CN116969679A - Leadless low-melting point glass-based sealing material, preparation method and application thereof - Google Patents

Leadless low-melting point glass-based sealing material, preparation method and application thereof Download PDF

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Publication number
CN116969679A
CN116969679A CN202310909990.XA CN202310909990A CN116969679A CN 116969679 A CN116969679 A CN 116969679A CN 202310909990 A CN202310909990 A CN 202310909990A CN 116969679 A CN116969679 A CN 116969679A
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China
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glass
lead
sealing material
teo
based sealing
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Chinese (zh)
Inventor
林慧兴
任海深
何飞
张奕
谢天翼
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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Priority to CN202310909990.XA priority Critical patent/CN116969679A/en
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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
    • 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
    • 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
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/028—Sealing means characterised by their material
    • H01M8/0282—Inorganic material
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations

Abstract

The invention relates to a lead-free low-melting-point glass-based sealing material, and a preparation method and application thereof. The composition of the lead-free low-melting-point glass-based sealing material is V 2 O 5 ‑TeO 2 -RO glass, wherein RO is at least one of the alkaline earth oxides MgO, caO, srO, baO.

Description

Leadless low-melting point glass-based sealing material, preparation method and application thereof
Technical Field
The invention relates to a lead-free low-melting-point glass-based sealing material, and a preparation method and application thereof, and belongs to the technical field of low-temperature sealing.
Background
The low-melting point sealing glass is glass with a sealing temperature of less than 600 ℃, is a novel inorganic sealing material, and is an interlayer glass capable of sealing glass, ceramic, metal and composite materials (matrix materials) with each other. Has good stability and mechanical property, and is mainly used for OLED, plasma display, solar heat collecting tube, vacuum fluorescent display, medium (vacuum) glass, high-power semiconductor shell base, sensor, metal packaging shell, low-temperature solid oxide battery (LT-SOC) and the like. In practical applications, the sealing temperature and the thermal expansion coefficient of the low-melting-point sealing glass are always the focus of attention.
The type of matching matrix material (hereinafter referred to as substrate) required for the low-melting point sealing glass is also relatively good. For example, sealing glass used in OLED applications needs to match cover glass, and sealing temperature is lower than 500 ℃ and thermal expansion coefficient (7-8) ppm/DEG C, and can be sealed by laser. For example, in LT-SOC, it is required to form an airtight structure with a ceramic with a high expansion coefficient and a stainless steel with a high expansion coefficient, the sealing temperature is required to be lower than 500 ℃, the thermal expansion coefficient (10-13) ppm/. Degree.C, and the working temperature is required to be 600-700 ℃. For another example, in copper alloy, silicon aluminum alloy, aluminum alloy based feed-through element or metal package housing, it is required that the sealing temperature of the sealing glass is not more than 450-600 deg.C, and the thermal expansion coefficient is (10-17) ppm/. Deg.C.
Currently, low-melting glass is mainly divided into two major categories, lead glass and lead-free glass. Although lead-acid salt glass has ultralow sealing temperature, excellent wettability and adjustable thermal expansion coefficient, lead is heavy metal, and lead ions are gradually dissolved out due to corrosion of water, acid rain, atmosphere and the like after lead vitrification is abandoned, so that serious pollution of underground water quality is caused, and serious influence is brought to life safety of people, especially brain development of children. On the other hand, in the production of lead-containing glass, the flying of dust during the batching process and the volatilization of lead during the glass melting process can cause harm to the operation workers and the environment. The european union has begun to impose regulations on the regulations of the regulations for the forbidden use of certain harmful substances in electronic and electrical equipment, which generally forbid the use of harmful substances such as lead, cadmium, mercury, thallium, hexavalent chromium and compounds thereof in products such as electronics and automobiles. Green, environmental-friendly, lead-free has become a development direction of the electronic manufacturing industry.
At present, lead-free sealing glass is mainly divided into three systems: phosphate systems, bismuthate systems, and vanadate systems. Wherein vanadate glass, as reported in Chinese patent 1 (application No. 201410143646.5), has a softening temperature lower than 450 ℃, and the low melting point V with the thermal expansion coefficient of (4.9-12.5) ppm/DEG C can be controlled by controlling the glass and the low expansion crystalline ceramic filler 2 O 5 -ZnO-B 2 O 3 Glass-based sealing materials. Vanadate glass system published by Chinese patent 2-4 (publication No. CN1738776A, publication No. CN1787978A and publication No. CN 101016196A) is B 2 O 3 -V 2 O 5 -ZnO-BaO-P 2 O 5 The glass system has a transition temperature Tg of (280-500) DEG C and a thermal expansion coefficient adjustable within the range of (8-12) ppm/. DEG C. Hitachi (HITACHI) (Li Jinwei, sun Shibing, span, et al, lead-free Low temperature sealing glass research development Profile [ J)]2018 (3) 4.) A V is published in China building technology 2 O 5 -P 2 O 5 The low melting point glass has a sealing temperature of less than 340 ℃ and a thermal expansion coefficient of less than 9.0 ppm/DEG C, but cannot meet the lead-free requirement due to lead.
