CN111087173A - Negative expansion filler and preparation method and application thereof - Google Patents
Negative expansion filler and preparation method and application thereof Download PDFInfo
- Publication number
- CN111087173A CN111087173A CN201911401606.5A CN201911401606A CN111087173A CN 111087173 A CN111087173 A CN 111087173A CN 201911401606 A CN201911401606 A CN 201911401606A CN 111087173 A CN111087173 A CN 111087173A
- Authority
- CN
- China
- Prior art keywords
- negative expansion
- negative
- filler
- series
- expansion
- 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
- 239000000945 filler Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 121
- 239000011521 glass Substances 0.000 claims abstract description 37
- 241000219991 Lythraceae Species 0.000 claims abstract description 28
- 235000014360 Punica granatum Nutrition 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims description 39
- 238000005245 sintering Methods 0.000 claims description 37
- 238000000227 grinding Methods 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 241000508269 Psidium Species 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 229910003069 TeO2 Inorganic materials 0.000 claims description 2
- 229910052878 cordierite Inorganic materials 0.000 claims description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000174 eucryptite Inorganic materials 0.000 claims description 2
- -1 phosphorosilicate Chemical compound 0.000 claims description 2
- 238000005336 cracking Methods 0.000 abstract description 15
- 239000000758 substrate Substances 0.000 abstract description 12
- 230000008602 contraction Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- 239000001856 Ethyl cellulose Substances 0.000 description 4
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 229920001249 ethyl cellulose Polymers 0.000 description 4
- 235000019325 ethyl cellulose Nutrition 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000004372 laser cladding Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- 229920001621 AMOLED Polymers 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- RUJPNZNXGCHGID-UHFFFAOYSA-N (Z)-beta-Terpineol Natural products CC(=C)C1CCC(C)(O)CC1 RUJPNZNXGCHGID-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- QJVXKWHHAMZTBY-GCPOEHJPSA-N syringin Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 QJVXKWHHAMZTBY-GCPOEHJPSA-N 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to a negative expansion filler and a preparation method and application thereof, wherein the preparation raw material of the negative expansion filler comprises a negative expansion material; the negative expansion material comprises at least two types of white pomegranate series negative expansion materials, or comprises at least two types of perovskite series negative expansion materials, or comprises a combination of at least one type of white pomegranate series negative expansion material and at least one type of perovskite series negative expansion material. The negative expansion filler provided by the invention has positive expansion in the c-axis direction and negative thermal expansion (contraction phenomenon) in the a/b-axis direction along with the rise of temperature, so that the whole expansion and cracking are inhibited, and the thermal expansion coefficient of the Frit material can be adjusted by adjusting the type and the proportion of the negative expansion filler, so that the Frit material is matched with the thermal expansion coefficient of a glass substrate, and the cracking caused by stress is prevented.
Description
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to a negative expansion filler and a preparation method and application thereof.
Background
With the market demand, Organic Light Emitting Diode (OLED) display screens are becoming the main trend in the future, and active matrix organic light emitting diodes or active matrix organic light emitting diode packages (Frit packages) are becoming the current packaging methods. The presence of organic layer materials in OLED devices that are extremely sensitive to moisture and oxygen greatly reduces the lifetime of OLED display devices. In order to solve this problem, various materials are mainly used in the prior art to isolate the organic layer material of the OLED from the outside.
The main sealing method in the prior art is Frit sealing (hermetic sealing of Frit composition), in which Frit is filled in the sealing area of the upper and lower substrates of the OLED display panel, and then the Frit is melted by moving and heating a laser beam to form a sealed sealing connection, and any crack or corrosion in the sealing area will cause the failure of the sealing. Therefore, the requirements on the bonding capability and the corrosion resistance of the Frit material are high. However, the prior art has the following problems:
(1) in the current packaging technology, Frit is used for realizing the adhesion of a glass substrate and a Thin Film Transistor (TFT) substrate; the Frit material is generally selected to function as a flux by itself: the self-fluxing elements generally comprise B and Si, the higher the content, the higher the hardness and the greater the tendency to crack, although Si and oxides provide a Frit material with sufficient hardness and a greater risk of cracking.
(2) Frit packaging requires high temperature melting by laser, and these stresses are often difficult to release due to rapid heating and cooling during laser cladding, bound by the surrounding cooler substrate during subsequent solid state cooling shrinkage, and once released, can cause cracking and debonding.
(3) Usually, cracks are mostly perpendicular to the laser scanning direction during single laser cladding, and the cracks are distributed in parallel, and because of mutual superposition of residual stress, the cladding layer cracks more sensitively in multiple overlapping laser cladding, and the cracks on the cladding layer have and are netted distribution, also have the condition that main cracks have branch cracks, increase the risk of cracking more.
