CN104232961B - A kind of high-strength height hard Cu-Cr composite and its preparation method and application - Google Patents
A kind of high-strength height hard Cu-Cr composite and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to metal-base composites preparing technical field, disclose a kind of high-strength height hard Cu Cr composite and its preparation method and application.This preparation method comprises the following steps: Cu powder and Cr powder are as raw material, pre-ball-milling treatment is carried out in one of which raw material is placed in high-energy planetary formula ball mill, add another kind of raw material and grinding aid carries out mixing and ball milling process, in discharge plasma sintering stove, it is sintered densification after powder drying after ball milling, obtains high-strength height hard Cu Cr composite.The present invention is with relatively low enhancing phase addition (Cr content can as little as 8at.%), obtain the high-strength height hard Cu Cr composite of high starch yield, its excellent in mechanical performance, hardness reaches 250～330Hv, compression yield strength reaches 900～1000MPa, keeping good plasticity, compression ratio reaches 8～25%, is with a wide range of applications at construction applications simultaneously.
Description
Technical field
The invention belongs to metal-base composites preparing technical field, particularly to a kind of hard Cu-Cr of high-strength height
Composite and its preparation method and application.
Background technology
Metal-base composites, owing to comparing respective metal matrix material, has higher mechanical property and protects simultaneously
Hold certain plasticity, it is possible to be widely used in fretting wear as structural material, Plastic Forming is processed and other
Construction applications.In recent years, research worker prepares metal-base composites to improve metal material at interpolation hardening constituent
Material mechanical property aspect expands substantial amounts of research.Wherein, the enhancing added includes pure metals, carbon mutually
Compound, oxide, boride and the mixture of variety classes hardening constituent, the preparation method used has powder
End metallurgy, extrusion casint, rapid solidification, electric arc melting, liquid metal infiltration and Laser Processing etc..
In order to obtain higher mechanical property, when preparing metal-base composites, some are generally taked to arrange
Execute, such as, add the enhancing phase (being smaller in size than 100nm) of nanoscale, and add the increasing of high level
Strong phase (volume fraction is more than 10%) (ChaS.I., KimK.T., ArshadS.N., MoC.B., HongS.H.,
Advanced Materials,2005,17(11),1377-1381.)(DaoushW.M.,LimB.K.,MoC.B.,
NamD.H.,HongS.H.,Materials Science and Engineering:A,2009,513-514,
247-253.).Nanometer reinforcing phase has higher strengthening efficiency, but its preparation cost is high, is unfavorable for extensive
Commercial production.And add the enhancing of high level while improving production cost, also can deteriorate material
Plasticity and other physical properties.Thus select economical and practical raw material, add less amount of enhancing identical time
Simple efficient method is utilized to prepare good mechanical performance energy large-scale production and be effectively applied to actual life
Metal-base composites in work, is the problem that present invention seek to address that.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, the primary and foremost purpose of the present invention is to provide a kind of high
The preparation method of strong high hard Cu-Cr composite, this preparation method process is easily achieved, and is suitable to industrialization rule
Mould produces.
Another object of the present invention is the high-strength height hard Cu-Cr composite providing said method to prepare.Gained
Cu-Cr composite have excellence mechanical property, keep higher plasticity simultaneously.
Still a further object of the present invention is to provide above-mentioned high-strength height hard Cu-Cr composite in construction applications
Application.
The purpose of the present invention is realized by following proposal:
The preparation method of a kind of high-strength height hard Cu-Cr composite, comprises the following steps: Cu powder and Cr
Powder, as raw material, carries out pre-ball-milling treatment in one of which raw material is placed in high-energy planetary formula ball mill,
Add another kind of raw material and grinding aid carries out mixing and ball milling process, in electric discharge etc. after powder drying after ball milling
It is sintered densification in ion sintering furnace, obtains high-strength height hard Cu-Cr composite.
In described raw material, the content of Cr is the 8～10% of total amount atomic percentage, preferably 8at.%.
