CN106882977A - The preparation method of the whisker modified carbon/carbon compound material of zirconium carbide - Google Patents

The preparation method of the whisker modified carbon/carbon compound material of zirconium carbide Download PDF

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CN106882977A
CN106882977A CN201710094698.1A CN201710094698A CN106882977A CN 106882977 A CN106882977 A CN 106882977A CN 201710094698 A CN201710094698 A CN 201710094698A CN 106882977 A CN106882977 A CN 106882977A
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zrc
carbon
whisker
composite preforms
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CN106882977B (en
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李克智
周璇
赵志刚
石郭戈
李伟
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Northwestern Polytechnical University
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    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
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Abstract

The invention discloses a kind of preparation method of the whisker modified carbon/carbon compound material of zirconium carbide, the technical problem of the whisker modified carbon/carbon compound material poor mechanical property of zirconium carbide for solving existing method preparation.Technical scheme is in carbon fiber surface deposition pyrolysis carbon protective layer first using chemical vapor deposition; ZrC presomas are introduced into C/C composite preforms using microwave-hydrothermal method again; then ZrC presomas are changed into ZrC whiskers; it is densified using chemical vapor deposition again afterwards, is finally given the whisker modified C/C composites of ZrC.Composite prepared by the present invention is carbon zirconium two phase material, without other impurities, ZrC whiskers are evenly distributed in C/C composites, the draw ratio of ZrC whiskers is big, can form good mechanical interlocked with carbon base body, interface cohesion between whisker and whisker is good, so as to improve the interface cohesion of carbon fiber and carbon base body, significantly improves the bending strength of C/C composites.

Description

The preparation method of the whisker modified carbon/carbon compound material of zirconium carbide
Technical field
The present invention relates to a kind of preparation method of composite, more particularly to a kind of whisker modified carbon/carbon of zirconium carbide (ZrC) (C/C) preparation method of composite.
Background technology
C/C composites because receiving the extensive concern of researchers with a series of excellent performances, for example：It is high-strength Degree, high ratio modulus, low-density, high heat conductance, low thermal coefficient of expansion, resistance to ablation, thermal shock resistance be good, especially with temperature Its intensity is raised to go up not down, be widely used in rocket tube and larynx lining, aeroplane brake discses, the end cap of aircraft and Thermal protection system of the leading edge of a wing etc..C/C composites have many excellent high-temperature behaviors in oxygen-free environment, but C/C is compound Material begins to oxidation in 370 DEG C of aerobic environment, at 2000 DEG C with regard to severe oxidation, so as to influence its use.Largely grind Study carefully and show, its anti-oxidant Burning corrosion resistance energy can be significantly improved to ZrC superhigh temperature ceramics are introduced in C/C composites.But tradition Preparation method such as liquid impregnation and high-temperature fusion impregnating, it is skeleton to use low-density C/C composites, by circulate impregnate Although the ceramic phase that the mode of cracking or high-temperature fusion dipping is introduced, these methods improve the anti-oxidant anti-of C/C composites Ablation property, but the ceramic phase particle diameter for preparing is generally large, and skewness is easily reunited in carbon base body, causes carbon fiber and carbon The interface cohesion of matrix is deteriorated, so as to the mechanical property of the modified C/C composites of ZrC can be influenceed.So developing new preparation work Skill prepares the ceramic phase of special appearance, realizes that ceramic phase even dispersion is distributed, improve the interface cohesion of carbon fiber and carbon base body from And the mechanical property that improves C/C composites is significant.
Document 1 " microstructure of Shen Xuetao, Li Wei .C/C-ZrC composites and mechanical property research [J], inorganic material Journal .2015,30 (5)：459-466 " discloses a kind of preparation method of C/C-ZrC composites, and the method is with density 0.2g/cm3Acupuncture carbon felt be material skeleton, using zirconium oxychloride aqueous solution impregnate carbon felt, in conjunction with chemical vapour deposition technique The modified C/C composites of ZrC have been prepared with high temperature graphitization technique, when ZrC contents are 12.08wt%, its bending Intensity is 42.5MPa, than it is unmodified when improve 70%, but the method needs 2500 DEG C of high temperature graphitization treatment, prepared ZrC ceramic phases be nanoscale, micron order and submicron particles, particle is in carbon base body in the distribution of segregation state, nanometer and micro- Combine weaker between the particle of meter level, cause the interface cohesion of carbon fiber-carbon base body to weaken, in higher close of micron particles content Collection carbon fiber region, the interface cohesion of carbon fiber-carbon base body further weakens, and is unfavorable for further carrying for material mechanical performance It is high.