Therefore, there is a need in the art to develop a Frit material having crack resistance.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a negative expansion filler, in particular to a negative expansion material with adjustable thermal expansion coefficient, which is applied to a Frit material and has excellent cracking resistance.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a negative expansion filler, which is prepared from raw materials comprising a negative expansion material;
the negative expansion material comprises at least two types of white pomegranate series negative expansion materials, or comprises at least two types of perovskite series negative expansion materials, or comprises a combination of at least one type of white pomegranate series negative expansion material and at least one type of perovskite series negative expansion material.
The invention provides a novel negative expansion filler, which is prepared by adopting at least two negative expansion materials, wherein the two negative expansion materials can be selected from a pomegranate series negative expansion material and a perovskite series negative expansion material, the negative expansion filler disclosed by the invention has the advantages that positive expansion is generated in the c-axis direction along with the rise of temperature, negative thermal expansion (contraction phenomenon) is generated in the a/b-axis direction, and the whole expansion cracking is inhibited, as shown in figure 1.
The negative expansion filler provided by the invention can keep negative thermal expansion within the range of 25-500 ℃, and the thermal expansion coefficient is-15.2 multiplied by 10-6From/° C to-0.4 × 10-6The thermal expansion coefficient of the negative expansion filler can be adjusted by adjusting the type and the proportion of the negative expansion material, and the thermal expansion coefficient of the Frit material containing the negative expansion filler is adjusted to be matched with the thermal expansion coefficient of the glass substrate, so that the cracking caused by stress is prevented.
The second object of the present invention is to provide a method for preparing the negative expansion filler, which comprises the steps of: mixing negative expansion materials, and sintering to obtain the negative expansion filler;
the negative expansion material comprises at least two types of white pomegranate series negative expansion materials, or comprises at least two types of perovskite series negative expansion materials, or comprises a combination of at least one type of white pomegranate series negative expansion material and at least one type of perovskite series negative expansion material.
The invention also aims to provide a glass frit composition, in particular to provide a crack-resistant glass frit composition, and particularly to provide a crack-resistant glass frit composition with adjustable thermal expansion coefficient, wherein the glass frit composition comprises a glass base material and the negative expansion filler.
The Frit composition provided by the invention is a Frit material, and the negative expansion material provided by the invention is added, so that the thermal expansion coefficient of the Frit composition can be adjusted to be matched with that of a glass substrate, and the Frit composition has good anti-cracking performance.
The fourth object of the present invention is to provide an organic electroluminescent device encapsulated with the glass frit composition of the second object.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a novel negative expansion filler, which is prepared by adopting at least two negative expansion materials, wherein the two negative expansion materials can be selected from a pomegranate series negative expansion material and a perovskite series negative expansion material, the negative expansion filler disclosed by the invention has the advantages that positive expansion is generated in the c-axis direction along with the rise of temperature, negative thermal expansion (contraction phenomenon) is generated in the a/b-axis direction, and the whole expansion cracking is inhibited, as shown in figure 1.
The negative expansion filler provided by the invention can keep negative thermal expansion within the range of 25-500 ℃, and the thermal expansion coefficient is-15.2 multiplied by 10-6From/° C to-0.4 × 10-6The thermal expansion coefficient of the negative expansion filler can be adjusted by adjusting the type and the proportion of the negative expansion material, and the thermal expansion coefficient of the Frit material containing the negative expansion filler is adjusted to be matched with the thermal expansion coefficient of the glass substrate, so that the cracking caused by stress is prevented.
Drawings
Fig. 1 is a schematic diagram of the working principle of the negative expansion filler provided by the invention.
Detailed Description
The invention aims to provide a negative expansion filler, which is prepared from raw materials including a negative expansion material;
the negative expansion material comprises at least two types of white pomegranate series negative expansion materials, or comprises at least two types of perovskite series negative expansion materials, or comprises a combination of at least one type of white pomegranate series negative expansion material and at least one type of perovskite series negative expansion material.
The invention provides a novel negative expansion filler, which is prepared by adopting at least two negative expansion materials, wherein the two negative expansion materials can be selected from a pomegranate series negative expansion material and a perovskite series negative expansion material, the negative expansion filler disclosed by the invention has the advantages that positive expansion is generated in the c-axis direction along with the rise of temperature, negative thermal expansion (contraction phenomenon) is generated in the a/b-axis direction, and the whole expansion cracking is inhibited, as shown in figure 1.
The negative expansion filler provided by the invention can keep negative thermal expansion within the range of 25-500 ℃, and the thermal expansion coefficient is-15.2 multiplied by 10-6From/° C to-0.4 × 10-6The thermal expansion coefficient of the negative expansion filler can be adjusted by adjusting the type and the proportion of the negative expansion material, and the thermal expansion coefficient of the Frit material containing the negative expansion filler is adjusted to be matched with the thermal expansion coefficient of the glass substrate, so that the cracking caused by stress is prevented.
In one embodiment, the negative expansion filler is Na1-xZr2P3-xSixO12Or MyN1-yTi4P6O12(ii) a Wherein 0. ltoreq. x.ltoreq.1, e.g. 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95 etc., 0. ltoreq. y.ltoreq.1, e.g. 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95 etc., M and N are each independently selected from any one of Mg, Ca, Sr or Ba.
