CN111112881B - Graphene modified low-temperature solder and preparation method thereof - Google Patents
Graphene modified low-temperature solder and preparation method thereof Download PDFInfo
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- CN111112881B CN111112881B CN202010003929.5A CN202010003929A CN111112881B CN 111112881 B CN111112881 B CN 111112881B CN 202010003929 A CN202010003929 A CN 202010003929A CN 111112881 B CN111112881 B CN 111112881B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/362—Selection of compositions of fluxes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/36—Electric or electronic devices
Abstract
The invention relates to the technical field of low-temperature solders, in particular to a graphene modified low-temperature solder and a preparation method thereof. The graphene modified low-temperature solder at least comprises the following components in percentage by weight: 0.1-0.5% of graphene, and the balance of solder alloy. The graphene modified low-temperature solder provided by the invention has an excellent effect on the reinforcement of the solder by compounding the silver-plated graphene and the gold particle-loaded graphene, and simultaneously solves the problem that the graphene floats in the soldering process of the solder, so that the toughness and the strength of the solder are more excellent. In addition, the silver-plated graphene is prepared by a specific method, so that the dispersibility of the silver-plated graphene in a solder matrix is enhanced, the tensile strength and the ductility of the solder are improved, and the drop toughness of a welding point is further improved.
Description
Technical Field
The invention relates to the technical field of low-temperature solders, in particular to a graphene modified low-temperature solder and a preparation method thereof.
Background
The progress of modern electronic manufacturing technology has led to the development of electronic information systems toward miniaturization, densification and multi-functionalization, and the integration level, the number of components and the number of I/O pins of the systems have been increased. In order to integrate a plurality of chips or devices with different functions into a system, the thermal influence of the packaging process temperature on various chips and devices must be reduced, and particularly for thermal mismatch, heat-sensitive materials, flexible substrates, multi-layered chips, built-in devices and the like, the packaging interconnection must be completed under the condition of the lowest temperature possible, namely, low-temperature packaging.
Lowering the soldering temperature requires the use of Low Temperature Solders (LTS) which are commonly used alloys containing Bi, with bismuth contents generally higher than 40%, typically Sn42Bi58 eutectic alloys or alloys close to the eutectic point. The alloy containing bismuth has insufficient toughness due to the characteristics of bismuth, and the tin-bismuth alloy is particularly brittle, so that the vibration falling performance of a corresponding welding spot is only 1-10% of that of the conventional high-temperature alloy. Often fail to meet actual performance requirements. Therefore, toughness reinforcement of low-temperature solder is a real requirement.
Graphene is one of the materials with the highest known strength, has good toughness and can be bent, the theoretical Young modulus of the graphene reaches 1.0TPa, and the inherent tensile strength is 130 GPa. The reduced graphene modified by the hydrogen plasma also has very good strength, and the average modulus can be larger than 0.25 TPa. Due to the excellent physical and chemical properties of the graphene, the graphene has an attractive application prospect in the field of composite solders. However, since graphene has high specific surface energy, is not easily dispersed in a metal solder matrix, and has poor interface bonding property with the solder matrix, how to play a role in enhancing graphene in lead-free solder is to prepare a new generation of solder with excellent performance and environmental protection, which is an important problem to be solved urgently in the electronic industry.
Disclosure of Invention
In order to solve the technical problem, a first aspect of the present invention provides a graphene modified low-temperature solder, which at least comprises the following components, by weight: 0.1-0.5% of graphene, and the balance of solder alloy.
As a preferable technical solution of the present invention, the graphene includes silver-plated graphene.
As a preferred technical solution of the present invention, the preparation of the silver-plated graphene comprises acidification, activation and silver plating of pure graphene.
As a preferable technical scheme of the invention, the thickness of the pure graphene is 0.5-10nm, and the diameter of the pure graphene is 0.5-10 μm.
As a preferred technical scheme of the present invention, in the acidification of the pure graphene, an acidification liquid is a combination of concentrated sulfuric acid, ethanol, and citric acid, wherein a weight ratio of the acidification liquid to the pure graphene is 1: (0.05-0.2): (0.1-0.5).
As a preferable technical solution of the present invention, the graphene further includes gold particle-loaded graphene.
In a preferred embodiment of the present invention, the particle size of the gold particle-loaded graphene is 5 to 30 nm.
As a preferred technical scheme of the present invention, the weight ratio of the silver-plated graphene to the gold particle-loaded graphene is 100: (0.01-0.1).
