A kind of graphene-ZnOw-Tin Composite Material and preparation method thereofTechnical field
The invention belongs to technical field of welding materials, and in particular to a kind of graphene-ZnOw-Tin Composite MaterialAnd preparation method thereof.
Background technology
With the arrival of information age, electronics industry has obtained the fast of the product such as swift and violent development, computer, mobile phoneSpeed popularization, makes electronic industry become one of most noticeable and most potential industry.The prosperous also band of electronic industryThe development of electronics manufacturing closely related therewith is moved, as the key links during electronic manufacture, Electronic PackagingImportance it is also increasingly notable.And soldering becomes the desirable technique for ensuring conductive interconnection between Electronic Packaging component.Solder is madeFor a kind of connecting material, it is responsible for during Electronic Packaging and realizes appointing for the functions such as mechanical connection, electrical equipment connection and heat exchangeBusiness.
Traditional tin-kupper solder alloy is long with its cheap cost, good electric conductivity and excellent soldering processes performanceIt has been widely used in since phase in component package and printed circuit board (PCB) assembling, it is extremely important in electronic-packaging processes so as to becomeBrazing material.But lead can cause potential hazard to health and natural environment.With the development of electronics industry, super large ruleSolder joint is less and less in vlsi die, and be subject to mechanics, attack a vital point and calorifics load is increasingly heavier, the requirement to solder is more nextIt is higher.The creep-resistant property of traditional tin-lead alloy is poor, it is impossible to meets the requirement of modern electronics industry.Therefore, lead-free solderDevelopment and application, it is responsible for environmental protection and improves the dual role of Quality of electronic products.
There are the series alloys such as tin-copper, tin-silver-copper, tin-zinc than more typical in the lead-free solder of prior art.ButUp to the present, a kind of lead-free solder that can replace traditional tin-kupper solder completely is not still developed.Strengthen solder performancePossible ways be that the second phase is introduced in general solder, become composite solder.
Graphene, at present by the carbon material of extensive concern, is the most thin two-dimentional material that the current mankind are had found as a kind ofMaterial, its microstructure is with sp by carbon atom2What hybrid form was formed by connecting.Because graphene has stable conjugation electricity in itselfSubsystem, thus many excellent physical characteristics can be shown.Such as：The intensity of graphene is more than 100 times of steel, is reached130GPa, it is the material of the maximum intensity obtained at present；The thermal conductivity of graphene is 5 × 103 Wm-1K-1, it is the 3 of diamondTimes；Graphene has known highest carrier mobility, is 1.5 × 104 cm2·V-1S-1；In addition, graphene also hasThere are some other special nature, the ferromagnetism and room-temperature quantum Hall effect of such as room temperature.Just because of the property of these protrusions, graphiteAlkene it is novel for development, high performance polymer composite material provide possible approach.
The content of the invention
It is an object of the invention to provide a kind of graphene-ZnOw-Tin Composite Material and preparation method thereof, itsConnecting material of the alternative traditional tin-kupper solder as super large-scale integration, overcomes lead element in traditional tin-kupper solderThe environment and health problem brought, and there is mechanical property higher than existing lead-free solder, more reliable, it is that one kind meets the modern timesThe composite of electronics industry development trend.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of graphene-ZnOw-Tin Composite Material, it is raw materials used including graphene, ZnOw and tin,Its weight ratio is 1 ~ 4：0.5~1.5：94.5~98.5.Wherein, the purity of the tin is 99.9%.