Na1-xZr2P3-xSixO12Is a chemical formula of a product obtained by compounding at least two types of pomegranate series negative expansion materials; myN1-yTi4P6O12Is the chemical formula of the product obtained after compounding at least two perovskite series negative expansion materials.
In a specific embodiment, the negative expansion material comprises a combination of at least one guava series negative expansion material and at least one perovskite series negative expansion material.
The negative expansion filler compounded by the white pomegranate series negative expansion material and the perovskite series negative expansion material can generate negative thermal expansion in the directions of two crystal axes or three crystal axes, so that the thermal expansion coefficient of the whole glass composition is reduced, and the effect of matching with the thermal expansion coefficient of the substrate is achieved.
In one embodiment, the mass ratio of the pomegranate-series negative expansion material to the perovskite-series negative expansion material is 0.5:1 to 3:1, for example, 0.7:1, 0.9:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, or the like.
According to the invention, the white pomegranate series negative expansion material and the perovskite series negative expansion material are preferably compounded according to the proportion of 0.5: 1-3: 1, and the negative thermal expansion effect can be exerted in the range, so that the effect of adjusting the overall thermal expansion coefficient is achieved. The excessive negative expansion materials of the white pomegranate series can cause severe material shrinkage and severe volume change, stress microcracks are generated, the mechanical strength of the material is reduced, the insufficient negative expansion materials of the white pomegranate series can cause unobvious thermal expansion adjusting effect, and thermal stress separation is generated.
In one embodiment, the pomegranate series negative expansion material comprises NaZr2P3O12And/or NaTi2P3O12。
In one embodiment, the perovskite-series negative expansion material comprises CaZr4P6O24And/or SrTi4P6O24。
In one embodiment, the raw materials for preparing the negative expansion filler further comprise any one or at least two of cordierite, β -eucryptite, silica, phosphorosilicate, cristobalite or quartz.
Quartzes, tridymite, cristobalite and fused quartz are among the four major classes of quartz. They are all silica minerals, but the crystal structures are different, called homogeneous.
The second object of the present invention is to provide a method for preparing the negative expansion filler, which comprises the steps of: mixing negative expansion materials, and sintering to obtain the negative expansion filler;
the negative expansion material comprises at least two types of white pomegranate series negative expansion materials, or comprises at least two types of perovskite series negative expansion materials, or comprises a combination of at least one type of white pomegranate series negative expansion material and at least one type of perovskite series negative expansion material.
In one embodiment, the preparation method comprises the following steps:
(1) mixing the negative expansion materials, grinding for the first time, screening, and grinding for the second time to obtain a premix;
(2) and drying the premix, sequentially performing primary sintering and secondary sintering, and cooling to obtain the negative expansion filler.
The preparation process of the negative expansion filler provided by the invention adopts twice grinding and twice sintering, and the reason for doing so is that twice grinding ensures sufficient grinding and uniform particle size; and the two-time sintering is performed to realize the sufficiency of sintering, and the structural defects of the composite material are reduced by using heat preservation, so that the composite filler with good performance is obtained.
In one embodiment, in step (1), the first grinding vessel comprises a ceramic crucible.
In one embodiment, in step (1), the second grinding vessel comprises an agate crucible.
In one embodiment, in step (1), the second grinding media comprises absolute ethanol.
The second grinding is preferably carried out in absolute ethanol, since ethanol is free of impurities and has good volatility, and ensures the purity of the material system while fully wetting the material.
In one embodiment, in step (1), the sieving results in particles having a size < 1 μm, e.g., 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, etc.
In one embodiment, in step (1), the particle size distribution of the particles obtained after the second grinding is as follows: d75Less than 5 μm, e.g., 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, etc., D50< 2.5. mu.m, e.g. 1 μm, 1.5. mu.m, 2 μm, 2.4. mu.m, etc., D25< 1.5. mu.m, for example, 0.5. mu.m, 0.6. mu.m, 0.7. mu.m, 0.8. mu.m, 0.9. mu.m, 1. mu.m, 1.1. mu.m, 1.2. mu.m, 1.3. mu.m, 1.4. mu.m, etc.
In the invention, the particles with the particle size distribution are obtained through secondary grinding, and the contact area of different materials is increased in the particle size range, so that the effects of full reaction and thorough sintering are realized.
In one embodiment, in the step (2), the drying temperature is 100-120 ℃, for example, 102 ℃, 104 ℃, 106 ℃, 108 ℃, 110 ℃, 112 ℃, 114 ℃, 116 ℃, 118 ℃ and the like.
In a specific embodiment, in the step (2), the drying time is 8-12 h, for example, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h, and the like.
In one embodiment, in the step (2), the temperature of the first sintering is 700 to 900 ℃, for example, 720 ℃, 740 ℃, 760 ℃, 780 ℃, 800 ℃, 820 ℃, 840 ℃, 860 ℃, 880 ℃ and the like.