In a preferred embodiment of the present invention, the solder alloy is selected from any one of a tin-bismuth alloy, a tin-copper alloy, a tin-silver-copper alloy, and a tin-zinc alloy.
The second aspect of the invention provides a preparation method of the graphene modified low-temperature solder, which at least comprises the following steps:
(1) putting graphene into absolute ethyl alcohol, performing ultrasonic treatment for 1-2h, transferring to a ball mill, performing ball milling for 10-50min, taking out and drying to obtain ground graphene;
(2) and adding the ground graphene into the molten solder alloy, stirring for 10-30min under the protection of nitrogen, and cooling and forming to obtain the graphene.
Has the advantages that: the graphene modified low-temperature solder provided by the invention has the advantages that through compounding of silver-plated graphene and gold particle-loaded graphene, an excellent effect is achieved on the reinforcement of the solder, the floating problem of the graphene in the welding process is solved, and the toughness and the strength of the solder are more excellent. In addition, the silver-plated graphene is prepared by a specific method, so that the dispersibility of the silver-plated graphene in a solder matrix is enhanced, the tensile strength and the ductility of the solder are improved, and the drop toughness of a welding point is further improved.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
In order to solve the technical problem, a first aspect of the present invention provides a graphene modified low temperature solder, which at least comprises the following components, by weight: 0.1-0.5% of graphene, and the balance of solder alloy.
Preferably, the graphene modified low-temperature solder comprises the following components in percentage by weight: 0.3% of graphene, and the balance of solder alloy.
Silver-plated graphene
In the present invention, the graphene includes silver-plated graphene.
Preferably, the raw material of the silver-plated graphene is pure graphene.
Preferably, the pure graphene has a thickness of 0.5 to 10nm and a diameter of 0.5 to 10 μm.
More preferably, the pure graphene has a thickness of 0.5 to 5nm and a diameter of 0.5 to 5 μm.
In the present invention, the source of the pure graphene is not particularly limited, and may be mentioned, but not limited to, Nanjing Xiapong materials science and technology Co., Ltd., No. XF 001W.
Preferably, the preparation of the silver-plated graphene comprises acidification, activation and silver plating of pure graphene.
In the invention, the preparation method of the silver-plated graphene at least comprises the following steps:
(1) acidification of pure graphene: adding pure graphene into the acidizing fluid, carrying out ultrasonic treatment for 2-4h, stirring for 1-3h at the temperature of 50-70 ℃, and naturally cooling to room temperature; centrifuging, washing with water for multiple times until the pH value of washing liquor is 7, filtering, and drying to obtain acidified graphene;
(2) and (3) activation: adding the acidified graphene into the sensitizing solution, stirring for 20-40min, centrifuging, and washing with water for multiple times until the pH value of a washing solution is 7 to obtain sensitized graphene; adding the sensitized graphene into the activating solution, stirring for 20-40min, centrifuging, washing with water for multiple times until the pH value of the washing solution is 7, filtering, and drying to obtain activated graphene;
(3) silver plating: ultrasonically dispersing the activated carbon nano tube in electroplating solution, ultrasonically treating for 10-30min, then electroplating, centrifuging after electroplating, washing with water for multiple times until the pH value of the washing solution is 7, filtering, and drying to obtain the final product.
Preferably, in the step (1), the acidizing fluid is a combination of concentrated sulfuric acid, ethanol and citric acid, and the weight ratio of the acidizing fluid to the total weight of the acidizing fluid is 1: (0.05-0.2): (0.1-0.5).
More preferably, the weight ratio of the concentrated sulfuric acid, the ethanol and the citric acid is 1: 0.1: 0.25.
preferably, in the step (2), the sensitizing solution is an aqueous solution of stannous chloride and hydrochloric acid; the concentration of the stannous chloride is 0.05-0.2M; the concentration of the hydrochloric acid is 0.1-0.4M.
More preferably, the concentration of the stannous chloride is 0.1M; the concentration of the hydrochloric acid is 0.2M.
Preferably, in the step (2), the activating solution is an aqueous solution of palladium chloride, hydrochloric acid and cerium nitrate; the concentration of the palladium chloride is (0.001-0.005) M; the concentration of the hydrochloric acid is (0.1-0.5) M; the concentration of the cerium nitrate is (0.005-0.02) M.
Preferably, the concentration of the palladium chloride is 0.0025M; the concentration of the hydrochloric acid is 0.25M; the concentration of the cerium nitrate is 0.01M.
Preferably, in the step (3), the electroplating solution is a combination of silver nitrate, cerium nitrate, potassium citrate, glucose, ethanol and water.
