CN112551902A - Low-melting-point glass powder containing alkaline earth metal and preparation method and application thereof - Google Patents

Low-melting-point glass powder containing alkaline earth metal and preparation method and application thereof Download PDF

Info

Publication number
CN112551902A
CN112551902A CN201910912406.XA CN201910912406A CN112551902A CN 112551902 A CN112551902 A CN 112551902A CN 201910912406 A CN201910912406 A CN 201910912406A CN 112551902 A CN112551902 A CN 112551902A
Authority
CN
China
Prior art keywords
melting
glass
mol
earth metal
alkaline earth
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.)
Pending
Application number
CN201910912406.XA
Other languages
Chinese (zh)
Inventor
伍治伦
林慧兴
任海深
姚晓刚
张奕
谢天翼
姜少虎
何飞
赵相毓
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Institute of Ceramics of CAS
Original Assignee
Shanghai Institute of Ceramics of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Ceramics of CAS filed Critical Shanghai Institute of Ceramics of CAS
Priority to CN201910912406.XA priority Critical patent/CN112551902A/en
Publication of CN112551902A publication Critical patent/CN112551902A/en
Pending legal-status Critical Current

Links

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
    • C03C12/00—Powdered glass; Bead compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
    • B23P19/00—Machines for simply fitting together or separating metal parts or objects, or metal and non-metal parts, whether or not involving some deformation; Tools or devices therefor so far as not provided for in other classes
    • 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
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Glass Compositions (AREA)

Abstract

The invention relates to low-melting-point glass powder containing alkaline earth metal, a preparation method and application thereof, wherein the low-melting-point glass powder containing alkaline earth metal comprises the following raw material components: 30-70 mol% of Bi2O3, 10-30 mol% of B2O3, 10-30 mol% of ZnO and 0-20 mol% of a compound containing R, wherein the sum of the mol% of the components is 100 mol%; the R-containing compound is selected from at least one of RO, RF2 and RCl2, wherein R is at least one of Ca, Sr and Ba; preferably, the alkaline earth metal-containing low-melting-point glass frit has the following raw material components: bi2O 3: 40-60 mol%, B2O 3: 20-30 mol%, ZnO: 20-30 mol%, R-containing compound: 5-10 mol%, and the sum of the mol percentages of the components is 100 mol%.