The temperature of the first sintering is preferably 700-900 ℃, and the melting reaction of the low-melting-point compound is realized in the temperature range, so that the effect of one-time light sintering is realized. Too high a temperature may result in over-firing, and too low a temperature may result in incomplete primary sintering.
In a specific embodiment, in the step (2), the time for the first sintering is 0.5 to 1.5 hours, such as 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour, 1 hour, 1.1 hour, 1.2 hours, 1.3 hours, 1.4 hours, and the like.
In one embodiment, in the step (2), the temperature of the second sintering is 1000 to 1200 ℃, such as 1010 ℃, 1020 ℃, 1030 ℃, 1040 ℃, 1050 ℃, 1060 ℃, 1070 ℃, 1080 ℃, 1090 ℃, 1100 ℃, 1110 ℃, 1120 ℃, 1130 ℃, 1140 ℃, 1150 ℃, 1160 ℃, 1170 ℃, 1180 ℃, 1190 ℃ and the like.
The temperature of the second sintering is further preferably 1000-1200 ℃, and the second sintering is realized within the temperature range, so that the effect of dense sintering of the material is achieved. Too high a temperature results in energy waste, and too low a temperature may result in insufficient reaction of the high melting point compound.
In a specific embodiment, in the step (2), the time for the second sintering is 2 to 4 hours, such as 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, and the like.
It is a further object of the present invention to provide a glass frit composition comprising a glass binder and a negative expansion filler according to one of the objects.
The Frit composition provided by the invention is a Frit material, and the negative expansion material provided by the invention is added, so that the thermal expansion coefficient of the Frit composition can be adjusted to be matched with that of a glass substrate, and the Frit composition has good anti-cracking performance.
In a specific embodiment, the mass fraction of the negative expansion filler is 10 to 38%, such as 15%, 20%, 25%, 30%, 35%, etc., based on 100% of the total mass of the glass base material and the negative expansion filler.
In a specific embodiment, the mass fraction of the glass base material is 62 to 90%, such as 65%, 70%, 75%, 80%, 85%, 88%, etc., based on 100% of the total mass of the glass base material and the negative expansion filler.
In one embodiment, the glass substrate includes Bi2O3-SiO2-Mn2O3Mixture, V2O5-ZnO-TeO2Mixture, BaO3-ZnO-P2O5Mixture, B2O3-ZnO-SnO mixtures or P2O5Any one or a combination of at least two of ZnO-SnO mixtures.
In one embodiment, the glass frit composition further comprises an organic binder and a solvent.
In one embodiment, the organic binder comprises any one or a combination of at least two of ethyl cellulose, phenolic resins, propylene glycol, mixtures of ethyl cellulose and phenolic resins, ester polymers, methacrylate polymers of lower alcohols, butyl carbitol acetate, dibutyl phthalate, ethyl acetate, α -terpineol, β -terpineol, or alcohol-alcohol ester mixtures.
In a specific embodiment, the solvent includes any one of diethylene glycol butyl ether, diethylene glycol butyl ether acetate, terpineol, cyclohexanone, cyclopentanone, hexylene glycol, a mixture of high-boiling alcohols and alcohol esters, or a combination of at least two thereof.
The fourth object of the present invention is to provide an organic electroluminescent device encapsulated with the glass frit composition of the second object.
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a white pomegranate series composite negative expansion filler, and the preparation method comprises the following steps:
(1) adding NaZr with the mass ratio of 0.5:12P3O12And NaTi2P3O12Mixing, grinding for the first time in a ceramic crucible, sieving, and grinding for the second time in an agate crucible by using absolute ethyl alcohol as a medium until the particle size distribution is as follows: d75＜5μm，D50＜2.5μm，D25Less than 1.5 μm, to obtain a premix;
(2) drying the premix at 110 ℃ for 10h, performing primary sintering at 800 ℃ for 1h, performing secondary sintering at 1100 ℃ for 3h, and cooling to obtain the negative expansion filler Na1-xZr2P3-xSixO12And x is 0.
Example 2
The difference from the example 1 is that the raw material is NaZr with the mass ratio of 1:12P3O12And NaTi2P3O12To obtain the negative expansion filler Na1-xZr2P3-xSixO12And x is 0.25.
Example 3
The difference from the example 1 is that the raw material is NaZr with the mass ratio of 1.5:12P3O12And NaTi2P3O12To obtain the negative expansion filler Na1-xZr2P3-xSixO12And x is 0.5.
Example 4
The difference from the example 1 is that the raw material is NaZr with the mass ratio of 2:12P3O12And NaTi2P3O12To obtain the negative expansion filler Na1-xZr2P3-xSixO12And x is 0.75.
Example 5
The difference from the example 1 is that the raw material is NaZr with the mass ratio of 2.5:12P3O12And NaTi2P3O12To obtain the negative expansion filler Na1-xZr2P3-xSixO12And x is 1.
Example 6
The difference from example 5 is that the second sintering was not performed.