The present invention only need to add the Cr of as little as 8at.% as strengthening phase, the mechanical property that high-strength height is hard can be obtained
Composite that can be excellent, and the enhancing phase content owing to adding is low, can keep again good tough of composite
Property so as to get composite can be more widely applicable for various fields.
Described grinding aid is preferably dehydrated alcohol.Grinding aid used amount is raw material quality 70～
90%.
Preferably, when selecting Cu powder to carry out pre-ball-milling treatment, add grinding aid ball milling together.Preferably add
Enter Cu opaque amount 70～the grinding aid of 90%, more preferably 80wt%, and be dried after pre-ball milling and remove
Subsequent treatment is carried out again after removing grinding aid.
The time of described pre-ball-milling treatment is preferably 15～25h.
The time that described mixing and ball milling processes is preferably 90～110h.
Preferably, in above-mentioned preparation method, the diameter of abrading-ball used by ball milling is respectively 15,10 and 6mm, right
Answering mass ratio is 1:3:1, and ratio of grinding media to material is 10:1, and drum's speed of rotation is 226rpm.Ball grinder used and mill
Ball is preferably stainless steel.Pre-ball-milling treatment of the present invention is identical with the technological parameter that mixing and ball milling processes
As mentioned above.
Preferably, described sintering densification process process conditions be sintering pressure be 30～40MPa, burn
Junction temperature is 650～800 DEG C, and temperature retention time is 6～10min.
During the invention described above preparation method, described be dried the most preferably in vacuum drying oven 50～
20～30h it are dried at a temperature of 60 DEG C.
Preferably, the powder body after described pre-ball-milling treatment can first carry out above-mentioned the most again putting into ball mill after drying
In carry out subsequent treatment with unclassified stores.
In order to the present invention is better achieved, the purity of raw materials Cu powder and Cr powder all not less than 99%,
Powder size is no more than 75 μm.
In order to the present invention is better achieved, mechanical milling process is the most all carried out under inert gas shielding atmosphere, more
Preferably carry out under argon gas atmosphere is protected.
Specifically, the preparation method of the high-strength height hard Cu-Cr composite of the present invention, comprise the following steps:
Method one: weigh Cu powder (purity >=99%, powder size≤75 μm) and dehydrated alcohol grinding aid
Be placed in high-energy planetary formula ball mill, pre-ball-milling treatment 15～25h under argon gas atmosphere is protected, dried with
Cr powder (purity >=99%, powder size≤75 μm) and the mixing of dehydrated alcohol grinding aid, add high energy
In planetary ball mill, and under argon gas atmosphere is protected, mixing and ball milling processes 90～110h, obtains composite powder
Body, is sintered densification after drying in discharge plasma sintering stove, obtains the hard Cu-Cr of high-strength height
Composite.
Wherein, ball grinder and Material quality of grinding balls are rustless steel, and ball radius used is respectively 15,10 and 6
Mm, corresponding mass is than for 1:3:1, and ratio of grinding media to material is 10:1, and drum's speed of rotation is 226rpm, dehydrated alcohol
Quality is the 70～90% of powder quality, and Cr powder shared atomic percent in mixed powder is 8%, described
Being dried and be all dried 20～30h in vacuum drying oven at a temperature of 50～60 DEG C, sintering pressure is 30～40
MPa, sintering temperature is 650～800 DEG C, and temperature retention time is 6～10min.
Method two: weigh Cr powder (purity >=99%, powder size≤75 μm) and be placed in high-energy planetary formula ball
In grinding machine, pre-ball-milling treatment 15～25h under argon gas atmosphere is protected, then by Cr powder and the Cu of pre-ball milling
After powder (purity >=99%, powder size≤75 μm) and the mixing of dehydrated alcohol grinding aid, add high energy
In planetary ball mill, under argon gas atmosphere is protected, mixing and ball milling processes 90～110h, obtains composite granule,
In discharge plasma sintering stove, it is sintered densification after drying, obtains the hard Cu-Cr of high-strength height and be combined
Material.