Preferably, the electroplating solution consists of 1L of water, 100g of a mixture of silver nitrate, cerium nitrate and potassium citrate, 20-40g of glucose and 40-50mL of ethanol.
Preferably, the plating solution consists of 1L of water, 100g of a mixture of silver nitrate, cerium nitrate and potassium citrate, 30g of glucose and 45mL of ethanol.
Preferably, the weight ratio of the silver nitrate to the cerium nitrate to the potassium citrate is 1: (0.8-1.2): (1.5-2.5).
More preferably, the weight ratio of the silver nitrate, the cerium nitrate and the sodium citrate is 1: 1: 2.
preferably, in the step (3), the electroplating process parameters are as follows: the electroplating power is 90-110W, the electroplating temperature is 15-30 ℃, and the current density is 1-5A/dm2Electroplating time is 20-50 min.
Most preferably, in the present invention, the method for preparing silver-plated graphene at least comprises the following steps:
(1) acidification of pure graphene: adding 40g of pure graphene into 2L of acidizing fluid, carrying out ultrasonic treatment for 3h, stirring for 2h at the temperature of 60 ℃, and naturally cooling to room temperature; centrifuging, washing with water for multiple times until the pH value of washing liquor is 7, filtering, and drying to obtain acidified graphene; the acidizing fluid is a combination of concentrated sulfuric acid, ethanol and citric acid, and the weight ratio is 1: 0.1: 0.25;
(2) and (3) activation: adding 40g of acidified graphene into 2L of sensitizing solution, stirring for 30min, centrifuging, and washing with water for multiple times until the pH value of washing liquor is 7 to obtain sensitized graphene; adding 40g of sensitized graphene into 2L of activating solution, stirring for 30min, centrifuging, washing with water for multiple times until the pH value of washing liquor is 7, filtering, and drying to obtain activated graphene; the sensitizing solution is a mixed solution of 0.1M stannous chloride and 0.2M hydrochloric acid; the activating solution is a mixed solution of 0.0025M palladium chloride, 0.25M hydrochloric acid and 0.01M cerium nitrate;
(3) silver plating: ultrasonically dispersing 5g of activated carbon nano tube in electroplating liquid, ultrasonically treating for 10-30min, and then electroplating, wherein the electroplating process parameters are as follows: the plating power is 100W, the plating temperature is 25 ℃, and the current density is 3A/dm2Electroplating for 30 min; after the electroplating is finished, centrifugingWashing with water for several times until the pH value of the washing liquid is 7, filtering, and drying to obtain the final product; the electroplating solution consists of 1L of water, 25g of silver nitrate, 25g of cerium nitrate, 50g of potassium citrate, 30g of glucose and 45mL of ethanol.
In the process of preparing silver-plated graphene, pure graphene with small size is selected as a raw material, the specific surface area of the pure graphene is very high, agglomeration is very easy to occur in the acidification process, and if the pure graphene is prepared from the conventional acidification liquid of concentrated sulfuric acid and concentrated nitric acid, the compatibility of the finally prepared silver-plated graphite in a solder alloy is influenced to a certain extent. However, the inventor unexpectedly finds that when the acidizing fluid is compounded by concentrated sulfuric acid, ethanol and citric acid, the dispersion uniformity of the silver-plated graphene can be remarkably improved, and the toughness of the solder prepared by the acidizing fluid can be remarkably improved. The inventor conjectures that when concentrated sulfuric acid, ethanol and citric acid are mixed according to a specific proportion to be used as an acidizing solution, pure graphene can be in a dispersed and stretched state, active sites are uniformly acidized and activated, silver plating is uniform, compatibility of the graphene with alloy solder is improved, and toughness of the solder is improved.
Gold particle-loaded graphene
In the invention, the graphene further comprises gold particle-loaded graphene.
More preferably, the particle size of the gold particle-supported graphene is 5 to 30 nm.
Most preferably, the particle size of the gold particle-supported graphene is 14 nm.
In the present invention, the source of the gold particle-loaded graphene is not particularly limited, and may be mentioned but not limited to Nanjing Xiancheng nanomaterial science and technology Co., Ltd, number XF 046.
Preferably, the weight ratio of the silver-plated graphene to the gold particle-loaded graphene is 100: (0.01-0.1).