Description

Low-melting-point glass powder containing alkaline earth metal and preparation method and application thereof
Technical Field
The invention relates to low-melting-point glass powder containing alkaline earth metal, a preparation method thereof and application thereof in aluminum and aluminum alloy sealing, belonging to the technical field of aluminum and aluminum alloy sealing.
Background
Metal-glass sealing techniques are widely used for metal enclosures for electronic devices. With the development of light-weight and high-performance electronic devices, there is an urgent need to replace high-density kovar alloy, steel, copper and other materials with lighter aluminum. Because the aluminum alloy has the characteristics of low melting point (660 ℃), high thermal expansion coefficient (15-24 multiplied by 10 < -6 >/DEG C) and the like, the sealing glass has the performance requirements of low melting point and high expansion. Meanwhile, the electronic device needs to cope with various severe environments such as different temperatures, humidity, impact and the like in the using process, and the sealing glass needs to have good air tightness, aging resistance, electrical insulation and high mechanical strength so as to ensure the safe and stable operation of the device.
At present, low melting glass for sealing aluminum and aluminum alloy is mainly classified into two types of lead glass and lead-free glass. Lead ions are gradually dissolved out due to the erosion of water, acid rain, atmosphere and the like after lead vitrification waste, so that the underground water quality is seriously polluted, the life safety of people is ensured, and the brain development of children is seriously influenced. On the other hand, in the production of lead-containing glass, the flying of dust in the batching process and the volatilization of lead in the glass melting process can cause harm to operation workers and the environment. The european union has started to enforce the regulations on the prohibition of the use of certain hazardous substances in electronic and electrical equipment, and has generally prohibited the use of hazardous substances such as lead, cadmium, mercury, thallium, hexavalent chromium and compounds thereof in products such as electronics and automobiles. The green, environment-friendly and lead-free development direction of the electronic manufacturing industry is formed.
At present, the lead-free aluminum sealing glass is mainly divided into three systems: vanadate system, phosphate system, bismuthate system. Wherein, the vanadate glass, as the Chinese patent CN201410143646.5), reports a softening temperature lower than 450 ℃ and a thermal expansion coefficient of 4.9-12.5 multiplied by 10-6V controllable at/° C2O5-ZnO-B2O3A low melting point glass. However, vanadate glass has a layered structure, is easy to absorb moisture, is easy to form bubbles in a sintering system, and has the problems of matching of thermal expansion coefficients and the like in use. Phosphate glasses, such as: the Chinese patent CN108164150A discloses a glass with the mol percentage of P2O5：35～45％、SnO：15～28％、Bi2O3：15～27％、ZnO2：3～7％、SiO2：1～3％、Na2O：2～4％、K2O: 1-4%, BaO: 2 to 5% and WO3: 2-4%. Although the insulation resistance and the air leakage rate meet the standard after the phosphate glass is sealed with the aluminum shell, the phosphate glass has extremely poor chemical stability, and simultaneously has the problems of easy water absorption, poor electrical insulation property and the like. Bismuthate glasses, such as Bi disclosed in Japanese patent laid-open No. 20061434802O3-B2O3The glass component and the sealing material adopting the component comprise the following components: bi2O330～60mol％、B2O3 10～35mol％、WO30.1-5 mol%, the glass is easy to crystallize in the sealing process, and the crystallization can cause the sealing temperature of the glass to rise, destroy the internal crystal framework of the aluminum shell and the contact pin, and leave serious potential safety hazards. Therefore, in order to ensure the stability of the sealing member and improve the reliability and the competitiveness of the device, the development of a novel bismuthate aluminum alloy sealing glass is urgently needed.
Disclosure of Invention
Aiming at the technical problems that the existing bismuthate sealing glass is easy to crystallize and has lower thermal expansion coefficient, the invention provides low-melting-point glass powder containing alkaline earth metal, a preparation method thereof and application thereof in aluminum and aluminum alloy sealing.
In a first aspect, the present invention provides an alkaline earth metal-containing low-melting-point glass frit, which comprises the following raw material components: 30 to 70 mol% of Bi2O3、10～30mol％B2O310-30 mol% of ZnO and 0-20 mol% of a compound containing R, wherein the sum of the mol% of the components is 100 mol%; the R-containing compound is selected from RO and RF2、RCl2Wherein R is at least one of Ca, Sr and Ba; preferably, the alkaline earth metal-containing low-melting-point glass frit has the following raw material components: bi2O3：40～60mol％、B2O3: 20-30 mol%, ZnO: 20-30 mol%, R-containing compound: 5-10 mol%, and the sum of the mol percentages of the components is 100 mol%.
In the present disclosure, by introducing alkaline earth metal ions (Ca)2+、Sr2+、Ba2+) Inhibit glass crystallization, improve chemical stability, adjust glass transition point and softening point, simultaneously improve the thermal expansion coefficient of glass, and promote the development of electronic devices to light weight and high performance.
