CN109280833A - A kind of preparation method of tungsten copper composite material - Google Patents
A kind of preparation method of tungsten copper composite material Download PDFInfo
- Publication number
- CN109280833A CN109280833A CN201811418537.4A CN201811418537A CN109280833A CN 109280833 A CN109280833 A CN 109280833A CN 201811418537 A CN201811418537 A CN 201811418537A CN 109280833 A CN109280833 A CN 109280833A
- Authority
- CN
- China
- Prior art keywords
- tungsten
- powder
- composite material
- copper
- copper composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
-
- B22F1/0007—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1017—Multiple heating or additional steps
- B22F3/1021—Removal of binder or filler
- B22F3/1025—Removal of binder or filler not by heating only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
- B22F3/225—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by injection molding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
- C22C2026/002—Carbon nanotubes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention belongs to the technical fields of composite material, disclose a kind of preparation method of tungsten-copper composite material.Method: tungsten powder, copper powder, carbon nanotube and binder are used into injection moulding, degreasing is sintered in atmosphere of hydrogen, obtains the tungsten-copper composite material of electric-conductivity heat-conductivity high；The dosage of the tungsten powder, copper powder and carbon nanotube meets the following conditions: by mass percentage, tungsten 74~84.8%, copper 15~25%, carbon nanotube 0.2~1%；The binder, including the following component being calculated in mass percent: paraffin 60~70%, high density polyethylene (HDPE) 10~16%, ethylene-vinyl acetate copolymer 15~20%, stearic acid 1~4%, antioxidant 0~0.5%.The hardness of gained tungsten-copper composite material is big, and conductivity and thermal conductivity are high.The present invention can inject complex-shaped sample in the way of injection moulding, be suitable for efficiently large-scale production field.
Description
Technical field
The invention belongs to technical field of composite preparation, and in particular to a kind of tungsten-copper composite material preparation method.
Background technique
Tungsten-copper composite material is the pseudo-alloy of the tungsten of low heat expansion and the copper composition of high conductivity high-termal conductivity, has height
The advantages that fusing point, high intensity, high rigidity, good resistance to arc erosion, is widely used in manufacturing electronic package material, heat sink material
The high-temperature components such as material, edm electrode and rocket nozzle larynx lining, tail vane.With the high speed development of electronics industry, height is led
The requirement of the tungsten-copper composite material of hot high conductivity is also higher and higher, dimensional accuracy higher direction hair more complicated towards shape
Exhibition.Since the physical difference of tungsten and copper is larger, (for existing tungsten-copper composite material since tungsten is immiscible with copper, sintering densification is tired
Difficulty, porosity is larger, and the thermal conductivity of material is low), therefore tungsten-copper alloy cannot be produced with fusion casting, generally use powder
The method production of metallurgy.But the tungsten-copper composite material of powder metallurgy process production at present mostly uses greatly compression molding, traditional mould
The shape of product and size of the method preparation of pressing formation are restricted.And it is generallyd use in powder metallurgic method and seeps copper to improve cause
Density, but needing to machine after seeping copper increases production cost and period to handle sample, if not using the side for seeping copper
Method, material are difficult to densify.
Carbon nanotube (CNTs) has high specific stiffness, specific strength, high conductance due to its own special tubular structure
The features such as rate, high heat conductance and high-wearing feature, can make composite material exhibits using carbon nanotube as the reinforcement of composite material
Good mechanical property and physical property out, but at present by the simple method such as mechanical mixture or solvent as mixing hand
Section can not make carbon nanotube realize uniform dispersion under enough contents.
Summary of the invention
The shortcomings that in order to overcome the prior art and shortcoming, the purpose of the present invention is to provide a kind of electric-conductivity heat-conductivity highs
The preparation method of property tungsten-copper composite material.The present invention can prepare complex-shaped, dimensional accuracy height using the method for injection moulding
Sample, while can big batch high efficiency production, production cost is effectively reduced.The present invention due to being mixed into a binder simultaneously
Carbon nanotube, improves the agglomeration of CNTs, disperses it in tungsten copper matrix, improves the electric conductivity of composite material
With thermal conductivity；Method of the invention, there has also been a degree of raisings for consistency and hardness for material.
The purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of tungsten-copper composite material includes the following steps: tungsten powder, copper powder, carbon nanotube and bonding
Agent uses injection moulding, and degreasing is sintered in atmosphere of hydrogen, obtains the tungsten-copper composite material of electric-conductivity heat-conductivity high；
The dosage of the tungsten powder, copper powder and carbon nanotube meets the following conditions: by mass percentage,
Tungsten (W) 74~84.8%
Copper (Cu) 15~25%
Carbon nanotube (CNTs) 0.2~1%
And inevitable trace impurity.
The binder, including the following component being calculated in mass percent:
The sum of said components mass percent is 100%.
The volume ratio of the tungsten powder, total dosage of copper powder and carbon nanotube and binder is 1:(0.92~1.22).It is described
Tungsten powder, copper powder, carbon nanotube and binder total amount be the useful load of 48~55vol%.
Tungsten powder purity >=99.95%, 2.8~3.2 μm of average particle size；Copper powder purity >=99.50%, average particle size
9.0~11.0 μm；Carbon nanotube is multi-walled carbon nanotube, is curled by Sheet Graphite, a diameter of 60~100nm, long
Degree is 5~15 μm.
The condition of the injection are as follows: the temperature of injection is 120~160 DEG C, and the pressure of injection is 80~120bar, and mould temperature is
30~50 DEG C.
The degreasing includes solvent degreasing and thermal debinding, refers to the green compact of injection moulding successively carrying out solvent degreasing and heat
Degreasing；The solvent of the solvent degreasing is normal heptane；The thermal debinding is to heat degreasing under the atmosphere of hydrogen；Solvent degreasing
Temperature is 30~60 DEG C, and the time of solvent degreasing is 2~10h；The temperature of thermal debinding is 600~900 DEG C, and the time of thermal debinding is
30~60min.
When carrying out thermal debinding, using step-up temperature degreasing；Specific steps are as follows: in a hydrogen atmosphere, with 5~10 DEG C/min
Be warming up to 250~300 DEG C, be then warming up to 330~400 DEG C with 1~3 DEG C/min, keep the temperature 20~35min, then with 1~3 DEG C/
Min is warming up to 450~500 DEG C, keeps the temperature 20~30min, is warming up to 550 DEG C with 1~3 DEG C/min, later with 10 DEG C/min heating
To 600~900 DEG C, 30~60min is kept the temperature.
The preparation method of the tungsten-copper composite material, specifically comprises the following steps:
(1) tungsten powder, copper powders are mixed, obtains mixed metal powder；
(2) carbon nanotube is mixed with binder, the binder after obtaining carbon nano-tube modification；
(3) by after carbon nano-tube modification binder and mixed metal powder be kneaded, extruding pelletization, injection moulding obtains
Obtain green compact；
(4) solvent degreasing and thermal debinding are successively used to green compact, obtains degreased green body；
(5) degreased green body is sintered, obtains highly conductive high-termal conductivity tungsten-copper composite material.
Mixing described in step (1) refers to that mixing powder machine using V-type mixes powder；
It is 20~40r/min that the V-type, which mixes powder machine revolving speed, and mixing time is 10~15h；Mixed powder cavity is stainless steel, and
Inert gas shielding is not necessarily to during mixed powder.
Carbon nanotube described in step (2) is carbon nanotube after purification, and the purifying refers to be handled using acid oxidase, is had
Body refer to by CNTs water, the concentrated sulfuric acid, concentrated nitric acid mixed solution in ultrasonic disperse, then be added chelating agent EDTA microwave add
Heat, cooled and filtered are washed to neutrality, and carbon nanotube after purification is dried to obtain.
The water, the concentrated sulfuric acid (concentration 98%), concentrated nitric acid (concentration 67%) volume ratio be 3:1:3, the ultrasonic disperse time
For 20~40min, low fiery heating time is 20~40min in microwave；The mass ratio of carbon nanotube and EDTA are 1:4.
The condition of mixing described in step (2) is that 0.8~1.5h is stirred at 130~150 DEG C.
The temperature of mixing described in step (3) is 130~150 DEG C, and the time of mixing is 1.0~2.0h.
The condition of injection described in step (3) are as follows: the temperature of injection is 120~160 DEG C, the pressure of injection is 80~
120bar, mould temperature are 30~50 DEG C.
The solvent of the solvent degreasing described in step (4) is normal heptane；The thermal debinding is added under the atmosphere of hydrogen
Thermal debinding.