More preferably, the weight ratio of the silver-plated graphene to the gold particle-loaded graphene is 100: 0.05.
the solder using the alloy of tin-bismuth series as the matrix has the excellent performance of low welding temperature, but the bismuth has larger brittleness, so that the welding point has the problem of high brittleness and easy damage. The inventors have found that carbon can affect the toughness and weldability of alloy steels. Therefore, the inventor adds a proper amount of graphene into the matrix alloy solder for modification in the research process. However, the inventor finds that the conventionally selected graphene cannot be uniformly dispersed in the tin alloy, the uniformity of the graphene is difficult to control, and the graphene cannot play a good reinforcing role. The inventor surprisingly finds that silver-plated graphene and gold particle-loaded graphene are compounded according to a certain proportion, and the excellent effect of reinforcing the solder is achieved. The inventor conjectures that the compatibility between the silver-plated graphene and the matrix alloy of the solder is greatly improved, and particularly, the silver-plated graphene is compounded by selecting gold particles with the average particle size of 5-30nm to load the graphene and carrying out specific silver plating on pure graphene with the thickness of 0.5-10nm and the diameter of 0.5-10 mu m. The compatibility between the silver-plated graphene with a large size and the gold particle-loaded graphene with a small size in the solder matrix alloy can be obviously improved, and the floating problem of the silver-plated graphene with a large size can be obviously reduced, so that the toughness and the strength of the solder are obviously improved. The inventor unexpectedly finds that the drop toughness of the solder is better when the addition amount of the gold particle loaded graphene is 0.01-0.1% of silver-plated graphene.
Aminated graphene
In the invention, the graphene further comprises aminated graphene.
Preferably, the weight ratio of the silver-plated graphene to the aminated graphene is 1: (0.05-0.15).
More preferably, the weight ratio of the silver-plated graphene to the aminated graphene is 1: 0.1.
preferably, the aminated graphene is at least one selected from the group consisting of polyethylene glycol-modified aminated graphene, octadecylamine-modified aminated graphene, tetraethylenepentamine-modified aminated graphene and piperazine-modified aminated graphene.
More preferably, the aminated graphene is polyethylene glycol-modified aminated graphene.
Preferably, the nitrogen content of the polyethylene glycol modified aminated graphene is 5-10 wt%.
In the present invention, the source of the polyethylene glycol modified aminated graphene is not particularly limited, and may be mentioned but not limited to Nanjing Xiancheng nanometer materials science and technology Co., Ltd, number XF 005.
The inventor unexpectedly discovers in the experimental process that the compounding of the aminated graphene and the silver-plated graphene produces a synergistic effect, so that the tensile strength of the prepared solder is further improved. The inventor thinks that the possible reason is that the aminated graphene surface is modified with a small amount of polar amino groups, so that the aminated graphene has a certain adsorption effect on silver-plated graphene, the bonding strength between the graphene and a solder alloy is stabilized, and the welding stability of the solder is improved when the solder is molten. Meanwhile, the silver-plated graphene can enhance the dispersibility of the aminated graphene in the solder, reduce the agglomeration of the aminated graphene and further improve the tensile strength and the ductility of the solder. The inventor finds that the mechanical property effect of the prepared solder is the most excellent especially when the polyethylene glycol modified aminated graphene is selected.
Solder alloy
In the present invention, the solder alloy is selected from any one of a tin-bismuth alloy, a tin-copper alloy, a tin-silver-copper alloy, and a tin-zinc alloy.
Preferably, the solder alloy is a tin-bismuth series alloy.
Examples of the tin-bismuth series alloy include Sn42Bi58, sn64.5bi35cu0.5, and sn64.6bi35ag0.4.
Preferably, the tin-bismuth-based alloy is Sn42Bi 58.
The source of the Sn42Bi58 is not particularly limited, and there may be mentioned, but not limited to, cast-alloy materials of Nanogong.
The second aspect of the invention provides a preparation method of the graphene modified low-temperature solder, which at least comprises the following steps:
(1) putting graphene into absolute ethyl alcohol, performing ultrasonic treatment for 1-2h, transferring to a ball mill, performing ball milling for 10-50min, taking out and drying to obtain ground graphene;
(2) and adding the ground graphene into the molten solder alloy, stirring for 10-30min under the protection of nitrogen, and cooling and forming to obtain the graphene.
Preferably, the feed-liquid ratio of the graphene to the absolute ethyl alcohol in the step (1) is (10-30) g/L.
Most preferably, the preparation method of the graphene modified low-temperature solder comprises the following steps:
(1) putting graphene into absolute ethyl alcohol, wherein the material-liquid ratio is 15g/L, carrying out ultrasonic treatment for 1.5h, transferring to a ball mill, carrying out ball milling for 30min, taking out and drying to obtain ground graphene;
(2) and adding the ground graphene into the molten solder alloy, stirring for 20min under the protection of nitrogen, and cooling and forming to obtain the graphene.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
Embodiment 1 provides a graphene modified low-temperature solder, which at least comprises the following components in percentage by weight: 0.3% of graphene, and the balance of solder alloy.