" Yang Xin, Su Zhean, Huang Qizhong wait .ZrC mass fractions to the shadow of C/C-ZrC composite materials properties to document 2 Ring [J], Central South University's journal .2013,44 (2):508-514 " discloses a kind of method of the modified C/C composites of ZrC, the party Be introduced into ZrC in C/C composites using matrix modification technology by method, in conjunction with chemical vapor deposition and high temperature graphitization technique system Standby C/C-ZrC composites, when the mass fraction of ZrC is 12.89wt%, its bending strength be 100.60MPa~ 120.20MPa, but composite prepared by the method needed in 2000 DEG C of heat treatments, and wherein ZrC ceramic phases are nanoscale Grain, in the formal distribution of segregation state in carbon base body.
In published C/C-ZrC composite material and preparation method thereofs, preparation temperature all more than 2000 DEG C, prepared ZrC It is nanometer, micro to submicro particles, the combination of grain boundary face is weaker, causes the interface cohesion of carbon fiber-carbon base body to weaken, And ZrC particles exist in carbon base body in the form of segregation state, skewness causes the interface of carbon fiber-carbon base body to be tied Close and weaken, influence the further raising of C/C-ZrC composite materials properties.
The content of the invention
In order to overcome the shortcomings of the whisker modified carbon/carbon compound material poor mechanical property of zirconium carbide prepared by existing method, this Invention provides a kind of preparation method of the whisker modified carbon/carbon compound material of zirconium carbide.The method is using microwave-hydrothermal method by before ZrC Drive body and introduce C/C composite preforms, by 1400 DEG C~1600 DEG C heat treatments, ZrC presomas are transformed into ZrC whiskers, Using chemical vapor deposition be densified again and obtain the whisker modified C/C composites of ZrC.Hydro-thermal method has subcritical and super Mass transfer speed is fast under critical fluids state and the characteristics of strong penetration, in conjunction with microwave, can not only effectively improve material Preparation efficiency, and generation material easily form Dispersed precipitate in the composite.Carbon fiber precast body used it is close It is 0.40g/cm to spend3~0.45g/cm3, the porosity of appropriateness is easy to the diffusion of ZrC presomas so that ZrC is in C/C composites Middle distribution is more uniform, and is first heat-treated to be densified again and can further avoid the reunion of ceramics.Mechanical strength of whisker etc. In adjacent interatomic force, the height-oriented structure of whisker makes it have high intensity, high-modulus, high elongation rate, and its intensity is far above Other chopped strands, can be used as composite material reinforcement body, and the ZrC whiskers that the present invention is prepared are evenly distributed, and draw ratio is big, Between whisker and whisker and whisker is good with the interface cohesion of carbon base body, the interface knot of carbon fiber-carbon base body can be effectively improved Close, strengthen C/C composites, improve the Burning corrosion resistance energy and mechanical property of C/C composites.
The technical solution adopted for the present invention to solve the technical problems：A kind of whisker modified carbon/carbon compound material of zirconium carbide Preparation method, be characterized in comprising the following steps：
Step one, with natural gas as carbon source, be 0.40g/cm by density using chemical vapor deposition3~0.45g/cm3's Carbon fiber precast body is placed in cvd furnace, deposits one layer of pyrolytic carbon, and depositing temperature is 1050 DEG C~1150 DEG C, and sedimentation time is 3h ~6h, obtains C/C composite preforms.
