CN101066840B - No-lead RE doped sealing glass powder with low smelting point and its production process - Google Patents
No-lead RE doped sealing glass powder with low smelting point and its production process Download PDFInfo
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- CN101066840B CN101066840B CN2007101113863A CN200710111386A CN101066840B CN 101066840 B CN101066840 B CN 101066840B CN 2007101113863 A CN2007101113863 A CN 2007101113863A CN 200710111386 A CN200710111386 A CN 200710111386A CN 101066840 B CN101066840 B CN 101066840B
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- 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
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
- C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
-
- 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
- C03C12/00—Powdered glass; Bead compositions
-
- 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
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
-
- 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
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/17—Silica-free oxide glass compositions containing phosphorus containing aluminium or beryllium
-
- 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
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
-
- 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
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
-
- 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
Abstract
The present invention discloses one kind of no-lead RE doped sealing glass powder with low smelting point for vacuum glass sealing and its preparation process. The no-lead sealing glass powder has P2O5, SnO and ZnO as basic glass oxides and mixed RE oxide of La, Yt and Nd added, with the weight ratio between the basic glass oxides and the mixed RE oxide being (30.0-381.5) to (0.12-19.0). The no-lead sealing glass powder of the present invention with doping mixed RE oxide has lowered glass smelting and sealing temperature, raised chemical stability and lowered thermal expansion coefficient of glass as well as lowered environmental pollution. It is used in sealing electronic device and element and vacuum glass.
Description
Technical field
The invention belongs to field of glass production technology.Being specifically related to a kind of glass powder, specifically is a kind of P that is applied to the vacuum glass sealing-in of doped with rare-earth elements
2O
5-SnO-ZnO is the manufacture method of lead-free low-melting-point glass powder and this glass powder.
Background technology
Low melting point, to have more low-expansion glass powder be the seal, sealing materials that the vacuum glass goods adopt in process of production usually.
At present, the selected material of most of vacuum glass sealing-in is leaded seal glass, as PbO-B
2O
3-SiO
2System or PbO-ZnO-B
2O
3Be glass.These glass transition temperatures are less than 400 ℃, thermal expansivity 90～100 * 10
-7/ ℃, good sealing-in material (particle diameter 10～40 μ m) can the long period in the sealing-in process flows and crystallization fully not.But the plumbous oxide content 30～80%wt. in this seal glass belongs to high pbo glass.Flint glass has 10～12%wt.PbO to enter flue gas by volatilization approximately and is discharged in the atmosphere or is condensed into micronic dust and drop to ground when producing, and atmosphere, soil, river etc. are polluted; Flint glass in use also can be by contacting with human skin or by in the respiratory tract suction body health being caused damage; Also can contaminated soil and underground water after same lead glass is discarded.Along with the raising of modern society's environmental consciousness, plumbous hazardness to human and environment has caused that the whole society pays much attention to, and the application of lead-containing materials also more and more is restricted in the world wide.Therefore, provide a kind of lead-free sealing glass material to become the problem that must solve instantly as early as possible.
At present, domestic and international existing barium crown sealed glass and glass powder have following several usually.
The fair 5-85490 in the flat Hitachi of Japan has proposed a class V
2O
5-P
2O
5-Tl
2O-TeO
2-R
2O glass, main component are V
2O
5, P
2O
5, contain the oxide compound of sodium, potassium, rubidium, caesium, tellurium etc. simultaneously, can finish 400～500 ℃ sealing-in, the coefficient of expansion (70～130) * 10
-7/ ℃.Not leaded in the composition of this glass, but owing to contain a certain amount of highly toxic substance thallium oxide (TlO
2) and noble metal tellurium (Te) etc., thereby cost is very high.It mainly is used as the seal, sealing materials and the magnetic gap compaction material of high-performance magnetic head.
The U.S. Pat 2002019303 of NIPPON electronic glass application has proposed a kind of P
2O
5The sealing glass powder of-SnO-ZnO system, be used for 430～500 ℃ sealing-in, owing to contain a large amount of SnO in this glass powder prescription, oxidation extremely easily in the glass smelting process, need under nitrogen and reducing atmosphere condition, produce, thereby industrialization is difficult to realize on a large scale, and this glass chemistry stability is not fine, this patent does not propose better terms of settlement to above defective, thereby makes it be subjected to bigger restriction in application.
