CN105541345A - Method for preparing superfine hafnium carbide ceramic powder - Google Patents

Method for preparing superfine hafnium carbide ceramic powder Download PDF

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Publication number
CN105541345A
CN105541345A CN201511008996.1A CN201511008996A CN105541345A CN 105541345 A CN105541345 A CN 105541345A CN 201511008996 A CN201511008996 A CN 201511008996A CN 105541345 A CN105541345 A CN 105541345A
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China
Prior art keywords
hafnium carbide
powder
hafnium
preparation
precursor
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CN201511008996.1A
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Inventor
王为民
鲁栋良
傅正义
王皓
张金咏
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/5607—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
    • C04B35/5622—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides based on zirconium or hafnium carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/666—Applying a current during sintering, e.g. plasma sintering [SPS], electrical resistance heating or pulse electric current sintering [PECS]

Abstract

The invention belongs to the field of specific ceramic powder, and particularly relates to a method for preparing superfine hafnium carbide ceramic powder. The method comprises the following steps: (1) preparing hafnium carbide precursor powder by adopting a liquid-phase precursor conversion method; (2) conducting pyrolysis treatment on the hafnium carbide precursor powder to obtain a hafnium carbide precursor pyrolysis product; and (3) heating the hafnium carbide precursor pyrolysis product in PAS to obtain the hafnium carbide powder. The invention further provides a preparation method for synthesizing the superfine hafnium carbide ceramic powder at low temperature, wherein the precursor powder is prepared by the liquid-phase precursor conversion method. The preparation method is simple in process and strong in repeatability, and the prepared hafnium carbide powder has high purity, small size and good dispersion and has a good application prospect.