Because bismuth and lead are positioned adjacently in the periodic table of elements, bismuth and lead have many similar properties such as high polarizability, high refraction and dispersion ratios according to the diagonal and adjacent principles, and two types of glass systems are similar in viscosity, characteristic temperature, expansion coefficient and the like. Bi2O3SiO capable of being combined with glass forming body2、B2O3Or P2O5The components are co-melted and have a relatively wide glass forming range even when only 1 wt% of SiO is used2Or B2O3When present, glass is also readily formed. In addition, the bismuthate low-temperature sealing glass is not easy to recover in the melting process, is harmless to the environment and human bodies, and belongs to environment-friendly glass. Accordingly, bismuthate glass is considered to be the best alternative to lead glass. In the present invention, Bi2O3Optional composition rangeThe content of the polymer is 35-75 mol%, and the preferable composition range is 40-60 mol%. When the content is less than 40 mol%, the softening point of the glass cannot be sufficiently lowered, and the sealing effect cannot be expected; when the content is more than 75 mol%, part of Bi may be caused2O3Is reduced to separate out bismuth metal, and glass is not easy to form.
B2O3Is one of the most basic oxides in many low-melting glasses and is also an important network former in the glass, and can accelerate glass homogenization, reduce the viscosity of the glass and reduce crystallization capacity at high temperature so as to enable the glass to be formed more easily. After the glass is formed, the thermal stability, chemical stability and fluidity of the glass can be improved, and the expansion coefficient and surface tension of the glass can be reduced. In the present invention, B2O3An optional composition range is 15 to 35 mol%, and a preferable composition range is 20 to 30 mol%. When the content is less than 15 mol%, the glass does not act as a cosolvent to accelerate the clarification of the glass and reduce the crystallization capacity of the glass; and when the content is more than 35 mol%, B is contained in the glass during melting2O3The water vapor is volatilized, so that a devitrified skin is formed on the surface of molten glass due to the reduction of volatilization, and the glass is formed by BO3]The trihedron increases, the thermal expansion coefficient of the glass increases instead, and the softening point temperature of the glass increases significantly. ZnO is an important glass network regulating oxide, can reduce the softening point of glass, regulate the thermal expansion coefficient and improve the chemical stability, the thermal stability and the refractive index of the glass. In the experiment, the optional composition range of ZnO in the glass is 15-35 mol%, and the preferred composition range is 20-30 mol%. When the content is less than 15 mol%, glass is not easily formed, and the thermal expansion coefficient of the glass is obviously increased; when the content is more than 35 mol%, the softening point temperature of the glass is increased, the fluidity of the glass is deteriorated, and the crystallization is liable to occur.
R-containing compounds (e.g., RO, RF)2、RCl2Etc. wherein R is one or more of Ca, Sr and Ba), the addition of the glass can obviously reduce the crystallization tendency of the glass, improve the chemical stability, the thermal stability, the mechanical strength, the refractive index and the like of the glass, and simultaneously can adjust the thermal expansion of the glassCoefficient and sealing temperature. However, the amount of the glass is not so large that the thermal stability of the glass is deteriorated. The optional composition range is 0 to 15 mol%, and the preferable composition range is 0.5 to 15 mol%, and more preferably 5 to 10 mol%.
Preferably, the low-melting-point glass powder containing the alkaline earth metal further contains nitrate or/and hypochlorite, and the adding amount is 1-5 wt% of the total mass of the raw material components. Wherein the nitrate or/and hypochlorite (NaNO)3、KNO3、NaClO3、KClO3One or more) of the above compounds can inhibit Bi from being added in the high-temperature melting process3+Is reduced to Bi2+、Bi+、Bi0。
Preferably, the low melting point glass powder containing the alkaline earth metal has a softening temperature of 366.3-407.4 ℃, a glass transition temperature of 354.5-408.1 ℃ and an expansion coefficient of (10.7-13.5) x 10-6/℃(25～300℃)。
Preferably, the sealing temperature of the low-melting-point glass containing the alkaline earth metal is 400-480 ℃.
In a second aspect, the present invention provides a method for preparing the alkaline earth metal-containing low-melting-point glass frit as described above, comprising:
s1: weighing a Bi source, a B source, a Zn source and an R source according to the molar ratio of the raw material components of the low-melting-point glass powder containing the alkaline earth metal, and mixing to obtain a mixture (for example, weighing the raw materials corresponding to the components respectively, adding a little distilled water, and then performing planetary ball milling and mixing uniformly);
s2: directly putting the mixture obtained in the step S1 into a corundum crucible in a glass melting furnace at 850-1000 ℃, preserving heat for 0.5-1.5 hours, and quenching the melted glass liquid to obtain glass fragments;
s3: and (4) crushing the glass fragments in the step (S2) to obtain the low-melting-point glass powder containing the alkaline earth metal. The crushing mode can be planetary ball milling for 1-6 hours to obtain the low-melting-point glass powder containing alkaline earth metal.
Preferably, the melting temperature is 900-950 ℃, the heat preservation time is 0.5-1 hour, and the low melting temperature and short-time heat preservation can inhibit Bi3+The ions are reduced, and the effects of energy conservation and emission reduction are achieved.
Preferably, the Bi source is Bi2O3Or/and Bi (NO)3)3(ii) a The B source is selected from Bolbostemma rhizome and/or H3BO3(ii) a The Zn source is selected from ZnO and ZnCO3At least one of; the R source is selected from RCO3、R(NO3)2、RCl2、RF2At least one of (1).