Wherein, ball grinder and Material quality of grinding balls are rustless steel, and ball radius used is respectively 15,10 and 6
Mm, corresponding mass is than for 1:3:1, and ratio of grinding media to material is 10:1, and drum's speed of rotation is 226rpm, dehydrated alcohol
Quality is the 70～90% of powder quality, and Cr powder shared atomic percent in mixed powder is 8%, described
Being dried and be all dried 20～30h in vacuum drying oven at a temperature of 50～60 DEG C, sintering pressure is 30～40
MPa, sintering temperature is 650～800 DEG C, and temperature retention time is 6～10min.
The high-strength height hard Cu-Cr composite purity that the invention described above method prepares is high, mechanical property is excellent
Different, keep higher plasticity, it is possible to be widely used in fretting wear, Plastic Forming as structural material simultaneously
Processing and other construction applications.
The preparation method of the present invention can prepare and strengthen the composite that phase small and dispersed is distributed, purity is high,
And the utilization rate of raw materials of preparation method of the present invention is high, technique is simple, easy to operate, can heavy industrialization
Produce.
The mechanism of the present invention is:
The present invention combines pure powder body ball milling, mixed powder ball milling and discharge plasma sintering technique, this invention
Method uses cheap raw material, in conjunction with the pre-ball milling of pure powder body, mixed powder ball milling and electric discharge etc. from
Sub-sintering technology, with relatively low enhancing phase addition (Cr content can as little as 8at.%, 8.14vol.%), i.e.
Obtain excellent in mechanical performance, keep the high-strength height hard Cu-Cr composite of good plasticity simultaneously.
The present invention, relative to prior art, has such advantages as and beneficial effect:
1, the inventive method preparation process add a large amount of dehydrated alcohol as grinding aid, make mixed powder end
With wet grinding state, effectively slow down powder body reunion in mechanical milling process and bonding phenomenon, and to powder body pollution
Degree is relatively low, additionally, compare dry grinding and only add the grinding aid of less content, wet grinding also ensures that acquisition
The powder of high starch yield.
2, the present invention uses high-energy-milling to prepare powder body, and this technique passes through abrading-ball repeatedly touching powder body
Hit and abrasive action, make powder body experience repeatedly coldwelding and broken, thus reach refinement, uniformly mixing and
The effect of alloying.High-energy ball milling is utilized first one of which raw material powder body to be carried out pre-ball-milling treatment, abrading-ball
Collision effect continuous to powder body makes the defect concentrations such as the internal dislocation of powder body increase, and promotes the refinement of crystal grain,
It is obtained in that the hardening powder that crystallite dimension is tiny, in follow-up mixing and ball milling, is conducive to obtaining less crystalline substance
The powder of particle size, realizes strengthening phase small and dispersed simultaneously and is distributed in matrix, the more preferable mechanics of final acquisition
Performance.Using high-energy ball milling to prepare powder, it is not necessary to expensive equipment, technique is simple, easy and simple to handle, system
Without the generation of waste water, waste gas and waste residue during Bei, meet the requirement of environmental protection and energy saving.Additionally, due to use
The vacuum tank of good airproof performance, is passed through argon simultaneously and carries out atmosphere protection, it is thus possible to effectively prevent powder body from existing
Oxidative phenomena in mechanical milling process, so that it is guaranteed that powder process quality.
3, the present invention uses discharge plasma sintering technique that composite granule is sintered densification, should
Technology is the electric field clear powder resin particle surface oxide and the gas of absorption utilizing applying pulse heavy current to be formed
Body, thus purify and activated material, and utilize heavy current Short Time Heating powder body to be sintered at low pressures
Fine and close, it is possible to prepare high-quality sintered body with relatively low temperature and relatively short period of time.Utilize plasma discharging
Sintering process is sintered, and is characterized in simple to operate, sintering temperature is low, programming rate is fast, sintering time
Short, single-piece energy consumption is low, sintered body consistency is high and crystal grain is tiny, is a kind of near-net-shape and green preparation skill
Art.
4, the present invention uses relatively inexpensive raw material to prepare metal-base composites, its excellent in mechanical performance, firmly
Degree reaches 250～330Hv, and compression yield strength reaches 900～1000MPa, keeps good moulding simultaneously
Property, compression ratio reaches 8～25%, and prepared composite is with a wide range of applications at construction applications.