Description

A kind of preparation method of ultra-fine hafnium carbide ceramic powder
Technical field
The invention belongs to special cermacis field of powder preparation, be specifically related to a kind of preparation method of ultra-fine hafnium carbide ceramic powder.
Background technology
The carbide of transition metal can be divided into MC (TiC, ZrC, HfC), M by composition 2c (Mo 2c,W 2and M C) 3c (Mn 3c, Fe 3c) three classes, they have metalluster, and electrical and thermal conductivity is good, and thermal expansivity is little, and hardness is large, and fusing point is high, and some fusing point even exceedes original metal.If the fusing point of TiC, TaC, ZrC, HfC is at more than 3400K (close to 4000K), therefore, they are desirable high temperature materials, are used as the core of rocket and the nozzle material of rocket.Wherein HfC pottery is noticeable especially.
Hafnium oxide and carbon synthetic powder in inertia or reducing atmosphere is used in the preparation of HfC pottery usually traditionally, and its reaction equation is: HfO 2+ 3C → HfC+2CO, the temperature of reaction of this reaction is at 1900-2300 DEG C, but the synthesis temperature of this method is too high, powdered material coarse grains.Liquid precursor conversion method utilizes liquid-phase chemistry, in a liquid reactant is realized the Homogeneous phase mixing of atomic size, homogeneous phase solution is made solute and separated from solvent by all means, solute forms the particle of definite shape and size, obtain the low-down amorphous precursor of crystallinity, because its crystallinity is lower, therefore it has larger specific surface area, considerably increase the activity of its reaction, obviously can reduce the synthesis temperature of synthesis hafnium carbide powder, therefore, special attention is subject in recent years.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, object is the preparation method providing a kind of ultra-fine hafnium carbide ceramic powder.
For achieving the above object, the technical solution used in the present invention is:
A preparation method for ultra-fine hafnium carbide ceramic powder, is characterized in that, comprise the steps:
(1) liquid precursor conversion method is adopted to prepare hafnium carbide presoma: the ratio being 1:0.2 ~ 0.3:0.4 ~ 0.6 according to mol ratio takes oxychlorination hafnium, Whitfield's ointment and citric acid; Oxychlorination hafnium and Whitfield's ointment are joined in dehydrated alcohol, after backflow, stirring, forms composite solution, then add citric acid in composite solution, continue to stir for some time, obtain precursor solution; Then adopt the solvent in rotary distillation method removal precursor solution, obtain hafnium carbide presoma;
(2) hafnium carbide presoma is carried out pyrolysis processing, obtain hafnium carbide presoma pyrolysis product;
(3) hafnium carbide presoma pyrolysis product is placed in plasma activated sintering stove (PAS) to heat-treat, obtains hafnium carbide powder.
In such scheme, the temperature of step (1) described backflow is 50 ~ 65 DEG C, and the time of backflow is 1 ~ 2h.
In such scheme, the technique of step (2) described pyrolysis processing is: pyrolysis temperature 700 ~ 900 DEG C, temperature rise rate 4 DEG C/min, soaking time 0.5 ~ 1h, and work atmosphere is argon gas.
In such scheme, step (3) described process of thermal treatment is: thermal treatment temp 1550 ~ 1600 DEG C, temperature rise rate 100 ~ 300 DEG C/min, soaking time 4min ~ 6min, and work atmosphere is argon gas.
Beneficial effect of the present invention is as follows: the preparation method that the invention provides a kind of hafnium carbide of synthesizing superfine at low temperatures ceramic powder, and wherein, presoma powder is obtained by liquid precursor conversion method; Preparation method's technique of the present invention is simple, and repeatability is strong, and the hafnium carbide powder purity prepared is high, particle diameter is little, good dispersity, has good application prospect.
Accompanying drawing illustrates:
Fig. 1 is that hafnium carbide powder (a) prepared by embodiment 1 is composed with the XRD figure of hafnium carbide standard substance (b).
Fig. 2 is the SEM collection of illustrative plates of hafnium carbide powder prepared by embodiment 1.
Fig. 3 is that hafnium carbide powder (a) prepared by embodiment 2 is composed with the XRD figure of hafnium carbide standard substance (b).
Fig. 4 is the SEM collection of illustrative plates of hafnium carbide powder prepared by embodiment 2.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1
A preparation method for ultra-fine hafnium carbide ceramic powder, prepares by the following method:
(1) liquid precursor conversion method prepares hafnium carbide presoma powder: take oxychlorination hafnium 10g, Whitfield's ointment 1..01g, citric acid 1.03g; Be blended in the dehydrated alcohol of 200ml by oxychlorination hafnium and Whitfield's ointment, reflux under 50 DEG C of conditions 1h, then stirring at room temperature formed composite solution, then add citric acid stir 2h obtain precursor solution; With Rotary Evaporators under 60 DEG C of conditions by the solvent evaporated away in precursor solution, obtain hafnium carbide presoma powder;
(2) preparation of presoma pyrolysis product: the hafnium carbide presoma powder of preparation is put into graphite jig, then tube furnace pyrolysis is placed in, obtain hafnium carbide presoma pyrolysis product, wherein pyrolysis temperature is 700 DEG C, temperature rise rate is 4 DEG C/min, soaking time is 0.5h, and work atmosphere is argon gas;
(3) synthesis of hafnium carbide powder: hafnium carbide presoma pyrolysis product is put into special mould, is then placed in PAS thermal treatment synthesis hafnium carbide powder; Described thermal treatment temp is 1550 DEG C, and temperature rise rate is 100 DEG C/min, and soaking time is 4min, and work atmosphere is argon gas.
The XRD figure spectrum of the hafnium carbide powder that the present embodiment prepares is shown in Fig. 1, and the X-ray diffractometer manufactured by Japanese Rigaku company is measured, and as can be seen from the figure, obtained powder is hafnium carbide crystalline material, and its purity is higher.Fig. 2 is the SEM collection of illustrative plates of the present embodiment sample, and as can be seen from Figure, prepared powder is spherical, and particle diameter is at 100 ~ 300nm, better dispersed.
Embodiment 2
A preparation method for ultra-fine hafnium carbide ceramic powder, prepares by the following method:
(1) liquid precursor conversion method prepares hafnium carbide presoma powder: take oxychlorination hafnium 10g, Whitfield's ointment 2.02g, citric acid 1.53g; Be blended in the dehydrated alcohol of 200ml by oxychlorination hafnium and Whitfield's ointment, reflux under 65 DEG C of conditions 1h, then stirring at room temperature formed composite solution, then add citric acid stir 2h obtain precursor solution; With Rotary Evaporators under 60 DEG C of conditions by the solvent evaporated away in precursor solution, obtain hafnium carbide presoma powder;
(2) preparation of presoma pyrolysis product: the hafnium carbide presoma powder of preparation is put into graphite jig, then tube furnace pyrolysis is placed in, obtain hafnium carbide presoma pyrolysis product, wherein pyrolysis temperature is 900 DEG C, temperature rise rate is 4 DEG C/min, soaking time is 1h, and work atmosphere is argon gas;
(3) synthesis of hafnium carbide powder: hafnium carbide presoma pyrolysis product is put into special mould, is then placed in PAS thermal treatment synthesis hafnium carbide powder; Described thermal treatment temp is 1600 DEG C, and temperature rise rate is 300 DEG C/min, and soaking time is 6min, and work atmosphere is 0.2bar argon gas.
Fig. 3 is the XRD figure spectrum of the present embodiment sample, and the X-ray diffractometer manufactured by Japanese Rigaku company is measured, and as can be seen from the figure, obtained powder is hafnium carbide crystalline material, and its purity is higher.Fig. 4 is the SEM collection of illustrative plates of the present embodiment sample, as can be seen from Figure, prepared powder is spherical, and particle diameter is at 300 ~ 700nm, better dispersed.
Obviously, above-described embodiment is only for the example done clearly is described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And therefore amplified apparent change or variation are still within the protection domain of the invention.