In a third aspect, the invention provides a glass paste (low-melting-point glass paste preparation) containing alkaline earth metal-containing low-melting-point glass powder, wherein the alkaline earth metal-containing low-melting-point glass powder is uniformly mixed with an organic solvent to form glass paste; preferably, at least one of silane coupling agent, stearic acid, stearate and polyvinyl butyral (PVB) alcohol solution with the weight percent of 2-12% is added into the alkaline earth metal-containing low-melting-point glass powder as a modifier for ball milling, mixing and modifying before mixing, wherein the adding amount of the modifier is less than 10% by weight of the total amount of the alkaline earth metal-containing low-melting-point glass powder. Specifically, the method comprises the following steps: s1: adding one or more of silane coupling agent, stearic acid or stearate and 2-12 wt% of PVB alcohol solution into glass powder for ball milling modification; s2: the obtained modified glass frit obtained in S1 is uniformly mixed with an organic solvent to form a glass paste.
Preferably, the modifier comprises one or more of a silane coupling agent, stearic acid or stearate and a PVB alcohol solution with the content of 2-12 wt%, the adding amount of the modifier is less than 10wt% of the total amount of the raw material components of the glass powder, and the modifier can inhibit the problem of layering of the glass slurry during long-term storage.
Preferably, the mass ratio of the organic solvent to the alkaline earth metal-containing low-melting-point glass powder is (15-25): (75-85).
Preferably, the organic solvent comprises at least one of a carrier, a plasticizer, a binder and a dispersing agent, wherein the carrier comprises alcohols, ketones or/and ethers, the plasticizer is selected from benzoic acids or/and glycols, the binder is selected from celluloses or/and polyvinyl alcohols, and the dispersing agent is selected from at least one of fish oil, linseed oil, span-85, triethanolamine and soybean lecithin.
In a fourth aspect, the invention provides a glass preform containing the alkaline-earth-metal-containing low-melting-point glass powder, wherein the alkaline-earth-metal-containing low-melting-point glass powder and a granulating agent are mixed, pressed and molded, and pre-sintered at the glass softening point temperature of the alkaline-earth-metal-containing low-melting-point glass powder to obtain the glass preform; the granulating agent comprises paraffin and PVB alcohol solution with the concentration of 3-12 wt%. Specifically, the method comprises the following steps: s1: the low-melting-point glass powder (glass powder or low-melting-point glass powder) containing alkaline earth metal needs to be granulated by spraying: the preparation method comprises the steps of uniformly mixing low-melting-point glass powder, a granulating agent and alcohol, and granulating and forming by adopting closed circulation spray drying equipment, wherein the solid content is 50-70%, and the granulating agent comprises paraffin and PVB alcohol solution with the concentration of 3-10 wt%. S2: pressing the granulated glass powder obtained in the step S1 into a green body by using an automatic press; s3: and sintering the glass preform in S2 at a certain temperature to obtain the glass preform.
Preferably, the addition amount of the granulating agent is 1-5 wt% of the low-melting-point glass powder containing alkaline earth metal.
Preferably, the pre-sintering temperature is 375-425 ℃, and the time is 0.2-1.5 hours; preferably, the temperature increase rate of the pre-firing is 1 to 5 ℃/min.
In a fifth aspect, the invention provides an application of the glass slurry in sealing aluminum and aluminum alloy, wherein the glass slurry is coated on the surface of the aluminum and aluminum alloy, and is kept at 400-480 ℃ for 0.5-2 hours in an atmospheric atmosphere to realize sealing matching with the aluminum and aluminum alloy; preferably, the temperature is raised to 400-480 ℃ at a rate of 1-5 ℃/min.
In a sixth aspect, the invention provides an application of the glass prefabricated member in sealing aluminum and aluminum alloy, wherein the glass prefabricated member is put into an aluminum and aluminum alloy connector and is subjected to heat preservation for 0.5-2 hours at 400-480 ℃ in an atmospheric atmosphere to realize sealing matching with the aluminum and the aluminum alloy; preferably, the temperature is raised to 400-480 ℃ at a rate of 5-10 ℃/min.
The invention has the following remarkable advantages:
(1) the aluminum alloy sealing glass of the invention is prepared by introducing RO/RF2/RCl2(R isCa. One or more of Sr and Ba) can obviously reduce the crystallization tendency of the glass, improve the chemical stability, the thermal stability, the mechanical strength, the refractive index and the like of the glass, and avoid the serious potential safety hazard caused by the crystallization that the sealing temperature of the glass is raised and the internal crystal framework of the aluminum shell and the contact pin is damaged;
(2) the sealing temperature (400-480 ℃) and the expansion coefficient (10-13.5 multiplied by 10) of the aluminum alloy sealing glass of the invention-6V DEG C) to meet the requirement of low-temperature high expansion of aluminum alloy sealing. Meanwhile, the sealing glass does not contain toxic components such as Pb, V, Te and the like, is harmless to human bodies and environment, and is green and environment-friendly;
(3) compared with the traditional sealing glass, the sealing glass of the invention can realize matching sealing in the atmosphere without special nucleation or crystallization treatment and protective atmosphere, has simple process and good chemical stability, and can meet the sealing requirements of aluminum devices in the fields of electronics, automobiles and the like.
Drawings
FIG. 1 is a photograph of a pre-fired glass preform (a) and a post-fired glass preform (b);
FIG. 2 is a flow chart of the preparation of a low melting point glass paste;
FIG. 3 is a flow chart of the use of a low melting point glass paste;
FIG. 4 is a DSC curve of example 1 and comparative example 1;