The patent and research of vanadate glass are focused on regulating and controlling the thermal expansion coefficient, sealing temperature and chemical stability of low-melting-point glass, and little attention is paid to the heat conduction performance of the glass. In practical application, the sealing glass material in the copper alloy and aluminum alloy high-power communication module and LT-SOC needs to bear the temperature of 50-600 ℃ inequality, besides the stability of the sealing structure, the non-uniformity of the temperature field can lead to the stable gradient of the device, so the sealing material with high heat conductivity coefficient can improve the temperature impact resistance.
Disclosure of Invention
Therefore, the invention aims to provide a lead-free low-melting-point glass-based sealing material with adjustable (5-17) ppm/DEG C thermal expansion coefficient, adjustable working temperature from room temperature to 600 ℃ and sealing reliability and application thereof.
In a first aspect, the present invention provides a lead-free low-melting glass-based sealing material, the lead-free low-melting glassThe composition of the base sealing material is V 2 O 5 -TeO 2 -RO glass, wherein RO is at least one of the alkaline earth oxides MgO, caO, srO, baO.
Preferably, the particle size d50=0.8-20 μm and d90=5-70 μm of the lead-free low-melting glass-based sealing material; when RO is MgO, V 2 O 5 -TeO 2 MgO glass having a composition of TeO 2 Is 10 to 90mol percent, V 2 O 5 0 to 70mol% and not containing 0, 20 to 40mol% MgO;
alternatively, when RO is CaO, V 2 O 5 -TeO 2 CaO glass having a composition of TeO 2 Is 10 to 90mol percent, V 2 O 5 0 to 70mol percent, 0 is not contained, and 20 to 40mol percent of CaO is contained;
alternatively, when RO is SrO, V 2 O 5 -TeO 2 The composition of the SrO glass is TeO 2 0 to 90mol% and no 0, V 2 O 5 0 to 90mol% and not 0, 10 to 40mol% SrO;
or, when RO is BaO, V 2 O 5 -TeO 2 The composition of the BaO glass is TeO 2 0 to 90mol% and no 0, V 2 O 5 0 to 60mol percent, 0 is not contained, and 10 to 40mol percent of BaO is not contained.
Preferably, the glass transition temperature of the lead-free low-melting-point glass-based sealing material is 260-350 ℃, the glass softening temperature is 270-340 ℃, and the crystallization starting temperature is 320-500 ℃.
Preferably, the lead-free low-melting glass-based sealing material has a thermal expansion coefficient of 10-17 ppm/DEG C between 25 and 250 ℃.
Preferably, the leadless low-melting point glass-based sealing material is amorphous or microcrystalline;
when the lead-free low-melting glass-based sealing material is in a crystalline state, the crystalline phase thereof is RO-TeO 2 Basal crystalline phase or/and RO-V 2 O 5 A basal crystalline phase;
the RO-TeO 2 The basal crystal phase comprises Ba 3 TeO 6 、Ba 2 TeO 5 、BaTeO 3 、Ca 2 TeO 5 、Sr 2 TeO 5 At least one of (a) and (b);
the O-V 2 O 5 The basal crystal phase comprises Ba 2 V 2 O 7 、Ba 3 [VO 4 ] 2 、Ba 0.18 Te 2 O 4.95 At least one of (a) and (b);
preferably, when the lead-free low melting point glass-based sealing material is in a crystalline state, the glass thermal stability temperature difference Δt thereof is in the range of 25 to 170 ℃.
Preferably, the composition of the lead-free low-melting glass-based sealing material is V 2 O 5 -TeO 2 -RO glass + xwt% inorganic filler, wherein xwt% does not exceed 50wt%;
the composition of the inorganic filler is selected from MgO and Al 2 O 3 、AlN、Si 3 N 4 At least one of cordierite, beta-eucryptite, beta-spodumene, quartz glass frit and eucryptite glass frit;
the morphology of the inorganic filler is granular inorganic filler, short fiber inorganic filler or flaky inorganic filler;
preferably, the particle size of the granular inorganic filler is 100nm to 10 μm;
preferably, the short fibrous inorganic filler has a diameter of 1um to 30 um and a length of 5 to 100 um;
preferably, the diameter of the flaky inorganic filler is 0.5 um-30 um, and the thickness is more than 100nm.
Preferably, when the lead-free low melting point glass-based sealing material contains not more than 50wt% of an inorganic filler, the thermal expansion coefficient thereof at 25-250 ℃ is 5-14 ppm/DEG C, and the thermal conductivity thereof is (1-5) W/m.K.