The preparation method of the graphene-ZnOw-Tin Composite Material comprises the following steps：
1）In a nitrogen environment, the glass putty by tin ultrasonic atomizatio into 200 mesh；
2）Gained glass putty, graphene, ZnOw are taken in proportion, is mixed in V-type and 2h is mixed in powder machine, and mixing rotating speed is10r/min；
3）By step 2）Gained mixed powder, which is put into VC high efficient mixers, mixes 10min, and mixing rotating speed is 100r/min；
4）By step 3）Gained mixed powder is placed in stirring ball mill simultaneously with high-carbon-chromium bearing steel matter abrading-ball, ball materialWeight ratio be 5：1, liquid nitrogen is then charged with to after being totally submerged abrading-ball, low temperature ball milling 2h；
5）Powder after ball milling is taken out, is placed in inert gas shielding case and is cooled to room temperature, is then charged into mould hotPressure sintering, the pressure of sintering are 50MPa, 600 DEG C of temperature, sintering time 2h；
6）Base substrate extrusion process after hot pressed sintering is molded, processing temperature is 350 DEG C, extrusion ratio 20：1, institute is madeState graphene-ZnOw-Tin Composite Material.
The remarkable advantage of the present invention is：
（1）Graphene has good mechanics, electrically and thermally property, can turn into the excellent enhancing phase of conventional solder.Theoretical calculation shows that graphene mechanical property is substantially better than other crystal whisker materials, has very high rigidity；And graphene is low closeDegree and good structural stability, make it have tempting application prospect in composite solder field.The present invention is appropriate by addingThe graphene of ratio, the contact resistance of contact can be reduced, improve the performances such as resistance fusion welding, make its enhancing as lead-free solderPhase, reach green, the reliable requirement of welding, instead of traditional tin-kupper solder, improve the performance of lead-free solder；
（2）ZnOw stable performance, mechanical performance are superior, can be used as supporting material, increase the machinery of composite solderIntensity and tensile modulus of elasticity.Importantly, ZnOw is mixed with graphene, both can be made effectively and uniformly to disperseIn tin, solves the problem that graphene can not be effectively and uniformly dispersed in tin.
（3）Graphene, ZnOw and tin are directly mixed powder by the present invention, using the process of powder metallurgy, notDestroy on the basis of graphene original structure, improve dispersiveness of the graphene in matrix solder, technique is simple, is adapted to big ruleMould produces.
Embodiment
In order that content of the present invention easily facilitates understanding, with reference to embodiment to of the present inventionTechnical scheme is described further, but the present invention is not limited only to this.
Embodiment 1
1）In a nitrogen environment, the glass putty by the tin ultrasonic atomizatio of purity 99.9% into 200 mesh；
2）By weight 95.5：4：0.5 weighs gained glass putty, graphene, ZnOw, mixes in powder machine and mixes in V-type2h, mixing rotating speed are 10r/min；
3）By step 2）Gained mixed powder, which is put into VC high efficient mixers, mixes 10min, and mixing rotating speed is 100r/min；
4）By step 3）Gained mixed powder is placed in stirring ball mill simultaneously with high-carbon-chromium bearing steel matter abrading-ball, ball materialWeight ratio be 5：1, liquid nitrogen is then charged with to after being totally submerged abrading-ball, low temperature ball milling 2h；
5）Powder after ball milling is taken out, is placed in inert gas shielding case and is cooled to room temperature, is then charged into mould hotPressure sintering, the pressure of sintering are 50MPa, 600 DEG C of temperature, sintering time 2h；
6）Base substrate extrusion process after hot pressed sintering is molded, processing temperature is 350 DEG C, extrusion ratio 20：1, institute is madeState graphene-ZnOw-Tin Composite Material.
Embodiment 2
1）In a nitrogen environment, the glass putty by the tin ultrasonic atomizatio of purity 99.9% into 200 mesh；
2）By weight 95：4：1 weighs gained glass putty, graphene, ZnOw, is mixed in V-type in powder machine and mixes 2h, mixedConjunction rotating speed is 10r/min；
3）By step 2）Gained mixed powder, which is put into VC high efficient mixers, mixes 10min, and mixing rotating speed is 100r/min；
4）By step 3）Gained mixed powder is placed in stirring ball mill simultaneously with high-carbon-chromium bearing steel matter abrading-ball, ball materialWeight ratio be 5：1, liquid nitrogen is then charged with to after being totally submerged abrading-ball, low temperature ball milling 2h；
5）Powder after ball milling is taken out, is placed in inert gas shielding case and is cooled to room temperature, is then charged into mould hotPressure sintering, the pressure of sintering are 50MPa, 600 DEG C of temperature, sintering time 2h；
6）Base substrate extrusion process after hot pressed sintering is molded, processing temperature is 350 DEG C, extrusion ratio 20：1, institute is madeState graphene-ZnOw-Tin Composite Material.