Have, 200310103592.1 of Chinese Jingdongfang Science and Technology Group Co., Ltd application has proposed a kind of V again
2O
5-P
2O
5-Sb
2O
3The glass powder of system, 400～500 ℃ of sealing temperatures, but V
2O
5Poisonous under steam condition, need in the production to take measures to avoid it to people and atmospheric harm, and V
2O
5Price is also relatively more expensive, and this has all limited its application.
In addition, adopt bismuth oxide (Bi in addition
2O
3) substitute the bismuth-containing system glass of plumbous oxide.But the cost of bismuth oxide is too high, usage quantity is big, and sealing temperature is higher, the coefficient of expansion is too big, has influenced its application in practice.
Summary of the invention
The sealing glass powder sealing temperature is higher in order to solve in the prior art, poor chemical stability, be difficult to problems such as preparation, the object of the present invention is to provide the P of the doped with rare-earth elements oxide compound that a kind of sealing temperature is low, chemical stability good, be easy to prepare
2O
5-SnO-ZnO is a sealing by fusing glass powder without lead.
Another object of the present invention is to provide a kind of method that is used to make above-mentioned sealing by fusing glass powder without lead, this method not only makes the manufacturing processed of glass powder be easy to carry out, and can be according to different characteristic requirements, adjust every set of dispense ratio flexibly, to satisfy vacuum glass to the requirement of sealing glass powder at melting temperature sealing, the coefficient of expansion.
To achieve these goals, the present invention is by the following technical solutions:
A kind of no-lead RE doped sealing glass powder with low smelting point is at P
2O
5-SnO-ZnO is added with the mixed rare-earth elements oxide compound in the oxide component of glass proportioning, described rare earth element is selected from three kinds of lanthanum, yttrium and neodymiums, the ratio of weight and number (30.0～381.5) in the described sealing glass powder between basic oxide aggregate of contained glass and the described mixed rare-earth oxide: (0.12～19.0).
The ratio of weight and number of described mixed rare-earth oxide is: La
2O
30.01～5.0, Y
2O
30.1～8.0, Nd
2O
30.01～6.0
The described glass compound that is added with rare earth element contains the oxide compound component of following parts by weight: P
2O
530.0～60.0, SnO 0～70.0, SnF
20～70.0, ZnO 0～8.5, ZnF
20～10.0, Li
2O 0～12.0, Na
2O 0～15.0, K
2O 0～10.0, and MgO 0～10.0, MgF
20～10.0, CaO 0～8.0, CaF
20～8.0, SrO 0～6.0, and BaO 0～16.0, B
2O
30～25.0, Al
2O
30～5.0, AlF
30～5.0, Sb
2O
30～20.0, Fe
2O
30～8.0, WO
30～5.0, La
2O
30.01～5.0, Y
2O
30.1～8.0, Nd
2O
30.01～6.0; SnO+SnF wherein
220, ZnO+ZnF
23.0, MgO+MgF
22.0, CaO+CaF
22.0, Al
2O
3+ AlF
32.0.
Glass powder itself has lower sealing temperature, the lower coefficient of expansion and better chemical stability, can satisfy the sealing-in requirement of vacuum glass.For the low-melting lead-free sealing glass powder that can obtain to mate with the vacuum glass coefficient of expansion, also can in glass powder, sneak into low-expansion filler, the coefficient of expansion is in (120～60) * 10
-7/ ℃, the weight percent of filler is no more than 40%.