The temperature of solvent degreasing is 30~60 DEG C, and time of solvent degreasing is 2~10h, thermal debinding 600~900 DEG C into
30~60min of row heat preservation.
When carrying out thermal debinding, using step-up temperature degreasing；Specific steps are as follows: in a hydrogen atmosphere, with 5~10 DEG C/min
Be warming up to 250~300 DEG C, be then warming up to 330~400 DEG C with 1~3 DEG C/min, keep the temperature 20~35min, then with 1~3 DEG C/
Min is warming up to 450~500 DEG C, keeps the temperature 20~30min, is warming up to 550 DEG C with 1~3 DEG C/min, later with 10 DEG C/min heating
To 600~900 DEG C, 30~60min is kept the temperature.
The temperature of sintering described in step (5) is 1050~1200 DEG C, and sintering time is 1~3h.
Composite material and preparation method of the invention have the following advantages that and the utility model has the advantages that
(1) binder provided by the invention is the Multi-component binder modified by CNTs after purification, not only can be de-
It is effectively removed when rouge, and the agglomeration of CNTs can be improved, disperse it uniformly in binder substrate, to improve
The intensity and conformality of green compact.
(2) tungsten-copper composite material provided by the invention is made of tungsten copper addition carbon nanotube, and CNTs can improve tungsten
The electric conductivity and thermal conductivity of carbon/carbon-copper composite material.
(3) after the sintering, the small stratiform of carbon nanotube therein is hollow for tungsten-copper composite material provided by the invention
Structure feature strengthens capillary force action, and the consistency of tungsten-copper composite material is made to have raising by a small margin, while improving hard
Degree and wearability.
(4) tungsten-copper composite material provided by the invention can disposably be configured to more complicated shape using injection moulding
Shape, high production efficiency and be not necessarily to following process, advance the development of tungsten-copper composite material precise treatment.
Detailed description of the invention
Fig. 1 is the XRD spectra of mixed tungsten copper powder in embodiment 1；
Fig. 2 is the TG-DSC curve graph of the binder in embodiment 3 after carbon nano-tube modification；
Fig. 3 is the SEM figure that green compact are injected in embodiment 5；
Fig. 4 is the SEM figure of tungsten-copper composite material after being sintered in embodiment 5.
Specific embodiment
Below with reference to examples and drawings, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.CNTs is carbon nanotube after purification in embodiment.
Embodiment 1
Step 1: W powder, Cu powder and CNTs are claimed according to the ratio of 79.5wt%W, 20wt%Cu and 0.5wt%CNTs
It takes, tungsten powder and copper powder is poured into V-type and mixed in powder machine, adjusting revolving speed is 30r/min, mixes 12h, is then sieved to obtain ingredient
Uniformly, without the tungsten copper powder obviously reunited；
Step 2: by binder with 66.9wt%PW, 20wt%EVA, 10wt%HDPE, 3wt%SA, 0.1wt%BHT
Ratio weighs；In addition, the volume ratio of the tungsten powder, total dosage of copper powder and carbon nanotube and binder is 1:1.2；By binder
It is added in blender with CNTs in 150 DEG C of stirring 1h, obtains modified binder；Then by modified binder and tungsten copper powder
It is added in rubber mixing machine, 140 DEG C of mixing 2h, using extruder extruding pelletization, injection machine is added in the feeding prepared
Middle injection, injection temperature are 160 DEG C, injection pressure 110bar, and mould temperature is 40 DEG C, obtain green compact；
Step 3: green compact being completely immersed in 40 DEG C of normal heptane and impregnate 6h, make PW and SA partial removal therein, then
Will green compact it is dry after be put into thermal debinding in tube furnace, in a hydrogen atmosphere, be warming up to 300 DEG C with 10 DEG C/min, then with 3 DEG C/
Min is warming up to 330 DEG C, keeps the temperature 30min, is then warming up to 450 DEG C with 3 DEG C/min, keeps the temperature 30min, is warming up to 1 DEG C/min
550 DEG C, 700 DEG C are warming up to 10 DEG C/min later, keeps the temperature 30min；
Step 4: using hydrogen furnace after thermal debinding, be sintered in a hydrogen atmosphere in 1200 DEG C, keep the temperature furnace cooling after 2h, obtain
To tungsten-copper composite material.