FIG. 5 is an XRD pattern after the non-heat treatment and the heat treatment at 425 ℃ for 0.5 hour of example 1 and comparative example 1;
FIG. 6 is an SEM image of a cross section of a sealed glass-aluminum alloy interface between example 1 and comparative example 1.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the present disclosure, the raw material components of the alkaline earth metal-containing low-melting-point glass frit include: bi2O3：35～70mol％、B2O3: 10-30 mol%, ZnO: 10-30 mol%, RO: 5-20 mol%, wherein R is one or more of Ca, Sr and Ba, and the mol percentage of each componentThe sum of the ratios is 100 mol%. In an alternative embodiment, the alkaline earth metal-containing low-melting-point glass frit has the following raw material components: bi2O3：40～60mol％、B2O3: 20-30 mol%, ZnO: 20-30 mol%, RO: 5-10 mol%, and the sum of the mol percentages of the components is 100 mol%. In the present invention, the addition of alkaline earth metal to the glass ensures that the glass has a reduced softening point of 360 to 425 ℃ and a high thermal expansion coefficient (10 to 13.5X 10)-6/° c) and excellent water resistance, acid resistance and alkali resistance, has good wettability with aluminum alloy, can be completely melted below 500 ℃, has strong bonding force with the aluminum alloy, and does not crack.
In an alternative embodiment, the sealing temperature of the alkaline earth metal-containing low-melting-point glass is 400-480 ℃.
The method for producing the alkali earth metal-containing low-melting-point glass frit is exemplarily described below.
And (2) according to the mol percentage composition range of the raw material components of the low-melting-point glass powder containing the alkaline earth metal, carrying out ball milling and uniformly mixing on a Bi source, a B source, a Zn source and an R source to obtain a mixture. The oxide raw materials are introduced as follows: bi2O3From Bi2O3、Bi(NO3)3Introduced as a Bi source. B is2O3From Boerhans and Hegan3BO3Introduced as a B source. ZnO is prepared from ZnO and ZnCO3And one or more of (a) and (b) is introduced as a Zn source. From RCO3、R(NO3)2、RCl2、RF2One or more of them are introduced as R source (wherein R is one or more of Ca, Sr and Ba).
And melting the mixture in a silicon-molybdenum high-temperature furnace at 850-1000 ℃, and preserving heat for 0.5-1 hour to obtain glass liquid.
Pouring the melted glass liquid into a double-roller machine filled with compressed air and cold water for rapid cooling to obtain glass slag.
And further crushing and sieving the glass broken slag (or called glass slag) to obtain the low-melting-point glass powder containing the alkaline earth metal. The crushing mode can be planetary ball milling, and the granularity of the glass powder is controlled to be 2-4 mu m under D50. And performing planetary ball milling on the broken glass residues to obtain glass powder, and placing the glass powder in an alumina tank, wherein the ball milling medium is zirconia balls, the rotating speed is 300-500 r/min, and the time is 0.5-6 h.
In one embodiment of the present invention, an appropriate amount of an organic solvent is added to the alkaline earth metal-containing low-melting-point glass frit to prepare a glass paste having a viscosity suitable for screen printing, which is used for sealing an aluminum-aluminum alloy. Wherein, the mass ratio of the organic solvent to the low-melting-point glass powder containing the alkaline earth metal can be as follows: (15-25 wt%): (75 to 85 wt%). The glass paste further contains at least one of a carrier, a plasticizer, a binder, a dispersant, and the like. In an alternative embodiment, the carrier comprises: one or more of alcohols, ketones and ethers organic solvents. The plasticizer comprises: benzoic acids, glycols, and the like. The adhesive comprises: cellulose and polyvinyl alcohol. The dispersant comprises: fish oil, oleum Lini, span-85, triethanolamine, and soybean lecithin. Fig. 2 shows a flow chart of the preparation of the low melting point glass paste (i.e., of the glass paste), and it can be seen from the chart that the preparation process of the glass paste is simple and applicable to industrialization.
In another embodiment of the present invention, a proper amount of granulating agent is added to the alkali earth metal-containing low-melting glass powder, and the mixture is molded and presintered (calcined) at a glass softening point temperature to obtain a glass preform having a certain strength, which is used for sealing aluminum and aluminum alloys. The granulating agent comprises: paraffin, PVB alcohol solution (the concentration can be 3-12 wt%), and the like. The granulating agent can account for 1-5 wt% of the low-melting-point glass powder containing alkaline earth metal. The temperature of the pre-sintering is 375-425 ℃, and the heat preservation time is 0.5-2 hours. Preferably, the temperature rise rate of the pre-sintering is 1-5 ℃/min.
Compared with the traditional glass-ceramic sealing process, the sealing process containing the alkaline-earth metal low-melting-point glass powder does not need special nucleation or crystallization treatment, does not need protective atmosphere, can realize sealing in atmospheric atmosphere, has simple process and good chemical stability, and can meet the sealing requirements of aluminum devices in the fields of electronics, automobiles and the like.
In one embodiment of the invention, the prepared glass paste is uniformly coated on the surfaces of aluminum and aluminum alloy by screen printing, and then is subjected to sealing matching with the aluminum alloy in an atmospheric atmosphere at a temperature rise rate of 1-5 ℃/min to 400-475 ℃ for 0.5-2 h, as shown in fig. 3. Wherein the heating rate can be 1-3 ℃/min.
In another embodiment of the invention, the prepared glass prefabricated member is put into an aluminum and aluminum alloy connector, and is subjected to heat preservation for 0.5-2 h at the temperature rising rate of 5-10 ℃/min to 400-480 ℃ in the atmospheric atmosphere, so that the sealing matching with the aluminum alloy is realized.