Step 2, according to ZrOCl2·8H2O is 1 with the mass ratio of deionized water:5~1:6, zirconium source will be contained ZrOCl2·8H2O dissolves in deionized water, stirring and dissolving, according to the 3.5%~4.5% of reaction solution gross mass, adds HCl in NaOH and in solution, stirring and dissolving, now solution is white emulsion, according to ZrOCl2·8H2In O and sucrose Zr and The mol ratio of C is 1:3~1:5 add sucrose, and stirring is completely dissolved sucrose, and addition quality is reaction solution gross mass 0.4% ~0.8% catalyst n iCl2·6H2O, stirring and dissolving, according to the 1.8%~2.4% of reaction solution gross mass, adds whisker Growth auxiliary agent NaF, stirring and dissolving obtains light green color emulsion.
Step 3, the C/C composite preforms for preparing step one are immersed in the emulsion of step 2 preparation, immersion Time 30min~50min.
Step 4, the C/C composite preforms and emulsion in step 3 are transferred to liner in the lump for polytetrafluoroethyl-ne In the reactor of alkene, reactor is sealed, is put into microwave reaction/clear up instrument, reacted at 160 DEG C~180 DEG C 40min~ 90min question responses are completely cooled down to room temperature, take out reactor, take out precast body, and 12h is dried in 60 DEG C~90 DEG C of drying box ~36h, obtains the C/C composite preforms containing ZrC presomas.
Step 5, repeat step three and step 4, constantly to introducing ZrC presomas in C/C composite preforms, until The quality of ZrC presomas accounts for the 30%~50% of precast body gross mass.
Step 6, by step 5 prepare the C/C composite preforms containing ZrC presomas be placed in corundum crucible, Corundum crucible is placed in the crystal vessel of sealing, and high-temperature heat treatment is carried out in high temperature furnace, with argon gas be protection gas, with 3 DEG C/ The heating rate of min~6 DEG C/min is warmed up to 1400 DEG C~1600 DEG C, is incubated 2h~3h, naturally cools to room temperature, obtains ZrC Whisker modified C/C composite preforms.
Step 7, the whisker modified C/C composite preforms of ZrC for being prepared step 6 using chemical vapor deposition stove are entered Row densification, with natural gas as carbon source, depositing temperature is 1050 DEG C~1150 DEG C, and sedimentation time is 120h~150h, deposition knot Room temperature is cooled to after beam, the whisker modified C/C composites of ZrC are obtained.
The beneficial effects of the invention are as follows：The density of the carbon fiber precast body that the preparation method is used is 0.40g/cm3~ 0.45g/cm3, composite preform is soaked using ZrC precursor solutions, ZrC presomas is fully permeated composite pre- Body processed；And the ZrC presomas of microwave-hydrothermal method generation diffusivity under the microwave hydrothermal system pressure of 1.0MPa~2.2MPa is strong, The inside of C/C composite preforms can be uniformly spread to, will not be reunited in the outer layer of composite preform；It is first that carbon is fine Dimension precast body is placed in one layer of pyrolytic carbon of deposition in chemical vapor deposition, is effectively guaranteed the carbon fiber in carbon thermal reduction and is not damaged Wound；Prepared ZrC whiskers micron different from the past, sub-micron, nano level ZrC particles, ZrC whiskers prepared by the present invention It is evenly distributed, draw ratio is big, and interface cohesion is good between whisker, whisker and carbon base body form good mechanical interlocked, so that and carbon Good interface cohesion is formed between matrix, the interface cohesion of carbon fiber-carbon base body is improve.ZrC whiskers prepared by the present invention Its bending strength of modified C/C composites is 126.34MPa~139.36MPa, and the bending strength of background technology is 100.60MPa~120.20MPa, the bending strength of material is significantly improved.
The present invention is elaborated with reference to the accompanying drawings and detailed description.
Brief description of the drawings
Fig. 1 is the flow chart of the preparation method of the whisker modified carbon/carbon compound material of zirconium carbide of the present invention.
Fig. 2 is the X ray diffracting spectrum of the whisker modified carbon/carbon compound material of zirconium carbide prepared by the embodiment of the present invention one (XRD)。
Fig. 3 is the scanning electron microscopic picture of the whisker modified carbon/carbon compound material of zirconium carbide prepared by the embodiment of the present invention one (SEM)。
Fig. 4 is the partial enlarged drawing of Fig. 3.