The hardness of tungsten-copper composite material manufactured in the present embodiment is 47.5HRC, and conductivity and thermal conductivity are respectively
26.2IACS% and 195W/mK.The XRD spectra of mixed tungsten copper powder is as shown in Figure 1 in the present embodiment.
Embodiment 2
Step 1: W powder, Cu powder and CNTs are claimed according to the ratio of 79.0wt%W, 20wt%Cu and 1.0wt%CNTs
It takes；Tungsten powder and copper powder are poured into V-type to mix in powder machine, adjusting revolving speed is 30r/min, mixes 12h, is then sieved to obtain ingredient
Uniformly, without the tungsten copper powder obviously reunited；
Step 2: by binder with 66.9wt%PW, 20wt%EVA, 10wt%HDPE, 3wt%SA, 0.1wt%BHT
Ratio weighs；In addition, the volume ratio of the tungsten powder, total dosage of copper powder and carbon nanotube and binder is 1:1.2；By binder
It is added in blender with CNTs in 150 DEG C of stirring 1h, then mixed binder and tungsten copper powder is added in rubber mixing machine,
The feeding prepared is added in injection machine and injects using extruder extruding pelletization by 140 DEG C of mixing 2h, injection temperature
It is 160 DEG C, injection pressure 110bar, mould temperature is 40 DEG C, obtains injection green compact；
Step 3: injection green compact being completely immersed in 6h in 40 DEG C of normal heptane, make PW and SA partial removal therein, then
Will green compact it is dry after be put into thermal debinding in tube furnace, in a hydrogen atmosphere, be warming up to 300 DEG C with 10 DEG C/min, then with 3 DEG C/
Min is warming up to 330 DEG C, keeps the temperature 30min, is then warming up to 450 DEG C with 3 DEG C/min, keeps the temperature 30min, is warming up to 1 DEG C/min
550 DEG C, 700 DEG C are warming up to 10 DEG C/min later, keeps the temperature 30min；
Step 4: using hydrogen furnace after thermal debinding, be sintered in a hydrogen atmosphere in 1200 DEG C, keep the temperature furnace cooling after 2h, obtain
To tungsten-copper composite material.
The hardness of tungsten-copper composite material manufactured in the present embodiment is 42.2HRC, and conductivity and thermal conductivity are respectively
27.7IACS% and 201W/mK.
Embodiment 3
Step 1: W powder, Cu powder and CNTs are claimed according to the ratio of 79.8wt%W, 20wt%Cu and 0.2wt%CNTs
It takes；Tungsten powder and copper powder are poured into V-type to mix in powder machine, adjusting revolving speed is 30r/min, mixes 12h, is then sieved to obtain ingredient
Uniformly, without the tungsten copper powder obviously reunited；
Step 2: by binder with 66.9wt%PW, 20wt%EVA, 10wt%HDPE, 3wt%SA, 0.1wt%BHT
Ratio weighs；In addition, the volume ratio of the tungsten powder, total dosage of copper powder and carbon nanotube and binder is 1:1.2；By binder
It is added in blender with CNTs in 150 DEG C of stirring 1h, then mixed binder and tungsten copper powder is added in rubber mixing machine,
The feeding prepared is added in injection machine and injects using extruder extruding pelletization by 140 DEG C of mixing 2h, injection temperature
It is 160 DEG C, injection pressure 110bar, mould temperature is 40 DEG C, obtains injection green compact；
Step 3: injection green compact are completely immersed in 6h in 40 DEG C of n-heptane solution, make PW and SA partial removal therein,
Then it will be put into thermal debinding in tube furnace after green compact drying, in a hydrogen atmosphere, 300 DEG C is warming up to 10 DEG C/min, then with 3
DEG C/min is warming up to 330 DEG C, 30min is kept the temperature, is then warming up to 450 DEG C with 3 DEG C/min, keeps the temperature 30min, with 1 DEG C/min heating
To 550 DEG C, 700 DEG C are warming up to 10 DEG C/min later, keeps the temperature 30min；
Step 4: using hydrogen furnace after thermal debinding, be sintered in a hydrogen atmosphere in 1200 DEG C, keep the temperature furnace cooling after 2h, obtain
To tungsten-copper composite material.