The manufacture method of above-mentioned sealing by fusing glass powder without lead may further comprise the steps at least:
Step 1: form mineral, the compound that takes by weighing various oxide compounds or correspondence according to above-mentioned glass, thorough mixing is made compound;
Step 2: admixtion was dried 2～3 hours down at 100～300 ℃;
Step 3: the material that obtains in the step 2 is pulverized, ground, and sneak into reducing substances;
Step 4: the compound that obtains in the step 3 was melted 1～3 hour down at 800～1200 ℃;
Step 5: the melt liquid of compound in the step 4 is cured cooling, grinds to form the host glass powder;
Also can comprise:
Step 6: choosing or preparing the coefficient of expansion is (-120～60) * 10
-7/ ℃ filler;
Step 7: with step 5 and 6 resulting glass powder and filler thorough mixing.
Beneficial effect of the present invention is:
The present invention adopts mixed rare-earth oxide and other oxide doped and modified technology, has both reduced the sealing temperature (save energy, enhance productivity) of glass, has also improved the chemical stability of glass, has also reduced the coefficient of expansion of glass; Simultaneously do not contain the heavy metal oxide that environment is had severe contamination in the sealing by fusing glass powder without lead provided by the invention,, can be controlled at the content of composition that environment is polluted minimum as plumbous oxide etc.; Can directly carry out nontoxic, pollution-free sealing-in to electronic devices and components or vacuum glass, the real target that realizes " environmental protection ", and the processing and manufacturing process is simple and direct, can realize the large-scale industrial production of serialization.
Description of drawings
Fig. 1 is the manufacturing process flow diagram of sealing by fusing glass powder without lead of the present invention.
Embodiment
No-lead RE doped sealing glass powder with low smelting point of the present invention contains P
2O
5-SnO-ZnO is basic oxide component of glass and mixed rare-earth elements oxide compound, and described rare earth element is selected from three kinds of lanthanum, yttrium and neodymiums.
P
2O
5-SnO-ZnO is that basic oxide compound of glass and rare earth oxide are to be mixed to found by raw material phosphorus oxide, tin protoxide, tin protofluoride, zinc oxide, zinc fluoride, magnesium oxide, magnesium fluoride, boric acid, aluminum oxide, aluminum fluoride, weisspiessglanz, Quilonum Retard, soda ash, salt of wormwood, lime carbonate, Calcium Fluoride (Fluorspan), Strontium carbonate powder, barium carbonate, ferric oxide, Tungsten oxide 99.999 and the rare-earth tailing that contains lanthanum trioxide, yttrium oxide and Neodymium trioxide to form; In manufacturing processed, said components is taken by weighing the back by weight percentage mix, and handle 280 ℃ of oven dry, the processing back is ground, is pulverized, and sneaks into reductive agent, after melting 2 hours under 1100 ℃, cool off on iron plate, the glass fragment is pulverized, grinds, sieves can obtain glass powder.
In the no-lead RE doped sealing glass powder with low smelting point of the present invention, in the product of the different coefficients of expansion, use, can also add filler for adapting to.The available filler comprises fused silica powder, eucryptite, aluminium titanates, wolframic acid zirconium etc.Described filler can make through pulverize, grind, sieve (greater than 200 orders).To can be made into a kind of no-lead RE doped sealing glass powder with low smelting point of the present invention behind glass powder that make and the selected filler thorough mixing.
The process of the above preparation of the present invention no-lead RE doped sealing glass powder with low smelting point is with reference to shown in Figure 1.
Be described further in conjunction with specific embodiments with the oxide compound component in the sealing by fusing glass powder without lead of above admixtion production and ratio of weight and number, performance index and concrete processing request.
Embodiment 1:
Step 1: the composition according to example in the table 11 calculates and takes by weighing starting compound (gram), P
2O
538.5 SnO 70.0, ZnO 8.5, and MgO 10.0, B
2O
325.0, Al
2O
35.0, Sb
2O
320.0, Li
2O 12.0, Na
2O 15.0, K
2O 10.0, and CaO 8.0, and SrO 6.0, and BaO 16.0, Fe
2O
38.0, WO
35.0, La
2O
31.0, Y
2O
3, 8.0, Nd
2O
36.0.
Step 2: the above-mentioned raw material that takes by weighing is mixed, and 280 ℃ of oven dry processing, handle the back and grind, pulverize (about 200 orders), sneaking into 0.3 gram powdered carbon is that reductive agent (can be selected 0.1～0.3wt%) of raw material total amount in the step 1, after melting 2 hours under 1100 ℃, on iron plate, cool off, will cool off then glass fragment that the back forms pulverize, grind, sieve (200 orders～220 orders) form glass powder.