In a second aspect, the present invention provides a method for preparing a lead-free low melting point glass-based sealing material, comprising:
(1) Weighing V 2 O 5 Powder, teO 2 Mixing the powder and RO source powder to obtain mixed powder; preferably, the R source powder is RO, RCO 3 、R(NO 3 ) 2 、RCl 2 、RF 2 At least one of (a) and (b);
(2) And melting the obtained mixed powder at 900-1000 ℃ for 0.5-2 hours, and cooling and crushing to obtain the lead-free low-melting-point glass-based sealing material.
Preferably, the mixing is carried out in a mixer; setting parameters of the mixer comprises the following steps: 60-120 r/min and 3-12 hours.
Preferably, the temperature rising rate of the melting is 1-10 ℃/min; the crushing mode is planetary ball milling, the rotating speed of the planetary ball milling is 100-500 rpm, and the time is 0.5-6 hours.
In a third aspect, the invention provides the use of a lead-free low melting point glass-based sealing material in glass, ceramic, metal and alloy seals.
Preferably, the first original element and the second element are sealed by the lead-free low-melting glass-based sealing material; the first element is selected from one of a glass element, a ceramic element, a metal element and a metal alloy element; the second element is selected from one of a glass element, a ceramic element, a metal element and a metal alloy element;
preferably, the metal alloy element comprises at least one of copper alloy, aluminum alloy, silicon aluminum alloy, stainless steel.
In a fourth aspect, the present invention provides the use of a lead-free low melting point glass-based sealing material, preferably having a particle size d50=0.8-20 μm and d90=5-70 μm, as a joint connection and/or feedthrough in the manufacture of an organic light emitting diode device, a low temperature solid oxide fuel cell and/or electrolysis cell, a feedthrough and/or a metal package housing.
In a fifth aspect, the present invention provides a preform made of a lead-free low melting glass-based sealing material having a particle size preferably d50=10 to 20 μm and d90=40 to 70 μm.
In a sixth aspect, the present invention provides a green sheet prepared from a lead-free low-melting glass-based sealing material, wherein the lead-free low-melting glass-based sealing material has a particle size of preferably d50=5 to 10 μm and d90=20 μm.
Seventh prescriptionThe invention provides a slurry prepared by using a lead-free low-melting-point glass-based sealing material, wherein the grain size of the lead-free low-melting-point glass-based sealing material is preferably D 50 ＝D50＝0.8～2μm，D90≤5μm。
In an eighth aspect, the present invention provides an application of a lead-free low-melting glass-based sealing material as an additive in preparing an amorphous glass material or a microcrystalline glass material, wherein the grain size of the lead-free low-melting glass-based sealing material is preferably d50=0.8-20 μm, and d90=5-70 μm.
The beneficial effects are that:
(1) The sealing temperature of the aluminum alloy sealing glass is 300-480 ℃, and the expansion coefficient ((5-17) multiplied by 10) -6 And the temperature is/DEG C), and the requirements of sealing low temperature and high expansion in different requirements are met. Meanwhile, the sealing glass does not contain toxic components such as Pb, is harmless to human bodies and the environment, and is environment-friendly;
(2) Compared with the traditional sealing glass, the sealing glass provided by the invention has the advantages that no special nucleation or crystallization treatment is needed, no protective atmosphere is needed, the matching sealing can be realized under the atmosphere, the process is simple, the chemical stability is good, and the sealing requirement of aluminum devices in the fields of electronics, automobiles and the like can be met.
Drawings
FIG. 1 is V 2 O 5 -TeO 2 -glass forming region design of RO (r=ca, sr, ba) low melting point glass;
FIG. 2 is V 2 O 5 -TeO 2 XRD diffractogram of RO-system low melting point glass (a) ro=cao, (b) (ro=sro, (c) ro=bao;
FIG. 3 shows DSC curves of examples 6-10, from which it can be seen that with V 2 O 5 /TeO 2 The decrease in the ratio gradually increases the glass transition temperature from 267.7 ℃ to 332.9 ℃. The degree of shielding of the charge in the nucleus from anions or electrons versus T g Has an influence, T g In connection with which the raising is first effected. The degree of shielding of the charge in the nucleus is related to the polarization ability of the anions and cations. The smaller the polarizability of the ions, the higher the transition temperature and softening temperature of the glass. Furthermore, the reduction of the degree of ion shielding can be achieved by reducing the ratio of anions to cations, thereby increasingTransition temperature and softening temperature of large glass. When V is 2 O 5 /TeO 2 The decrease in the ratio, the increase in the glass transition temperature, is caused by the decrease in the ratio of anions to cations, which reduces the degree of ion shielding;
FIG. 4 is a graph showing the thermal expansion coefficient of examples 6 to 10, from which it is understood that when the content of the alkaline earth metal SrO is 20mol%, V is followed 2 O 5 Reduction of content and TeO 2 The CTE of glass is increasing with increasing content. In addition, due to V 5+ And Te (Te) 4+ The different properties of the ions and their effect on the structure of the glass network. Compared with V 5+ ，Te 4+ Has relatively fewer positive charges, larger ionic radius, and lower binding capacity to oxygen ions, thus [ VO 4 ]Tetrahedra are easily transited by states [ TeO 3+1 ]And triangular cone [ TeO ] 3 ]Group substitution so that the glass network structure becomes evacuated;
fig. 5 is an SEM image of a cross-section of the glass-aluminum alloy interface after sealing in example 10, from which it is clear that the aluminum alloy interface is tightly bonded to the low melting point glass coating, without gaps, and an effective seal is achieved.