Example 7
The difference from example 5 is that the second grinding to a particle size distribution: d75 is less than 10 μm, D50 is less than 8 μm, and D25 is less than 5 μm.
Examples 8 to 11
The difference from example 5 is that the temperatures of the first sintering were 700 ℃ (example 8), 900 ℃ (example 9), 600 ℃ (example 10) and 1000 ℃ (example 11), respectively.
Examples 12 to 15
The difference from example 5 is that the temperatures of the second sintering were 1000 ℃ (example 12), 1200 ℃ (example 13), 900 ℃ (example 14) and 1300 ℃ (example 15), respectively.
Example 16
The difference from example 5 is that the time for the first sintering was 8 hours and the time for the second sintering was 0.5 hours.
Example 17
The difference from example 5 is that the time for the first sintering was 12 hours and the time for the second sintering was 1.5 hours.
Example 18
The embodiment provides a perovskite series composite negative expansion filler, and the preparation method comprises the following steps:
(1) adding CaZr with the mass ratio of 0.5:14P6O24And SrTi4P6O24Mixing, grinding for the first time in a ceramic crucible, sieving, and grinding for the second time in an agate crucible by using absolute ethyl alcohol as a medium until the particle size distribution is as follows: d75＜5μm，D50＜2.5μm，D25Less than 1.5 μm, to obtain a premix;
(2) drying the premix at 110 ℃ for 10h, performing primary sintering at 800 ℃ for 1h, performing secondary sintering at 1100 ℃ for 3h, and cooling to obtain the negative expansion filler MyN1-yTi4P6O12And y is 0.
Example 19
The difference from example 18 is that the starting material is CaZr in a mass ratio of 1.1:14P6O24And SrTi4P6O24Obtaining the negative expansion filler MyN1-yTi4P6O12And y is 0.25.
Example 20
The difference from example 18 is that the starting material is CaZr in a mass ratio of 1.8:14P6O24And SrTi4P6O24Obtaining the negative expansion filler MyN1-yTi4P6O12And y is 0.5.
Example 21
The difference from example 18 is that the starting material is CaZr in a mass ratio of 2.2:14P6O24And SrTi4P6O24Obtaining the negative expansion filler MyN1-yTi4P6O12And y is 0.75.
Example 22
The difference from example 18 is that the starting material is CaZr in a mass ratio of 2.6:14P6O24 AndSrTi4P6O24obtaining the negative expansion filler MyN1-yTi4P6O12And y is 1.
Example 23
The invention provides a white pomegranate series/perovskite series composite negative expansion filler, which is prepared by the following steps:
(1) adding NaZr with the mass ratio of 2.5:12P3O12(white pomegranate) and CaZr4P6O24Mixing perovskite, grinding for the first time in a ceramic crucible, screening, grinding for the second time in an agate crucible by taking absolute ethyl alcohol as a medium until the particle size distribution is as follows: d75＜5μm，D50＜2.5μm，D25Less than 1.5 μm, to obtain a premix;
(2) and drying the premix at 110 ℃ for 10h, performing primary sintering at 800 ℃ for 1h, performing secondary sintering at 1100 ℃ for 3h, and cooling to obtain the negative expansion filler.
Examples 24 to 27
The difference from example 23 is that NaZr2P3O12And CaZr4P6O24Are 0.5:1 (example 24), 3:1 (example 25), 0.3:1 (example 26) and 3.2:1 (example 27), respectively.
Comparative example 1
The difference from example 5 is that NaZr2P3O12Replaced by equal amounts of SiO2And obtaining the negative expansion filler D1.
Comparative example 2
The difference from example 21 is that CaZr4P6O24By replacing with an equal amount of TiO2And obtaining the negative expansion filler D2.
Performance test 1
The negative expansion fillers obtained in the above examples and comparative examples were subjected to a Coefficient of Thermal Expansion (CTE) test by the following specific method:
the negative expansion filler is made into a small block sample of 5 multiplied by 5mm, and the temperature is raised to 600 ℃ by utilizing TMA (Thermo-mechanical analysis) at the temperature of 10 ℃ per minute, and the thermal expansion coefficient and the negative thermal expansion temperature range are measured. The test results are shown in table 1.
TABLE 1
As can be seen from Table 1, the negative expansion filler provided by the invention has a proper thermal expansion coefficient, and realizes negative thermal expansion in a wide temperature range, and the thermal expansion coefficient is-15.2 multiplied by 10-6From/° C to-0.4 × 10-6The negative thermal expansion temperature is 25-500 ℃. The main reason is that the filling ions in the structural gaps play an important role in determining the structure and the expansibility, and large ion substitution can effectively reduce the anisotropy of thermal expansion, reduce the amount of interstitial ions and reduce the thermal expansion coefficient, and the thermal expansion coefficient can be adjusted by adjusting the content of the interstitial ions.
Comparative example 1 NaZr2P3O12Replacement by SiO2The coefficient of thermal expansion is significantly reduced, comparative example 2 CaZr4P6O24Substituted by TiO2The thermal expansion coefficient is also reduced, so that the effect of reducing the thermal expansion coefficient is better when two materials selected from the white pomegranate series material and the perovskite series material are compounded compared with the other materials.