Step 3: adopt three classes or four quartz-like glass preforms to prepare the fused silica powder filler, with its grinding, pulverize, sieve (200 orders～220 orders) can make filler.
Step 4: calculate and take by weighing the fused silica powder filler that step 3 is made, the glass powder thorough mixing (employing ball-grinding machine) that volume ratio with 29% (accounting for the ratio of the cumulative volume of glass powder and filler) and step 2 are made is made this routine no-lead RE doped sealing glass powder with low smelting point.
Finished product detection:
1, glass powder compound mensuration: adopt the industry standard SJ/T10893-96 of China Electronics to carry out;
2, the finished product coefficient of expansion is measured: adopt the industry standard SJ/T11036-96 of China Electronics to carry out;
3, sealing by fusing working temperature: adopt the industry standard SJ/T11038-96 of China Electronics to carry out;
4, softening temperature: adopt the industry standard SJ/T11038-96 of China Electronics to carry out;
5, mobile column diameter: adopt ministry of Machinery and Electronics Industry of China ministerial standard SJ-3232.3-89 to carry out;
6, water-fast chemical stability experiment: adopt the industry standard SJ/T11035-96 of China Electronics to carry out.This standard with particle sample in distilled water in 98 ℃ of following heating certain hours, the alkali that upper water is separated out after with the hydrolysis of hydrochloric acid standard solution titration glass then.According to the volume of used hydrochloric acid or be converted into the amount of separating out sodium oxide, determine the hydrolysis grade of the anti-water chemistry stability of glass, chemical stability reduces successively from 1 grade to 5 grades.
Determining of anti-water chemistry stability hydrolysis grade
| Rank | Every gram glass consumes the volume V ml/g of 0.01ml/L HCl | The every gram glass sodium oxide amount of separating out W μ g/g |
| 1 | V≤0.10 | W≤31 |
| 2 | 0.10<V≤0.20 | 31<W≤62 |
| 3 | 0.20<V≤0.85 | 62<W≤264 |
| 4 | 0.85<V≤2.00 | 264<W≤620 |
| 5 | 2.00<V≤3.50 | 620<W≤1085 |
Detected result:
480 ℃ of present embodiment product sealing temperatures, mobile column diameter is 25.0mm, has good flowability, the coefficient of expansion is 71 * 10
-7/ ℃, softening temperature is for being 396 ℃, 1 grade of chemical stability; Illustrate that the present embodiment product has lower sealing temperature and softening temperature, and have the lower coefficient of expansion, good flowability and chemical stability.
The present invention can realize the adjustment of the coefficient of expansion, sealing by fusing working temperature by the component of adjusting glass powder and kind and the content of adjusting filler, thus adapt to different glass, pottery or and metal between sealing-in.