The hardness of tungsten-copper composite material manufactured in the present embodiment is 49.1HRC, and conductivity and thermal conductivity are respectively
23.2IACS% and 177W/mK.TG-DSC curve graph such as Fig. 2 institute of binder in the present embodiment after carbon nano-tube modification
Show.
Embodiment 4
Step 1: W powder, Cu powder and CNTs are claimed according to the ratio of 84.5wt%W, 15wt%Cu and 0.5wt%CNTs
It takes；Tungsten powder and copper powder are poured into V-type to mix in powder machine, adjusting revolving speed is 30r/min, mixes 12h, is then sieved to obtain ingredient
Uniformly, without the tungsten copper powder obviously reunited；
Step 2: by binder with 66.9wt%PW, 20wt%EVA, 10wt%HDPE, 3wt%SA, 0.1wt%BHT
Ratio weighs；In addition, the volume ratio of the tungsten powder, total dosage of copper powder and carbon nanotube and binder is 1:1.2；By binder
It is added in blender with CNTs in 150 DEG C of stirring 1h, then mixed binder and tungsten copper powder is added in rubber mixing machine,
The feeding prepared is added in injection machine and injects using extruder extruding pelletization by 140 DEG C of mixing 2h, injection temperature
It is 160 DEG C, injection pressure 110bar, mould temperature is 40 DEG C, obtains injection green compact；
Step 3: injection green compact are completely immersed in 6h in 40 DEG C of n-heptane solution, make PW and SA partial removal therein,
Then it will be put into thermal debinding in tube furnace after green compact drying, in a hydrogen atmosphere, 300 DEG C is warming up to 10 DEG C/min, then with 3
DEG C/min is warming up to 330 DEG C, 30min is kept the temperature, is then warming up to 450 DEG C with 3 DEG C/min, keeps the temperature 30min, with 1 DEG C/min heating
To 550 DEG C, 700 DEG C are warming up to 10 DEG C/min later, keeps the temperature 30min；
Step 4: using hydrogen furnace after thermal debinding, be sintered in a hydrogen atmosphere in 1200 DEG C, keep the temperature furnace cooling after 2h, i.e.,
Tungsten-copper composite material can be obtained.
The hardness of tungsten-copper composite material manufactured in the present embodiment is 48.4HRC, and conductivity and thermal conductivity are respectively
25.6IACS% and 189W/mK.
Embodiment 5
Step 1: W powder, Cu powder and CNTs are claimed according to the ratio of 79.2wt%W, 20wt%Cu and 0.8wt%CNTs
It takes；Tungsten powder and copper powder are poured into V-type to mix in powder machine, adjusting revolving speed is 30r/min, mixes 12h, is then sieved to obtain ingredient
Uniformly, without the tungsten copper powder obviously reunited；
Step 2: by binder with 66.9wt%PW, 20wt%EVA, 10wt%HDPE, 3wt%SA, 0.1wt%BHT
Ratio weighs；In addition, the volume ratio of the tungsten powder, total dosage of copper powder and carbon nanotube and binder is 1:1.2；By binder
It is added in blender with CNTs in 150 DEG C of stirring 1h, then mixed binder and tungsten copper powder is added in rubber mixing machine,
The feeding prepared is added in injection machine and injects using extruder extruding pelletization by 140 DEG C of mixing 2h, injection temperature
It is 160 DEG C, injection pressure 110bar, mould temperature is 40 DEG C, obtains injection green compact；
Step 3: injection green compact are completely immersed in 6h in 40 DEG C of n-heptane solution, make PW and SA partial removal therein,
Then it will be put into thermal debinding in tube furnace after green compact drying, in a hydrogen atmosphere, 300 DEG C is warming up to 10 DEG C/min, then with 3
DEG C/min is warming up to 330 DEG C, 30min is kept the temperature, is then warming up to 450 DEG C with 3 DEG C/min, keeps the temperature 30min, with 1 DEG C/min heating
To 550 DEG C, 700 DEG C are warming up to 10 DEG C/min later, keeps the temperature 30min；
Step 4: using hydrogen furnace after thermal debinding, be sintered in a hydrogen atmosphere in 1200 DEG C, keep the temperature furnace cooling after 2h, obtain
To tungsten-copper composite material.