It is understood from the comparison between examples 5 and 6 that the thermal expansion coefficient can be further reduced by performing the secondary sintering (example 5).
As can be seen from comparative examples 5 and 7, the particle size distribution after the second grinding was controlled to D75＜5μm，D50＜2.5μm，D25In the range of < 1.5 μm (example 5), the thermal expansion coefficient is favorably further decreased, and the effect becomes worse beyond this range (example 7).
It can be seen from comparison of examples 3 and 8 to 11 that when the temperature of the first sintering is in the range of 700 to 900 ℃ (examples 3 and 8 to 9), the lowest thermal expansion coefficient can be obtained on the basis of ensuring no energy waste, and the energy is wasted because the temperature is too low (example 10), the thermal expansion coefficient is increased, and the temperature is too high (example 11).
It can be seen from comparison of examples 3 and 12 to 15 that when the temperature of the first sintering is within the range of 1000 to 1200 ℃ (examples 3 and 12 to 13), the lowest thermal expansion coefficient can be obtained while ensuring no waste of energy, and when the temperature is too low (example 14), the thermal expansion coefficient is increased, and when the temperature is too high (example 15), the energy is wasted.
It is understood from comparative examples 5 and 23 that the use of a mixture of a guava negative expansion material and a perovskite material (example 23) further reduces the coefficient of thermal expansion of the material compared to the same type of mixture (example 5).
Comparative examples 23 to 27 show that when the ratio of the guava negative expansion material to the perovskite material is in the range of 0.5 to 3:1 (examples 23 to 25), the obtained composite filler has a more suitable thermal expansion coefficient, and when the ratio is too low (example 26), the thermal expansion coefficient is increased, and when the ratio is too high (example 27), the thermal expansion coefficient is too low (as low as-15.2 × 10)-6/° c), only a small amount of filler can be added when adjusting the thermal expansion coefficient of the glass frit, however, a small amount of filler is difficult to be uniformly dispersed in the glass frit, and the practical application is not facilitated.
Application examples 1 to 4 and comparative application examples 1 to 2
Application examples 1-4 and comparative application examples 1-2 respectively provide a glass frit composition, and the preparation method comprises the following steps:
mixing ethyl cellulose with TEXANOL ester alcohol to obtain a solution with ethyl cellulose concentration of 2 wt%, and mixing the solution with negative expansion filler and glass base material (Bi)2O3-SiO2-Mn2O3Mixture) was mixed and the system viscosity was adjusted to 110 kcps.
The types of the negative expansion fillers and the mass ratio of the negative expansion fillers to the glass base material are detailed in table 2.
Performance test 2
The CTE test was performed on the resulting frit compositions of the corresponding example and the comparative example in the same manner as in performance test 1. The test results are shown in Table 2
TABLE 2
As can be seen from table 2, when the negative expansion filler provided by the present invention is added to the glass base material, the thermal expansion coefficient can be adjusted to match the glass base material, thereby preventing cracking. This is primarily due to the ability of the composite filler to produce negative thermal expansion in the direction of two or three crystallographic axes, thereby reducing the coefficient of thermal expansion of the overall glass composition.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (11)
1. The negative expansion filler is characterized in that the preparation raw material of the negative expansion filler comprises a negative expansion material;
the negative expansion material comprises at least two types of white pomegranate series negative expansion materials, or comprises at least two types of perovskite series negative expansion materials, or comprises a combination of at least one type of white pomegranate series negative expansion material and at least one type of perovskite series negative expansion material.
2. The negative expansion filler according to claim 1, wherein the negative expansion filler is Na1-xZr2P3-xSixO12Or MyN1-yTi4P6O12(ii) a Wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and M and N are respectively and independently selected from any one of Mg, Ca, Sr or Ba.
3. The negative expansion filler according to claim 1, wherein the negative expansion material comprises a combination of at least one of the guava series negative expansion materials and at least one of the perovskite series negative expansion materials.
4. The negative expansion filler according to claim 3, wherein the mass ratio of the white pomegranate series negative expansion material to the perovskite series negative expansion material is 0.5:1 to 3: 1.
5. The negative expansion filler according to claim 1, wherein the raw material for preparing the negative expansion filler further comprises any one or at least two of cordierite, β -eucryptite, silica, phosphorosilicate, cristobalite, and quartz.
6. A method for preparing the negative expansion filler according to any one of claims 1 to 5, wherein the method comprises the following steps: mixing negative expansion materials, and sintering to obtain the negative expansion filler;
the negative expansion material comprises at least two types of white pomegranate series negative expansion materials, or comprises at least two types of perovskite series negative expansion materials, or comprises a combination of at least one type of white pomegranate series negative expansion material and at least one type of perovskite series negative expansion material.