Following table 1 has exemplified six kinds of components differences of the present invention's preparation and has had the sealing by fusing glass powder without lead of the different coefficients of expansion, sealing temperature, example 2～6 and reference examples adopt the method preparation identical with embodiment 1 and detect, and their performance perameter is also described in table 1:
Table 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Reference examples | |
| P 2O 5 | 38.5 | 35.5 | 32.5 | 36.5 | 30.0 | 60.0 | 38.5 |
| SnO | 70.0 | — | 40.5 | 32.5 | 35.0 | 52.0 | 70.0 |
| SnF 2 | — | 70.0 | 20.0 | 30.0 | 15.0 | 11.0 | — |
| ZnO | 8.5 | 2.0 | — | 3.75 | 5.0 | 3.6 | 8.5 |
| ZnF 2 | — | 10.0 | 8.5 | 7.2 | 8.0 | 1.2 | — |
| MgO | 10.0 | 8.0 | 6.5 | 8.0 | — | 3.5 | 10.0 |
| MgF 2 | — | 10.0 | 7.5 | 9.0 | 10.0 | 2.4 | — |
| B 2O 3 | 25.0 | 18.0 | 8.0 | 14.0 | — | 7.2 | 25.0 |
| Al 2O 3 | 5.0 | — | 2.5 | 4.0 | 3.2 | 1.1 | 5.0 |
| AlF 3 | — | 5.0 | 3.5 | 2.0 | 4.8 | 1.6 | — |
| Sb 2O 3 | 20.0 | 12.0 | 10.0 | — | 15.0 | 8.0 | 20.0 |
| Li 2O | 12.0 | 9.8 | 7.5 | 4.0 | — | 3.0 | 12.0 |
| Na 2O | 15.0 | — | 7.2 | 9.0 | 14.0 | 2.8 | 15.0 |
| K 2O | 10.0 | 5.0 | 8.0 | — | 4.2 | 5.2 | 10.0 |
| CaO | 8.0 | 5.4 | 6.5 | — | 6.0 | 3.1 | 8.0 |
| CaF 2 | — | 4.2 | 3.6 | 8.0 | 2.6 | 0.6 | — |
| SrO | 6.0 | 2.2 | 1.5 | 4.8 | — | 3.4 | 6.0 |
| CaO | 8.0 | 5.4 | 6.5 | - | 6.0 | 3.1 | 8.0 |
| BaO | — | 9.0 | 7.1 | 15.0 | 6.0 | 16.0 | — |
| Fe 2O 3 | 8.0 | 3.5 | 2.5 | — | 4.2 | 5.0 | 8.0 |
| WO 3 | — | 4.2 | 1.8 | 5.0 | 2.2 | 3.0 | — |
| La 2O 3 | 5.0 | 0.8 | 0.3 | 0.6 | 0.01 | 3.5 | — |
| Y 2O 3 | 8.0 | 6.0 | 3.5 | 0.1 | 4.2 | 0.1 | — |
| Nd 2O 3 | 6.0 | 3.6 | 0.01 | 2.0 | 4.2 | 0.3 | — |
| The coefficient of expansion (* 10 -7/℃) | 98.0 | 73.8 | 106.0 | 112.0 | 97.0 | 86.75 | 135.0 |
| The filler title (volume, %) | Fused silica powder 29% | Eucryptite 25% | Aluminium titanates 21% | Wolframic acid zirconium 15% | Fused silica powder 14% | Aluminium titanates 35% | |
| Softening temperature (℃) | 396 | 267 | 340 | 309 | 350 | 380 | 423 |
| Sealing temperature (℃) | 480 | 358 | 422 | 380 | 412 | 460 | 500 |
| The finished product coefficient of expansion (* 10 -7/℃) | 71.0 | 73.8 | 77.4 | 74.1 | 75.1 | 72.0 | 73.0 |
| Column diameter (mm) flows | 25.0 | 24.5 | 22.0 | 23.5 | 21.8 | 23.1 | 22.0 |
| Chemical stability | 1 grade | 1 grade | 1 grade | 1 grade | 1 grade | 1 grade | 3 grades |
By detecting as can be known, the sealing by fusing glass powder without lead that the present invention prepares (referring to embodiment 1-6), sealing temperature can significantly reduce, do not add rare earth element in the same old way, temperature reduces more than 20 ℃; Sealing by fusing glass powder without lead of the present invention by changing filling kind and addition, can obtain the glass powder of the different coefficients of expansion; Sealing by fusing glass powder without lead of the present invention, chemical stability is good, can reach 1 grade standard after testing, the ability acid attack, when being used for the sealing-in of electronic product to the pickling subsequent disposal better tolerance of electronic devices and components.