The graphene comprises silver-plated graphene, gold particle-loaded graphene and aminated graphene, and the weight ratio is 100: 0.05: 10.
the preparation method of the silver-plated graphene comprises the following steps:
(1) acidification of pure graphene: adding 40g of pure graphene into 2L of acidizing fluid, carrying out ultrasonic treatment for 3h, stirring for 2h at the temperature of 60 ℃, and naturally cooling to room temperature; centrifuging, washing with water for multiple times until the pH value of washing liquor is 7, filtering, and drying to obtain acidified graphene; the acidizing fluid is a combination of concentrated sulfuric acid, ethanol and citric acid, and the weight ratio is 1: 0.1: 0.25; the pure graphene is purchased from Nanjing Xiancheng materials science and technology Limited, and is numbered XF 001W;
(2) activation of pure graphene: adding 40g of acidified graphene into 2L of sensitizing solution, stirring for 30min, centrifuging, and washing with water for multiple times until the pH value of washing liquor is 7 to obtain sensitized graphene; adding 40g of sensitized graphene into 2L of activating solution, stirring for 30min, centrifuging, washing with water for multiple times until the pH value of washing liquor is 7, filtering, and drying to obtain activated graphene; the sensitizing solution is a mixed solution of 0.1M stannous chloride and 0.2M hydrochloric acid; the activating solution is a mixed solution of 0.0025M palladium chloride, 0.25M hydrochloric acid and 0.01M cerium nitrate;
(3) silver plating of pure graphene: ultrasonically dispersing 5g of activated carbon nano tube in electroplating liquid, ultrasonically treating for 10-30min, and then electroplating, wherein the electroplating process parameters are as follows: the plating power is 100W, the plating temperature is 25 ℃, and the current density is 3A/dm2Electroplating for 30 min; after the electroplating is finished, centrifuging, washing with water for multiple times until the pH value of the washing liquor is 7, filtering and drying to obtain the compound copper-base alloy; the electroplating solution consists of 1L of water, 25g of silver nitrate, 25g of cerium nitrate, 50g of potassium citrate, 30g of glucose and 45mL of ethanol.
The gold particles are loaded with graphene and purchased from Nanjing Xiancheng nanomaterial science and technology Co., Ltd, serial number XF 046.
The aminated graphene is polyethylene glycol modified aminated graphene, and is purchased from Nanjing Xiancheng nanomaterial science and technology Limited company with the serial number XF 005.
The solder alloy is Sn42Bi58 purchased from cast-alloy materials, Inc. of Nanogong.
The preparation method of the graphene modified low-temperature solder comprises the following steps:
(1) putting graphene into absolute ethyl alcohol, wherein the material-liquid ratio is 15g/L, carrying out ultrasonic treatment for 1.5h, transferring to a ball mill, carrying out ball milling for 30min, taking out and drying to obtain ground graphene;
(2) and adding the ground graphene into the molten solder alloy, stirring for 20min under the protection of nitrogen, and cooling and forming to obtain the graphene.
Example 2
Embodiment 2 provides a graphene modified low-temperature solder, which at least comprises the following components in percentage by weight: 0.1% of graphene, and the balance solder alloy.
The graphene comprises silver-plated graphene, gold particle-loaded graphene and aminated graphene, and the weight ratio is 100: 0.01: 5.
the preparation method of the silver-plated graphene comprises the following steps:
(1) acidification of pure graphene: adding 40g of pure graphene into 2L of acidizing fluid, carrying out ultrasonic treatment for 3h, stirring for 2h at the temperature of 60 ℃, and naturally cooling to room temperature; centrifuging, washing with water for multiple times until the pH value of washing liquor is 7, filtering, and drying to obtain acidified graphene; the acidizing fluid is a combination of concentrated sulfuric acid, ethanol and citric acid, and the weight ratio is 1: 0.1: 0.25; the pure graphene is purchased from Nanjing Xiancheng materials science and technology Limited, and is numbered XF 001W;
(2) activation of pure graphene: adding 40g of acidified graphene into 2L of sensitizing solution, stirring for 30min, centrifuging, and washing with water for multiple times until the pH value of washing liquor is 7 to obtain sensitized graphene; adding 40g of sensitized graphene into 2L of activating solution, stirring for 30min, centrifuging, washing with water for multiple times until the pH value of washing liquor is 7, filtering, and drying to obtain activated graphene; the sensitizing solution is a mixed solution of 0.1M stannous chloride and 0.2M hydrochloric acid; the activating solution is a mixed solution of 0.0025M palladium chloride, 0.25M hydrochloric acid and 0.01M cerium nitrate;
(3) silver plating of pure graphene: ultrasonically dispersing 5g of activated carbon nano tube in electroplating liquid, ultrasonically treating for 10-30min, and then electroplating, wherein the electroplating process parameters are as follows: the plating power is 100W, the plating temperature is 25 ℃, and the current density is 3A/dm2Electroplating for 30 min; after the electroplating is finished, centrifuging, washing with water for multiple times until the pH value of the washing liquor is 7, filtering and drying to obtain the compound copper-base alloy; the electroplating solution consists of 1L of water, 25g of silver nitrate, 25g of cerium nitrate, 50g of potassium citrate, 30g of glucose and 45mL of ethanol.