Fig. 5 be 1 in Fig. 4 at energy spectrum diagram (EDS).
Specific embodiment
Following examples reference picture 1-5.
Embodiment one：
(1) it is 0.4g/cm by density using chemical vapor deposition with natural gas as carbon source3Carbon fiber precast body place In cvd furnace, one layer of pyrolytic carbon is deposited, depositing temperature is 1050 DEG C, and sedimentation time is 3h, obtains C/C composite precasts Body；
(2) by 6g ZrOCl8H2O is dissolved in the deionized water of 30ml, treats ZrOCl8H2O is completely dissolved, and adds HCl in the NaOH of 1.6g and in solution, stirring and dissolving, now solution is white emulsion, is 1 according to the mol ratio of Zr and C: 3 add 3.93g sucrose granules, and stirring is completely dissolved sucrose, adds 0.2g catalyst ns iCl2·6H2O, stirring and dissolving is added 0.8gNaF as whisker growth auxiliary agent, stirring and dissolving obtains light green color emulsion.
(3) C/C composite preforms prepared by step (1) are immersed in the emulsion of step (2) preparation, immersion Time 30min.
(4) it is polytetrafluoroethylene (PTFE) the C/C composite preforms and emulsion in step (3) to be transferred into liner in the lump In reactor, reactor is sealed, be put into microwave reaction/clear up instrument, 90min are reacted at 160 DEG C, question response is completely cooled down to Room temperature, takes out reactor, takes out precast body, and 36h is dried in 60 DEG C of drying box, obtains the C/C composite woods containing ZrC presomas Material precast body.
(5) repeat the above steps (3) and step (4), constantly to ZrC presomas are introduced in C/C composite preforms, directly Quality to ZrC presomas accounts for the 30% of precast body gross mass.
(6) the C/C composite preforms containing ZrC presomas prepared by step (5) are placed in corundum crucible, corundum Crucible is placed in the crystal vessel of sealing, and high-temperature heat treatment is carried out in high temperature furnace, is protection gas with argon gas, with 3 DEG C/min's Heating rate is warmed up to 1400 DEG C, is incubated 2h, naturally cools to room temperature, takes out sample, obtains the whisker modified C/C composite woods of ZrC Material precast body.
(7) the whisker modified C/C composite preforms of ZrC for being prepared step (6) using chemical vapor deposition stove are carried out Densification, with natural gas as carbon source, depositing temperature is 1050 DEG C, and sedimentation time is 120h, and deposition is cooled to room temperature after terminating, and obtains It is 1.96g/cm to density3The whisker modified C/C composites of ZrC.
Fig. 2 is the XRD spectrum of the whisker modified C/C composites of ZrC prepared by the present embodiment, as can be seen from the figure multiple Condensation material illustrates that the ZrC presomas in material are completely reformed into ZrC by the phase composition of C, ZrC two.
Fig. 3 is the SEM pictures of the whisker modified C/C composites of ZrC prepared by the present embodiment, and Fig. 4 is that the part of Fig. 3 is put Big figure, as can be seen from the figure ZrC whiskers are more, are evenly distributed in carbon base body, and diameter of whiskers is 200nm-1 μm, and length is several micro- To more than ten microns, the tip of whisker does not find the catalyst of droplet-like to rice, by document, ZrC whiskers in the present embodiment Growth mechanism for Ostwald ripening (Ostwald ripening), the i.e. growth course of ZrC be generation ZrC particles Constantly it is dissolved in the NaF for having melted, is separated out from NaF when ZrC reaches finite concentration, forms ZrC whiskers.
Fig. 5 be 1 in Fig. 4 at EDS figures, as can be seen from the figure whisker include two kinds of elements of C and Zr, illustrate it is of the invention must The whisker for arriving is ZrC whiskers.
The whisker modified C/C composites of ZrC that the present embodiment is obtained, bending strength is 139.36MP.