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof.
In the present disclosure, the raw material components of the lead-free low melting point glass material include: teO (TeO) 2 ：0～70mol％、V 2 O 5 :0 to 90mol percent of RO:0 to 40mol percent, wherein R is one or more of Mg, ca, sr, ba, and the sum of the mol percent of each component is 100mol percent.
In the present invention, the addition of alkaline earth metal to glass ensures that the glass has a reduced softening point of 360 to 425 ℃ and a high thermal expansion coefficient ((10 to 17) ×10) -6 High temperature/DEG C) and excellent water resistance, acid resistance and alkali resistance, has good wettability with aluminum alloy, can be completely melted below 500 ℃, has strong binding force with the aluminum alloy and does not crack.
In alternative embodiments, the sealing temperature of the lead-free low melting point glass may be 300 to 600 ℃.
In the invention, V is prepared by adopting a high-temperature melting method 2 O 5 -TeO 2 RO (R=Ca, sr, ba) -based low melting point glass, V in FIG. 1 (a) was prepared by adding 20mol% of each element by a conventional melting method 2 O 5 -TeO 2 21 glasses of different composition in RO (r=ca, sr, ba) system. And V is combined with 2 O 5 -TeO 2 No. 1-21 in RO (R=Ca, sr, ba) system are respectively ground and sieved, the glass forming condition of the melted sample is primarily observed, and then crystallization and amorphous of the glass are determined by XRD test (as shown in figure 2). And redesign and fuse V according to the result 2 O 5 -TeO 2 CaO No. 22-36 and V 2 O 5 -TeO 2 No. 22-35 of RO (r=sr, ba) to precision glass forming region. Finally, by accurately analyzing the XRD pattern of the second finishing chart, V is approximately determined 2 O 5 -TeO 2 Glass forming area diagram of RO (r=ca, sr, ba) low melting point glass. V (V) 2 O 5 -TeO 2 Glass forming region of CaO TeO 2 Is 10 to 90mol percent, V 2 O 5 0 to 70mol percent, 0 is not contained, and 20 to 40mol percent of CaO is contained; v (V) 2 O 5 -TeO 2 Glass forming region of SrO TeO 2 0 to 90mol% and no 0, V 2 O 5 0 to 90mol% and not 0, 10 to 40mol% SrO; v (V) 2 O 5 -TeO 2 Glass forming region of BaO: teO (TeO) 2 0 to 90mol% and no 0, V 2 O 5 0 to 60mol percent, 0 is not contained, and 10 to 40mol percent of BaO is not contained. The method for producing the lead-free low melting point glass is exemplified below.
And uniformly mixing the Te source, the V source and the R source according to the mol percentage composition range of the raw material components of the low-melting-point glass powder containing alkaline earth metals to obtain a mixture. The oxide feedstock was introduced as follows: teO (TeO) 2 And V 2 O 5 Are all introduced in oxide form. From RCO 3 、R(NO 3 ) 2 、RCl 2 、RF 2 Is introduced as a source of R (where R is one or more of Ca, sr, ba). The lead-free filler can be used according to application scenesInorganic filler with characteristics of negative or low expansion coefficient or high expansion coefficient and/or high heat conductivity coefficient. The inorganic filler with high heat conductivity and high expansion coefficient can be MgO or Al 2 O 3 One or more of inorganic filler with low expansion coefficient and high thermal conductivity can be AlN or Si 3 N 4 One or more of them. Weighing the raw materials of the basic glass powder, and mixing in a mixer for 3-12 hours to obtain a uniform mixture.
And (3) 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. As one example, the resulting mixture is melted at a temperature of 1-10deg.C/min to 900-1000deg.C for 0.5-2 hours.
And (3) rapidly quenching the molten glass liquid to obtain glass slag (or glass fragments).
In one embodiment of the invention, a method for applying an OLED seam connection includes: a) Further crushing and sieving the glass slag (or called glass slag) to obtain the lead-free low-melting-point glass powder. The grinding mode can be planetary ball milling, and the granularity of the glass powder is controlled to be D50=0.8-2 mu m, and D90 is less than or equal to 5 mu m. b) If necessary, uniformly mixing the lead-free filler and the low-melting glass to form a composite sealing material; c) The low-melting glass powder or the sealing material is added into a proper amount of organic solvent to be prepared into glass paste with viscosity suitable for screen printing. Wherein, the mass ratio of the organic solvent to the leadless low-melting glass powder can be as follows: (15-25 wt%): (75-85 wt%). In addition, the organic solvent includes a carrier, a binder, and the like. In an alternative embodiment, the binder is propylene. The carrier comprises: butanol, terpineol, ketones, and lipid organic solvents.