The gold particles are loaded with graphene and purchased from Nanjing Xiancheng nanomaterial science and technology Co., Ltd, serial number XF 046.
The aminated graphene is polyethylene glycol modified aminated graphene, and is purchased from Nanjing Xiancheng nanomaterial science and technology Limited company with the serial number XF 005.
The solder alloy is Sn42Bi58 purchased from cast-alloy materials, Inc. of Nanogong.
The preparation method of the graphene modified low-temperature solder comprises the following steps:
(1) putting graphene into absolute ethyl alcohol, wherein the material-liquid ratio is 15g/L, carrying out ultrasonic treatment for 1.5h, transferring to a ball mill, carrying out ball milling for 30min, taking out and drying to obtain ground graphene;
(2) and adding the ground graphene into the molten solder alloy, stirring for 20min under the protection of nitrogen, and cooling and forming to obtain the graphene.
Example 3
Embodiment 3 provides a graphene modified low-temperature solder, which at least comprises the following components in percentage by weight: 0.5% of graphene, and the balance solder alloy.
The graphene comprises silver-plated graphene, gold particle-loaded graphene and aminated graphene, and the weight ratio is 100: 0.1: 15.
the preparation method of the silver-plated graphene comprises the following steps:
(1) acidification of pure graphene: adding 40g of pure graphene into 2L of acidizing fluid, carrying out ultrasonic treatment for 3h, stirring for 2h at the temperature of 60 ℃, and naturally cooling to room temperature; centrifuging, washing with water for multiple times until the pH value of washing liquor is 7, filtering, and drying to obtain acidified graphene; the acidizing fluid is a combination of concentrated sulfuric acid, ethanol and citric acid, and the weight ratio is 1: 0.1: 0.25; the pure graphene is purchased from Nanjing Xiancheng materials science and technology Limited, and is numbered XF 001W;
(2) activation of pure graphene: adding 40g of acidified graphene into 2L of sensitizing solution, stirring for 30min, centrifuging, and washing with water for multiple times until the pH value of washing liquor is 7 to obtain sensitized graphene; adding 40g of sensitized graphene into 2L of activating solution, stirring for 30min, centrifuging, washing with water for multiple times until the pH value of washing liquor is 7, filtering, and drying to obtain activated graphene; the sensitizing solution is a mixed solution of 0.1M stannous chloride and 0.2M hydrochloric acid; the activating solution is a mixed solution of 0.0025M palladium chloride, 0.25M hydrochloric acid and 0.01M cerium nitrate;
(3) silver plating of pure graphene: ultrasonically dispersing 5g of activated carbon nano tube in electroplating liquid, ultrasonically treating for 10-30min, and then electroplating, wherein the electroplating process parameters are as follows: the plating power is 100W, the plating temperature is 25 ℃, and the current density is 3A/dm2Electroplating for 30 min; after the electroplating is finished, centrifuging, washing with water for multiple times until the pH value of the washing liquor is 7, filtering and drying to obtain the compound copper-base alloy; the electroplating solution consists of 1L of water, 25g of silver nitrate, 25g of cerium nitrate, 50g of potassium citrate, 30g of glucose and 45mL of ethanol.
The gold particles are loaded with graphene and purchased from Nanjing Xiancheng nanomaterial science and technology Co., Ltd, serial number XF 046.
The aminated graphene is polyethylene glycol modified aminated graphene, and is purchased from Nanjing Xiancheng nanomaterial science and technology Limited company with the serial number XF 005.
The solder alloy is Sn42Bi58 purchased from cast-alloy materials, Inc. of Nanogong.
