CN107227416B - A kind of M6C-type alloy carbide Fe3W3The preparation method of C - Google Patents
A kind of M6C-type alloy carbide Fe3W3The preparation method of C Download PDFInfo
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Abstract
The present invention discloses a kind of M6C-type alloy carbide Fe3W3The preparation method of C, belongs to new material technology field.The method of the invention Fe powder, WC powder are raw material, and raw material is utilized discharge plasma sintering after mixing（SPS）+ vacuum interface remelting process is sintered, then by obtained sintered specimen it is broken after carry out material phase analysis, other impurities object is mutually removed by acid wash, the processing such as acid, drying are carried out to powder, then again to powder sintered, finally obtains double carbide Fe3W3C-material.Ternary phase carbide Fe made from the method for the invention3W3C contains less impurity, and secondly preparation temperature is relatively low, obtained even tissue good mechanical properties, enhances steel for tungsten carbide（Iron）The research significance of based composites micro interface is great.
Description
Technical field
The present invention relates to a kind of M6C-type alloy carbide Fe3W3The preparation method of C, belongs to new material technology field.
Background technology
In material processing field, Fe3W3C ternary phase alloy carbides are found to be widely present in the obtained carbon of various methods
Among changing tungsten enhancing rich chromium cast iron, steel, the composite material interfaces such as potassium steel, and richness WC phases wear-resistant coating and ferrous alloy or
In the interface of hard alloy, Fe3W3C mutually has outstanding mechanical property compared to common hard.Fe3W3C enhances as tungsten carbide
The interface transition layer of iron base composite material can make that metallurgical binding occurs between matrix and reinforced phase, increase boundary strength.Such as profit
WC is made with high-energy ball milling+vacuum-sinteringp/ iron base composite material, experimental result are found：It is found by XRD and EDAX results
Interface is mainly mutually Fe3W3C；Interface mutually surrounding around tungsten carbide particle tightly, and the mode of metallurgical binding is presented；Again
Interfacial reaction Gibbs free energy is calculated according to thermodynamics of reactions formula, show that the generating mode of interface phase mainly hasWith,
And withBased on this reaction.And at present to Fe3W3C is single-phase
The research of performance and preparation lacks very much.Therefore research Fe3W3The property of C ternary phase alloy carbides, for above-mentioned composite material
The further investigation of interfacial structure and advanced optimizing is of great significance, and also can be used as the reason for developing relevant advanced composite material (ACM)
By support.
Chinese invention patent CN103819192A describes a kind of Fe, W, C ternary phase alloy carbide Fe3W3The system of C
Method is made, this method is that tri- kinds of powder of Fe, W, C are positioned over ball milling in ball mill, is then sintered, borrows by vacuum carbon tube furnace
Vacuum sealing technology is helped, anti-oxidant, the mold-filling capacity of molten metal are improved, to which Fe directly be made3W3C ternary phase alloy carbides
Object.The shortcomings that this method is three kinds of powder cannot to be made adequately to be uniformly mixed by ball milling, and powder easy tos produce agglomeration,
That is three kinds of powder cannot come into full contact with participation reaction, the Fe obtained to sintering3W3C purity is not high, and there are a large amount of Fe, W, C are mono-
Matter, and then it is not accurate enough to measure its performance；In addition, the proportioning and sintering temperature of three kinds of powder can all influence reaction product, generate
Fe6W6C、Fe3Other objects such as C are mutually difficult to control, and it is also not accurate enough finally to measure its performance.
Invention content
The present invention in view of the deficiency of the prior art, provides a kind of response characteristic that can greatly improve solid
And the uniformity of mixing powder, and significantly improve the ternary phase alloy carbide Fe of purity3W3The preparation method of C, the three of preparation
First phase alloy carbide Fe3W3It is single that there is C preferable dense structure's property, object to compare, and can be very good to test out its simultaneously comprehensive
The mechanical property of conjunction, the research for enhancing tungsten carbide steel-based composite material micro interface are most important.