Embodiment 3
1）In a nitrogen environment, the glass putty by the tin ultrasonic atomizatio of purity 99.9% into 200 mesh；
2）By weight 94.5：4：1.5 weigh gained glass putty, graphene, ZnOw, mix in powder machine and mix in V-type2h, mixing rotating speed are 10r/min；
3）By step 2）Gained mixed powder, which is put into VC high efficient mixers, mixes 10min, and mixing rotating speed is 100r/min；
4）By step 3）Gained mixed powder is placed in stirring ball mill simultaneously with high-carbon-chromium bearing steel matter abrading-ball, ball materialWeight ratio be 5：1, liquid nitrogen is then charged with to after being totally submerged abrading-ball, low temperature ball milling 2h；
5）Powder after ball milling is taken out, is placed in inert gas shielding case and is cooled to room temperature, is then charged into mould hotPressure sintering, the pressure of sintering are 50MPa, 600 DEG C of temperature, sintering time 2h；
6）Base substrate extrusion process after hot pressed sintering is molded, processing temperature is 350 DEG C, extrusion ratio 20：1, institute is madeState graphene-ZnOw-Tin Composite Material.
Embodiment 4
1）In a nitrogen environment, the glass putty by the tin ultrasonic atomizatio of purity 99.9% into 200 mesh；
2）By weight 96：3.5：0.5 weighs gained glass putty, graphene, ZnOw, mixes in powder machine and mixes in V-type2h, mixing rotating speed are 10r/min；
3）By step 2）Gained mixed powder, which is put into VC high efficient mixers, mixes 10min, and mixing rotating speed is 100r/min；
4）By step 3）Gained mixed powder is placed in stirring ball mill simultaneously with high-carbon-chromium bearing steel matter abrading-ball, ball materialWeight ratio be 5：1, liquid nitrogen is then charged with to after being totally submerged abrading-ball, low temperature ball milling 2h；
5）Powder after ball milling is taken out, is placed in inert gas shielding case and is cooled to room temperature, is then charged into mould hotPressure sintering, the pressure of sintering are 50MPa, 600 DEG C of temperature, sintering time 2h；
6）Base substrate extrusion process after hot pressed sintering is molded, processing temperature is 350 DEG C, extrusion ratio 20：1, institute is madeState graphene-ZnOw-Tin Composite Material.
Embodiment 5
1）In a nitrogen environment, the glass putty by the tin ultrasonic atomizatio of purity 99.9% into 200 mesh；
2）By weight 95.5：3.5：1 weighs gained glass putty, graphene, ZnOw, mixes in powder machine and mixes in V-type2h, mixing rotating speed are 10r/min；
3）By step 2）Gained mixed powder, which is put into VC high efficient mixers, mixes 10min, and mixing rotating speed is 100r/min；
4）By step 3）Gained mixed powder is placed in stirring ball mill simultaneously with high-carbon-chromium bearing steel matter abrading-ball, ball materialWeight ratio be 5：1, liquid nitrogen is then charged with to after being totally submerged abrading-ball, low temperature ball milling 2h；
5）Powder after ball milling is taken out, is placed in inert gas shielding case and is cooled to room temperature, is then charged into mould hotPressure sintering, the pressure of sintering are 50MPa, 600 DEG C of temperature, sintering time 2h；
6）Base substrate extrusion process after hot pressed sintering is molded, processing temperature is 350 DEG C, extrusion ratio 20：1, institute is madeState graphene-ZnOw-Tin Composite Material.