Claims (6)
1. a no-lead RE doped sealing glass powder with low smelting point comprises P
2O
5-SnO-ZnO is the basic oxide compound of glass, it is characterized in that: also adding has mixed rare-earth oxide, rare earth element in the described mixed rare-earth oxide is selected three kinds of lanthanum, yttrium and neodymiums, the ratio of weight and number (30.0～381.5) in the described sealing glass powder between basic oxide aggregate of contained glass and the described mixed rare-earth oxide: (0.12～19.0) for use;
The basic oxide compound of described glass is that the component of following portions by weight ratio is formed: P
2O
530.0～60.0, SnO 0～70.0, SnF
20～70.0, ZnO 0～8.5, ZnF
20～10.0, Li
2O 0～12.0, Na
2O 0～15.0, K
2O0～10.0, MgO 0～10.0, MgF
20～10.0, CaO 0～8.0, CaF
20～8.0, SrO 0～6.0, BaO0～16.0, B
2O
30～25.0, Al
2O
30～5.0, AlF
30～5.0, Sb
2O
30～20.0, Fe
2O
30～8.0 and WO
30～5.0; SnO+SnF wherein
2＞20.0, ZnO+ZnF
2＞3.0, MgO+MgF
2＞2.0, CaO+CaF
2＞2.0, Al
2O
3+ AlF
3＞2.0.
2. according to the described no-lead RE doped sealing glass powder with low smelting point of claim 1, it is characterized in that: described mixed rare-earth oxide is that the component of following portions by weight ratio is formed: La
2O
30.01～5.0, Y
2O
30.1～8.0, Nd
2O
30.01～6.0.
3. according to claim 1 or 2 described no-lead RE doped sealing glass powder with low smelting point, it is characterized in that: comprise also that wherein the coefficient of expansion is-120～60 * 10
-7/ ℃ filler, described filler is to be selected from a kind of in aluminium titanates, eucryptite, wolframic acid zirconium and the fused silica powder.
4. according to the described no-lead RE doped sealing glass powder with low smelting point of claim 3, it is characterized in that: the per-cent of described filler in the glass powder gross weight is no more than 40%.
5. the manufacture method of the arbitrary described barium crown sealed glass powder of aforesaid right requirement 1-4 is characterized in that, may further comprise the steps at least:
Step 1: form mineral, the compound that takes by weighing various oxide compounds or correspondence according to above-mentioned glass, thorough mixing is made compound;
Step 2: admixtion was dried 2～3 hours down at 100～300 ℃;
Step 3: the material that obtains in the step 2 is pulverized, ground, and sneak into reducing substances;
Step 4: the compound that obtains in the step 3 was melted 1～3 hour down at 800～1200 ℃;
Step 5: the melt liquid of compound in the step 4 is cured cooling, grinds to form glass powder.
6. manufacture method according to claim 5 is characterized in that, and is further comprising the steps of:
Step 6: choosing or preparing the described coefficient of expansion of claim 3 is (120～60) * 10
-7/ ℃ filler;
Step 7: resulting glass powder of step 5 and the described filler thorough mixing of step 6 are obtained sealing glass powder.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101113863A CN101066840B (en) | 2006-06-22 | 2007-06-19 | No-lead RE doped sealing glass powder with low smelting point and its production process |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610089374.0 | 2006-06-22 | ||
| CN200610089374 | 2006-06-22 | ||
| CN2007101113863A CN101066840B (en) | 2006-06-22 | 2007-06-19 | No-lead RE doped sealing glass powder with low smelting point and its production process |
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| Publication Number | Publication Date |
|---|---|
| CN101066840A CN101066840A (en) | 2007-11-07 |
| CN101066840B true CN101066840B (en) | 2010-08-25 |
Family
ID=38879563
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| US9359248B1 (en) | 2014-12-26 | 2016-06-07 | Shanghai Tianma AM-OLED Co., Ltd. | Low-temperature sealing glass frit and method for preparing composite filler in glass frit |
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| CN109052965B (en) * | 2018-09-07 | 2021-12-24 | 苏州融睿电子科技有限公司 | Combination, mixture, sealing glass and manufacturing method thereof |
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| CN111018352B (en) * | 2019-12-06 | 2022-05-20 | 西安赛尔电子材料科技有限公司 | Glass material for titanium and titanium alloy-kovar sealing and preparation method and application thereof |
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| CN113003940A (en) * | 2021-04-23 | 2021-06-22 | 贵州国锐鑫节能科技有限公司 | Low-melting-point low-expansion-coefficient glass powder and preparation method thereof |
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