CN111268911B - Welding composition, shell assembly, preparation method and electronic equipment - Google Patents

Welding composition, shell assembly, preparation method and electronic equipment Download PDF

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CN111268911B
CN111268911B CN202010110433.8A CN202010110433A CN111268911B CN 111268911 B CN111268911 B CN 111268911B CN 202010110433 A CN202010110433 A CN 202010110433A CN 111268911 B CN111268911 B CN 111268911B
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solder composition
ceramic substrate
glass
parts
ceramic
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CN111268911A (en
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贾玉虎
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Guangdong Oppo Mobile Telecommunications Corp Ltd
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Guangdong Oppo Mobile Telecommunications Corp Ltd
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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
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/04—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with articles made from glass
    • C04B37/045—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with articles made from glass characterised by the interlayer used
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/10—Glass interlayers, e.g. frit or flux

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

Abstract

The present application provides a solder composition for use in a ceramic and ∑ or ∑ based solder compositionOr sealing glass, which comprises the following components in percentage by weight: p2O545-65%, SnO 15-35%, ZnO 5-10%, MgO 3-10%, CaO 1-3%, SrO 2-5% and BaO 2-5%. The welding composition is used for sealing ceramic and/or glass, and can solve the problems of poor binding force and poor air tightness existing after the existing ceramic substrate and glass lens are bonded. The application also provides a shell assembly, a preparation method of the shell assembly and electronic equipment.

Description

Welding composition, shell assembly, preparation method and electronic equipment
Technical Field
The application relates to the technical field of shell materials, in particular to a welding composition, a shell assembly, a preparation method and electronic equipment.
Background
At present, a mobile phone or intelligent wearable device made of ceramic materials mainly bonds a glass lens on a ceramic substrate through glue (dispensing or back glue). However, the glue is easy to age and is easy to be corroded by water, so that the glass lens and the ceramic substrate have weak binding force, are easy to fall off, have poor air tightness and are not beneficial to long-term use of equipment.
Disclosure of Invention
The application provides a welding composition, and the welding composition is used for sealing ceramic and/or glass, and can solve the problems of poor binding force and poor air tightness existing after the existing ceramic substrate and glass lens are bonded. The technical scheme is as follows:
in a first aspect, the present application provides a solder composition for sealing ceramics and/or glass, comprising the following components in percentage by weight: p2O545-65%, SnO 15-35%, ZnO 5-10%, MgO 3-10%, CaO 1-3%, SrO 2-5% and BaO 2-5%.
In a second aspect, the present application provides a housing assembly comprising a ceramic substrate, a glass substrate, and a bonding layer disposed between the ceramic substrate and the glass substrate, the bonding layer being formed by soldering the solder composition of the first aspect of the present application.
In a third aspect, a method of making a housing assembly includes the steps of:
the method comprises the steps of taking a ceramic substrate and a glass substrate, arranging the solder composition according to the first aspect of the application between the ceramic substrate and the glass substrate, forming a connecting layer between the ceramic substrate and the glass substrate by the solder composition after welding, and then obtaining the shell component after finish machining.
In a fourth aspect, an electronic device includes a housing assembly and a display device, the display device is connected to the housing assembly, and the housing assembly is the housing assembly according to the third aspect of the present application or is manufactured by the manufacturing method according to the third aspect of the present application.
The welding composition is a material capable of being used for sealing ceramic and/or glass, and the welding composition has strong bonding force between the ceramic and the glass, is firm in structure and has good air tightness.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a housing assembly 100 according to an embodiment of the present disclosure;
fig. 2 is a sectional view along a-a of a housing assembly 100 according to an embodiment of the present disclosure;
FIG. 3 is a cross-sectional view taken along A-A of another housing assembly 100 provided by embodiments of the present application;
fig. 4 is a schematic structural diagram of an electronic device 200 according to an embodiment of the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. The embodiments listed in this application can be appropriately combined with each other.
The solder composition provided by one embodiment of the application is used for sealing ceramic and/or glass and comprises the following components in percentage by weight: p2O545-65%, SnO 15-35%, ZnO 5-10%, MgO 3-10%, CaO 1-3%, SrO 2-5% and BaO 2-5%.
The solder composition described herein can be used for sealing between ceramics, orA seal between ceramic and glass, or a seal between glass and glass. Wherein, P2O5(phosphorus pentoxide) as a main component of the solder composition, the P2O5Can react with other raw materials to form low-melting-point solder. P in the weight percentage stated in the present application2O5The chemical stability of the whole solder composition is improved. In one embodiment, said P2O5The weight percentage of the component (A) is 50-60%. For example, the P2O5Is specifically 45%, 48%, 50%, 52%, 53%, 54%, 56%, 58%, 60% or 65% by weight.
SnO (stannous oxide) energy with P2O5The reaction forms a low melting solder composition, increases the chemical stability of the solder composition, reduces the softening temperature of the solder composition, and reduces the viscosity of the solder composition during soldering. In one embodiment, the SnO is 20 to 35% by weight. For example, the SnO is specifically 15%, 18%, 20%, 22%, 25%, 27%, 30%, 32% or 35% by weight.