Embodiment 6
1）In a nitrogen environment, the glass putty by the tin ultrasonic atomizatio of purity 99.9% into 200 mesh；
2）By weight 95：3.5：1.5 weigh gained glass putty, graphene, ZnOw, mix in powder machine and mix in V-type2h, mixing rotating speed are 10r/min；
3）By step 2）Gained mixed powder, which is put into VC high efficient mixers, mixes 10min, and mixing rotating speed is 100r/min；
4）By step 3）Gained mixed powder is placed in stirring ball mill simultaneously with high-carbon-chromium bearing steel matter abrading-ball, ball materialWeight ratio be 5：1, liquid nitrogen is then charged with to after being totally submerged abrading-ball, low temperature ball milling 2h；
5）Powder after ball milling is taken out, is placed in inert gas shielding case and is cooled to room temperature, is then charged into mould hotPressure sintering, the pressure of sintering are 50MPa, 600 DEG C of temperature, sintering time 2h；
6）Base substrate extrusion process after hot pressed sintering is molded, processing temperature is 350 DEG C, extrusion ratio 20：1, institute is madeState graphene-ZnOw-Tin Composite Material.
Embodiment 7
1）In a nitrogen environment, the glass putty by the tin ultrasonic atomizatio of purity 99.9% into 200 mesh；
2）By weight 96.5：3：0.5 weighs gained glass putty, graphene, ZnOw, mixes in powder machine and mixes in V-type2h, mixing rotating speed are 10r/min；
3）By step 2）Gained mixed powder, which is put into VC high efficient mixers, mixes 10min, and mixing rotating speed is 100r/min；
4）By step 3）Gained mixed powder is placed in stirring ball mill simultaneously with high-carbon-chromium bearing steel matter abrading-ball, ball materialWeight ratio be 5：1, liquid nitrogen is then charged with to after being totally submerged abrading-ball, low temperature ball milling 2h；
5）Powder after ball milling is taken out, is placed in inert gas shielding case and is cooled to room temperature, is then charged into mould hotPressure sintering, the pressure of sintering are 50MPa, 600 DEG C of temperature, sintering time 2h；
6）Base substrate extrusion process after hot pressed sintering is molded, processing temperature is 350 DEG C, extrusion ratio 20：1, institute is madeState graphene-ZnOw-Tin Composite Material.
Embodiment 8
1）In a nitrogen environment, the glass putty by the tin ultrasonic atomizatio of purity 99.9% into 200 mesh；
2）By weight 96：3：1 weighs gained glass putty, graphene, ZnOw, is mixed in V-type in powder machine and mixes 2h, mixedConjunction rotating speed is 10r/min；
3）By step 2）Gained mixed powder, which is put into VC high efficient mixers, mixes 10min, and mixing rotating speed is 100r/min；
4）By step 3）Gained mixed powder is placed in stirring ball mill simultaneously with high-carbon-chromium bearing steel matter abrading-ball, ball materialWeight ratio be 5：1, liquid nitrogen is then charged with to after being totally submerged abrading-ball, low temperature ball milling 2h；
5）Powder after ball milling is taken out, is placed in inert gas shielding case and is cooled to room temperature, is then charged into mould hotPressure sintering, the pressure of sintering are 50MPa, 600 DEG C of temperature, sintering time 2h；
6）Base substrate extrusion process after hot pressed sintering is molded, processing temperature is 350 DEG C, extrusion ratio 20：1, institute is madeState graphene-ZnOw-Tin Composite Material.