The hardness of tungsten-copper composite material manufactured in the present embodiment is 43.5HRC, and conductivity and thermal conductivity are respectively
26.5IACS% and 191W/mK.The SEM figure of the injection green compact of the present embodiment is as shown in Figure 3；Sintered tungsten-copper composite material
SEM figure it is as shown in Figure 4.
1 die pressing of comparative example
Step 1: W powder, Cu powder and CNTs are claimed according to the ratio of 79.2wt%W, 20wt%Cu and 0.8wt%CNTs
It takes, pours into the mixed powder machine of V-type and mix, adjusting revolving speed is 30r/min, mixes 12h, is then sieved to obtain mixed-powder；
Step 2: mixed powder being poured into mold, compression moulding under press machine is placed in, pressure 200MPa is obtained
Green compact are suppressed to composite material；
Step 3: putting the green body into hydrogen furnace, 1200 DEG C of sintering are warming up to 10 DEG C/min in a hydrogen atmosphere, keep the temperature
Furnace cooling after 2h, can be obtained tungsten-copper composite material.
The hardness of tungsten-copper composite material manufactured in the present embodiment is 37.4HRC, and conductivity and thermal conductivity are respectively
16.3IACS% and 177W/mK.
Above-described embodiment is the preferred embodiment of the present invention, but the present invention and is not restricted by the embodiments, other
It is any done on the basis of the present invention unsubstantiality variation and replacement be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of tungsten-copper composite material, characterized by the following steps: by tungsten powder, copper powder, carbon nanotube
And binder uses injection moulding, degreasing is sintered in atmosphere of hydrogen, obtains the tungsten-copper composite material of electric-conductivity heat-conductivity high；
The dosage of the tungsten powder, copper powder and carbon nanotube meets the following conditions: by mass percentage,
Tungsten 74~84.8%
Copper 15~25%
Carbon nanotube 0.2~1%；
The binder, including the following component being calculated in mass percent:
2. the preparation method of tungsten-copper composite material according to claim 1, it is characterised in that: the tungsten powder, copper powder and carbon are received
Total dosage of mitron and the volume ratio of binder are 1:(0.92~1.22)；
The condition of the injection are as follows: the temperature of injection is 120~160 DEG C, and the pressure of injection is 80~120bar, mould temperature is 30~
50℃。
3. the preparation method of tungsten-copper composite material according to claim 1, it is characterised in that: the degreasing includes solvent degreasing
And thermal debinding, refer to and the green compact of injection moulding are successively subjected to solvent degreasing and thermal debinding；The solvent of the solvent degreasing is positive
Heptane；The thermal debinding is to heat degreasing under the atmosphere of hydrogen；
The temperature of solvent degreasing is 30~60 DEG C, and the time of solvent degreasing is 2~10h；The temperature of thermal debinding is 600~900 DEG C,
The time of thermal debinding is 30~60min.
4. the preparation method of tungsten-copper composite material according to claim 3, it is characterised in that: when carrying out thermal debinding, use
Step-up temperature degreasing；Specific steps are as follows: in a hydrogen atmosphere, 250~300 DEG C are warming up to 5~10 DEG C/min, then with 1~3
DEG C/min is warming up to 330~400 DEG C, 20~35min is kept the temperature, is then warming up to 450~500 DEG C with 1~3 DEG C/min, heat preservation 20
~30min is warming up to 550 DEG C with 1~3 DEG C/min, is warming up to 600~900 DEG C later with 10 DEG C/min, keeps the temperature 30~60min.
5. the preparation method of tungsten-copper composite material according to claim 1, it is characterised in that: specifically comprise the following steps:
(1) tungsten powder, copper powders are mixed, obtains mixed metal powder；
(2) carbon nanotube is mixed with binder, the binder after obtaining carbon nano-tube modification；
(3) by after carbon nano-tube modification binder and mixed metal powder be kneaded, extruding pelletization, injection moulding is given birth to
Base；
(4) solvent degreasing and thermal debinding are successively used to green compact, obtains degreased green body；
(5) degreased green body is sintered, obtains tungsten-copper composite material.
6. the preparation method of tungsten-copper composite material according to claim 5, it is characterised in that: sintering described in step (5)
Temperature is 1050~1200 DEG C, and sintering time is 1~3h, and the sintering carries out in atmosphere of hydrogen；
Carbon nanotube described in step (2) is carbon nanotube after purification, and the purifying refers to be handled using acid oxidase.
