阅读说明：本技术 一种改性富勒烯增强硬质合金的制备方法 (A kind of preparation method of modified fullerenes enhancing hard alloy ) 是由 张建国 原一高 张金江 阮钧 于 2019-09-16 设计创作，主要内容包括：本发明公开了一种改性富勒烯增强硬质合金的制备方法,其特征在于。在富勒烯表面进行化学镀镍对富勒烯进行改性；将改性富勒烯、碳化钨粉、钴粉配制的粉料与无水乙醇进行球磨；用无水乙醇冲洗磨球表面的粘附物,将所得的浆料真空干燥；将干燥后的粉末,置于成型模具中,加压成型；将预成型后的样品坯料,在真空烧结炉中烧结成型。本发明利用富勒烯优异的机械物理性能,提升改善硬质合金基体材料硬度与韧性难以同时兼顾的问题。同时,采用表面改性的方法,消除富勒烯本身高温抗氧化性能力低和与基体材料的结合力不强的问题。(The invention discloses a kind of preparation methods of modified fullerenes enhancing hard alloy, it is characterised in that.Chemical nickel plating is carried out in fullerene surface to be modified fullerene；Powder and dehydrated alcohol that modified fullerenes, tungsten carbide powder, cobalt powder are prepared are subjected to ball milling；The bur that abrading-ball surface is rinsed with dehydrated alcohol, resulting slurry is dried in vacuo；It is placed in the powder after drying in molding die, is press-formed；Specimen stock after will be preforming, the sinter molding in vacuum sintering furnace.The present invention mechanical and physical performance excellent using fullerene, being promoted, which improves carbide matrix material hardness, is difficult to the problem of combining with toughness.Meanwhile the method modified using surface, eliminate the not strong problem of the low and binding force with basis material of fullerene high-temperature oxidation resistance power itself.)

1. a kind of preparation method of modified fullerenes enhancing hard alloy, it is characterised in that.The following steps are included:

Step 1): chemical nickel plating is carried out in fullerene surface, fullerene is modified；

Step 2): powder and dehydrated alcohol that modified fullerenes, tungsten carbide powder, cobalt powder are prepared are subjected to ball milling；

Step 3): the bur on abrading-ball surface is rinsed with dehydrated alcohol, resulting slurry is dried in vacuo；

Step 4): the powder after drying is placed in molding die, extrusion forming；

Step 5): the specimen stock after will be preforming, the sinter molding in vacuum sintering furnace.

2. the preparation method of modified fullerenes enhancing hard alloy as described in claim 1, which is characterized in that the step 1) Comprising the following specific steps

Step 1.1): the oxidation processes of fullerene: fullerene powder is placed in strong acid solution, while heating water bath, is carried out Solution is washed with deionized to pH=7 in magnetic agitation after stirring；

Step 1.2): the sensitized treatment of fullerene: the fullerene after oxidation is placed in stannous chloride solution, heating water bath it is same When, magnetic agitation is carried out, solution is washed with deionized after stirring to pH=7；

Step 1.3): the activation processing of fullerene: the fullerene after sensitization is placed in palladium chloride solution, heating water bath it is same When, magnetic agitation is carried out, it is dry after solution to pH=7 is washed with deionized after stirring；

Step 1.4): the chemical nickel plating of fullerene: nickel sulfate solution is poured into enveloping agent solution, the fowler after being activated is added Alkene powder；PH value is adjusted to 10~11, is added reducing agent, heating water bath while carries out magnetic agitation, filtering, dry.

3. the preparation method of modified fullerenes enhancing hard alloy as claimed in claim 2, which is characterized in that the step 1.1) strong acid solution in is the mixed solution that the concentrated sulfuric acid and concentrated nitric acid are mixed with the ratio of volume ratio 1:1；Fullerene powder with The ratio of strong acid solution is 1g:(1000~1500) mL；The temperature of heating water bath is 70~80 DEG C.

4. the preparation method of modified fullerenes enhancing hard alloy as claimed in claim 2, which is characterized in that the step 1.2) stannous chloride solution in be mass concentration 36%~38%, stannous chloride, deionized water with (1~2) mL:(1.5~ 2) solution of the ratio mixing of g:50mL；The temperature of heating water bath is 40~50 DEG C.

5. the preparation method of modified fullerenes enhancing hard alloy as claimed in claim 2, which is characterized in that the step 1.3) palladium chloride solution in be palladium chloride, mass concentration 36%~38%, deionized water is with 1g:(40~50) mL:(1500 ~2000) solution of the ratio mixing of mL；The temperature of heating water bath is 40~50 DEG C.

6. the preparation method of modified fullerenes enhancing hard alloy as claimed in claim 2, which is characterized in that the step 1.4) concentration of the nickel sulfate solution in is 3~4g/L；Enveloping agent solution is sodium citrate, sodium carbonate, deionized water with 1.5g: 1g:(100~150) mL ratio mixing solution；The pH of enveloping agent solution is adjusted using the NaOH solution of mass concentration 30% Value；Reducing agent is ortho phosphorous acid sodium solution, and concentration is 0.02~0.06g/mL；The temperature of heating water bath is 70~80 DEG C.

7. the preparation method of modified fullerenes enhancing hard alloy as claimed in claim 2, which is characterized in that step 1.1), Step 1.2), step 1.3), the time of magnetic agitation is 1~2 hour in step 1.4).

8. the preparation method of modified fullerenes enhancing hard alloy as described in claim 1, which is characterized in that the step 2) In powder include modified fullerenes 0.1%~0.5% by percentage to the quality, tungsten carbide powder 92%~94% and surplus Cobalt powder；Dehydrated alcohol, powder, abrading-ball ratio be (1~1.5) mL:1g:(8~10) g, the revolving speed of ball milling is 400~ 500rpm, Ball-milling Time are 4~6h.

Technical field

The present invention relates to a kind of preparation methods of Cemented Carbide Properties enhancing, and in particular to a kind of to be increased using modified fullerenes The preparation method of strong hard alloy, belongs to metal forming preparation technical field.

Background technique

Hard alloy is important one of industrial materials, referred to as " industrial tooth ", in tool, mold, aerospace Equal fields are widely used.The common preparation method of cemented carbide material is sintered by carbide hard phase and metallic binding phase Ceramic-metal composite has the superior physical properties such as high rigidity, high-wearing feature, high red hardness.But hard alloy is simultaneously Belong to fragile material, in application process due to the contradictory problems of intensity and toughness, causes hard alloy that fracture, crackle etc. occurs Problem drastically influences the service performance of hard alloy.

Fullerene C₆₀With special ball shape, C₆₀Structure make it have special stability.In molecular level On, single C₆₀Molecule is very rigid, and special shape and the extremely strong ability for resisting ambient pressure make in as Material reinforcement body With great application potential.However due to C₆₀With small-size effect, easily reunite, it is difficult to give full play to its superiority Energy.In addition, the high-temperature oxidation and basis material binding force of fullerene are poor, in fullerene surface metal lining.To obtain Stronger inoxidizability and binding force with basis material.The obdurability of present invention application fullerene is many with its nano-meter characteristic Excellent properties adulterate the preparation process of hard alloy by modified fullerenes, promote the toughness of cemented carbide material, enhance hard The comprehensive performance of alloy.

Through the patent retrieval discovery to the prior art, Chinese Patent Application No. 200910091185.0 describes " a kind of low The industrialized process for preparing of the high performance WC-Co hard alloy of cost ", with WO_2.9、Co₃O₄It is that raw material prepares hard conjunction with carbon black Gold, the method not can guarantee the uniformity of carburizing reagent, be easy to cause institutional framework defect.Chinese Patent Application No.: 201210262916.5 describe " a kind of preparation method of graphene brazing ", with W nanopowder, nano Co and/or Nano Ni Powder and Cr₂O₃Powder mixing forms product through subsequent serial process.Equally exist distribution of carbides not Uniform problem, the obdurability of remaining graphene promote effect and are difficult to reach expected.

Summary of the invention

The technical problems to be solved by the present invention are: distribution of carbides is uneven in existing hard alloy, remaining graphene The problem of influencing the obdurability of hard alloy.

To solve the above-mentioned problems, the present invention provides a kind of modified fullerenes enhancing hard alloy preparation method, It is characterized in that.The following steps are included:

Step 1): chemical nickel plating is carried out in fullerene surface, fullerene is modified；

Step 2): powder and dehydrated alcohol that modified fullerenes, tungsten carbide powder, cobalt powder are prepared are subjected to ball milling；

Step 3): the bur on abrading-ball surface is rinsed with dehydrated alcohol, resulting slurry is dried in vacuo；

Step 4): the powder after drying is placed in molding die, extrusion forming；

Step 5): the specimen stock after will be preforming, the sinter molding in vacuum sintering furnace.