Accompanying drawing explanation
Fig. 1 is the microscopic structure obtaining Cu-Cr composite in the embodiment of the present invention 1.
Fig. 2 is to obtain the microscopic structure of Cu-Cr composite in the embodiment of the present invention 2 (containing partial enlargement
Figure).
Fig. 3 is the microscopic structure sintering Cu-Cr composite in comparative example.
Fig. 4 is sample X ray diffracting spectrum in the embodiment of the present invention 1.
Fig. 5 is sample X ray diffracting spectrum in the embodiment of the present invention 2.
Fig. 6 be the embodiment of the present invention 1～4 and comparative example in sinter the room temperature of Cu-Cr composite
Compression stress strain curve, wherein 1～4 corresponding embodiments 1～4,5 are comparative example.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but the embodiment party of the present invention
Formula is not limited to this.
Embodiment 1
Step one: pre-ball milling Cu powder
Precise Cu powder (purity >=99%, powder size≤75 μm) 500g, dehydrated alcohol 400g,
Being placed in 4L stainless steel jar mill, and add rustless steel abrading-ball, ratio of grinding media to material is 10:1, and ball radius is respectively
Being 15,10 and 6mm, corresponding mass ratio is for 1:3:1, after ball grinder is sealed, and first evacuation, then lead to
Argon, and continuously repeat operation twice, make mechanical milling process be in argon atmosphere.Arrange ball mill to turn
Speed is 226rpm.In order to prevent temperature in mechanical milling process too high, arrange after ball mill rotates forward 30min
Hesitation 30min, subsequently reverse direction rotates 30min, the most alternately, every ball milling 5h dead halt
Cooling, until ball milling 20h.After completing ball milling, shut down cooling ball grinding jar, and take out Cu powder, put
In vacuum drying oven, evacuation, arranging temperature is 50 DEG C, keeps 24h, it is thus achieved that dry pre-ball milling
Process Cu powder.
Step 2: mixing and ball milling Cu powder and Cr powder
Precise pre-ball milling Cu powder 466.8g, Cr powder (purity >=99%, powder size≤75 μm)
33.2g, dehydrated alcohol 400g, be placed in 4L stainless steel jar mill, and adds rustless steel abrading-ball, ball material
Than being 10:1, ball radius is respectively 15,10 and 6mm, and corresponding mass ratio is for 1:3:1, by ball grinder
After sealing, first evacuation, then lead to argon, and continuously repeat operation twice, make mechanical milling process be in argon and protect
Protect in atmosphere.Arranging drum's speed of rotation is 226rpm.In order to prevent temperature in mechanical milling process too high, arrange
Ball mill rotates forward hesitation 30min after 30min, and subsequently reverse direction rotates 30min, so replaces
Carrying out, every ball milling 5h dead halt cools down, until ball milling 100h.After completing ball milling, shut down cold
But ball grinder, and take out mixed powder, it is placed in vacuum drying oven, evacuation, arranging temperature is 50 DEG C,
Keep 24h, it is thus achieved that dry composite granule.
Step 3: sintered combined powder body
Precise composite granule 16.7g is placed in the graphite jig that internal diameter is 20.4mm, wherein powder body with
The thick graphite paper of one layer of 0.2mm is padded, in order to the demoulding between mould inner wall.Subsequently mould is put graphite
Insulation ring, is placed in discharge plasma sintering stove, starts sintering after evacuation 30min.3min is set
Interior temperature rises to 100 DEG C, heats up with the speed of 100 DEG C/min subsequently, rises to 700 DEG C, then 3min
Interior temperature rising to 750 DEG C, and be incubated 8min at such a temperature, omnidistance to keep pressure be 30MPa,
After insulation 8min, stove is cooled to room temperature, and takes out sample, obtains high-strength height hard Cu-Cr composite.