In another embodiment of the present invention, a method for applying a joint connection at an LT-SOC comprises: a) The glass cullet (or glass cullet) or glass cullet and inorganic filler are further crushed and sieved. The crushing mode can be planetary ball milling, and the granularity D50=5-10 μm of the glass powder is controlled; b) Uniformly mixing lead-free low-melting-point glass powder with an propenyl binder and an organic solvent carrier to form glass slurry; or obtaining a raw material belt through a tape casting process; c) And (3) after the glass slurry coating or raw material belt is assembled with the single cell and the stainless steel connecting piece, heating to 500-600 ℃ at 1-3 ℃/min, preserving heat for 10-60 min, removing the matters in the glass slurry, and vitrification and/or microcrystallization of the low-melting-point glass to finish packaging.
In another embodiment of the invention, a method of application in an aluminum alloy or copper alloy based feedthrough or metal package housing comprises: a) And further crushing and sieving the glass slag (or glass slag) or the glass fragments and the inorganic filler to obtain the leadless low-melting-point glass powder. The grinding mode can be planetary ball milling, and the granularity of the glass powder is controlled to be D50=10-20 mu m, and D90=40-70 mu m. b) Uniformly mixing low-melting-point glass or a uniform mixture of lead-free filler and low-melting-point glass with an propenyl binder and an organic solvent carrier to form glass slurry; c) Obtaining spherical granulating powder through a spray granulating process; e) And then forming and presintering (presintering) at the glass softening point temperature to obtain the glass prefabricated member with certain strength for sealing the threading part. The granulating agent is propylene adhesive and may account for 1-5 wt% of the low melting point glass powder. The presintering system is heated to 250-350 ℃ at a heating rate of 1-3 ℃/min, is kept for 0.5-2 hours, and is kept at 300-450 ℃ for 10-30 minutes at a heating rate of 5-20 ℃/min. d) The glass prefabricated member, the metal shell and the contact pin are placed in a sintering furnace to be heated to 320-500 ℃ at a heating rate of 5-100 ℃/min for 10-30 min, and sealing is completed.
Compared with the traditional glass ceramic sealing process, the sealing process of the lead-free low-melting-point glass does not need special nucleation or crystallization treatment, can realize sealing in the atmosphere without protective atmosphere, has simple process and good chemical stability, and can meet the sealing requirements of devices in the fields of electronics, automobiles and the like.
In one embodiment of the invention, after the prepared glass slurry is uniformly coated on the surfaces of aluminum and aluminum alloy through screen printing, the glass slurry is sealed under the atmosphere at the temperature rising rate of 1-5 ℃/min to 300-500 ℃ and the heat preservation time is 0.5-2 h. Wherein the temperature rising rate can be 1-3 ℃/min.
In another embodiment of the invention, the prepared glass prefabricated member, the metal shell and the contact pin are placed in a sintering furnace to be heated to 350-600 ℃ at a heating rate of 5-100 ℃/min for 10-30 min, and sealing is completed.
The invention provides an application method of lead-free low-melting-point glass in an aluminum alloy or copper alloy base feed-through piece or a metal packaging shell, which comprises the following steps:
s1: weighing raw materials of basic glass powder, and mixing in a mixer for 3-12 hours to obtain a uniform mixture;
s2: heating the mixture obtained in the step S1 to 900-1000 ℃ at a speed of 1-10 ℃/min to melt for 0.5-2 hours, and cooling molten glass to obtain glass fragments;
s3: ball milling the glass fragments obtained in the step S2 or the glass fragments and the inorganic filler for 0.5 to 3 hours by a planet to obtain lead-free low-melting-point glass powder with the particle size D50=10 to 30 mu m;
s4: uniformly mixing lead-free low-melting glass powder and/or high-heat-conductivity high-expansion inorganic filler or low-expansion high-heat-conductivity inorganic filler with an propenyl binder and an organic solvent carrier, and obtaining spherical granulating powder through a spray granulating process;
s5: pressing the spherical granulating powder into a green body with a specific shape through an automatic press;
s6: placing the green body in a sintering furnace, heating to 250-350 ℃ at a heating rate of 1-3 ℃/min, preserving heat for 0.5-2 hours, and preserving heat for 10-30 minutes at a heating rate of 5-20 ℃/min to 300-450 ℃ to finish densification, thereby obtaining a glass prefabricated member.
S7: the glass prefabricated member, the metal shell and the contact pin are placed in a sintering furnace to be heated to 320-500 ℃ at a heating rate of 5-100 ℃/min for 10-30 min, and sealing is completed.