The preparation method of the graphene modified low-temperature solder comprises the following steps:
(1) putting graphene into absolute ethyl alcohol, wherein the material-liquid ratio is 15g/L, carrying out ultrasonic treatment for 1.5h, transferring to a ball mill, carrying out ball milling for 30min, taking out and drying to obtain ground graphene;
(2) and adding the ground graphene into the molten solder alloy, stirring for 20min under the protection of nitrogen, and cooling and forming to obtain the graphene.
Example 4
The embodiment 4 is different from the embodiment 1 in that the graphene modified low-temperature solder at least comprises the following components in percentage by weight: 0.3% pure graphene, the balance being solder alloy; the pure graphene is purchased from Nanjing Xiancheng nanomaterial science and technology Limited.
Example 5
The embodiment 5 is different from the embodiment 1 in that the graphene modified low-temperature solder at least comprises the following components in percentage by weight: 0.3% of graphene, and the balance solder alloy; the graphene is silver-plated graphene.
Example 6
The embodiment 6 is different from the embodiment 1 in that the graphene modified low-temperature solder at least comprises the following components in percentage by weight: 0.3% of graphene, and the balance solder alloy; the graphene comprises silver-plated graphene and gold particle-loaded graphene, and the weight ratio is 100: 0.05.
example 7
The embodiment 7 is different from the embodiment 1 in that the graphene modified low-temperature solder at least comprises the following components in percentage by weight: 0.3% of graphene, and the balance solder alloy; the graphene comprises silver-plated graphene and aminated graphene, and the weight ratio is 100: 10.
example 8
The embodiment 8 is different from the embodiment 1 in that the graphene modified low-temperature solder at least comprises the following components in percentage by weight: 0.3% of graphene, and the balance solder alloy; the graphene comprises gold particle loaded graphene and aminated graphene, and the weight ratio is 0.05: 10.
example 9
The embodiment 9 is different from the embodiment 1 in that the graphene modified low-temperature solder at least comprises the following components in percentage by weight: 0.3% of graphene, and the balance solder alloy; the graphene comprises silver-plated graphene, palladium particle-loaded graphene and aminated graphene, and the weight ratio is 100: 0.05: 10; the palladium particle-loaded graphene is purchased from Nanjing Xiancheng nanomaterial science and technology Limited, and is numbered XF 031.
Example 10
The embodiment 10 is different from the embodiment 1 in that the graphene modified low-temperature solder at least comprises the following components in percentage by weight: 0.3% of graphene, and the balance solder alloy; the graphene comprises silver particle loaded graphene, gold particle loaded graphene and aminated graphene, and the weight ratio is 100: 0.05: 10.
example 11
Embodiment 11 differs from embodiment 1 in that the method for preparing silver-coated graphene comprises the following steps:
(1) acidification of pure graphene: adding 40g of pure graphene into 2L of acidizing fluid, carrying out ultrasonic treatment for 3h, stirring for 2h at the temperature of 60 ℃, and naturally cooling to room temperature; centrifuging, washing with water for multiple times until the pH value of washing liquor is 7, filtering, and drying to obtain acidified graphene; the acidizing fluid is a combination of concentrated sulfuric acid and concentrated nitric acid, and the weight ratio of the acidizing fluid to the concentrated nitric acid is 1: 0.25; the pure graphene is purchased from Nanjing Xiancheng materials science and technology Limited, and is numbered XF 001W;
(2) activation of pure graphene: adding 40g of acidified graphene into 2L of sensitizing solution, stirring for 30min, centrifuging, and washing with water for multiple times until the pH value of washing liquor is 7 to obtain sensitized graphene; adding 40g of sensitized graphene into 2L of activating solution, stirring for 30min, centrifuging, washing with water for multiple times until the pH value of washing liquor is 7, filtering, and drying to obtain activated graphene; the sensitizing solution is a mixed solution of 0.1M stannous chloride and 0.2M hydrochloric acid; the activating solution is a mixed solution of 0.0025M palladium chloride, 0.25M hydrochloric acid and 0.01M cerium nitrate;
(3) silver plating of pure graphene: ultrasonically dispersing 5g of activated carbon nano tube in electroplating liquid, ultrasonically treating for 10-30min, and then electroplating, wherein the electroplating process parameters are as follows: the electroplating power is 100W, the electroplating temperature is 25 ℃, the current density is 3A/dm2, and the electroplating time is 30 min; after the electroplating is finished, centrifuging, washing with water for multiple times until the pH value of the washing liquor is 7, filtering and drying to obtain the compound copper-base alloy; the electroplating solution consists of 1L of water, 25g of silver nitrate, 25g of cerium nitrate, 50g of potassium citrate, 30g of glucose and 45mL of ethanol.