Embodiment 2
Step one: pre-ball milling Cr powder
Precise Cr powder (purity >=99%, powder size≤75 μm) 500g, is placed in 4L rustless steel
In ball grinder, and adding rustless steel abrading-ball, ratio of grinding media to material is 10:1, and ball radius is respectively 15,10 and 6mm,
Corresponding mass ratio is for 1:3:1, after ball grinder is sealed, and first evacuation, then lead to argon, and continuously repeat behaviour
Make twice, make mechanical milling process be in argon atmosphere.Arranging drum's speed of rotation is 226rpm.In order to
Prevent temperature in mechanical milling process too high, ball mill be set and rotate forward hesitation 30min after 30min,
Subsequently reverse direction rotates 30min, and the most alternately, every ball milling 5h dead halt cools down, until ball milling 20
Till h.After completing ball milling, shut down cooling ball grinding jar, it is thus achieved that pre-ball-milling treatment Cr powder.
Step 2: mixing and ball milling Cu powder and Cr powder
Precise Cu powder (purity >=99%, powder size≤75 μm) 466.8g, pre-ball milling Cr powder
33.2g, dehydrated alcohol 400g, be placed in 4L stainless steel jar mill, and adds rustless steel abrading-ball, ball material
Than being 10:1, ball radius is respectively 15,10 and 6mm, and corresponding mass ratio is for 1:3:1, by ball grinder
After sealing, first evacuation, then lead to argon, and continuously repeat operation twice, make mechanical milling process be in argon and protect
Protect in atmosphere.Arranging drum's speed of rotation is 226rpm.In order to prevent temperature in mechanical milling process too high, arrange
Ball mill rotates forward hesitation 30min after 30min, and subsequently reverse direction rotates 30min, so replaces
Carrying out, every ball milling 5h dead halt cools down, until ball milling 100h.After completing ball milling, shut down cold
But ball grinder, and take out mixed powder, it is placed in vacuum drying oven, evacuation, arranging temperature is 50 DEG C,
Keep 24h, it is thus achieved that dry composite granule.
Step 3: sintered combined powder body
Precise composite granule 16.7g is placed in the graphite jig that internal diameter is 20.4mm, wherein powder body with
The thick graphite paper of one layer of 0.2mm is padded, in order to the demoulding between mould inner wall.Subsequently mould is put graphite
Insulation ring, is placed in discharge plasma sintering stove, starts sintering after evacuation 30min.3min is set
Interior temperature rises to 100 DEG C, heats up with the speed of 100 DEG C/min subsequently, rises to 700 DEG C, then 3min
Interior temperature rising to 750 DEG C, and be incubated 8min at such a temperature, omnidistance to keep pressure be 30MPa,
After insulation 8min, stove is cooled to room temperature, and takes out sample, obtains the Cu-Cr composite that high-strength height is hard.
Embodiment 3
Step one: pre-ball milling Cr powder
Precise Cr powder (purity >=99%, powder size≤75 μm) 500g, is placed in 4L stainless
In steel ball grinding jar, and adding rustless steel abrading-ball, ratio of grinding media to material is 10:1, and ball radius is respectively 15,10
And 6mm, corresponding mass ratio is for 1:3:1, after ball grinder is sealed, and first evacuation, then lead to argon, and
Continuously repeat operation twice, make mechanical milling process be in argon atmosphere.Arranging drum's speed of rotation is 226
rpm.In order to prevent temperature in mechanical milling process too high, arrange after ball mill rotates forward 30min and temporarily stop
Machine 30min, subsequently reverse direction rotates 30min, and the most alternately, every ball milling 5h dead halt cools down,
Until ball milling 20h.After completing ball milling, shut down cooling ball grinding jar, it is thus achieved that pre-ball-milling treatment Cr powder.
