation method thereof | |
| US20230348332A1 (en) | Mg-ta based dielectric ceramic for multi-layer ceramic capacitor and low-temperature preparation method thereof | |
| CN108218406B (en) | Low-temperature co-fired ceramic material with low dielectric constant and low loss and preparation method thereof | |
| CN112537947A (en) | Low-loss low-dielectric-constant microwave dielectric ceramic material and preparation method thereof | |
| CN103420670B (en) | Low-temperature sintered microwave ceramic material and preparation method thereof | |
| CN103951425B (en) | A kind of temperature-stable scheelite-type structure microwave-medium ceramics and preparation method thereof | |
| CN109320232B (en) | Ceramic material for microwave medium and preparation method thereof | |
| CN114751734A (en) | Dielectric material for low-temperature sintered Mg-Ti-Nb multilayer ceramic capacitor and preparation method thereof | |
| CN104387057B (en) | A kind of temperature-stable titanio spinelle microwave-medium ceramics and low temperature preparation method thereof | |
| US6844278B2 (en) | Dense lead-free glass ceramic for electronic devices | |
| CN104177085A (en) | Molybdenum-based temperature-stable microwave medium ceramic and preparation method thereof | |
| CN110723965A (en) | Fluxing agent-free LTCC microwave ceramic material and preparation method thereof | |
| CN111574213B (en) | Low-dielectric-constant LTCC material and preparation method thereof | |
| CN110256088A (en) | A kind of microwave-medium ceramics composite sintering agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |