CN103864144A - Method of directly growing carbon nanofibers on zirconium oxide substrate - Google Patents

Abstract

The invention discloses a method of directly growing carbon nanofibers on a zirconium oxide substrate. The method comprises the following steps: ultrasonically cleaning ZrO2 powder in deionized water or ethanol at room temperature, and filtering, evaporating a solvent and grinding to obtain clean ZrO2 powder; and paving the clean ZrO2 powder in a quartz ark, and placing the quartz ark in a tubular furnace and introducing a methane or acetylene carbon source for cleavage reaction to obtain carbon nanofibers growing on the ZrO2 powder substrate. The method disclosed by the invention has the advantages that by adopting industrially used ZrO2 as the substrate, the carbon nanofibers with good quality and high purity directly grow on the substrate under the condition of not adding any metal catalysts by way of controlling the pre-treatment mode and the growing process of the substrate. The method is simple in preparation process and equipment and easy to realize and popularize.

Description

The method of direct growth carbon nano fiber on zirconium white matrix

Technical field

The present invention relates to the method for direct growth carbon nano fiber on a kind of zirconium white matrix, belong to carbon and zirconic technical field of composite materials.

Background technology

Zirconium white (ZrO ₂) pottery has very excellent physics, chemical property, in industrial production, is widely applied, decline and the remarkable defect such as thermal shock resistance is lower as middle mechanical behavior under high temperature but there is also, and Composite is more effective solution route.By choosing whisker, platelet, fiber and the particle of high strength, high-modulus, make wild phase reinforcement and transformation toughening produce the effect of coordination plasticizing.Mechanical behavior under high temperature in improving in as far as possible keeping material room-temperature mechanical property.

Carbon nano fiber (CNFs) has high strength, high tenacity, and high elastic coefficient, thermal expansivity is little, and the physicals that the electroconductibility that thermostability is high and good etc. are excellent, is a kind of desirable 1-dimention nano strongthener.By CNFs and ZrO ₂mutually compound, be expected to improving ZrO ₂mechanical behavior under high temperature time keep its room-temperature mechanical property, improve the thermal shock resistance of material, be ZrO ₂widespread use foundation is provided.

At present, on ceramic powder matrix, prepare carbon nano fiber and generally adopt chemical Vapor deposition process.First by deposition-precipitation method, matrix is fully mixed with the salts solution of metal catalyst, through the titration of alkaline solution, obtain the oxyhydroxide mixed precipitation of matrix and metal catalyst.By after sedimentation and filtration, evaporate to dryness, calcining, obtain catalyst precursor.Catalyst precursor is passed into hydrocarbon gas after high temperature reduction under hydrogen atmosphere, thereby separate out carbon nano fiber on granules of catalyst.The metal catalyst the most often using comprises the transition metal such as Fe, Co, Ni.Although use this kind of method can preparing heavy nanometer carbon fibre, as the matrix material of pottery and carbon, the introducing of metal catalyst particles have increased the impurity phase in matrix material undoubtedly, and the performance of matrix material is had a negative impact.The report that employing chemical Vapor deposition process is prepared carbon nano fiber on ceramic matrix is a lot, but catalyst-free, and directly on ceramic matrix, growing nano carbon fiber does not also have relevant report.

Summary of the invention

The object of the present invention is to provide the method for direct growth carbon nano fiber on a kind of zirconium white matrix, the method has advantages of that process is simple, one-step synthesis.

The present invention is realized by following technical proposals, and a kind of method of direct growth carbon nano fiber on zirconium white matrix, is characterized in that comprising following process:

1) by particle diameter be the ZrO of 1 ~ 2 μ m ₂powder at room temperature in deionized water or in ethanol ultrasonic cleaning 10min ~ 15min, then after filtration, will leach thing in temperature 60 C ~ 100 ℃ solvent evaporated, through grind, obtain clean ZrO ₂powder;

2) the clean ZrO of step 1) gained ₂powder spreads in quartzy Noah's ark; quartzy Noah's ark is placed in to tube furnace crystal reaction tube flat-temperature zone; under argon shield; rise to after 900 ℃ ~ 1000 ℃ of temperature with 10 ℃/min of temperature rise rate; pass into methane or acetylene carbon source is carried out scission reaction 0.2h ~ 1h take flow velocity as 60 ~ 120ml/min to crystal reaction tube; then under argon gas atmosphere, furnace temperature is down to room temperature, obtains ZrO ₂the carbon nanofiber of growing on powder matrix.

The present invention has the following advantages: adopt conventional ZrO in industry ₂as matrix, by controlling pretreatment mode and the growth technique of matrix, in the situation that not adding any metal catalyst, directly on matrix, grow the carbon nano fiber that quality is good and purity is high.Preparation process and equipment are simple, are easy to realize and promote. ?

Accompanying drawing explanation

Fig. 1 be that in the present invention, embodiment mono-makes at ZrO ₂the SEM photo of direct growth carbon nano fiber on matrix.

Fig. 2 be that in the present invention, embodiment bis-makes at ZrO ₂the SEM photo of direct growth carbon nano fiber on matrix.

Embodiment

Below in conjunction with specific embodiment, particular content of the present invention is described as follows:

Embodiment mono-:

Take the ZrO that 2g particle diameter is 1 ~ 2 μ m ₂powder adds in the deionized water of 50ml, and the ultrasonic 10min of ultrasonic device take power as 400W, mixes, and leaches ZrO ₂add in culture dish, culture dish is put into 80 ℃ of vacuum-dryings of vacuum drying oven, obtain clean ZrO through grinding ₂powder.By clean ZrO ₂powder is placed in quartzy Noah's ark, quartzy Noah's ark is inserted to tube furnace silica tube flat-temperature zone, first pass into Ar rare gas element excluding air with the flow velocity of 200ml/min, then pass into Ar rare gas element and be warming up to 900 ℃ of temperature with the heat-up rate of 10 ℃/min with the flow velocity of 100ml/min; Then continue to pass into the C that flow velocity is 60ml/min ₂h ₂carry out cracking growth 1h, after growth finishes, under Ar atmosphere protection, be cooled to room temperature, obtain at ZrO ₂the CNFs composite powder material of growing on matrix.