The invention is realized by the following technical scheme：
A kind of M6C-type alloy carbide Fe3W3The preparation method of C, includes the following steps：
（1）Stoichiometrically weigh reduction Fe powder, WC powder（Fe/WC=(2~5):(1~3)）, first by WC particle and addition
Agent is uniformly mixed, and reduction Fe powder is then added and is mixed again, it is to carry out in the ball mill under protection of argon gas to mix powder twice
Ball milling；
（2）After ball-milled powder is cooled to room temperature, powder after mixing is placed in graphite jig, be then placed in electric discharge etc. from
Prefabricated blank is obtained after being sintered in sub- agglomerating plant；Sample after sintering is placed in progress vacuum interface weight in vacuum tube furnace
It is molten, promote it fully to react and obtains interface phase Fe3W3C；
（3）By step（2）Obtained sintered specimen is broken for powder, is mutually removed other impurities object by acid wash, right
Powder carries out acid, drying, compression process obtain ternary phase carbide Fe then again to pressed powder sintered3W3C materials
Material.
Reduced iron powder purity >=99.9% of the present invention, granularity are less than or equal to 150 μm；WC powder purity >=99.9%, grain
Degree is less than or equal to 150 μm.
Additive of the present invention is sodium metasilicate, CMC-Na or starch, and the quality of additive is WC particle quality
0.5%-3%。
Step of the present invention（1）The condition of middle ball milling is：Ball-milling Time is 0.5 ~ 50h, during abrading-ball using diameter 7 ~
The ratio of number of the steel ball of 12mm, big abrading-ball and small abrading-ball is 1:（5~6）, ratio of grinding media to material is（3~7）:1, drum's speed of rotation is：300
~500r/min。
Step of the present invention（2）In be put into the condition of discharge plasma sintering and be：Temperature is warming up to 350 DEG C -500 DEG C and is protected
Warm 30min-60min, then proceedes to be warming up to melting point metal 60% ~ 80% 5 ~ 10min of temperature, and impressed pressure is 8 kN
~9.4 kN。
The condition of vacuum interface remelting is：Temperature is risen to 500 DEG C from room temperature by the heating rate of 4 ~ 5 DEG C/min, then
1100 DEG C are warming up to by the heating rate of 5 ~ 10 DEG C/min, is warming up to by the heating rate of 3 ~ 5 DEG C/min and is less than more than 1100 DEG C
Equal to 1400 DEG C and keep the temperature 0.5 ~ 1h.
During acidification of the present invention：Pickle be 15%-20% sulfuric acid, nitrate acid and hydrofluoric acid mixed acid solution or
LK-45 steel material chemical pickling corrosion-retarding fog inhibitors, the mass percent concentration of nitric acid is 30%-35%, hydrogen in mixed acid solution
The mass percent concentration of fluoric acid is 20%-25%.
Step of the present invention（3）In again to powder sintered, sintering condition is：In electric discharge etc. from sintering furnace, by 4 ~ 5 DEG C/min
Heating rate temperature is risen to 500 DEG C from room temperature, then 1000 DEG C are warming up to by the heating rate of 5 ~ 10 DEG C/min, by 3 ~ 5
DEG C/heating rate of min is warming up to and is less than or equal to 1300 DEG C more than 1000 DEG C and keeps the temperature 0.5 ~ 1h, pressure be set as 10kN ~
20kN。
The Fe manufactured in the present embodiment after the remelting of interface3W3The mean breadth at the interfaces C is 50 ~ 60 μm, and normal interface
Only 15 μm, the measurement of volume fraction is carried out to the metallurgical structure of material using Image Pro softwares, measures ternary phase carbon
Compound Fe3W3The volume fraction of C is 95%-98%；Measuring its mechanical performance index is：Fe3W3C hardness is 11 ~ 12.76GPa, poplar
Family name 410 ~ 424.2GPa of modulus, Vickers hardness are 10 ~ 11.9GPa.