Claims (4)

1. a preparation method for ultra-fine hafnium carbide ceramic powder, is characterized in that, comprise the steps:
(1) liquid precursor conversion method is adopted to prepare hafnium carbide presoma: the ratio being 1:0.2 ~ 0.3:0.4 ~ 0.6 according to mol ratio takes oxychlorination hafnium, Whitfield's ointment and citric acid; Oxychlorination hafnium and Whitfield's ointment are joined in dehydrated alcohol, after backflow, stirring, forms composite solution, then add citric acid in composite solution, continue to stir for some time, obtain precursor solution; Then adopt the solvent in rotary distillation method removal precursor solution, obtain hafnium carbide presoma;
(2) hafnium carbide presoma is carried out pyrolysis processing, obtain hafnium carbide presoma pyrolysis product;
(3) hafnium carbide presoma pyrolysis product is placed in plasma activated sintering stove to heat-treat, obtains hafnium carbide powder.
2. preparation method according to claim 1, is characterized in that, the temperature of step (1) described backflow is 50 ~ 65 DEG C, and the time of backflow is 1 ~ 2h.
3. preparation method according to claim 1, is characterized in that, the technique of step (2) described pyrolysis processing is: pyrolysis temperature 700 DEG C ~ 900 DEG C, and temperature rise rate 4 DEG C/min, soaking time 0.5h ~ 1h, work atmosphere is argon gas.
4. preparation method according to claim 1, is characterized in that, step (3) described process of thermal treatment is: thermal treatment temp 1550 ~ 1600 DEG C, temperature rise rate 100 ~ 300 DEG C/min, soaking time 4 ~ 6min, and work atmosphere is argon gas.
CN201511008996.1A 2015-12-29 2015-12-29 Method for preparing superfine hafnium carbide ceramic powder Pending CN105541345A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107601508A (en) * 2017-09-12 2018-01-19 江苏理工学院 A kind of hafnium carbide nano material and preparation method thereof
CN111392726A (en) * 2020-03-09 2020-07-10 西安理工大学 Method for preparing TaC organic precursor and nano-particles thereof by rotary evaporation
CN111471962A (en) * 2020-02-21 2020-07-31 西安理工大学 Method for preparing ZrC organic precursor by rotary evaporation

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104016679A (en) * 2014-06-25 2014-09-03 中国人民解放军国防科学技术大学 Preparation method and application of carbide ceramic precursor

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104016679A (en) * 2014-06-25 2014-09-03 中国人民解放军国防科学技术大学 Preparation method and application of carbide ceramic precursor

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王延斌 等: "液相先驱体转化法制备HfC及其表征", 《稀有金属材料与工程》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107601508A (en) * 2017-09-12 2018-01-19 江苏理工学院 A kind of hafnium carbide nano material and preparation method thereof
CN111471962A (en) * 2020-02-21 2020-07-31 西安理工大学 Method for preparing ZrC organic precursor by rotary evaporation
CN111471962B (en) * 2020-02-21 2022-08-30 西安理工大学 Method for preparing ZrC organic precursor by rotary evaporation
CN111392726A (en) * 2020-03-09 2020-07-10 西安理工大学 Method for preparing TaC organic precursor and nano-particles thereof by rotary evaporation
CN111392726B (en) * 2020-03-09 2023-01-24 西安理工大学 Method for preparing TaC organic precursor and nano-particles thereof by rotary evaporation

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Application publication date: 20160504