Embodiment two：
(1) it is 0.42g/cm by density using chemical vapor deposition with natural gas as carbon source3Carbon fiber precast body put Put in cvd furnace, deposit one layer of pyrolytic carbon, depositing temperature is 1100 DEG C, and sedimentation time is 4.5h, obtains C/C composites pre- Body processed；
(2) by 7g ZrOCl8H2O is dissolved in the deionized water of 40ml, treats ZrOCl2·8H2O is completely dissolved, and adds Hydrochloric acid in the NaOH of 1.8g and in solution, stirring and dissolving, now solution is white emulsion, is according to the mol ratio of Zr and C 1:4 sucrose granules for adding 7.67g, stirring is completely dissolved sucrose, adds 0.4g catalyst ns iCl2·6H2O, stirring and dissolving, Add 1.0gNaF as the growth auxiliary agent of whisker, stirring and dissolving obtains light green color emulsion.
(3) C/C composite preforms prepared by step (1) are immersed in the emulsion of step (2) preparation, during immersion Between 40min.
(4) it is polytetrafluoroethylene (PTFE) the C/C composite preforms and emulsion in step (3) to be transferred into liner in the lump In reactor, reactor is sealed, be put into microwave reaction/clear up instrument, 60min are reacted at 170 DEG C, question response is completely cooled down to Room temperature, takes out reactor, takes out precast body, is placed in 80 DEG C of drying box and dries 24h, obtains the C/C containing ZrC presomas and is combined Prefabricated body.
(5) repeat the above steps (3) and step (4), constantly to ZrC presomas are introduced in C/C composite preforms, directly Quality to ZrC presomas accounts for the 40% of precast body gross mass.
(6) the C/C composite preforms containing ZrC presomas prepared by step (5) are placed in corundum crucible, corundum Crucible is placed in the crystal vessel of sealing, and high-temperature heat treatment is carried out in high temperature furnace, is protection gas with argon gas, with 4 DEG C/min's Heating rate is warmed up to 1500 DEG C, is incubated 2.5h, naturally cools to room temperature, takes out sample, obtains the whisker modified C/C of ZrC and is combined Prefabricated body.
(7) the whisker modified C/C composite preforms of ZrC for being prepared step (6) using chemical vapor deposition stove are carried out Densification, with natural gas as carbon source, depositing temperature is 1100 DEG C, and sedimentation time is 140h, and deposition is cooled to room temperature after terminating, and obtains It is 1.95g/cm to density3The whisker modified C/C composites of ZrC.
The bending strength of the whisker modified C/C composites of ZrC that the present embodiment is obtained is 130.72MPa.
Embodiment three：
(1) it is 0.45g/cm by density using chemical vapor deposition with natural gas as carbon source3Carbon fiber precast body put Put in cvd furnace, deposit one layer of pyrolytic carbon, depositing temperature is 1150 DEG C, and sedimentation time is 6h, obtains C/C composite precasts Body；
(2) by 6g ZrOCl8H2O is dissolved in the deionized water of 36ml, treats ZrOCl2·8H2O is completely dissolved, and adds Hydrochloric acid in the NaOH of 2g and in solution, stirring and dissolving, now solution is white emulsion, is 1 according to the mol ratio of Zr and C:5 Add the sucrose granules of 6.56g, stirring and dissolving to treat that sucrose is completely dissolved, add 0.6g catalyst ns iCl2·6H2O, stirring 5min, adds 1.2gNaF as the growth auxiliary agent of whisker, and stirring and dissolving obtains light green color emulsion.
(3) C/C composite preforms prepared by step (1) are immersed in the emulsion of step (2) preparation, during immersion Between 50min.
(4) it is polytetrafluoroethylene (PTFE) the C/C composite preforms and emulsion in step (3) to be transferred into liner in the lump In reactor, reactor is sealed, be put into microwave reaction/clear up instrument, 40min are reacted at 180 DEG C, question response is completely cooled down to Room temperature, takes out reactor, takes out precast body, and 12h is dried in 90 DEG C of drying box, obtains the C/C composite woods containing ZrC presomas Material precast body.
(5) repeat the above steps (3) and step (4), constantly to ZrC presomas are introduced in C/C composite preforms, directly Quality to ZrC presomas accounts for the 50% of precast body gross mass.