Beneficial effects of the present invention：
（1）WC particle is mixed with additive first, is stirred evenly, so that particle in the composite material that subsequent forming obtains
It is evenly distributed, and effectively reduces the agglomeration of WC particle, system is made fully to participate in reaction.
（2）Due to Fe3W3The mechanical property of C ternary phase alloy carbides lacks always in-depth study so far, and reason is just
It is：Since the uniform mixing of tri- kinds of raw material powders of Fe/W/C is very because of difficulty, and reaction product is sufficiently complex, therefore Fe3W3C is three
It is difficult directly to synthesize under kind raw material proportioning；The invention firstly uses discharge plasma sinterings can make powder Fast Sintering and cause
Density ratio utilizes the height of hydraulic press compacting, and the interface area reacted under vacuum or inert gas shielding using tube furnace
Remelting, promote Fe powder and WC powder fully react and reaction product stablize, more Fe can be obtained3W3C object boundaries.
（3）By making pickle by oneself, by Fe obtained3W3Impurity in C removes, and effectively increases Fe3W3C-material it is pure
Degree, it is more accurate to the test of mechanical property behind, and used corrosion inhibiter is environment friendly and pollution-free.
Description of the drawings
Fig. 1 is embodiment 1 by tungsten carbide granule reinforced steel matrix composite material SEM shape appearance figures made from the remelting of interface.
Fig. 2 is M made from embodiment 16C-type alloy carbide Fe3W3The XRD diffracting spectrums of C.
Specific implementation mode
Invention is further described in detail by the following examples, but protection scope of the present invention be not limited to it is described
Content.
Embodiment 1
A kind of M described in the present embodiment6C-type alloy carbide Fe3W3The preparation method of C, specifically includes following steps：
（1）Reproducibility iron powder is weighed respectively（Purity is 99.9%, and granularity is less than 150 μm）With WC powder（Purity is 99.9%, grain
Degree is less than 150 μm）, the stoichiometric ratio of two kinds of powder is Fe/WC=2:1.
（2）Mixed powder：Using XQM-4L planetary ball mills to WC particle and sodium metasilicate（Quality is the 2% of WC particle quality）
It is uniformly mixed, it is 0.5h to mix the powder duration, then Fe powder and the mixed-powder of WC powder and sodium metasilicate are carried out ball and mix powder, and mixed powder is held
The continuous time is 20h, and the other conditions of mechanical milling process are twice：The mass ratio of ball material is 3:1, large and small abrading-ball uses diameter
The ratio of number of the respectively steel ball of 12mm, 7mm, big abrading-ball and small abrading-ball is 1:5, drum's speed of rotation 300r/min ensure
Two kinds of powder are adequately uniformly mixed.
（3）Sintering：Powder is placed in graphite jig, discharge plasma sintering is set（SPS）Sintering parameter be：It will be warm
Degree makes sodium metasilicate start to volatilize when being increased to 350 DEG C from room temperature, continue slowly to be warming up to 500 DEG C and keep the temperature 30min can be by silicic acid
Sodium all excludes, and temperature is then warming up to 920 DEG C, 5 min of soaking time, and impressed pressure is 8 kN, in entire sintering process
Vacuumize protection.Then sintered sample is placed in vacuum tube furnace, is passed through argon gas protection：By the heating speed of 5 DEG C/min
Temperature is risen to 500 DEG C by rate from room temperature, is then warming up to 1100 DEG C by the heating rate of 6 DEG C/min, by the heating speed of 4 DEG C/min
Rate is warming up to 1340 DEG C and keeps the temperature 0.5h, and object phase Fe is contained after taking-up3W3The composite material of C.