Step 2: mixing and ball milling Cu powder and Cr powder
Precise Cu powder (purity >=99%, powder size≤75 μm) 466.8g, pre-ball milling Cr
Powder 33.2g, dehydrated alcohol 400g, be placed in 4L stainless steel jar mill, and adds rustless steel abrading-ball,
Ratio of grinding media to material is 10:1, and ball radius is respectively 15,10 and 6mm, and corresponding mass is than for 1:3:1, by ball
After grinding jar seals, first evacuation, then lead to argon, and continuously repeat operation twice, make mechanical milling process be in
In argon atmosphere.Arranging drum's speed of rotation is 226rpm.In order to prevent temperature in mechanical milling process too high,
Arranging ball mill and rotate forward hesitation 30min after 30min, subsequently reverse direction rotates 30min, so
Alternately, every ball milling 5h dead halt cools down, until ball milling 100h.After completing ball milling, stop
Machine cooling ball grinding jar, and take out mixed powder, it is placed in vacuum drying oven, evacuation, arranging temperature is
50 DEG C, keep 24h, it is thus achieved that dry composite granule.
Step 3: sintered combined powder body
Precise composite granule 16.7g is placed in the graphite jig that internal diameter is 20.4mm, wherein powder body
And pad the thick graphite paper of one layer of 0.2mm between mould inner wall, in order to the demoulding.Subsequently mould is put stone
Ink insulation ring, is placed in discharge plasma sintering stove, starts sintering after evacuation 30min.3min is set
Interior temperature rises to 100 DEG C, heats up with the speed of 100 DEG C/min subsequently, rises to 600 DEG C, then 3min
Interior temperature rising to 650 DEG C, and be incubated 8min at such a temperature, omnidistance to keep pressure be 30MPa,
After insulation 8min, stove is cooled to room temperature, and takes out sample, obtains high-strength height hard Cu-Cr composite.
Embodiment 4
Step one: pre-ball milling Cr powder
Precise Cr powder (purity >=99%, powder size≤75 μm) 500g, is placed in 4L stainless
In steel ball grinding jar, and adding rustless steel abrading-ball, ratio of grinding media to material is 10:1, and ball radius is respectively 15,10
And 6mm, corresponding mass ratio is for 1:3:1, after ball grinder is sealed, and first evacuation, then lead to argon, and
Continuously repeat operation twice, make mechanical milling process be in argon atmosphere.Arranging drum's speed of rotation is 226
rpm.In order to prevent temperature in mechanical milling process too high, arrange after ball mill rotates forward 30min and temporarily stop
Machine 30min, subsequently reverse direction rotates 30min, and the most alternately, every ball milling 5h dead halt cools down,
Until ball milling 20h.After completing ball milling, shut down cooling ball grinding jar, it is thus achieved that pre-ball-milling treatment Cr powder.
Step 2: mixing and ball milling Cu powder and Cr powder
Precise Cu powder (purity >=99%, powder size≤75 μm) 466.8g, pre-ball milling Cr
Powder 33.2g, dehydrated alcohol 400g, be placed in 4L stainless steel jar mill, and adds rustless steel abrading-ball,
Ratio of grinding media to material is 10:1, and ball radius is respectively 15,10 and 6mm, and corresponding mass is than for 1:3:1, by ball
After grinding jar seals, first evacuation, then lead to argon, and continuously repeat operation twice, make mechanical milling process be in
In argon atmosphere.Arranging drum's speed of rotation is 226rpm.In order to prevent temperature in mechanical milling process too high,
Arranging ball mill and rotate forward hesitation 30min after 30min, subsequently reverse direction rotates 30min, so
Alternately, every ball milling 5h dead halt cools down, until ball milling 100h.After completing ball milling, stop
Machine cooling ball grinding jar, and take out mixed powder, it is placed in vacuum drying oven, evacuation, arranging temperature is
50 DEG C, keep 24h, it is thus achieved that dry composite granule.
Step 3: sintered combined powder body
Precise composite granule 16.7g is placed in the graphite jig that internal diameter is 20.4mm, wherein powder body
And pad the thick graphite paper of one layer of 0.2mm between mould inner wall, in order to the demoulding.Subsequently mould is put stone
Ink insulation ring, is placed in discharge plasma sintering stove, starts sintering after evacuation 30min.3min is set
Interior temperature rises to 60 DEG C, heats up with the speed of 100 DEG C/min subsequently, rises to 760 DEG C, then 3min
Interior temperature rising to 800 DEG C, and be incubated 8min at such a temperature, omnidistance to keep pressure be 40MPa,
After insulation 8min, stove is cooled to room temperature, and takes out sample, obtains high hard high hard Cu-Cr composite.