Preferably, the step 1) comprising the following specific steps

Step 1.1): the oxidation processes of fullerene: fullerene powder is placed in strong acid solution, while heating water bath, Magnetic agitation is carried out, solution is washed with deionized after stirring to pH=7；

Step 1.2): the sensitized treatment of fullerene: the fullerene after oxidation is placed in stannous chloride solution, heating water bath While, magnetic agitation is carried out, solution is washed with deionized after stirring to pH=7；

Step 1.3): the activation processing of fullerene: the fullerene after sensitization is placed in palladium chloride solution, heating water bath Meanwhile magnetic agitation is carried out, it is dry after solution to pH=7 is washed with deionized after stirring；

Step 1.4): the chemical nickel plating of fullerene: nickel sulfate solution is poured into enveloping agent solution, is added after being activated Fullerene powder；PH value is adjusted to 10~11, is added reducing agent, heating water bath while carries out magnetic agitation, and filtering, drying are It can.

It is highly preferred that the strong acid solution in the step 1.1) is that the concentrated sulfuric acid and concentrated nitric acid are mixed with the ratio of volume ratio 1:1 The mixed solution of conjunction；Fullerene powder and the ratio of strong acid solution are 1g:(1000~1500) mL；The temperature of heating water bath is 70 ~80 DEG C.

It is highly preferred that the stannous chloride solution in the step 1.2) is the hydrochloric acid of mass concentration 36%~38%, chlorination Stannous, deionized water are with (1~2) mL:(1.5~2) solution of the ratio of g:50mL mixing；The temperature of heating water bath is 40~50 ℃。

It is highly preferred that palladium chloride solution in the step 1.3) be palladium chloride, mass concentration 36%~38% hydrochloric acid, Deionized water is with 1g:(40~50) mL:(1500~2000) mL ratio mixing solution；The temperature of heating water bath is 40~50 ℃。

It is highly preferred that the concentration of the nickel sulfate solution in the step 1.4) is 3~4g/L；Enveloping agent solution is citric acid Sodium, sodium carbonate, deionized water are with 1.5g:1g:(100~150) solution of the ratio of mL mixing；Using mass concentration 30% The pH value of NaOH solution adjusting enveloping agent solution；Reducing agent is ortho phosphorous acid sodium solution, and concentration is 0.02~0.06g/mL；Water The temperature of bath heating is 70~80 DEG C.

It is highly preferred that the time of magnetic agitation is 1~2 in step 1.1), step 1.2), step 1.3), step 1.4) Hour.

Preferably, the powder in the step 2) includes modified fullerenes 0.1%~0.5% by percentage to the quality, The cobalt powder of tungsten carbide powder 92%~94% and surplus；Dehydrated alcohol, powder, abrading-ball ratio be (1~1.5) mL:1g:(8~ 10) g, the revolving speed of ball milling are 400~500rpm, and Ball-milling Time is 4~6h.

The present invention utilizes the unique caged carbon molecules structure of Fullerene C20 and its high intensity and toughness, with carbonization Tungsten and the common mixed sintering of cobalt, realize the reinforcing effect of hard alloy.In order to reduce fullerene since small-size effect causes to roll into a ball Poly- phenomenon, while its high-temperature oxidation resistance and the binding force with basis material are promoted, place is modified to fullerene surface first Reason, in fullerene C₆₀Surface carries out chemical nickel plating processing.

The present invention mechanical and physical performance excellent using fullerene, being promoted improves carbide matrix material hardness and toughness It is difficult to the problem of combining.Meanwhile the method modified using surface, eliminate fullerene high-temperature oxidation resistance power itself it is low and The not strong problem with the binding force of basis material.

Compared with prior art, the beneficial effects of the present invention are:

(1) the modified fullerene in surface has coated metallic particles due to surface, considerably reduces agglomeration, promotes it High-temperature oxidation resistance and binding force intensity with other materials；

(2) be mixed with hard alloy using modified fullerenes and tungsten carbide powder, cobalt powder, the hardness that enhancing hard closes with it is tough Property, promote its resistance to crack extension ability.

Detailed description of the invention

Fig. 1 is the surface topography SEM figure of modified fullerenes in embodiment 1；

Fig. 2 is common WC-wt.8%Co hard alloy substrate crack propagation pattern SEM figure；

Fig. 3 is hard alloy substrate crack propagation pattern SEM figure prepared by embodiment 1.

Specific embodiment

In order to make the present invention more obvious and understandable, hereby with preferred embodiment, and attached drawing is cooperated to be described in detail below.