The term "softening temperature" as used herein is one of the important parameters of solder, mainly the temperature at which a substance softens, which has an important correlation to the soldering temperature of solder. The solder with low softening temperature can be applied to various parts which cannot resist high temperature. The softening point temperature is the temperature at which the material begins to soften.
ZnO (zinc oxide) can be used in the present application with or without P2O5SnO, which are co-reacted to form a low melting point solder, improves the chemical stability of the solder composition, and can adjust the thermal expansion coefficient of the solder composition and improve the wettability of the solder composition with a glass substrate or a ceramic substrate, particularly zirconia ceramics. In one embodiment, the ZnO is present in an amount of 5 to 8% by weight. For example, the ZnO may be specified as 5%, 6%, 7%, 8%, 9% or 10% by weight.
The term "wettability" as used herein means: the better the solder spreads on the substrate after melting, the better the wettability, and the larger the spread area. The solder composition described herein has good wettability; the solder composition is effective to spread on the surface of a glass substrate or a ceramic substrate when soldering is performed.
The MgO (magnesium oxide) can react with other components to form the low-melting-point solder, so that the chemical stability of the solder composition can be improved, the thermal expansion coefficient of the solder composition can be adjusted, and the wettability between the solder composition and a glass substrate or a ceramic substrate can be improved. In one embodiment, the MgO is present in an amount of 3 to 8% by weight. For example, the weight percentage of MgO is specifically 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.
The CaO (calcium oxide) can react with other components to form low-melting-point solder, and the chemical stability and the thermal expansion coefficient of the solder composition can be improved. In one embodiment, the CaO is 1-2% by weight. For example, the CaO may be specified as 1%, 1.5%, 2%, 2.5% or 3% by weight.
The SrO (strontium oxide) can reduce the softening temperature of the solder composition and reduce the viscosity of the solder composition during welding. The weight percent range of SrO described herein facilitates, on the one hand, improving the viscosity of the solder composition and, on the other hand, facilitating control of the coefficient of thermal expansion of the solder composition. In one embodiment, the SrO is 2-3% by weight. For example, the weight percentage of SrO is specifically 2%, 3%, 4%, 4.5% or 5%.
BaO (barium oxide) described herein can reduce the softening temperature of the solder composition and reduce the viscosity of the solder composition during soldering. In one embodiment, the BaO is present in an amount of 2 to 3% by weight. For example, the BaO is specifically 2%, 3%, 4% or 5% by weight.
In an embodiment of the present application, a ratio of the weight of SnO, ZnO, MgO, CaO, and SrO to the weight of SnO is less than or equal to 5/3. The solder composition with the weight percentage can be beneficial to improving the bonding strength and the air tightness between ceramics and glass.
In an embodiment of the present application, the solder composition further includes MnO2、CuO、B2O3、K2O and Na2One or more of O. Optionally, the MnO2、CuO、B2O3、K2O and Na2The weight percentage of O is 0-2%, 0-2% and 0-2% respectively. Wherein, the MnO is2、CuO、B2O3、K2O and Na2The percentages by weight of O may or may not be equal.
Wherein, the MnO is2(manganese dioxide) can improve the chemical stability of the solder composition. The weight percentages described herein are advantageous for controlling the coefficient of thermal expansion of the solder composition. For example, the MnO2Is in particular 0.1%, 0.5%, 1% or 2% by weight.
CuO (copper oxide) as described herein can improve the chemical stability of the solder composition. For example, the CuO is specifically 0.1%, 0.3%, 1%, or 2% by weight.
B in the present application2O3(boron oxide) can improve the chemical stability of the solder composition and reduce the coefficient of thermal expansion. High content of B2O3Which is detrimental to lowering the softening temperature of the solder composition described herein. For example, the B2O3Is specifically 0.1%, 1%, 1.5% or 2% by weight.
This application said K2O (potassium oxide) can lower the softening temperature of the solder composition. High levels of solder composition can increase solder devitrification, leading to increased solder difficulty. For example, the K2The percentage by weight of O is in particular 0.1%, 0.5%, 1% or 2%.
The present application describes Na2O (sodium oxide) can lower the softening temperature of the solder composition. For example, the Na2The percentage by weight of O is in particular 0.1%, 0.5%, 1% or 2%.
In one embodiment, the solder composition comprises the following components in percentage by weight: p2O5 50-56％，SnO 25-30％，ZnO 5-7％，MgO 4-7％，CaO 1-3％，SrO 2-3％，BaO 2-3％，MnO2And/or 0.5-1.5% of CuO, B2O3 1-1.8%, and K2O and/or Na20.3 to 0.8 percent of O. In another embodiment, the solder composition comprises the following components in percentage by weight: p is2O5 54％，SnO 27％，ZnO 6％，MgO 3％，CaO 2％，SrO 2％，BaO 3％，MnO2 1％，B2O31.5%, and K2O 0.5％。
In the embodiment of the application, the welding temperature of the solder composition is lower, so that the welding efficiency can be improved, and the energy consumption can be saved. In one embodiment, the solder composition has a soldering temperature of 300-350 ℃. In another embodiment, the solder composition has a soldering temperature of 300-350 ℃. For example, the solder composition has a soldering temperature of, in particular, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃ or 350 ℃.
Specifically, when the soldering temperature is too low, insufficient softening of the solder composition is easily caused, the viscosity of the solder composition is large, the solder composition is difficult to wet sufficiently with the ceramic substrate and/or the glass substrate, and further, poor bonding force and poor airtightness of the structure after soldering are caused. When the welding temperature is too high, the glass substrate is not resistant to high temperature, and particularly the stress layer on the surface of the glass substrate is easy to relax due to the high temperature of the glass substrate subjected to strengthening treatment, so that the strengthening effect is attenuated; therefore, the strength of the glass substrate is easily affected by the welding at high temperature.
In an embodiment of the present application, the solder composition further includes an organic additive including one or more of an organic solvent, a binder, and a plasticizer. Optionally, the solvent comprises one or more of terpineol, ethanol, acetone, toluene, and xylene; the binder comprises an epoxy resin or an acrylic resin; the plasticizer comprises dimethyl phthalate or polyethylene glycol. Alternatively, the epoxy resin may be a bisphenol a type epoxy resin. The acrylic resin comprises at least one of ethyl methacrylate, cyclohexyl methacrylate and n-propyl methacrylate.
In one embodiment, the organic additive simultaneously comprises an organic solvent, a binder and a plasticizer, and the mass ratio of the organic solvent to the binder to the plasticizer is (6-8): (1-2): (1-2). For example, in the organic additive, the weight percentage of the organic solvent is 60% -80%; the weight percentage of the binder is 10% -20%; the weight percentage of the plasticizer is 10% -20%. The organic additive with the weight ratio can adjust the dispersion performance of the welding composition to a certain degree, so that a connecting layer formed by the welding composition after welding is more uniform.
The organic solvent can dissolve the binder and the plasticizer, so that the welding composition is in a slurry state, and the slurry-state welding composition can be adjusted to a required viscosity. In one embodiment, the organic solvent is 65% to 75% by weight. For example, the organic solvent is specifically 60%, 65%, 70%, 75% or 80% by weight.
The binder in the organic additive has a dispersing effect, can promote uniform dispersion of components in the welding composition, and can improve the bonding strength between a film layer formed by the dried welding composition and a welding substrate. Wherein the organic additive-containing solder composition may be dried by baking. In one embodiment, the binder is present in an amount of 13% to 17% by weight. For example, the binder is specifically 10%, 13%, 15%, 17%, or 20% by weight.
The plasticizer in the organic additive can improve the tensile strength, the toughness and the extensibility of a film layer formed by the dried welding composition, and prevents the film layer from warping and cracking in the drying process. In one embodiment, the plasticizer is present in an amount of 13% to 17% by weight. For example, the weight percentage of the plasticizer is specifically 10%, 13%, 15%, 17%, or 20%.
In an embodiment of the present application, when the welding composition includes an organic additive, the organic additive is 30-40% by weight of the welding composition.
The solder composition provided by one embodiment of the application can be prepared by the following method, including:
the solder composition is prepared by uniformly mixing the raw materials of the components, heating the mixture in an inert or reducing atmosphere to form molten liquid, transferring the molten liquid to cold water for water quenching, and grinding and drying the molten liquid.
Optionally, the heating temperature is 1100-1300 ℃, and the time is 30-60 min. The heating time here is the holding time after the heating temperature is reached. In one embodiment, the heating time is 40-60 min.
Wherein the purpose of the inert or reducing atmosphere is to prevent Sn2+Is oxidized to Sn4+(ii) a Since the solder composition described herein is a low melting point solder, for example, the solder composition may contain a P-Sn-Zn low melting point material, SnO and P in the solder composition2O5ZnO can form P-Sn-Zn low-melting-point substances more easily, while SnO2Is more stable than SnO, and the SnO in the whole system2The increased content is not favorable for lowering the softening point temperature Tg of the welding composition.
Alternatively, the grinding process may make the particle size of the solder composition particles described herein uniform, respectively. In one embodiment, the solder composition particles have a particle size D50 of less than 10 μm. In another embodiment, the solder composition particles have a particle size D50 of 0.1 to 8 μm. The particle size range of the particles can make the dispersion more uniform on one hand and is beneficial to controlling the thermal expansion coefficient of the solder composition on the other hand.
The application the welding composition is a material that can be used for realizing the sealing-in of pottery and/or glass, adopts the very strong cohesion has between the pottery that the welding composition carries out the sealing-in and the glass, and sound construction, and the gas tightness is good, is difficult for intaking or advances grey in long-term use.
As shown in fig. 1 and 2, another embodiment of the present application provides a case assembly 100 including a ceramic substrate 10, a glass substrate 20, and a connection layer 30 disposed between the ceramic substrate 10 and the glass substrate 20, wherein the connection layer 30 is formed by soldering from a solder composition.
In the embodiment of the application, the solder composition comprises the following components in percentage by weight: p2O5 45-65％、SnO 15-35%, ZnO 5-10%, MgO 3-10%, CaO 1-3%, SrO 2-5% and BaO 2-5%. Optionally, the solder composition further comprises MnO2、CuO、B2O3、K2O and Na2One or more of O. Optionally, the MnO2、CuO、B2O3、K2O and Na2The weight percentage of O is 0-2%, 0-2% and 0-2% respectively. In this embodiment, the specific definition of the solder composition is the same as that described in the previous embodiment, and the description of this embodiment is omitted.
In the embodiment of the application, after the connection layer 30 is arranged between the ceramic substrate 10 and the glass substrate 20, the glass substrate 20 has outstanding bonding strength, and can be firmly fixed on the ceramic substrate 10 and is not easy to fall off; and the ceramic substrate 10 and the glass substrate 20 are connected compactly, and the air tightness is high.
In this embodiment, the bonding strength between the ceramic substrate and the glass substrate is greater than 10 MPa. In another embodiment, the bonding strength between the ceramic substrate and the glass substrate is 14 to 20 MPa. In a third embodiment, the bonding strength between the ceramic substrate and the glass substrate is 14 to 17 MPa.
In the present embodiment, the thickness of the connection layer 30 may be adjusted based on the actual gap between the ceramic substrate 10 and the glass substrate 20. When the gap between the ceramic substrate and the glass substrate is larger, the thickness of the connecting layer is increased; when the gap between the ceramic substrate and the glass substrate is relatively small, the thickness of the connecting layer is also small. In one embodiment, the tie layer has a thickness of 0.1mm to 1 mm. In another embodiment, the tie layer has a thickness of 0.1mm to 0.2 mm. For example, the tie layer may be specified to have a thickness of 0.1mm, 0.12mm, 0.15mm, 0.18mm, 0.2mm, 0.3mm, 0.5mm, 0.8mm, 0.9mm, or 1 mm.
In this embodiment, the housing assembly 100 may be, but is not limited to, a housing of an electronic device, such as a mobile phone housing or a housing of a smart watch.
Optionally, the peripheral side frame of the housing assembly 100 may include, but is not limited to, at least one of a USB hole, an earphone hole, a peripheral side key hole, and an antenna slot.
In this embodiment, the ceramic matrix comprises a zirconia ceramic matrix; the glass substrate comprises a glass cover plate, a glass lens or a sapphire glass lens. For example, the glass substrate may be an electronic device camera lens. The glass substrate can also be an aluminosilicate glass lens. Optionally, when the glass substrate is a glass lens, the glass lens may be white glass which is not subjected to strengthening treatment, or may be strengthened glass which is subjected to primary or secondary strengthening treatment. Herein, the solder composition has different wettabilities for different glass lenses; wherein the solder composition has better wettability with white glass than strengthened glass lenses.
The shape and size of the ceramic substrate 10 may be prepared in advance based on actual specific applications. For example, when applied to a mobile terminal, the ceramic substrate is prepared in the shape of a case or a rear cover of the mobile terminal.
In the present embodiment, the ceramic substrate 10 may be manufactured by dry pressing, casting, or injection molding from a commercially available ceramic material.
In one embodiment, the material to be formed is a ceramic granulated powder. The forming mode is dry pressing forming. Further, the step of preparing the zirconia ceramic powder into a material to be molded and molding to obtain the zirconia green body comprises the following steps: and preparing the zirconia ceramic powder into ceramic granulation powder, and performing dry pressing to obtain a zirconia green body. Further, the step of preparing the zirconia ceramic powder into ceramic granulated powder includes: adding water and organic matters into the zirconia ceramic powder, grinding, drying and granulating to obtain ceramic granulated powder. Among them, the organic substance is a substance commonly used in the art for preparing ceramic granulated powder, and may be, for example, a defoaming agent, a plasticizer, a binder, an organic solvent, or the like. The drying mode is spray drying. The drying method is not limited to spray drying, and other drying methods, such as drying, may be used.
In one embodiment, the slurry to be formed is a casting slurry. The forming mode is casting forming. Further, the step of preparing the zirconia ceramic powder into a material to be molded and molding to obtain the zirconia green body comprises the following steps: preparing the zirconia ceramic powder into casting slurry, and performing casting molding to obtain a zirconia green body. Further, the step of preparing the zirconia ceramic powder into a casting slurry comprises: adding organic matters into the zirconia ceramic powder, and grinding to obtain the ceramic tape-casting slurry. Among them, the organic substance is a substance commonly used in the art for preparing the casting slurry, and may be, for example, a defoaming agent, a plasticizer, a binder, an organic solvent, or the like.
In one embodiment, the material to be molded is injection molded feed. The molding mode is injection molding. Further, the step of preparing the zirconia ceramic powder into a material to be molded and molding to obtain the zirconia green body comprises the following steps: and preparing the zirconia ceramic powder into injection molding feed, and performing injection molding to obtain a zirconia green body. Further, the step of preparing the zirconia ceramic powder into the injection molding feed comprises: adding organic matters into the zirconia ceramic powder, banburying and granulating to obtain the injection molding feed. Among them, the organic substance is a substance commonly used in the art for preparing injection molding feedstock, and may be, for example, a binder, a plasticizer, a lubricant, a dispersant, etc.
When dry pressing and tape casting are adopted, the formed ceramic green body can be subjected to isostatic pressing, wherein the parameters of the isostatic pressing are as follows: the range of pressure P is: p is more than or equal to 0 and less than or equal to 250MPa, and the temperature T is as follows: t is more than 0 and less than 100 ℃. The effects of the isostatic pressing treatment include: (1) reducing density differences at different positions of the green body; (2) reducing the content of pores in the green body; (3) the isostatic pressing treatment is beneficial to reducing the sintering deformation of the ceramic and improving the strength of the sintered ceramic.
Optionally, after the isostatic pressing, a shell degreasing and sintering process may be performed, and the method specifically includes:
and (3) degreasing the green body subjected to isostatic pressing at 300-600 ℃, and sintering at 1300-1500 ℃ for 1-3 h to make the ceramic more compact. The density of the ceramic sintered blank after the shell degreasing and sintering process is more than 99.9 percent. Wherein the green body may be a zirconia ceramic green body. In one embodiment, the ceramic sintered compact may also be rough machined, for example by flat grinding, laser cutting or CNC processes to obtain a ceramic matrix with holes, having a 2D or 2.5D or 3D shape, or being white or black or colored.
In this embodiment, the surface of the ceramic substrate may further include a plurality of holes, and the connection layer is partially filled in the holes. The number and size of the holes on the surface of the ceramic matrix can be related to the compactness of the ceramic matrix without limitation. When the ceramic matrix has high density, the number of holes on the surface of the ceramic matrix is small, and the size is small; when the density of the ceramic matrix is low, the number of holes on the surface of the ceramic matrix is large, and the size of the ceramic matrix is large.
In the shell component, the ceramic substrate and the glass substrate are tightly connected through the connecting layer formed by the solder composition, and the bonding strength between the ceramic substrate and the glass substrate is high, so that the ceramic substrate and the glass substrate are effectively prevented from loosening, and the service life of the shell component is greatly prolonged; and in the shell component, the air tightness between the ceramic substrate and the glass substrate is high. Therefore, the housing assembly can be widely applied to devices requiring connection of a ceramic substrate and a glass substrate, such as electronic devices.
Another embodiment of the present application provides a method for manufacturing a housing assembly, including the steps of:
taking a ceramic substrate and a glass substrate, then arranging a solder composition between the ceramic substrate and the glass substrate, after welding, forming a connecting layer between the ceramic substrate and the glass substrate by the solder composition, and then carrying out finish machining treatment to obtain the shell component. The solder composition is the solder composition described in the previous embodiment of the present application, and the description of this embodiment is not repeated.
Optionally, the step of welding comprises: and after the solder composition is arranged between the ceramic substrate and the glass substrate, welding is carried out at the temperature of 300-350 ℃, and the cooling rate of the welding is lower than 10 ℃/min. In the preparation method, the cooling rate in the range is beneficial to preventing stress concentration of the glass substrate and the welding line caused by the excessively high cooling rate, and the problems of poor bonding force and even cracking existing between the welded ceramic substrate and the glass substrate are reduced.
Optionally, the finishing process comprises: one or more of flat grinding, CNC machining, polishing, screen printing, and coating. The finishing process steps described herein may be selected based on the particular application at hand. For example, the finishing process step may be used to adjust the thickness, surface roughness or flatness of the housing assembly. Or trimming the edges and holes of the shell assembly through the finish machining treatment step. The finishing process described herein may also, but is not limited to, include other finishing processes that are currently available.
Optionally, after the step of disposing the solder composition between the ceramic substrate and the glass substrate and before the step of soldering, the method further comprises the steps of: the solder composition is subjected to a drying process. For example, when the solder composition includes an organic additive, the solder composition is more uniformly applied to a predetermined bonding surface between a ceramic substrate and a glass substrate, and then the solder composition is more uniformly applied in a dry state by a drying process, which is advantageous in improving the bonding strength and sealing property of the final bonded structure. In one embodiment, the drying temperature is 100-120 ℃ and the drying time is 10-40 min.
Another embodiment of the present application provides a method for manufacturing a housing assembly, including the steps of: taking a ceramic substrate and a glass substrate, wherein the ceramic substrate is provided with an accommodating hole, accommodating the glass substrate in the accommodating hole, forming a gap between the periphery of the edge of the glass substrate and the periphery of the hole wall of the accommodating hole, filling a solder composition into the gap, then carrying out welding treatment to enable the solder composition in the gap to form a connecting layer, and then carrying out finish machining treatment to obtain the shell assembly. In one embodiment, the receiving hole is a through hole. In another embodiment, the receiving hole is a stepped hole, see fig. 3. When the accommodating hole 101 is a stepped hole, the hole wall of the accommodating hole 101 has a stepped structure, and the glass substrate 20 is located on the stepped structure of the accommodating hole 101; in this case, the solder composition 30 may be provided between the hole wall of the housing hole 101 and the glass substrate 20, or may be provided between the stepped structure of the housing hole 101 and the glass substrate 20. The glass substrate is not limited to being joined to the ceramic substrate after being accommodated in the accommodating hole of the ceramic substrate, and may be joined to the ceramic substrate after being joined to the glass substrate as needed. For example, a ceramic substrate may be disposed opposite a glass substrate, and the welding composition may be disposed between the ceramic substrate and the glass substrate, and then welded to join the ceramic substrate and the glass substrate. The manufacturing method of the present embodiment can be used for, but is not limited to, fixing and connecting a ceramic cover plate and a camera lens in an electronic device.
As shown in fig. 4, another embodiment of the present application provides an electronic device 200, which includes a housing assembly 100 and a display device 201, wherein the display device 201 is connected to the housing assembly 100. The specific definition of the housing assembly 100 is the same as that described in the previous embodiment, and the description of this embodiment is omitted.
Alternatively, the electronic device 200 provided herein is an electronic device that requires a housing assembly to be connected to a glass substrate. For example, the electronic device 200 includes, but is not limited to, mobile terminals such as mobile phones, tablet computers, notebook computers, palm computers, wearable devices, smart bands, smart watches, pedometers, and fixed terminals such as digital TVs, desktop computers, and the like.
The composition and overall properties of the solder compositions according to the examples of the present application will be described below by way of specific examples, wherein comparative examples are designed based on the examples of the present application. It will be understood by those skilled in the art that the following examples are illustrative of the present application only and should not be taken as limiting the scope of the present application. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by manufacturers, and are all conventional products commercially available.
Example 1
A method of making a housing assembly comprising the steps of:
taking a ceramic substrate and a glass lens, arranging a solder composition between the ceramic substrate and the glass lens, welding for 40min at 340 ℃, forming a connecting layer between the ceramic substrate and the glass lens after the cooling rate is about 5-8 ℃/min, and then carrying out further finish machining to obtain a shell assembly, wherein the solder composition comprises the following components in parts by weight: p2O554 parts of SnO 27 parts, ZnO 6 parts, MgO 3 parts, CaO 2 parts, SrO 2 parts and BaO 3 parts.
Example 2
A method of making a housing assembly comprising the steps of:
taking a ceramic substrate and a glass lens, arranging a solder composition between the ceramic substrate and the glass lens, welding for 40min at 320 ℃, forming a connecting layer between the ceramic substrate and the glass lens after the cooling rate is about 5-8 ℃/min, and then carrying out further finish machining to obtain a shell assembly, wherein the solder composition comprises the following components in parts by weight: p2O554 parts of SnO 27 parts, ZnO 6 parts, MgO 3 parts, CaO 2 parts, SrO 2 parts, BaO 3 parts and MnO21 part, B2O31.5 parts, and K20.5 part of O.
Example 3
A method of making a housing assembly comprising the steps of:
taking a ceramic substrate and a glass lens, arranging a solder composition between the ceramic substrate and the glass lens, welding for 40min at 350 ℃, forming a connecting layer between the ceramic substrate and the glass lens after the cooling rate is about 5-8 ℃/min, and then carrying out further finish machining to obtain a shell assembly, wherein the solder composition comprises the following components in parts by weight: p2O554 parts of SnO 27 parts, ZnO 6 parts, MgO 3 parts, CaO 2 parts, SrO 2 parts, BaO 3 parts and MnO21 part of, B2O31.5 parts, K20.5 part of O and an organic additive, wherein the organic additive accounts for 35 percent of the total mass of the solder composition, and the organic additive comprises the following components in percentage by weight: 70 percent of terpineol, 7.5 percent of epoxy resin, 7.5 percent of acrylic resin and o-terpineolAnd 15% of dimethyl phthalate.
Example 4
A method of making a housing assembly comprising the steps of:
taking a ceramic substrate and a glass lens, arranging a solder composition between the ceramic substrate and the glass lens, welding for 40min at 350 ℃, forming a connecting layer between the ceramic substrate and the glass lens after the cooling rate is about 5-8 ℃/min, and then carrying out further finish machining to obtain a shell assembly, wherein the solder composition comprises the following components in parts by weight: p2O554 parts of SnO 27 parts, ZnO 6 parts, MgO 3 parts, CaO 2 parts, SrO 2 parts, BaO 3 parts, CuO 2 parts and K20.5 part of O, Na20.5 part of O and an organic additive, wherein the organic additive accounts for 35 percent of the total mass of the solder composition, and the organic additive comprises the following components in percentage by weight: 70% of terpineol, 7.5% of epoxy resin, 7.5% of acrylic resin and 15% of dimethyl phthalate.
Example 5
A method of making a housing assembly comprising the steps of:
taking a ceramic substrate and a glass lens, arranging a solder composition between the ceramic substrate and the glass lens, welding for 40min at 350 ℃, forming a connecting layer between the ceramic substrate and the glass lens after the cooling rate is about 5-8 ℃/min, and then carrying out further finish machining to obtain a shell assembly, wherein the solder composition comprises the following components in parts by weight: p2O554 parts of SnO 27 parts, ZnO 6 parts, MgO 3 parts, CaO 2 parts, SrO 2 parts, BaO 3 parts and MnO20.5 part of CuO, 0.5 part of B2O31.5 parts, K20.2 part of O, Na20.3 part of O and an organic additive, wherein the organic additive accounts for 35 percent of the total mass of the solder composition, and the organic additive comprises the following components in percentage by weight: 70% of terpineol, 7.5% of epoxy resin, 7.5% of acrylic resin and 15% of dimethyl phthalate.
Comparative example 1
A method of making a housing assembly comprising the steps of:
taking a ceramic substrate and a glass lens,then, arranging a solder composition between the ceramic substrate and the glass lens, welding for 40min at 320 ℃, wherein after the cooling rate is about 5-8 ℃/min, a connecting layer is formed between the ceramic substrate and the glass lens, and then carrying out further finish machining treatment to obtain the shell assembly, wherein the solder composition comprises the following components in parts by weight: p2O543 parts of SnO 27 parts, ZnO 6 parts, MgO 3 parts, CaO 2 parts, SrO 2 parts, BaO 3 parts and MnO21 part of, B2O31.5 parts, and K20.5 part of O.
Comparative example 2
A method of making a housing assembly comprising the steps of:
taking a ceramic substrate and a glass lens, arranging a solder composition between the ceramic substrate and the glass lens, welding for 40min at 320 ℃, forming a connecting layer between the ceramic substrate and the glass lens after the cooling rate is about 5-8 ℃/min, and then carrying out further finish machining to obtain a shell assembly, wherein the solder composition comprises the following components in parts by weight: p2O565 parts, SnO 27 parts, ZnO 6 parts, MgO 3 parts, CaO 2 parts, SrO 2 parts, BaO 3 parts and MnO21 part of, B2O31.5 parts, and K20.5 part of O.
Comparative example 3
A method of making a housing assembly comprising the steps of:
taking a ceramic substrate and a glass lens, arranging a solder composition between the ceramic substrate and the glass lens, welding for 40min at 320 ℃, forming a connecting layer between the ceramic substrate and the glass lens after the cooling rate is about 5-8 ℃/min, and then carrying out further finish machining to obtain a shell assembly, wherein the solder composition comprises the following components in parts by weight: p2O565 parts, SnO 13 parts, ZnO 6 parts, MgO 3 parts, CaO 2 parts, SrO 2 parts, BaO 3 parts and MnO21 part of, B2O31.5 parts, and K20.5 part of O.
Comparative example 4
A method of making a housing assembly comprising the steps of:
ceramic baseThe shell component comprises a ceramic substrate and a glass lens, wherein a solder composition is arranged between the ceramic substrate and the glass lens, and is welded at 320 ℃ for 40min, the cooling rate is about 5-8 ℃/min, a connecting layer is formed between the ceramic substrate and the glass lens, and then the shell component is obtained after further finish machining treatment, wherein the solder composition comprises the following components in parts by weight: p2O565 parts, SnO 40 parts, ZnO 6 parts, MgO 3 parts, CaO 2 parts, SrO 2 parts, BaO 3 parts and MnO21 part of, B2O31.5 parts, and K20.5 part of O.
Comparative example 5
A method of making a housing assembly comprising the steps of:
taking a ceramic substrate and a glass lens, arranging a solder composition between the ceramic substrate and the glass lens, welding for 40min at 320 ℃, forming a connecting layer between the ceramic substrate and the glass lens after the cooling rate is about 5-8 ℃/min, and then carrying out further finish machining to obtain a shell assembly, wherein the solder composition comprises the following components in parts by weight: p2O565 parts, SnO 13 parts, ZnO 6 parts, MgO 3 parts, CaO 2 parts, SrO 2 parts, BaO 3 parts and MnO21 part of, B2O31.5 parts, and K20.5 part of O.
Comparative example 6
A method of making a housing assembly comprising the steps of:
taking a ceramic substrate and a glass lens, arranging a solder composition between the ceramic substrate and the glass lens, welding at 250 ℃ for 40min, forming a connecting layer between the ceramic substrate and the glass lens after the cooling rate is about 5-8 ℃/min, and then carrying out further finish machining to obtain a shell assembly, wherein the solder composition comprises the following components in parts by weight: p2O565 parts, SnO 13 parts, ZnO 6 parts, MgO 3 parts, CaO 2 parts, SrO 2 parts, BaO 3 parts and MnO21 part of, B2O31.5 parts, and K20.5 part of O.
Comparative example 7
A method of making a housing assembly comprising the steps of:
taking a ceramic substrate and a glass lens, arranging a solder composition between the ceramic substrate and the glass lens, welding for 40min at 320 ℃, forming a connecting layer between the ceramic substrate and the glass lens after the cooling rate is about 5-8 ℃/min, and then carrying out further finish machining to obtain a shell assembly, wherein the solder composition comprises the following components in parts by weight: p2O565 parts, SnO 13 parts, ZnO 6 parts, CaO 2 parts, SrO 2 parts, BaO 3 parts and MnO21 part of, B2O31.5 parts, and K20.5 part of O.
Effects of the embodiment
(1) Welding bonding force and air tightness test
The case assembly samples prepared in examples 1 to 3 and comparative examples 1 to 7 were tested for the welding bonding force between the ceramic substrate and the glass lens and the airtightness of the case assembly samples in this order. Wherein, the welding bonding force is as follows: testing the bonding strength (shear) by a universal tester according to the test method for the tensile and shear bonding strength of the interface of the fine ceramic of GB/T31541-2015; airtightness: the tightness is measured by a direct pressure type air tightness tester (air pressure is 20KPa), the tightness is expressed by leakage values, and the smaller the leakage value is, the better the tightness is; specifically, the method comprises the following steps: and (3) putting a sample to be tested into the direct-pressure type air tightness tester, keeping the air pressure for 5s at 20KPa, and automatically detecting the leakage value by the direct-pressure type air tightness tester. The results of the weld bonding force and the air tightness test are shown in table 1.