In the present disclosure, the softening temperature of the alkaline earth metal-containing low-melting-point glass frit is 366.3 to 407.4 ℃ as measured by a Netzsch DIL402C type thermal expansion analyzer. The glass transition temperature of the alkaline-earth-metal-containing low-melting-point glass powder is 354.5-408.1 ℃ as measured by a Netzsch DSC 404C type Differential Scanning Calorimetry (DSC, Differential Scanning Calorimetry, Germany). The expansion coefficient of the low-melting-point glass powder containing the alkaline earth metal is (10-13.5) x 10 measured by a Netzsch DIL402C type thermal expansion analyzer-6/℃。
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1:
(1) according to the glass mixture ratio of example 1 in table 1, the total mass is 500g, and the corresponding raw materials are calculated and weighed: bi2O3、H3BO3、ZnO、SrCO3、NaNO3Adding a proper amount of absolute ethyl alcohol into the prepared materials, carrying out planetary ball milling for 1 hour, discharging, and drying in a constant-temperature drying oven at 110 ℃ to obtain a mixture;
(2) placing the mixture obtained in the step (1) in a 950 ℃ silicon-molybdenum high-temperature furnace, preserving heat for 45min, and clarifying to obtain glass liquid;
(3) pouring the molten glass melted in the step (2) into a double-roller machine filled with compressed air and cold water for rapid cooling to obtain glass slag or glass sheets;
(4) mixing the glass broken slag obtained in the step (3) with the following raw materials: carrying out planetary ball milling for 3h with the ball ratio of 1:4 to ensure that the granularity of the glass powder is 3 mu m when D50 is obtained, drying and sieving with a 200-mesh sieve to obtain the glass powder;
(5) adding the glass powder obtained in the step (4) into a PVB alcohol solution with the concentration of 7.5 wt% according to 5wt% of the glass mass, carrying out planetary ball milling for 2 hours, and sieving with a 200-mesh sieve to obtain modified glass powder;
(6) mixing the modified glass powder obtained in the step (5) with an organic solvent according to the condition that the solid content is 85 wt%, and preparing into glass slurry with viscosity suitable for silk-screen printing;
(7) mixing the glass powder obtained in the step (4) with 3 wt% of PVB, granulating, molding, pre-sintering at a heating rate of 1 ℃/min to 425 ℃, and preserving heat for 0.5 hour to finally obtain a glass prefabricated member with certain strength;
(8) carrying out surface ultrasonic cleaning, drying and other process pretreatment on an aluminum alloy device to be sealed;
(9) uniformly coating the prepared glass slurry on the surface of the aluminum alloy treated in the step (7) through screen printing, heating to 450 ℃ at a heating rate of 2 ℃/min in an atmospheric atmosphere, and preserving heat for 0.5 h;
(10) and (3) putting the prepared glass prefabricated member into the aluminum alloy connector processed in the step (7), heating to 450 ℃ at the heating rate of 5 ℃/min in the atmosphere, and preserving heat for 0.5 h.
Example 2:
a batch was prepared according to the glass formulation of example 2 in table 1, with other steps and parameters as in example 1.
Example 3:
a batch was prepared according to the glass formulation of example 3 in table 1, with other steps and parameters as in example 1.
Example 4:
a batch was prepared according to the glass formulation of example 4 in table 1, with other steps and parameters as in example 1.
Example 5:
a batch was prepared according to the glass formulation of example 5 in table 1, with other steps and parameters as in example 1.
Example 6:
a batch was prepared according to the glass formulation of example 6 in table 1, with other steps and parameters as in example 1.
Example 7:
a batch was prepared according to the glass formulation of example 7 in table 1, with other steps and parameters as in example 1.
Example 8:
a batch was prepared according to the glass formulation of example 8 in table 1, with other steps and parameters as in example 1.
Example 9:
a batch was prepared according to the glass formulation of example 9 in table 1, with other steps and parameters as in example 1.
Comparative example 1:
a batch was prepared according to the glass formulation of comparative example 1 in table 1, with other steps and parameters as in example 1.
Comparative example 2:
a batch was prepared according to the glass formulation of comparative example 2 in table 1, with other steps and parameters as in example 1.
Table 1 shows the composition (mole percentage) of the alkaline earth metal-containing low-melting-point glass frits obtained in examples 1 to 10 and comparative example 1:
Figure BDA0002215118720000081
Figure BDA0002215118720000091
fig. 1 shows that the sealing glass preform can be matched and sealed directly with the aluminum alloy preform.
Fig. 4 is DSC curves of example 1 and comparative example 1, and it can be seen that no crystallization peak is detected in the DSC curve of example 1, but a significant crystallization peak appears in comparative example 1.
Fig. 5 is an XRD pattern after the heat treatment of example 1 and comparative example 1 and the heat treatment at 425 ℃ for 0.5 hour, and it can be seen from the XRD pattern that example 1 does not precipitate a crystalline phase during the heat treatment, and comparative example 1 precipitates a crystalline phase.
FIG. 6 is SEM images of the sealed cross sections of example 1 and comparative example 1, and it can be seen that the sealing interface of example 1 and aluminum alloy has good matching, no crack and no bubble, and completely meets the sealing requirement; the sealing interface between the comparative example 1 and the aluminum alloy has obvious cracking caused by mismatched expansion coefficients and bubbles, and the bubbles are generated because the bubbles enter gas after the cracks are generated due to mismatched expansion coefficients, so that the sealing requirements cannot be met.