7. The method of claim 6, comprising the steps of:
(1) mixing the negative expansion materials, grinding for the first time, screening, and grinding for the second time to obtain a premix;
(2) and drying the premix, sequentially performing primary sintering and secondary sintering, and cooling to obtain the negative expansion filler.
8. A glass frit composition comprising a glass binder and the negative expansion filler of any one of claims 1 to 5.
9. The glass frit composition according to claim 8, wherein the negative expansion filler is present in an amount of 10 to 38% by mass based on 100% by mass of the total mass of the glass base material and the negative expansion filler.
10. The glass frit composition according to claim 9, wherein the glass binder comprises Bi2O3-SiO2-Mn2O3Mixture, V2O5-ZnO-TeO2Mixture, BaO3-ZnO-P2O5Mixture, B2O3-ZnO-SnO mixtures or P2O5Any one or a combination of at least two of ZnO-SnO mixtures.
11. An organic electroluminescent device, wherein the organic electroluminescent device is encapsulated with the glass frit composition according to any one of claims 8 to 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911401606.5A CN111087173B (en) | 2019-12-30 | 2019-12-30 | Negative expansion filler and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911401606.5A CN111087173B (en) | 2019-12-30 | 2019-12-30 | Negative expansion filler and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111087173A true CN111087173A (en) | 2020-05-01 |
| CN111087173B CN111087173B (en) | 2022-11-04 |
Family
ID=70396926
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911401606.5A Active CN111087173B (en) | 2019-12-30 | 2019-12-30 | Negative expansion filler and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111087173B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113381027A (en) * | 2021-02-07 | 2021-09-10 | 南京工业大学 | Negative expansion material composite cobalt-based perovskite material, preparation method and solid oxide fuel cell |
| WO2024153210A1 (en) * | 2023-01-20 | 2024-07-25 | 华为技术有限公司 | Inorganic material and preparation method therefor, and resin composition |
| CN119409441A (en) * | 2025-01-03 | 2025-02-11 | 天津大学 | A low thermal expansion mineral casting and preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3642504A (en) * | 1967-07-01 | 1972-02-15 | Jenaer Glaswerk Schott & Gen | GLASS CONVERTIBLE TO TRANSPARENT GLASS CERAMICS CONTAINING AlPO{11 |
| US20090179567A1 (en) * | 2004-12-16 | 2009-07-16 | Matsushita Electric Industrial Co., Ltd. | Plasma display panel, method of producing the same, and sealing member |
| CN101891470A (en) * | 2010-06-21 | 2010-11-24 | 郑州大学 | A kind of sintering synthesis method of negative thermal expansion material Zr2P2MO12 |
| CN101928137A (en) * | 2010-09-10 | 2010-12-29 | 中国地质大学（北京） | A kind of Ca4(1+x)/5Mg(1+x)/5Zr4Si2xP(6-2x)O24 phosphate negative expansion ceramic material and its preparation method |
| US20120325789A1 (en) * | 2010-03-29 | 2012-12-27 | Noriaki Masuda | Sealing material and paste material using same |
| CN103449436A (en) * | 2013-09-17 | 2013-12-18 | 盐城工学院 | Method for preparing negative-expansion manganese-carbon compound (Mn3SnC) with perovskite-like structure |
| US20140196502A1 (en) * | 2011-07-27 | 2014-07-17 | Noriaki Masuda | Glass substrate with sealing material layer, organic el device using same, and manufacturing method for electronic device |
| US20150041712A1 (en) * | 2012-03-29 | 2015-02-12 | Merck Patent Gmbh | Composite ceramic which comprises a conversion phosphor and a material having a negative coefficient of thermal expansion |
| JP2015081216A (en) * | 2013-10-23 | 2015-04-27 | 株式会社ノリタケカンパニーリミテド | Conductive bonding material |
| US20150123156A1 (en) * | 2012-06-15 | 2015-05-07 | Osram Gmbh | Optoelectronic Semiconductor Component |
| CN109071325A (en) * | 2013-05-10 | 2018-12-21 | 康宁股份有限公司 | Sealing device comprising transparent laser welding region |
-
2019
- 2019-12-30 CN CN201911401606.5A patent/CN111087173B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3642504A (en) * | 1967-07-01 | 1972-02-15 | Jenaer Glaswerk Schott & Gen | GLASS CONVERTIBLE TO TRANSPARENT GLASS CERAMICS CONTAINING AlPO{11 |
| US20090179567A1 (en) * | 2004-12-16 | 2009-07-16 | Matsushita Electric Industrial Co., Ltd. | Plasma display panel, method of producing the same, and sealing member |
| US20120325789A1 (en) * | 2010-03-29 | 2012-12-27 | Noriaki Masuda | Sealing material and paste material using same |
| CN101891470A (en) * | 2010-06-21 | 2010-11-24 | 郑州大学 | A kind of sintering synthesis method of negative thermal expansion material Zr2P2MO12 |
| CN101928137A (en) * | 2010-09-10 | 2010-12-29 | 中国地质大学（北京） | A kind of Ca4(1+x)/5Mg(1+x)/5Zr4Si2xP(6-2x)O24 phosphate negative expansion ceramic material and its preparation method |