（5）Acidification：Obtained sintered specimen is broken for powder with high energy ball mill, material phase analysis is done to powder, according to
Material phase analysis is mutually removed other impurities object by acid wash as a result, the sulfuric acid solution that compound concentration is 15%, is carried out to powder
Acid, drying, compression process are gone, then it is sintered with plasma discharging method again, sintering condition is：By the heating speed of 4 DEG C/min
Temperature is risen to 500 DEG C by rate from room temperature, is then warming up to 1000 DEG C by the heating rate of 5 DEG C/min, by the heating speed of 3 DEG C/min
Rate is warming up to 1100 DEG C, and keeps the temperature 0.5h at this temperature, and pressure is set as 10kN, that is, finally obtains ternary phase alloy carbide
Fe3W3C-material.
Ternary phase alloy carbide Fe manufactured in the present embodiment3W3The XRD diffracting spectrums of C-material are as shown in Fig. 2, SEM shapes
Looks figure is as shown in Figure 1, the Fe after the remelting of interface as seen from Figure 13W3The mean breadth at the interfaces C is 50 μm, and normal boundary
There was only 15 μm in face；The ternary phase alloy carbide Fe that the present embodiment is prepared as seen from Figure 23W3C purity is very high, measures
Ternary phase carbide Fe3W3The volume fraction of C is 95%；Its hardness 11GPa, Young's modulus 410GPa are measured using nano impress,
It is 10 GPa to measure its micro-vickers hardness.
Embodiment 2
A kind of M described in the present embodiment6C-type alloy carbide Fe3W3The preparation method of C, specifically includes following steps：
（1）Reproducibility iron powder is weighed respectively（Purity is 99.9%, and granularity is less than 150 μm）With WC powder（Purity is 99.9%, grain
Degree is less than 150 μm）, the stoichiometric ratio of two kinds of powder is Fe/WC=3:1.
（2）Mixed powder：Using XQM-4L planetary ball mills to WC particle and CMC-Na（Quality is WC particle quality
2.5%）It is uniformly mixed, it is 1h to mix the powder duration, then Fe powder and the mixed-powder of WC powder and CMC-Na are carried out ball milling and mix powder,
The mixed powder duration is 30h, and the other conditions of mechanical milling process are twice：The mass ratio of ball material is 5:1, large and small abrading-ball is adopted
It is respectively the steel ball of 11mm, 8mm with diameter, the ratio of number of big abrading-ball and small abrading-ball is 1:5.5, drum's speed of rotation 400r/
Min ensures that two kinds of powder are adequately uniformly mixed；
（3）Sintering：Powder is placed in graphite jig, discharge plasma sintering is set（SPS）Sintering parameter be：It will be warm
When degree is increased to 400 DEG C from room temperature, 15%CMC-Na is made to start to volatilize, continues slowly to be warming up to 450 DEG C and keep the temperature 40min and can incite somebody to action
CMC-Na is all excluded, and temperature is then warming up to 1100 DEG C, soaking time 8min, impressed pressure is 8.5 kN, entire to be sintered
Protection is vacuumized in the process.Then sintered sample is placed in vacuum tube furnace, argon gas protection is passed through, by 4 DEG C/min's
Temperature is risen to 500 DEG C by heating rate from room temperature, is then warming up to 1100 DEG C by the heating rate of 7 DEG C/min, by 4 DEG C/min's
Heating rate is warming up to 1360 DEG C and keeps the temperature 0.6h, and object phase Fe is contained after taking-up3W3The composite material of C.
（5）Acidification：Obtained sintered specimen is broken for powder with high energy ball mill, material phase analysis is done to powder, according to
Material phase analysis as a result, prepare mass percent concentration be 30% nitric acid -20% hydrofluoric acid mixed acid solution, pass through pickling
Method mutually removes other impurities object, carries out acid, drying, compression process to powder, is then burnt again to it with plasma discharging method
Knot, sintering condition are：Temperature is risen to 500 DEG C from room temperature by the heating rate of 5 DEG C/min, then presses the heating speed of 6 DEG C/min
Rate is warming up to 1050 DEG C, is warming up to 1200 DEG C by the heating rate of 4 DEG C/min, and keep the temperature 1h at this temperature, pressure is set as
15kN finally obtains ternary phase alloy carbide Fe3W3C-material.