Embodiment 9
1）In a nitrogen environment, the glass putty by the tin ultrasonic atomizatio of purity 99.9% into 200 mesh；
2）By weight 95.5：3：1.5 weigh gained glass putty, graphene, ZnOw, mix in powder machine and mix in V-type2h, mixing rotating speed are 10r/min；
3）By step 2）Gained mixed powder, which is put into VC high efficient mixers, mixes 10min, and mixing rotating speed is 100r/min；
4）By step 3）Gained mixed powder is placed in stirring ball mill simultaneously with high-carbon-chromium bearing steel matter abrading-ball, ball materialWeight ratio be 5：1, liquid nitrogen is then charged with to after being totally submerged abrading-ball, low temperature ball milling 2h；
5）Powder after ball milling is taken out, is placed in inert gas shielding case and is cooled to room temperature, is then charged into mould hotPressure sintering, the pressure of sintering are 50MPa, 600 DEG C of temperature, sintering time 2h；
6）Base substrate extrusion process after hot pressed sintering is molded, processing temperature is 350 DEG C, extrusion ratio 20：1, institute is madeState graphene-ZnOw-Tin Composite Material.
Embodiment 10
1）In a nitrogen environment, the glass putty by the tin ultrasonic atomizatio of purity 99.9% into 200 mesh；
2）By weight 97：2.5：0.5 weighs gained glass putty, graphene, ZnOw, mixes in powder machine and mixes in V-type2h, mixing rotating speed are 10r/min；
3）By step 2）Gained mixed powder, which is put into VC high efficient mixers, mixes 10min, and mixing rotating speed is 100r/min；
4）By step 3）Gained mixed powder is placed in stirring ball mill simultaneously with high-carbon-chromium bearing steel matter abrading-ball, ball materialWeight ratio be 5：1, liquid nitrogen is then charged with to after being totally submerged abrading-ball, low temperature ball milling 2h；
5）Powder after ball milling is taken out, is placed in inert gas shielding case and is cooled to room temperature, is then charged into mould hotPressure sintering, the pressure of sintering are 50MPa, 600 DEG C of temperature, sintering time 2h；
6）Base substrate extrusion process after hot pressed sintering is molded, processing temperature is 350 DEG C, extrusion ratio 20：1, institute is madeState graphene-ZnOw-Tin Composite Material.
Embodiment 11
1）In a nitrogen environment, the glass putty by the tin ultrasonic atomizatio of purity 99.9% into 200 mesh；
2）By weight 96.5：2.5：1 weighs gained glass putty, graphene, ZnOw, mixes in powder machine and mixes in V-type2h, mixing rotating speed are 10r/min；
3）By step 2）Gained mixed powder, which is put into VC high efficient mixers, mixes 10min, and mixing rotating speed is 100r/min；
4）By step 3）Gained mixed powder is placed in stirring ball mill simultaneously with high-carbon-chromium bearing steel matter abrading-ball, ball materialWeight ratio be 5：1, liquid nitrogen is then charged with to after being totally submerged abrading-ball, low temperature ball milling 2h；
5）Powder after ball milling is taken out, is placed in inert gas shielding case and is cooled to room temperature, is then charged into mould hotPressure sintering, the pressure of sintering are 50MPa, 600 DEG C of temperature, sintering time 2h；
6）Base substrate extrusion process after hot pressed sintering is molded, processing temperature is 350 DEG C, extrusion ratio 20：1, institute is madeState graphene-ZnOw-Tin Composite Material.
Embodiment 12
1）In a nitrogen environment, the glass putty by the tin ultrasonic atomizatio of purity 99.9% into 200 mesh；
2）By weight 96：2.5：1.5 weigh gained glass putty, graphene, ZnOw, mix in powder machine and mix in V-type2h, mixing rotating speed are 10r/min；
3）By step 2）Gained mixed powder, which is put into VC high efficient mixers, mixes 10min, and mixing rotating speed is 100r/min；
4）By step 3）Gained mixed powder is placed in stirring ball mill simultaneously with high-carbon-chromium bearing steel matter abrading-ball, ball materialWeight ratio be 5：1, liquid nitrogen is then charged with to after being totally submerged abrading-ball, low temperature ball milling 2h；
5）Powder after ball milling is taken out, is placed in inert gas shielding case and is cooled to room temperature, is then charged into mould hotPressure sintering, the pressure of sintering are 50MPa, 600 DEG C of temperature, sintering time 2h；
6）Base substrate extrusion process after hot pressed sintering is molded, processing temperature is 350 DEG C, extrusion ratio 20：1, institute is madeState graphene-ZnOw-Tin Composite Material.