Claims (14)

1. An alkaline earth metal-containing low-melting-point glass frit is characterized in that the alkaline earth metal-containing low-melting-point glass frit comprises the following raw material components: 30 to 70 mol% of Bi2O3、10～30mol％B2O310-30 mol% of ZnO and 0-20 mol% of a compound containing R, wherein the sum of the mol% of the components is 100 mol%; the R-containing compound is selected from RO and RF2、RCl2Wherein R is at least one of Ca, Sr and Ba; preferably, the alkaline earth metal-containing low-melting-point glass frit has the following raw material components: bi2O3：40～60mol％、B2O3: 20-30 mol%, ZnO: 20-30 mol%, R-containing compound: 5-10 mol%, and the sum of the mol percentages of the components is 100 mol%.
2. The alkali-earth-metal-containing low-melting-point glass powder according to claim 1, wherein the alkali-earth-metal-containing low-melting-point glass powder further comprises nitrate or/and hypochlorite, and the addition amount is 1-5 wt% of the total mass of the raw material components.
3. The alkali-earth-metal-containing low-melting-point glass frit according to claim 1 or 2, wherein the glass transition temperature of the alkali-earth-metal-containing low-melting-point glass frit is 354.5 to 408.1 ℃, the softening temperature of 366.3-407.4 ℃, the sealing temperature of 400-480 ℃, and the expansion coefficient of (10-13.5) x 10-6/℃。
4. A method for producing an alkaline earth metal-containing, low-melting-point glass frit according to any one of claims 1 to 3, comprising:
s1: weighing a Bi source, a B source, a Zn source and an R source according to the molar ratio of the raw material components of the low-melting-point glass powder containing the alkaline earth metal, and mixing to obtain a mixture;
s2: melting the mixture obtained in the step S1 at 850-1000 ℃ for 0.5-1.5 hours, and then carrying out quenching to obtain glass fragments;
s3: and (4) crushing the glass fragments in the step (S2) to obtain the low-melting-point glass powder containing the alkaline earth metal.
5. The method according to claim 4, wherein the Bi source is Bi2O3Or/and Bi (NO)3)3(ii) a The B source is selected from Bolbostemma rhizome and/or H3BO3(ii) a The Zn source is selected from ZnO and ZnCO3At least one of; the R source is selected from RCO3、R(NO3)2、RCl2、RF2At least one of (1).
6. The alkali-earth-metal-containing low-melting-point glass frit according to claim 4 or 5, wherein the particle size of the alkali-earth-metal-containing low-melting-point glass frit is D50=2 to 4 μm.
7. A glass paste containing the alkaline earth metal-containing low-melting-point glass frit according to any one of claims 1 to 3, wherein the alkaline earth metal-containing low-melting-point glass frit is uniformly mixed with an organic solvent to form a glass paste; preferably, at least one of silane coupling agent, stearic acid, stearate and polyvinyl butyral (PVB) alcohol solution with the weight percent of 2-12% is added into the alkaline earth metal-containing low-melting-point glass powder as a modifier for ball milling, mixing and modifying before mixing, wherein the adding amount of the modifier is less than 10% by weight of the total amount of the alkaline earth metal-containing low-melting-point glass powder.
8. The glass paste according to claim 7, wherein the mass ratio of the organic solvent to the alkaline earth metal-containing low-melting-point glass frit is (15 to 25): (75-85).
9. The glass paste according to claim 7 or 8, wherein the organic solvent comprises at least one of a carrier, a plasticizer, a binder, and a dispersant; preferably, the carrier comprises alcohols, ketones or/and ethers, the plasticizer is selected from benzoic acids or/and glycols, the binder is selected from celluloses or/and polyvinyl alcohols, and the dispersant is selected from at least one of fish oil, linseed oil, span-85, triethanolamine and soybean lecithin.
10. A glass preform containing the alkaline earth metal-containing low-melting-point glass frit according to any one of claims 1 to 3, wherein the alkaline earth metal-containing low-melting-point glass frit and the granulating agent are mixed and press-molded, and pre-fired at a glass softening point temperature of the alkaline earth metal-containing low-melting-point glass frit to obtain a glass preform; the granulating agent comprises paraffin, PVB alcohol solution with the concentration of 3-12 wt% or PVA water solution with the concentration of 1-6 wt%.
11. The glass preform according to claim 10, wherein the granulating agent is added in an amount of 1 to 5wt% based on the alkali earth metal-containing low-melting-point glass frit.
12. The glass preform according to claim 10 or 11, wherein the pre-firing molding temperature is 375-425 ℃ and the holding time is 0.2-1.5 hours; preferably, the temperature increase rate of the pre-firing is 1 to 5 ℃/min.
13. The use of the glass paste according to any one of claims 7 to 9 for sealing aluminum and aluminum alloys, wherein the glass paste is coated on the surface of aluminum and aluminum alloys, and is kept at 400 to 480 ℃ for 0.5 to 2 hours in an atmospheric atmosphere to realize sealing matching with the aluminum and aluminum alloys; preferably, the temperature is raised to 400-480 ℃ at a rate of 1-5 ℃/min.
14. The use of the glass preform of any one of claims 10-12 in sealing aluminum and aluminum alloys, wherein the glass preform is placed in an aluminum and aluminum alloy connector and is subjected to heat preservation at 400-480 ℃ for 0.5-2 hours in an atmospheric atmosphere to achieve sealing matching with the aluminum and aluminum alloys; preferably, the temperature is raised to 400-480 ℃ at a rate of 5-10 ℃/min.
CN201910912406.XA 2019-09-25 2019-09-25 Low-melting-point glass powder containing alkaline earth metal and preparation method and application thereof Pending CN112551902A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910912406.XA CN112551902A (en) 2019-09-25 2019-09-25 Low-melting-point glass powder containing alkaline earth metal and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910912406.XA CN112551902A (en) 2019-09-25 2019-09-25 Low-melting-point glass powder containing alkaline earth metal and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN112551902A true CN112551902A (en) 2021-03-26