The Fe manufactured in the present embodiment after the remelting of interface3W3The mean breadth at the interfaces C is 55 μm, and normal interface is only
There are 15 μm, measures ternary phase carbide Fe3W3The volume fraction of C be 96%, using nano impress measure its hardness be 11.5GPa,
Young's modulus 415GPa, it is 10 .5GPa to measure its micro-vickers hardness.
Embodiment 3
A kind of M described in the present embodiment6C-type alloy carbide Fe3W3The preparation method of C, specifically includes following steps：
（1）Reproducibility iron powder is weighed respectively（Purity is 99.9%, and granularity is less than 150 μm）With WC powder（Purity is 99.9%, grain
Degree is less than 150 μm）, the stoichiometric ratio of two kinds of powder is Fe/WC=1:1.
（2）Mixed powder：Using XQM-4L planetary ball mills to WC particle and starch（Quality is the 3% of WC particle quality）It is mixed
It closes uniformly, it is 1.5h to mix the powder duration, then Fe powder and the mixed-powder of WC powder and starch are carried out ball milling and mix powder, and mixed powder continues
Time is 50h, and the other conditions of mechanical milling process are twice：The mass ratio of ball material is 7:1, large and small abrading-ball is using diameter point
Not Wei 10mm, 9mm steel ball, the ratio of number of big abrading-ball and small abrading-ball is 1:6, drum's speed of rotation 500r/min ensure two
Kind powder is adequately uniformly mixed.
（3）Sintering：Powder is placed in graphite jig, discharge plasma sintering is set（SPS）Sintering parameter be：It will be warm
When degree is increased to 450 DEG C from room temperature, starch is made to start to volatilize, continues slowly to be warming up to 500 DEG C and keep the temperature 60min and 70% can be formed sediment
Powder all excludes, and temperature is then warming up to 1200 DEG C, 10 min of soaking time, and impressed pressure is 9.4 kN, entire sintered
Protection is vacuumized in journey.Then sintered sample is placed in vacuum tube furnace, argon gas protection is passed through, by the liter of 5 DEG C/min
Temperature is risen to 500 DEG C by warm rate from room temperature, is then warming up to 1100 DEG C by the heating rate of 10 DEG C/min, by 5 DEG C/min's
Heating rate is warming up to 1400 DEG C and keeps the temperature 0.51h, and object phase Fe is contained after taking-up3W3The composite material of C.
（5）Acidification：Obtained sintered specimen is broken for powder with high energy ball mill, material phase analysis is done to powder, according to
Other impurities object is divided by as a result, preparation LK-45 steel material chemical pickling corrosion-retarding fog inhibitors by acid wash by material phase analysis
It goes, acid, drying, compression process is carried out to powder, then it is sintered with plasma discharging method again, sintering condition is：By 5
DEG C/temperature rises to 500 DEG C by the heating rate of min from room temperature, 1000 DEG C then are warming up to by the heating rate of 10 DEG C/min, is pressed
The heating rate of 5 DEG C/min is warming up to 1300 DEG C, and keeps the temperature 1.5h at this temperature, and pressure is set as 20kN, that is, finally obtains
Ternary phase alloy carbide Fe3W3C-material.
The Fe manufactured in the present embodiment after the remelting of interface3W3The mean breadth at the interfaces C is 60 μm, and normal interface is only
There are 15 μm, measures ternary phase carbide Fe3W3The volume fraction of C is 98%, and measuring its hardness using nano impress is
12.76GPa, Young's modulus 424.2GPa, it is 11.9GPa to measure its micro-vickers hardness.