(6) the C/C composite preforms containing ZrC presomas prepared by step (5) are placed in corundum crucible, corundum Crucible is placed in the crystal vessel of sealing, and high-temperature heat treatment is carried out in high temperature furnace, is protection gas with argon gas, with 6 DEG C/min's Heating rate is warmed up to 1600 DEG C, is incubated 3h, naturally cools to room temperature, takes out sample, obtains the whisker modified C/C composite woods of ZrC Material precast body.
(7) the whisker modified C/C composite preforms of ZrC for being prepared step (6) using chemical vapor deposition stove are carried out Densification, with natural gas as carbon source, depositing temperature is 1150 DEG C, and sedimentation time is 150h, and deposition is cooled to room temperature after terminating, and obtains It is 1.93g/cm to density3The whisker modified C/C composites of ZrC.
The whisker modified C/C composites bending strengths of ZrC that the present embodiment is obtained are 126.34MPa.
Compared with background technology, the whisker modified C/C composites of ZrC prepared by the present invention, ceramic phase ZrC whisker sizes It is small, it is evenly distributed in carbon base body, form good mechanical interlocked with carbon base body, improve carbon fiber and tied with the interface of carbon base body Close, substantially increase the bending strength of C/C composites.

Claims (1)

1. the preparation method of the whisker modified carbon/carbon compound material of a kind of zirconium carbide, it is characterised in that comprise the following steps：
Step one, with natural gas as carbon source, be 0.40g/cm by density using chemical vapor deposition3~0.45g/cm3Carbon it is fine Dimension precast body be placed in cvd furnace, deposit one layer of pyrolytic carbon, depositing temperature be 1050 DEG C~1150 DEG C, sedimentation time be 3h~ 6h, obtains C/C composite preforms；
Step 2, according to ZrOCl2·8H2O is 1 with the mass ratio of deionized water:5~1:6, by the ZrOCl containing zirconium source2· 8H2O dissolves in deionized water, stirring and dissolving, in addition NaOH and molten according to the 3.5%~4.5% of reaction solution gross mass HCl in liquid, stirring and dissolving, now solution is white emulsion, according to ZrOCl2·8H2The mol ratio of Zr and C in O and sucrose It is 1:3~1:5 add sucrose, and stirring is completely dissolved sucrose, and it is reaction solution gross mass 0.4%~0.8% to add quality Catalyst n iCl2·6H2O, stirring and dissolving, according to the 1.8%~2.4% of reaction solution gross mass, adds the growth auxiliary agent of whisker NaF, stirring and dissolving obtains light green color emulsion；
Step 3, the C/C composite preforms for preparing step one are immersed in the emulsion of step 2 preparation, soak time 30min~50min；
Step 4, the C/C composite preforms and emulsion in step 3 are transferred to liner in the lump for polytetrafluoroethylene (PTFE) In reactor, reactor is sealed, be put into microwave reaction/clear up instrument, reacted 40min~90min at 160 DEG C~180 DEG C and treat Reaction is completely cooled down to room temperature, takes out reactor, takes out precast body, and 12h~36h is dried in 60 DEG C~90 DEG C of drying box, Obtain the C/C composite preforms containing ZrC presomas；
Step 5, repeat step three and step 4, constantly to ZrC presomas are introduced in C/C composite preforms, until ZrC The quality of presoma accounts for the 30%~50% of precast body gross mass；
Step 6, by step 5 prepare the C/C composite preforms containing ZrC presomas be placed in corundum crucible, corundum Crucible is placed in the crystal vessel of sealing, and high-temperature heat treatment is carried out in high temperature furnace, is protection gas with argon gas, with 3 DEG C/min~6 DEG C/heating rate of min is warmed up to 1400 DEG C~1600 DEG C, is incubated 2h~3h, naturally cools to room temperature, obtain ZrC whiskers and change Property C/C composite preforms；
Step 7, the whisker modified C/C composite preforms of ZrC for being prepared step 6 using chemical vapor deposition stove are caused Densification, with natural gas as carbon source, depositing temperature is 1050 DEG C~1150 DEG C, and sedimentation time is 120h~150h, after deposition terminates Room temperature is cooled to, the whisker modified C/C composites of ZrC are obtained.
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