TABLE 1 weld bond and gas tightness leak value data sheet for each set of samples of the housing assemblies of examples and comparative examples
Figure GDA0003535268990000111
From the test results of each experimental group, the bonding strength between the ceramic substrate and the glass lens of the shell component sample prepared by the preparation method of the embodiment 1-5 is very high, and the numerical value is more than 10 MPa; the shell assembly samples were also good in air-tightness, and all of their air-tightness leakage values were 0. The shell component samples prepared by the preparation methods of comparative examples 1 to 7 are obviously inferior to the test effects of examples 1 to 5 in the present application in terms of the bonding strength between the ceramic substrate and the glass lens and the airtightness of the shell component samples.
The welding composition prepared by each embodiment of the application is a material capable of being used for realizing sealing of ceramic and/or glass, and the welding composition is adopted to have strong bonding force between the ceramic and the glass for sealing, has a firm structure and good air tightness. The welding temperature of the solder composition is 300-350 ℃, and is lower, so that the welding efficiency can be improved, and the energy consumption can be saved.
While the foregoing is directed to embodiments of the present application, it will be appreciated by those skilled in the art that various changes and modifications may be made without departing from the principles of the application, and it is intended that such changes and modifications be covered by the scope of the application.

Claims (19)

1. A solder composition for sealing ceramics and/or glass is characterized by comprising the following components in percentage by weight: p2O545-65% of SnO, 15-35% of SnO, 5-10% of ZnO, 3-10% of MgO, 1-3% of CaO, 2-5% of SrO and 2-5% of BaO, wherein the ratio of the weight of the SnO, the ZnO, the MgO, the CaO and the SrO to the weight of the SnO is less than or equal to 5/3.
2. The solder composition of claim 1, further comprising MnO2、CuO、B2O3、K2O and Na2One or more of O.
3. The solder composition of claim 2, in which the MnO is2、CuO、B2O3、K2O and Na2The weight percentage of O is 0-2%, 0-2% and 0-2% respectively.
4. The solder composition of claim 2, comprising the following components in weight percent: p2O5 50-56％，SnO 25-30％，ZnO 5-7％，MgO 3-7％，CaO 1-2％，SrO 2-3％，BaO 2-3％，MnO2And/or 0.5-1.5% of CuO, B2O31-1.8%, and K2O and/or Na2O0.3-0.8％。
5. The solder composition of claim 1, wherein the solder composition has a soldering temperature of 300-350 ℃.
6. The solder composition of claim 1, wherein the solder composition particles have a particle size D50 of less than 10 μ ι η.
7. The solder composition of any of claims 1-6, further comprising an organic additive comprising one or more of an organic solvent, a binder, and a plasticizer.
8. The solder composition of claim 7, wherein the organic additive comprises an organic solvent, a binder, and a plasticizer, and the mass ratio of the organic solvent, the binder, and the plasticizer is (6-8): (1-2): (1-2).
9. The solder composition of claim 7, wherein the solvent comprises one or more of terpineol, ethanol, acetone, toluene, and xylene; the binder comprises an epoxy resin or an acrylic resin; the plasticizer comprises dimethyl phthalate or polyethylene glycol.
10. The solder composition of claim 1, wherein the solder composition is prepared by a method comprising:
the solder composition is prepared by uniformly mixing the raw materials of the components, heating the mixture in an inert or reducing atmosphere to form molten liquid, transferring the molten liquid to cold water for water quenching, and grinding and drying the molten liquid.
11. The solder composition of claim 10, wherein the heating is at a temperature of 1100 ℃ and 1300 ℃ for a time of 30-60 min.
12. A housing component comprising a ceramic substrate, a glass substrate, and a joining layer disposed between said ceramic substrate and said glass substrate, said joining layer being formed by soldering from the solder composition of any of claims 1-11.
13. The housing assembly of claim 12, wherein the ceramic substrate and the glass substrate have a bond strength greater than 10 MPa.
14. The housing assembly of claim 12, wherein the ceramic matrix comprises a zirconia ceramic matrix; the glass substrate comprises a glass cover plate, a glass lens or a sapphire glass lens.
15. A method of making a housing assembly, comprising the steps of:
taking a ceramic substrate and a glass substrate, then arranging the solder composition as defined in any one of claims 1-11 between the ceramic substrate and the glass substrate, after welding, forming a connecting layer between the ceramic substrate and the glass substrate by the solder composition, and then carrying out finish machining to obtain the shell component.
16. The method of manufacturing of claim 15, wherein the step of welding comprises: and after the solder composition is arranged between the ceramic substrate and the glass substrate, welding is carried out at the temperature of 300-350 ℃, and the cooling rate of the welding is lower than 10 ℃/min.
17. The method of manufacturing of claim 15, wherein the finishing treatment comprises: one or more of flat grinding, CNC machining, polishing, screen printing, and coating.
18. The method of claim 15, wherein after the step of disposing the solder composition between the ceramic substrate and the glass substrate and before the step of soldering, further comprising the steps of: the solder composition is subjected to a drying process.
19. An electronic device comprising a housing assembly and a display device, wherein the display device is connected to the housing assembly, and the housing assembly is the housing assembly according to any one of claims 12 to 14 or is manufactured by the manufacturing method according to any one of claims 15 to 18.
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