Embodiment bis-:

Take the ZrO that 2g particle diameter is 1 ~ 2 μ m ₂powder adds in the ethanol of 50ml, and the ultrasonic 10min of ultrasonic device take power as 400W, mixes.Leach ZrO ₂add in culture dish, culture dish is put into 60 ℃ of vacuum-dryings of vacuum drying oven, obtain clean ZrO through grinding ₂powder.By clean ZrO ₂powder is placed in quartzy Noah's ark, quartzy Noah's ark is inserted to tube furnace silica tube flat-temperature zone, first pass into Ar rare gas element excluding air with the flow velocity of 200ml/min, then pass into Ar rare gas element and be warming up to 1000 ℃ of temperature with the heat-up rate of 10 ℃/min with the flow velocity of 100ml/min; Then continue to pass into the C that flow velocity is 120ml/min ₂h ₂carry out cracking growth 0.5h, after growth finishes, under Ar atmosphere protection, be cooled to room temperature, obtain at ZrO ₂the CNFs composite powder material of growing on matrix.

Embodiment tri-:

Take the ZrO that 2g particle diameter is 1 ~ 2 μ m ₂powder adds in the deionized water of 50ml, and the ultrasonic 10min of ultrasonic device take power as 400W, mixes, and leaches ZrO ₂add in culture dish, culture dish is put into 60 ℃ of vacuum-dryings of vacuum drying oven, obtain clean ZrO through grinding ₂powder.By clean ZrO ₂powder is placed in quartzy Noah's ark, quartzy Noah's ark is inserted to tube furnace silica tube flat-temperature zone, first pass into Ar rare gas element excluding air with the flow velocity of 200ml/min, then pass into Ar rare gas element and be warming up to 950 ℃ of temperature with the heat-up rate of 10 ℃/min with the flow velocity of 100ml/min; Then continue to pass into the CH that flow velocity is 60ml/min ₄carry out cracking growth 0.5h, after growth finishes, under Ar atmosphere protection, be cooled to room temperature, obtain at ZrO ₂the CNFs composite powder material of growing on matrix.

Embodiment tetra-:

Take the ZrO that 2g particle diameter is 1 ~ 2 μ m ₂powder adds in the deionized water of 50ml, and the ultrasonic 10min of ultrasonic device take power as 400W, mixes, and leaches ZrO ₂add in culture dish, culture dish is put into 80 ℃ of vacuum-dryings of vacuum drying oven, obtain clean ZrO through grinding ₂powder.By clean ZrO ₂powder is placed in quartzy Noah's ark, quartzy Noah's ark is inserted to tube furnace silica tube flat-temperature zone, first pass into Ar rare gas element excluding air with the flow velocity of 200ml/min, then pass into Ar rare gas element and be warming up to 950 ℃ of temperature with the heat-up rate of 10 ℃/min with the flow velocity of 100ml/min; Then continue to pass into the CH that flow velocity is 120ml/min ₄carry out cracking growth 0.5h, after growth finishes, under Ar atmosphere protection, be cooled to room temperature, obtain at ZrO ₂the CNFs composite powder material of growing on matrix.

Embodiment five:

Take the ZrO that 2g particle diameter is 1 ~ 2 μ m ₂powder adds in the deionized water of 50ml, and the ultrasonic 10min of ultrasonic device take power as 400W, mixes, and leaches ZrO ₂add in culture dish, culture dish is put into 100 ℃ of vacuum-dryings of vacuum drying oven, obtain clean ZrO through grinding ₂powder.By clean ZrO ₂powder is placed in quartzy Noah's ark, quartzy Noah's ark is inserted to tube furnace silica tube flat-temperature zone, first pass into Ar rare gas element excluding air with the flow velocity of 200ml/min, then pass into Ar rare gas element and be warming up to 1000 ℃ of temperature with the heat-up rate of 10 ℃/min with the flow velocity of 100ml/min; Then continue to pass into the CH that flow velocity is 120ml/min ₄carry out cracking growth 0.2h, after growth finishes, under Ar atmosphere protection, be cooled to room temperature, obtain at ZrO ₂the CNFs composite powder material of growing on matrix.

Claims (1)

1. a method for direct growth carbon nano fiber on zirconium white matrix, is characterized in that comprising following process:

1) by particle diameter be the ZrO of 1 ~ 2 μ m ₂powder at room temperature in deionized water or in ethanol ultrasonic cleaning 10min ~ 15min, then after filtration, will leach thing in temperature 60 C ~ 100 ℃ solvent evaporated, through grind, obtain clean ZrO ₂powder;

2) the clean ZrO of step 1) gained ₂powder spreads in quartzy Noah's ark; quartzy Noah's ark is placed in to tube furnace crystal reaction tube flat-temperature zone; under argon shield; rise to after 900 ℃ ~ 1000 ℃ of temperature with 10 ℃/min of temperature rise rate; pass into methane or acetylene carbon source is carried out scission reaction 0.2h ~ 1h take flow velocity as 60 ~ 120ml/min to crystal reaction tube; then under argon gas atmosphere, furnace temperature is down to room temperature, obtains ZrO ₂the carbon nanofiber of growing on powder matrix.

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