In the present invention, the thermal properties (CTE, DSC) of the glass during its use are one of the important indicators. Thermal properties of the lead-free low melting point glass were determined by differential thermal analysis (DSC) and coefficient of thermal expansion experiments, including glass transition temperature Tg, initial crystallization temperature Tc, crystallization peak temperature Tp, thermal stability Δt (Δt=tc-Tg), melting temperature Tm, and coefficient of thermal expansion CTE.
The glass transition temperature, crystallization onset temperature and crystallization peak temperature of the lead-free low melting point glass were measured using a Netzsch DSC 404C differential scanning calorimeter (DSC, differential Scanning Calorimetry, germany). The thermal expansion coefficient softening temperature of the lead-free low-melting point glass is measured by using a Netzsch DIL402C type thermal expansion analyzer. The thermal expansion coefficient of the alkaline earth metal-containing low melting point glass was measured using a Netzsch DIL402C thermal expansion analyzer.
The present invention will be further illustrated by the following examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
(1) See example 1 composition weighing 677.54g V in Table 1 2 O 5 、198.18g TeO 2 、124.28g CaCO 3 Adding the mixture into a mixer for mixing for 6 hours at the rotating speed of 900 r/min;
(2) Melting the uniform mixture obtained in the step (1) to 900 ℃ at a speed of 5 ℃/min for 1 hour, and then directly pouring the melted glass melt into deionized water for quenching to obtain glass fragments;
(3) Putting 500g of glass scraps plus 3000g of zirconia balls (with the diameter of 5 um) obtained in the step (2) into an alumina ceramic tank, and ball-milling for 2 hours in a planetary ball mill with the rotating speed of 300r/min to obtain D 50 ＝13.55μm，D 90 =45 μm glass frit;
(4) Stirring 1000g of glass powder obtained in the step (3) with 30g of propenyl binder and 300g of terpineol carrier for 2 hours, uniformly mixing, and obtaining spherical granulating powder through a spray granulating process;
(5) Pressing the spherical granulating powder into a green body with a specific shape through an automatic press;
(6) Placing the green body in a sintering furnace to reach 350 ℃ at a heating rate of 2 ℃/min, preserving heat for 0.5 hour, and preserving heat for 30 minutes at a heating rate of 20 ℃/min to reach 400 ℃ to finish densification, thereby obtaining the glass prefabricated member.
(7) And (3) placing the glass prefabricated member, the aluminum alloy shell and the contact pin into a graphite mold, placing the graphite mold into a sintering furnace, and preserving heat for 30 minutes at a temperature rising rate of 50 ℃/min to 470 ℃ to finish sealing.
Example 2
This embodiment 2 is different from embodiment 1 in that: v (V) 2 O 5 ＝50mol％、TeO 2 ＝30mol％，CaO＝20mol％。
Example 3
This embodiment 3 is different from embodiment 1 in that: v (V) 2 O 5 ＝40mol％、TeO 2 ＝40mol％，CaO＝20mol％。
Example 4
This embodiment 4 is different from embodiment 1 in that: v (V) 2 O 5 ＝30mol％、TeO 2 ＝50mol％，CaO＝20mol％。
Example 5
This embodiment 5 is different from embodiment 1 in that: v (V) 2 O 5 ＝20mol％、TeO 2 ＝60mol％，CaO＝20mol％。
Example 6
(1) See example 6 composition scale 736.78g V in Table 2 2 O 5 、92.36g TeO 2 、170.87g SrCO 3 Adding the mixture into a mixer for mixing for 6 hours at the rotating speed of 900 r/min;
(2) Melting the uniform mixture obtained in the step (1) to 900 ℃ at a speed of 5 ℃/min for 1 hour, and then directly pouring the melted glass melt into deionized water for quenching to obtain glass fragments;
(3) Putting 500g of glass scraps plus 3000g of zirconia balls (with the diameter of 5 um) obtained in the step (2) into an alumina ceramic tank, and ball milling for 5 hours in a planetary ball mill with the rotating speed of 450r/min to obtain D 50 ＝1.0μm，D 90 =3.0 μm glass frit;
(4) Uniformly mixing 750g of glass powder obtained in the step (3) with 30g of propenyl binder and 150g of terpineol carrier to obtain glass slurry;
(5) And uniformly coating the prepared glass slurry on the surface of the aluminum alloy through screen printing, and then under the atmosphere, heating to 400 ℃ at a heating rate of 2 ℃/min for 0.5h, so as to realize sealing.