Comparative example
Step one: mixing and ball milling Cu powder and Cr powder
Precise Cu powder (purity >=99%, powder size≤75 μm) 466.8g, Cr powder is (pure
Degree >=99%, powder size≤75 μm) 33.2g, dehydrated alcohol 400g, it is placed in 4L stainless steel ball
In grinding jar, and adding rustless steel abrading-ball, ratio of grinding media to material is 10:1, and ball radius is respectively 15,10 and 6mm,
Corresponding mass ratio is for 1:3:1, after ball grinder is sealed, and first evacuation, then lead to argon, and continuously repeat behaviour
Make twice, make mechanical milling process be in argon atmosphere.Arranging drum's speed of rotation is 226rpm.In order to
Prevent temperature in mechanical milling process too high, ball mill be set and rotate forward hesitation 30min after 30min,
Subsequently reverse direction rotates 30min, and the most alternately, every ball milling 5h dead halt cools down, until ball milling
Till 100h.After completing ball milling, shut down cooling ball grinding jar, and take out mixed powder, be placed in vacuum drying
In case, evacuation, arranging temperature is 50 DEG C, keeps 24h, it is thus achieved that dry composite granule.
Step 2: sintered combined powder body
Precise composite granule 16.7g is placed in the graphite jig that internal diameter is 20.4mm, wherein powder body
And pad the thick graphite paper of one layer of 0.2mm between mould inner wall, in order to the demoulding.Subsequently mould is put stone
Ink insulation ring, is placed in discharge plasma sintering stove, starts sintering after evacuation 30min.3min is set
Interior temperature rises to 100 DEG C, heats up with the speed of 100 DEG C/min subsequently, rises to 700 DEG C, then 3min
Interior temperature rising to 750 DEG C, and be incubated 8min at such a temperature, omnidistance to keep pressure be 30MPa.
After insulation 8min, stove is cooled to room temperature, and takes out sample, obtains Cu-Cr composite.
To embodiment 1～4 and the comparative example sample topography, phase and the mechanical property that prepare carry out
Detect sign as follows:
(1) sample surface morphology: use scanning electron microscope that sintered sample surface is carried out morphology observation and (see
Fig. 1～3), it can be seen that in the Cu-Cr composite that the present invention prepares, Cr strengthens phase Dispersed precipitate
In Cu matrix；And the Cr that the composite of comparative example exists large-size in Cu matrix strengthens
Phase, and this enhancing phase skewness.
(2) sample facies analysis: use X-ray diffractometer sample is carried out phase constituent sign (see Fig. 4,
5), not finding to exist other miscellaneous peaks, therefore prepared Cu-Cr composite purity is higher.
(3) mechanical property: using Vickers that sample is carried out hardness sign, test force is 2.94N,
Test result is the meansigma methods of 10 zones of different test values, and each test value deviation is all less than meansigma methods
5%；Use compression test that sintered sample carries out room temperature compression test, use wire cutting method to obtain
The sample of a size of Φ 3 × 4.5mm, compression strain speed is 1 × 10-3s-1, it is thus achieved that room temperature compression stress
Strain curve (sees Fig. 6).The mechanical property of measured sample is shown in Table 1.From table 1, system of the present invention
The standby high-strength height hard Cu-Cr composite obtained has the mechanical property of excellence, keeps good moulding simultaneously
Property；And under identical sintering condition, the composite that comparative example does not prepare through pre-ball milling powder body
The composite property of the mechanical property substantially relatively present invention is poor.