7. the preparation method of tungsten-copper composite material according to claim 6, it is characterised in that: the purifying is specifically referred to carbon
Nanotube water, the concentrated sulfuric acid, concentrated nitric acid mixed solution in ultrasonic disperse, chelating agent EDTA microwave heating is then added, it is cooling
Filtration washing is dried to obtain carbon nanotube after purification to neutrality afterwards.
8. the preparation method of tungsten-copper composite material according to claim 7, it is characterised in that: the water, the concentrated sulfuric acid, concentrated nitric acid
Volume ratio be 3:1:3, the ultrasonic disperse time is 20~40min, and low fiery heating time is 20~40min in microwave；Carbon nanometer
The mass ratio of pipe and EDTA are 1:4.
9. the preparation method of tungsten-copper composite material according to claim 5, it is characterised in that: mixing described in step (2)
Condition is that 0.8~1.5h is stirred at 130~150 DEG C；
The temperature of mixing described in step (3) is 130~150 DEG C, and the time of mixing is 1.0~2.0h；
Mixing described in step (1) refers to that mixing powder machine using V-type mixes powder；It is 20~40r/min that the V-type, which mixes powder machine revolving speed, is mixed
The powder time is 10~15h.
10. a kind of tungsten-copper composite material obtained by any one of claim 1~9 preparation method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811418537.4A CN109280833B (en) | 2018-11-26 | 2018-11-26 | Preparation method of tungsten-copper composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811418537.4A CN109280833B (en) | 2018-11-26 | 2018-11-26 | Preparation method of tungsten-copper composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109280833A true CN109280833A (en) | 2019-01-29 |
| CN109280833B CN109280833B (en) | 2020-08-18 |
Family
ID=65173108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811418537.4A Expired - Fee Related CN109280833B (en) | 2018-11-26 | 2018-11-26 | Preparation method of tungsten-copper composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109280833B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110964963A (en) * | 2019-12-16 | 2020-04-07 | 广东省材料与加工研究所 | Tungsten-copper alloy pipe and preparation method thereof |
| CN111992723A (en) * | 2020-09-10 | 2020-11-27 | 安徽德诠新材料科技有限公司 | Preparation method of high-thermal-conductivity metal radiating fin |
| CN112355304A (en) * | 2020-10-14 | 2021-02-12 | 陕西斯瑞新材料股份有限公司 | Processing technology for preparing CuW60-CuW90 metal profile part through injection molding |
| CN113070474A (en) * | 2021-03-29 | 2021-07-06 | 深圳市注成科技股份有限公司 | Preparation and forming method of nano tungsten-copper alloy radiating fin |
| CN113151723A (en) * | 2021-04-10 | 2021-07-23 | 广州市华司特合金制品有限公司 | Tungsten-copper alloy material applied to products in 5G field and preparation method thereof |
| CN113968748A (en) * | 2021-11-02 | 2022-01-25 | 株洲湘瓷科艺封接制造有限公司 | Ceramic sealing method based on heat sink material |
| CN116713465A (en) * | 2023-04-21 | 2023-09-08 | 合肥工业大学 | Special molding agent for tungsten-copper composite materials and its application, preparation method and application method |
| CN117358913A (en) * | 2022-06-30 | 2024-01-09 | 苏州铜宝锐新材料有限公司 | Metal powder compositions and their applications |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101589184A (en) * | 2006-11-16 | 2009-11-25 | 新泽西理工学院 | Rapid microwave process for purification of nanocarbon preparations |
| CN101667498A (en) * | 2009-10-13 | 2010-03-10 | 昆明理工大学 | Preparation method of W-Cu electrical contact |
| CN107130126A (en) * | 2017-04-28 | 2017-09-05 | 西安理工大学 | A kind of CNT strengthens the preparation method of tungsten-copper composite material |
-
2018
- 2018-11-26 CN CN201811418537.4A patent/CN109280833B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101589184A (en) * | 2006-11-16 | 2009-11-25 | 新泽西理工学院 | Rapid microwave process for purification of nanocarbon preparations |
| CN101667498A (en) * | 2009-10-13 | 2010-03-10 | 昆明理工大学 | Preparation method of W-Cu electrical contact |
| CN107130126A (en) * | 2017-04-28 | 2017-09-05 | 西安理工大学 | A kind of CNT strengthens the preparation method of tungsten-copper composite material |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110964963A (en) * | 2019-12-16 | 2020-04-07 | 广东省材料与加工研究所 | Tungsten-copper alloy pipe and preparation method thereof |