Example 7
This example 7 is different from example 6 in that: v (V) 2 O 5 ＝60mol％、TeO 2 ＝20mol％，SrO＝20mol％。
Example 8
This example 8 is different from example 6 in that: v (V) 2 O 5 ＝40mol％、TeO 2 ＝40mol％，SrO＝20mol％。
Example 9
This example 9 is different from example 6 in that: v (V) 2 O 5 ＝30mol％、TeO 2 ＝50mol％，SrO＝20mol％。
Example 10
This embodiment 10 is different from embodiment 6 in that: v (V) 2 O 5 ＝20mol％、TeO 2 ＝60mol％，SrO＝20mol％。
Example 11
(1) See example 11 composition weighing 211.98g V in Table 3 2 O 5 、558.03g TeO 2 、229.99g BaCO 3 Adding the mixture into a mixer for mixing for 6 hours at the rotating speed of 900 r/min;
(2) Melting the uniform mixture obtained in the step (1) to 900 ℃ at a speed of 5 ℃/min for 1 hour, and then directly pouring the melted glass melt into deionized water for quenching to obtain glass fragments;
(3) Putting 500g of glass scraps plus 3000g of zirconia balls (with the diameter of 5 um) obtained in the step (2) into an alumina ceramic pot, and ball milling for 2 hours in a planetary ball mill with the rotating speed of 300r/min to obtain D50=5.0 mu m glass powder;
(4) Mixing 100g of glass powder obtained in the step (3) with 3g of propenyl binder and 200g of terpineol carrier for planetary ball milling for 1 hour uniformly to form glass slurry;
(5) And (3) after the glass paste coating or raw material belt is assembled with the single cell and the stainless steel connecting piece, heating to 550 ℃ at 1 ℃/min, and preserving heat for 30min to finish packaging.
Example 12
This embodiment 12 is different from embodiment 11 in that: v (V) 2 O 5 ＝30mol％、TeO 2 ＝50mol％，BaO＝20mol％。
Example 13
This example 13 is different from example 11 in that: v (V) 2 O 5 ＝40mol％、TeO 2 ＝40mol％，BaO＝20mol％。
Example 14
This embodiment 14 is different from embodiment 11 in that: v (V) 2 O 5 ＝50mol％、TeO 2 ＝30mol％，BaO＝20mol％。
Example 15
This example 15 is different from example 11 in that: v (V) 2 O 5 ＝60mol％、TeO 2 ＝20mol％，BaO＝20mol％。。
Examples 16 to 19
Examples 16-19 refer to example 1 and specific compositional differences are shown in Table 4.
Examples 20 to 24
This example 20-24 is referred to example 6 and specific composition differences are shown in Table 5.
Examples 25 to 29
Examples 25-29 refer to example 11 for specific compositional differences, see Table 6.
Comparative example 1
This comparative example 1 is referred to example 1, except that: v (V) 2 O 5 ＝70mol％、TeO 2 ＝10mol％，CaO＝20mol％。
Comparative example 2
This comparative example 2 is different from example 11 in that: v (V) 2 O 5 ＝0mol％、TeO 2 ＝80mol％，BaO＝20mol％。
Table 1:
table 2:
table 3:
table 4:
table 5:
table 6:
table 7:
comparative example 1 Comparative example 2
V 2 O 5 70 0
TeO 2 10 80
CaO 20
BaO 0 20
Glass forming property Transparent state/finished glass Transparent state/finished glass
Glass transition temperature Tg/. Degree.C 403.1 378.1
Crystallization onset temperature TC1/°C 466.8 410.8
Crystallization peak temperature Tp 1/. Degree.C 512 446.6
。

Claims (17)

1. Leadless low-melting point glass-based sealing materialCharacterized in that the composition of the lead-free low-melting-point glass-based sealing material is V 2 O 5 -TeO 2 -RO glass, wherein RO is at least one of the alkaline earth oxides MgO, caO, srO, baO.
2. The lead-free low-melting glass-based sealing material according to claim 1, wherein the lead-free low-melting glass-based sealing material has a particle diameter d50=0.8 to 20 μm and d90=5 to 70 μm; when RO is MgO, V 2 O 5 -TeO 2 MgO glass having a composition of TeO 2 Is 10 to 90mol percent, V 2 O 5 0 to 70mol% and not containing 0, 20 to 40mol% MgO;
alternatively, when RO is CaO, V 2 O 5 -TeO 2 CaO glass having a composition of TeO 2 Is 10 to 90mol percent, V 2 O 5 0 to 70mol percent, 0 is not contained, and 20 to 40mol percent of CaO is contained;
alternatively, when RO is SrO, V 2 O 5 -TeO 2 The composition of the SrO glass is TeO 2 0 to 90mol% and no 0, V 2 O 5 0 to 90mol% and not 0, 10 to 40mol% SrO;
or, when RO is BaO, V 2 O 5 -TeO 2 The composition of the BaO glass is TeO 2 0 to 90mol% and no 0, V 2 O 5 0 to 60mol percent, 0 is not contained, and 10 to 40mol percent of BaO is not contained.
3. The lead-free low melting point glass-based sealing material according to claim 1 or 2, wherein the glass transition temperature of the lead-free low melting point glass-based sealing material is 260 to 350 ℃, the glass softening temperature is 270 to 340 ℃, and the crystallization initiation temperature is 320 to 500 ℃.