Embodiment 13
1）In a nitrogen environment, the glass putty by the tin ultrasonic atomizatio of purity 99.9% into 200 mesh；
2）By weight 97.5：2：0.5 weighs gained glass putty, graphene, ZnOw, mixes in powder machine and mixes in V-type2h, mixing rotating speed are 10r/min；
3）By step 2）Gained mixed powder, which is put into VC high efficient mixers, mixes 10min, and mixing rotating speed is 100r/min；
4）By step 3）Gained mixed powder is placed in stirring ball mill simultaneously with high-carbon-chromium bearing steel matter abrading-ball, ball materialWeight ratio be 5：1, liquid nitrogen is then charged with to after being totally submerged abrading-ball, low temperature ball milling 2h；
5）Powder after ball milling is taken out, is placed in inert gas shielding case and is cooled to room temperature, is then charged into mould hotPressure sintering, the pressure of sintering are 50MPa, 600 DEG C of temperature, sintering time 2h；
6）Base substrate extrusion process after hot pressed sintering is molded, processing temperature is 350 DEG C, extrusion ratio 20：1, institute is madeState graphene-ZnOw-Tin Composite Material.
Embodiment 14
1）In a nitrogen environment, the glass putty by the tin ultrasonic atomizatio of purity 99.9% into 200 mesh；
2）By weight 97：2：1 weighs gained glass putty, graphene, ZnOw, is mixed in V-type in powder machine and mixes 2h, mixedConjunction rotating speed is 10r/min；
3）By step 2）Gained mixed powder, which is put into VC high efficient mixers, mixes 10min, and mixing rotating speed is 100r/min；
4）By step 3）Gained mixed powder is placed in stirring ball mill simultaneously with high-carbon-chromium bearing steel matter abrading-ball, ball materialWeight ratio be 5：1, liquid nitrogen is then charged with to after being totally submerged abrading-ball, low temperature ball milling 2h；
5）Powder after ball milling is taken out, is placed in inert gas shielding case and is cooled to room temperature, is then charged into mould hotPressure sintering, the pressure of sintering are 50MPa, 600 DEG C of temperature, sintering time 2h；
6）Base substrate extrusion process after hot pressed sintering is molded, processing temperature is 350 DEG C, extrusion ratio 20：1, institute is madeState graphene-ZnOw-Tin Composite Material.
Embodiment 15
1）In a nitrogen environment, the glass putty by the tin ultrasonic atomizatio of purity 99.9% into 200 mesh；
2）By weight 98.5：1：0.5 weighs gained glass putty, graphene, ZnOw, mixes in powder machine and mixes in V-type2h, mixing rotating speed are 10r/min；
3）By step 2）Gained mixed powder, which is put into VC high efficient mixers, mixes 10min, and mixing rotating speed is 100r/min；
4）By step 3）Gained mixed powder is placed in stirring ball mill simultaneously with high-carbon-chromium bearing steel matter abrading-ball, ball materialWeight ratio be 5：1, liquid nitrogen is then charged with to after being totally submerged abrading-ball, low temperature ball milling 2h；
5）Powder after ball milling is taken out, is placed in inert gas shielding case and is cooled to room temperature, is then charged into mould hotPressure sintering, the pressure of sintering are 50MPa, 600 DEG C of temperature, sintering time 2h；
6）Base substrate extrusion process after hot pressed sintering is molded, processing temperature is 350 DEG C, extrusion ratio 20：1, institute is madeState graphene-ZnOw-Tin Composite Material.
After testing, the present invention gained graphene-ZnOw-Tin Composite Material tensile strength for 53.9MPa withOn, yield strength is more than 50.8MPa, and resistivity is less than 11.2 μ Ω cm-1。
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent withModification, it should all belong to the covering scope of the present invention.