| US20140196502A1 (en) * | 2011-07-27 | 2014-07-17 | Noriaki Masuda | Glass substrate with sealing material layer, organic el device using same, and manufacturing method for electronic device |
| US20150041712A1 (en) * | 2012-03-29 | 2015-02-12 | Merck Patent Gmbh | Composite ceramic which comprises a conversion phosphor and a material having a negative coefficient of thermal expansion |
| US20150123156A1 (en) * | 2012-06-15 | 2015-05-07 | Osram Gmbh | Optoelectronic Semiconductor Component |
| CN109071325A (en) * | 2013-05-10 | 2018-12-21 | 康宁股份有限公司 | Sealing device comprising transparent laser welding region |
| CN103449436A (en) * | 2013-09-17 | 2013-12-18 | 盐城工学院 | Method for preparing negative-expansion manganese-carbon compound (Mn3SnC) with perovskite-like structure |
| JP2015081216A (en) * | 2013-10-23 | 2015-04-27 | 株式会社ノリタケカンパニーリミテド | Conductive bonding material |
Non-Patent Citations (5)
| Title |
|---|
| 佟林松等: "烧结工艺对固相法合成ZrW_2O_8纯度的影响", 《稀有金属》 * |
| 刁志聪等: "负热膨胀材料的研究现状及展望", 《中国钨业》 * |
| 刘素英: "白榴石晶体对烤瓷材料热膨胀性能的影响", 《稀有金属材料与工程》 * |
| 殷海荣等: "先进负热膨胀材料的最新研究进展", 《中国陶瓷》 * |
| 王献立等: "负热膨胀材料的研究及应用", 《信息记录材料》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113381027A (en) * | 2021-02-07 | 2021-09-10 | 南京工业大学 | Negative expansion material composite cobalt-based perovskite material, preparation method and solid oxide fuel cell |
| WO2024153210A1 (en) * | 2023-01-20 | 2024-07-25 | 华为技术有限公司 | Inorganic material and preparation method therefor, and resin composition |
| CN119409441A (en) * | 2025-01-03 | 2025-02-11 | 天津大学 | A low thermal expansion mineral casting and preparation method thereof |
| CN119409441B (en) * | 2025-01-03 | 2025-06-17 | 天津大学 | A low thermal expansion mineral casting and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111087173B (en) | 2022-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI482743B (en) | A glass member having a sealing material layer and an electronic device using the same, and a method of manufacturing the same | |
| CN102245525B (en) | Sealing glass, glass member having sealing material layer, and electronic device and method for producing the same | |
| CN111087173B (en) | Negative expansion filler and preparation method and application thereof | |
| CN103328402B (en) | Glass member with sealing material layer, electronic device using same and method for producing same | |
| US10118856B2 (en) | Lead-free glass and sealing material | |
| CN106587641B (en) | Low melting point glass powder and glass ceramics for laser lighting | |
| KR20200071675A (en) | Glass composition, glass powder, sealing material, glass paste, sealing method, sealing package, and organic electroluminescence element | |
| KR101429192B1 (en) | Low Melting Temperature Glass Compositions for Laser-Based Sealing | |
| CN1283575C (en) | Glass composition and glass-forming material containing same | |
| JP4972954B2 (en) | Bismuth-based glass composition and bismuth-based sealing material | |
| KR101149812B1 (en) | Lead free frit composition for low temperature sealing and method for manufacturing of lead free paste composition comprising thereof | |
| JP6031846B2 (en) | Glass substrate with sealing material layer and organic EL device using the same | |
| WO2020153061A1 (en) | Glass powder and sealing material using same | |
| KR101162040B1 (en) | Glass composition for sealing of and display panel comprising the same | |
| CN116514401B (en) | Low-melting-point glass powder, compound thereof and electronic equipment | |
| KR101288046B1 (en) | Low Melting Temperature Glass Compositions for Laser-Based Sealing | |
| KR20080044771A (en) | Dielectric Powders for Display Devices | |
| CN104045236A (en) | Frit composition, frit paste composition and sealing method and electric device | |
| KR20110064760A (en) | Glass frit paste composition for sealing an electric element and a method for sealing an electrical element using the glass frit paste composition | |
| KR101408289B1 (en) | Low expznsion glass filler, method of preparing the same, and glass frit comprising the same | |
| TWI743229B (en) | Bismuth-based glass, manufacturing method of bismuth-based glass and sealing material | |
| KR102599424B1 (en) | Glass frit paste for sealing, method for manufacturing glass frit bar and vacuum glass assembly, window glass for construction | |
| KR20110064074A (en) | Novel glass frit, glass frit paste composition for sealing an electrical element, and a sealing method for an electrical element using the glass frit paste composition | |
| KR100833474B1 (en) | Low melting point glass composition and glass mixture for OLD sealing | |
| CN111741932A (en) | sealing composition |
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 |