Example 12
Embodiment 12 differs from embodiment 1 in that the graphene-modified low-temperature solder comprises at least the following components in percentage by weight: 0.3% of graphene, and the balance solder alloy; the graphene comprises silver-plated graphene, gold particle-loaded graphene and aminated graphene, and the weight ratio is 100: 0.05: 10; the aminated graphene is octadecylamine-modified aminated graphene.
Performance testing
First, the low-temperature solders prepared in examples 1 to 12 were prepared into low-temperature solder pastes, respectively.
The low-temperature soldering paste comprises 85% of low-temperature solder and 15% of soldering paste.
The flux paste comprises, by weight, 35 parts of rosin, 30 parts of a solvent, 8 parts of an active agent, 7 parts of a thickening agent and 12 parts of an additive; wherein the rosin is hydrogenated rosin and polymerized rosin, and the weight ratio of the hydrogenated rosin to the polymerized rosin is 4: 1, the solvent is diethylene glycol hexyl ether, the active agent is adipic acid and hexadecylamine hydrofluoride, and the weight ratio of the two is 20: 1, the additive is dodecanedioic acid, the thickening agent is hydrogenated castor oil and ethylene bis stearamide, and the weight ratio of the hydrogenated castor oil to the ethylene bis stearamide is 1: 1.
the preparation method of the low-temperature soldering paste comprises the following steps: putting rosin, a solvent, an active agent and an additive into a container, and stirring at 100 ℃ until the solution is transparent; and heating to 135 ℃, adding the thickening agent, stirring, melting and cooling to obtain the paste soldering flux for later use.
The low-temperature solder prepared in the embodiment is prepared into soldering powder with a certain specification, the soldering powder is mixed with the paste soldering flux according to a certain proportion, and a double-planetary mixer is used for mixing uniformly to prepare the low-temperature soldering paste.
1. Tensile strength: the test was performed according to the GB 26511989 standard.
2. And (3) drop test: the low temperature lead-free solder pastes prepared in examples 1-10 were tested in a drop test according to standard JESD22-B111 using a bga solder test chain from daisy chain using 1500G drop conditions.
The test results are shown in Table 1.
TABLE 1 test results of the performance of low temperature solder pastes prepared from the low temperature solders provided in examples 1-12
| Tensile strength/MPa | Number of falls/number of drops | |
| Example 1 | 60 | 83 |
| Example 2 | 51 | 69 |
| Example 3 | 57 | 78 |
| Example 4 | 17 | 8 |
| Example 5 | 28 | 13 |
| Example 6 | 37 | 28 |
| Example 7 | 33 | 34 |
| Example 8 | 36 | 19 |
| Example 9 | 46 | 65 |
| Example 10 | 33 | 30 |
| Example 11 | 38 | 37 |
| Example 12 | 47 | 62 |
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (5)
1. The graphene modified low-temperature solder is characterized by at least comprising the following components in percentage by weight: 0.1-0.5% of graphene, and the balance of solder alloy;
the graphene comprises silver-plated graphene and gold particle-loaded graphene;
the particle size of the gold particle-loaded graphene is 5-30 nm;
the weight ratio of the silver-plated graphene to the gold particle-loaded graphene is 100: (0.01-0.1).
2. The graphene-modified low-temperature solder according to claim 1, wherein the preparation of silver-plated graphene comprises acidification, activation and silver plating of pure graphene.
3. The graphene-modified low-temperature solder according to claim 2, wherein in the acidification of the pure graphene, an acidification liquid is a combination of concentrated sulfuric acid, ethanol and citric acid, and the weight ratio of the acidification liquid to the pure graphene is 1: (0.05-0.2): (0.1-0.5).
4. The graphene-modified low temperature solder according to claim 1, wherein the solder alloy is selected from any one of tin-bismuth series alloys, tin-copper alloys, tin-silver-copper alloys, and tin-zinc alloys.
5. The preparation method of the graphene modified low-temperature solder according to any one of claims 1 to 4, characterized by comprising at least the following steps:
(1) putting graphene into absolute ethyl alcohol, performing ultrasonic treatment for 1-2h, transferring to a ball mill, performing ball milling for 10-50min, taking out and drying to obtain ground graphene;
(2) and adding the ground graphene into the molten solder alloy, stirring for 10-30min under the protection of nitrogen, and cooling and forming to obtain the graphene.
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