| CN111992723A (en) * | 2020-09-10 | 2020-11-27 | 安徽德诠新材料科技有限公司 | Preparation method of high-thermal-conductivity metal radiating fin |
| CN111992723B (en) * | 2020-09-10 | 2023-10-10 | 安徽德诠新材料科技有限公司 | A method for preparing a highly thermally conductive metal heat sink |
| CN112355304A (en) * | 2020-10-14 | 2021-02-12 | 陕西斯瑞新材料股份有限公司 | Processing technology for preparing CuW60-CuW90 metal profile part through injection molding |
| CN113070474A (en) * | 2021-03-29 | 2021-07-06 | 深圳市注成科技股份有限公司 | Preparation and forming method of nano tungsten-copper alloy radiating fin |
| CN113151723A (en) * | 2021-04-10 | 2021-07-23 | 广州市华司特合金制品有限公司 | Tungsten-copper alloy material applied to products in 5G field and preparation method thereof |
| CN113968748A (en) * | 2021-11-02 | 2022-01-25 | 株洲湘瓷科艺封接制造有限公司 | Ceramic sealing method based on heat sink material |
| CN117358913A (en) * | 2022-06-30 | 2024-01-09 | 苏州铜宝锐新材料有限公司 | Metal powder compositions and their applications |
| CN116713465A (en) * | 2023-04-21 | 2023-09-08 | 合肥工业大学 | Special molding agent for tungsten-copper composite materials and its application, preparation method and application method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109280833B (en) | 2020-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109280833A (en) | A kind of preparation method of tungsten copper composite material | |
| CN106521204B (en) | A kind of preparation method of growth in situ graphene reinforced metal-matrix composite | |
| CN104988438B (en) | A kind of high-strength and high-conductivity carbon nanotube reinforced copper-based composite material and preparation method thereof | |
| CN107855533B (en) | A kind of method that combination injection molding technology prepares diamond/copper composite material | |
| CN103981381B (en) | Method for preparing nano aluminum oxide dispersion enhanced copper-base composite material according to sol-gel method | |
| CN103194629B (en) | Method for preparing tungsten molybdenum copper composite material | |
| CN101520287A (en) | Method for preparing radiator element with complicated shape | |
| CN104630526A (en) | A method for preparing carbon nanotube-reinforced copper matrix composites by microwave sintering | |
| CN102242303A (en) | In-situ nano TiC ceramic particle reinforced copper based composite material and preparation method thereof | |
| CN105382262A (en) | Manufacturing method of heat conduction copper pipe with inner groove | |
| CN110078513A (en) | Squeeze out the method that 3D printing prepares silicon carbide complex devices | |
| CN105252008A (en) | A method for preparing porous heat-conducting copper tubes using powder extrusion molding technology | |
| CN1297363C (en) | Method for producing high-volume fractional silicon-carbide particle reinforced aluminium-base composite material member | |
| CN102400028B (en) | Preparation method of metal matrix composite | |
| CN115383114B (en) | Preparation method of high-porosity Al-rich phase porous Ni-Al intermetallic compound | |
| CN102808141A (en) | Method for preparing carbon nanotubes reinforced Al-Mg alloy composite materials | |
| CN106623915A (en) | Activated sintering method of aluminum or aluminum alloy | |
| CN111996405A (en) | Method for preparing high-strength and high-conductivity copper alloy through metal injection molding | |
| CN105543526A (en) | Method for preparing high-compactness titanium or titanium alloy by using gel casting formation | |
| CN100457332C (en) | Injection molding process of AZ91 Mg alloy | |
| CN116926402B (en) | Flow pressure swing injection preparation method of aluminum electrolysis metal ceramic anode | |
| JP2007224359A (en) | Metal matrix composite powder, metal matrix composite and method for producing the same | |
| CN109182832A (en) | A kind of formula and a kind of powder injection molding process of carbon nanotube reinforced copper-base alloy | |
| CN116890113A (en) | A rheological pressure injection preparation method for large-scale powder metallurgy components | |
| CN104711496B (en) | Carbon Nanotubes/Magnesiuum Matrix Composite and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200818 |