Family

ID=75029299

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910912406.XA Pending CN112551902A (en) 2019-09-25 2019-09-25 Low-melting-point glass powder containing alkaline earth metal and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112551902A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114014527A (en) * 2021-11-01 2022-02-08 西安赛尔电子材料科技有限公司 Aluminum-sealed phosphate glass powder spray granulation method
CN114261987A (en) * 2021-10-25 2022-04-01 中国科学院上海硅酸盐研究所 BiOCl1-xBrxPowder and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000128574A (en) * 1998-10-21 2000-05-09 Nippon Electric Glass Co Ltd Bismuth-based glass composition
CN109455940A (en) * 2019-01-11 2019-03-12 福州布朗新材料技术有限公司 A kind of soft lead-free low-temperature seal glass and preparation method thereof
CN110217992A (en) * 2019-05-24 2019-09-10 江苏大学 A kind of preparation method of environment-friendly glass frit

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000128574A (en) * 1998-10-21 2000-05-09 Nippon Electric Glass Co Ltd Bismuth-based glass composition
CN109455940A (en) * 2019-01-11 2019-03-12 福州布朗新材料技术有限公司 A kind of soft lead-free low-temperature seal glass and preparation method thereof
CN110217992A (en) * 2019-05-24 2019-09-10 江苏大学 A kind of preparation method of environment-friendly glass frit

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杨远波等: "《BaO含量对Zn0-B2O3-Bi2O3-BaO系玻璃结构及性能的影响》", 《玻璃》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114261987A (en) * 2021-10-25 2022-04-01 中国科学院上海硅酸盐研究所 BiOCl1-xBrxPowder and preparation method and application thereof
CN114014527A (en) * 2021-11-01 2022-02-08 西安赛尔电子材料科技有限公司 Aluminum-sealed phosphate glass powder spray granulation method

Similar Documents

Publication Publication Date Title
JP4972954B2 (en) Bismuth-based glass composition and bismuth-based sealing material
EP3026028B1 (en) Vanadate glass material for use in sealing by local heating, flat display manufactured using same, and method for manufacturing said display
KR101389875B1 (en) Sealing material
JP5033339B2 (en) Glass composition
JP4930897B2 (en) Bi2O3-B2O3 sealing material
JP2006342044A (en) Vanadium phosphate base glass
KR101242636B1 (en) Vanadium-phosphate glass
JP5083706B2 (en) Bismuth-based glass composition and bismuth-based sealing material
KR101020143B1 (en) Bismuth-based sealing material and bismuth-based paste material
KR20140125780A (en) Coefficient of thermal expansion filler for vanadium-based frit materials and/or methods of making and/or using the same
JP2011084437A (en) Sealing material
CN114477768A (en) Lead-free low-melting-point sealing glass doped with fusible metal alloy and preparation method thereof
CN112551902A (en) Low-melting-point glass powder containing alkaline earth metal and preparation method and application thereof
JP5476691B2 (en) Sealing material
JP5083704B2 (en) Bismuth sealing material
US6809049B2 (en) Glass compositions and glass forming materials comprising said compositions
CN114590999A (en) Low-melting-point lead-free glass powder and preparation method thereof
KR101064228B1 (en) Lead-free glass frit composition for use in sealing
JP2007126319A (en) Bismuth-based lead-free glass composition
JP2008308393A (en) Lead-free low softening point glass, lead-free low softening point glass composition, lead-free low softening point glass paste, and fluorescent display tube
CN114685102B (en) Low-temperature glass slurry and preparation method thereof
KR100833474B1 (en) Hermetically sealed and low melted glass and glass composite in OLED
JP5257829B2 (en) Sealing material
CN109843818B (en) Sealing material paste
KR100823952B1 (en) Low Glass Transition Temp. and Non-Yellowish Dielectric Glass Material

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
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20210326