(4) flour extraction: ball milling dried powder are weighed (pre-ball milling Cr on electronic scale
Powder is dry grinding, it is not necessary to is dried, takes out and directly weigh after ball milling from ball grinder), powder after ball milling
The flour extraction that mass ratio is this powder of powder used in adding ball grinder before quality and ball milling to.For reality
Example 1, pre-ball milling Cu powder flour extraction is 96.1%, and after mixing and ball milling, flour extraction is 92.7%, for example
2～4, pre-grinding Cr powder flour extraction is 95.9%, and after mixing and ball milling, flour extraction is 93.1%, implements for contrast
Example, after mixing and ball milling, flour extraction is 92.1%.The dehydrated alcohol of visible employing high level carries out ball-milling treatment,
Be obtained in that higher flour extraction (ball milling pre-for Cr powder, owing to the hardness of Cr own is higher, compares Cu,
It is not susceptible to slimeball and wall sticking phenomenon, therefore carries out ball-milling treatment without adding grinding aid), it can be seen that,
Under this experiment condition, utilization rate of raw materials is higher.
The mechanical property parameters of table 1Cu-Cr composite
| Sample | Hardness (Hv) | Compression yield strength (MPa) | Compression ratio (%) |
| Example 1 | 303 | 934 | 21 |
| Example 2 | 327 | 970 | 13.7 |
| Example 3 | 257 | 926 | 8.7 |
| Example 4 | 303 | 947 | 11.8 |
| Comparative example | 246 | 757 | 34.1 |
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-mentioned reality
Execute the restriction of example, the change made under other any spirit without departing from the present invention and principle, modification,
Substitute, combine, simplify, all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (7)
1. the preparation method of a high-strength height hard Cu-Cr composite, it is characterised in that comprise the following steps:
Cu powder and Cr powder are as raw material, in described raw material, the content of Cr be total amount atomic percentage 8～
10%；Pre-ball-milling treatment, described pre-ball is carried out in one of which raw material is placed in high-energy planetary formula ball mill
The time that mill processes is 15～25h, adds another kind of raw material and grinding aid carries out mixing and ball milling process,
Amount is raw material quality the 70～90% of grinding aid used, the time that described mixing and ball milling processes be 90～
110h；In discharge plasma sintering stove, it is sintered densification after powder drying after ball milling, described
Sintering densification process process conditions for sintering pressure be 30～40MPa, sintering temperature be 650～
800 DEG C, temperature retention time is 6～10min, obtains high-strength height hard Cu-Cr composite.
The preparation method of high-strength height the most according to claim 1 hard Cu-Cr composite, its feature
Be: in described ball milling, the diameter of abrading-ball used is respectively 15,10 and 6mm, corresponding mass ratio for 1:3:1,
Ratio of grinding media to material is 10:1, and drum's speed of rotation is 226rpm.
The preparation method of high-strength height the most according to claim 1 hard Cu-Cr composite, its feature
It is: described grinding aid is dehydrated alcohol.
The preparation method of high-strength height the most according to claim 1 hard Cu-Cr composite, its feature
It is: described dry finger is dried 20～30h in vacuum drying oven at a temperature of 50～60 DEG C.
The preparation method of high-strength height the most according to claim 1 hard Cu-Cr composite, its feature
It is: when selecting Cu powder to carry out described pre-ball-milling treatment, adds grinding aid ball milling together.
6. a high-strength height hard Cu-Cr composite, it is characterised in that according to any one of Claims 1 to 5
The preparation method of described high-strength height hard Cu-Cr composite obtains.
High-strength height the most according to claim 6 hard Cu-Cr composite becomes in fretting wear, plasticity
Application in the construction applications of shape processing.
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| CN105945293A (en) * | 2016-04-26 | 2016-09-21 | 武汉大学 | High-hardness high-conductivity CuCr25 contact material and preparation method and application thereof |
| CN107345280A (en) * | 2016-05-06 | 2017-11-14 | 华为技术有限公司 | A kind of method for preparing Cu alloy material, Cu alloy material and equipment |
| CN110282717A (en) * | 2019-07-03 | 2019-09-27 | 中国海洋大学 | A kind of method of mechanical ball mill activation zeroth order aluminium removal water pollutant |
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| JPS616218A (en) * | 1984-02-23 | 1986-01-11 | ドドウコ・コマンデイ−トゲゼルシヤフト・ドクトル・オイゲン・デユルベヒテル | Powder metallurgical manufacture of electric contact piece of copper chromium solid solution for vacuum enclosed switch |
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