4. The lead-free low melting point glass-based sealing material according to claim 1 or 2, wherein the lead-free low melting point glass-based sealing material has a thermal expansion coefficient of 10 to 17ppm/°c between 25 and 250 ℃.
5. The lead-free low melting point glass-based sealing material according to claim 1 or 2, wherein the lead-free low melting point glass-based sealing material is amorphous or microcrystalline;
when the lead-free low-melting glass-based sealing material is in a crystalline state, the crystalline phase thereof is RO-TeO 2 Basal crystalline phase or/and RO-V 2 O 5 A basal crystalline phase;
the RO-TeO 2 The basal crystal phase comprises Ba 3 TeO 6 、Ba 2 TeO 5 、BaTeO 3 、Ca 2 TeO 5 、Sr 2 TeO 5 At least one of (a) and (b);
the O-V 2 O 5 The basal crystal phase comprises Ba 2 V 2 O 7 、Ba 3 [VO 4 ] 2 、Ba 0.18 Te 2 O 4.95 At least one of (a) and (b);
preferably, when the lead-free low melting point glass-based sealing material is in a crystalline state, the glass thermal stability temperature difference Δt thereof is in the range of 25 to 170 ℃.
6. The lead-free low melting point glass-based sealing material according to any one of claims 1 to 5, wherein the lead-free low melting point glass-based sealing material has a composition of V 2 O 5 -TeO 2 -RO glass + xwt% inorganic filler, wherein xwt% does not exceed 50wt%;
the composition of the inorganic filler is selected from MgO and Al 2 O 3 、AlN、Si 3 N 4 、LiAlSiO 4 And LiAl [ Si ] 2 O 6 ]At least one of (a) and (b);
the morphology of the inorganic filler is granular inorganic filler, short fiber inorganic filler or flaky inorganic filler; preferably, the particle size of the granular inorganic filler is 100nm to 10 μm;
preferably, the short fibrous inorganic filler has a diameter of 1 μm to 30 μm and a length of 5 μm to 100. Mu.m
Preferably, the inorganic filler in the form of flakes has a diameter of 0.5 μm to 30 μm and a thickness of > 100nm.
7. The lead-free low melting point glass-based sealing material according to claim 6, wherein when the lead-free low melting point glass-based sealing material contains not more than 50% by weight of the inorganic filler, the thermal expansion coefficient thereof at 25 to 250 ℃ is 5 to 14ppm/°c, and the thermal conductivity thereof is (1 to 5) W/m.k.
8. A method of making the lead-free low melting glass-based sealing material of any one of claims 1-7, comprising:
(1) Weighing V 2 O 5 Powder, teO 2 Mixing the powder and RO source powder to obtain mixed powder; preferably, the R source powder is RO, RCO 3 、R(NO 3 ) 2 、RCl 2 、RF 2 At least one of (a) and (b);
(2) And melting the obtained mixed powder at 900-1000 ℃ for 0.5-2 hours, and cooling and crushing to obtain the lead-free low-melting-point glass-based sealing material.
9. The method of claim 8, wherein the mixing is performed in a blender; setting parameters of the mixer comprises the following steps: the rotating speed is 600-1200 r/h, and the mixing time is 3-12 hours.
10. The production method according to claim 8 or 9, wherein the heating rate of the melting is 1 to 10 ℃/min; the crushing mode is planetary ball milling, the rotating speed of the planetary ball milling is 100-500 rpm, and the time is 0.5-6 hours.
11. Use of a lead-free low melting glass-based sealing material according to any one of claims 1 to 7 for glass, ceramic, metal and alloy sealing.
12. The use according to claim 11, wherein the first original element and the second element are sealed by the lead-free low melting glass-based sealing material; the first element is selected from one of a glass element, a ceramic element, a metal element and a metal alloy element; the second element is selected from one of a glass element, a ceramic element, a metal element and a metal alloy element;
preferably, the metal alloy element comprises at least one of copper alloy, aluminum alloy, silicon aluminum alloy, stainless steel.
13. Use of a lead-free low melting glass-based sealing material according to any of claims 1-7 as a joint connection and/or a feedthrough in the manufacture of an organic light emitting diode device, a low temperature solid oxide fuel cell and/or an electrolysis cell, a feedthrough and/or a metal packaging case.
14. A preform made from the lead-free low melting glass-based sealing material of any of claims 1-7.
15. A green sheet prepared from the lead-free low-melting glass-based sealing material of any one of claims 1 to 7.
16. A slurry prepared from the lead-free low melting glass-based sealing material of any one of claims 1-7.
17. Use of a lead-free low melting glass-based sealing material according to any one of claims 1 to 7 as additive in the preparation of an amorphous glass material or a glass ceramic material.
CN202310909990.XA 2023-07-24 2023-07-24 Leadless low-melting point glass-based sealing material, preparation method and application thereof Pending CN116969679A (en)

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