Claims (5)
1. a kind of M6C-type alloy carbide Fe3W3The preparation method of C, which is characterized in that include the following steps：
（1）Reduction Fe powder, WC powder are stoichiometrically weighed, is first uniformly mixed WC particle with additive, reduction is then added
Fe powder is mixed again, and it is to carry out ball milling in the ball mill under protection of argon gas to mix powder twice；
（2）After ball-milled powder is cooled to room temperature, powder after mixing is placed in graphite jig, is then placed in plasma discharging burning
Prefabricated blank is obtained after being sintered in knot equipment；Sample after sintering is placed in progress vacuum interface remelting in vacuum tube furnace, is promoted
So that it is fully reacted and obtains interface phase Fe3W3C；
（3）By step（2）Obtained sintered specimen is broken for powder, is mutually removed other impurities object by acid wash, to powder
Carry out acid, drying, compression process obtain ternary phase carbide Fe then again to powder sintered3W3C-material；
The additive is sodium metasilicate, CMC-Na or starch, and the quality of additive is the 0.5%-3% of WC particle quality；
Step（2）In be put into the condition of discharge plasma sintering and be：Temperature is warming up to 350 DEG C -500 DEG C and keeps the temperature 30min-
60min, then proceedes to be warming up to melting point metal 60% ~ 80% 5 ~ 10min of temperature, and impressed pressure is 8 kN ~ 9.4kN；
The condition of vacuum interface remelting is：Temperature is risen to 500 DEG C from room temperature by the heating rate of 4 ~ 5 DEG C/min, then press 5 ~
The heating rate of 10 DEG C/min is warming up to 1100 DEG C, is warming up to by the heating rate of 3 ~ 5 DEG C/min and is less than or equal to more than 1100 DEG C
1400 DEG C and 0.5 ~ 1h of heat preservation.
2. M according to claim 16C-type alloy carbide Fe3W3The preparation method of C, it is characterised in that：The reduction
Iron powder purity >=99.9%, granularity are less than or equal to 150 μm；WC powder purity >=99.9%, granularity are less than or equal to 150 μm.
3. M according to claim 16C-type alloy carbide Fe3W3The preparation method of C, it is characterised in that：Step（1）In
The condition of ball milling is：Ball-milling Time is 0.5 ~ 50h, and the steel ball of 7 ~ 12mm of diameter, big abrading-ball and small abrading-ball are used during abrading-ball
Ratio of number be 1:（5~6）, ratio of grinding media to material is（3~7）:1, drum's speed of rotation is：300~500r/min.
4. M according to claim 16C-type alloy carbide Fe3W3The preparation method of C, it is characterised in that：Acidification mistake
Cheng Zhong：Pickle is that 15%-20% sulfuric acid, the mixed acid solution of nitrate acid and hydrofluoric acid or LK-45 steel material chemical picklings are slow
Fog inhibitor is lost, the mass percent concentration of nitric acid is 30%-35% in mixed acid solution, and the mass percent concentration of hydrofluoric acid is
20%-25%。
5. M according to claim 16C-type alloy carbide Fe3W3The preparation method of C, it is characterised in that：Step（3）In
Again to powder sintered, sintering condition is：In electric discharge etc. from sintering furnace, by the heating rate of 4 ~ 5 DEG C/min by temperature from room temperature
500 DEG C are risen to, is then warming up to 1000 DEG C by the heating rate of 5 ~ 10 DEG C/min, is warming up to by the heating rate of 3 ~ 5 DEG C/min
It is less than or equal to 1300 DEG C more than 1000 DEG C and keeps the temperature 0.5 ~ 1h, pressure is set as 10kN ~ 20kN.
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| CN103695680A (en) * | 2013-12-11 | 2014-04-02 | 西安交通大学 | Fe, W and C ternary-phase carbide Fe6W6C and preparation method for same |
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| CN103695680A (en) * | 2013-12-11 | 2014-04-02 | 西安交通大学 | Fe, W and C ternary-phase carbide Fe6W6C and preparation method for same |
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