CN109607559A - A method for synthesizing ternary layered compounds using metal powder flux - Google Patents

A method for synthesizing ternary layered compounds using metal powder flux Download PDF

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CN109607559A
CN109607559A CN201910091841.0A CN201910091841A CN109607559A CN 109607559 A CN109607559 A CN 109607559A CN 201910091841 A CN201910091841 A CN 201910091841A CN 109607559 A CN109607559 A CN 109607559A
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powder
tih
temperature
flux
metal powder
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CN109607559B (en
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胡前库
吴庆华
周爱国
王李波
侯鸣
侯一鸣
秦双红
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Henan University of Technology
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Henan University of Technology
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Priority claimed from CN201810169742.5A external-priority patent/CN108328587A/en
Priority claimed from CN201810169743.XA external-priority patent/CN108275692A/en
Priority claimed from CN201810169741.0A external-priority patent/CN108439989A/en
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    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0602—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with two or more other elements chosen from metals, silicon or boron
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    • C04B35/58—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/58007—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on refractory metal nitrides
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Abstract

The present invention provides a kind of method using metal powder fluxing agent synthesis of ternary lamellar compound, and ternary layered compound is Ti3B2N, method include by TiH2Powder, unformed B powder and hexagonal AlN powder stir into mixture；Heat up and keep the temperature and to obtain under inert protective atmosphere in mixture plus after metal powder sample；Under inert protective atmosphere, after sample cooled to room temperature, then with dilute hydrochloric acid remove sample in remaining metal powder, obtain Ti3B2N.Metal powder fluxing agent is Al powder, Pb powder or Zn powder；To be warming up to 700~1000 DEG C when Al powder and keeping the temperature 2~12h；For be warming up to when Pb powder 600~900 DEG C and keep the temperature 12~for 24 hours；700~1000 DEG C when for Zn powder, 1~6h is kept the temperature.Ti can be greatly reduced in synthetic method provided by the invention3B2The synthesis temperature of N, the synthetic method is simple to operation, is suitble to industrial scale production, reduces production cost.

Description

A method of using metal powder fluxing agent synthesis of ternary lamellar compound
Technical field
The invention belongs to structural material fields, and in particular to be it is a kind of use metal powder fluxing agent synthesis of ternary laminarization The method for closing object.
Background technique
Ti3B2N is a kind of novel ternary layered compound, it has high-modulus (Young's modulus 430.22GPa, shearing mould Measure 181.06GPa), high intensity etc..Meanwhile Ti3B2N has very low density (theoretical density 4.80g/cm3)。
Chinese patent application 2016100610872 discloses a kind of new ceramics crystal Ti3B2N and preparation method thereof, the Shen Ti please be synthesized using high-temperature solid phase reaction method3B2N, but the synthesis temperature that this application needs is 1100-1200 DEG C higher, is unfavorable for The actual production of product, and high temperature production higher cost, and synthetic technology disclosed in this application is still immature, also needs to continue to change Into.
Therefore, other synthetic methods are found, synthesis temperature are reduced, for Ti3B2The practical application of N material has good Realistic meaning.
Summary of the invention
Object of the present invention is to overcome above-mentioned new material Ti in the prior art3B2The high problem defect of the synthesis temperature of N, and mention A kind of use metal powder Al, Pb and Zn fluxing agent out synthesizes Ti3B2The method of N.Synthetic method provided by the invention can be substantially Reduce Ti3B2The synthesis temperature of N is suitble to industrial scale production, reduces production cost.
To achieve the goals above, the invention provides the following technical scheme:
A method of using metal powder fluxing agent synthesis of ternary lamellar compound, the ternary layered compound is Ti3B2N synthesizes the Ti3B2The method of N includes:
First by TiH2Mixture is mixed evenly to obtain in powder, unformed B powder and hexagonal AlN powder；Then add in mixture Enter metal powder as fluxing agent and is uniformly mixed, tabletting, and be warming up to set temperature under inert protective atmosphere and keep the temperature certain Time obtains sample；Finally under inert protective atmosphere, after sample cooled to room temperature, then using in dilute hydrochloric acid removing sample Remaining metal powder fluxing agent, obtains Ti3B2N；
The metal powder fluxing agent is Al powder, Pb powder or Zn powder；
When addition metal powder fluxing agent be Al powder, be warming up under inert protective atmosphere 700~1000 DEG C and keep the temperature 2~ 12h；
When addition metal powder fluxing agent be Pb powder, be put into quartz ampoule after tabletting, by the stone under inert protective atmosphere English pipe be warming up to 600~900 DEG C and keep the temperature 12~for 24 hours；
When the metal powder fluxing agent of addition is Zn powder, it is warming up to 700~1000 DEG C under inert protective atmosphere, heat preservation 1~ 6h。
The method as described above for using metal powder fluxing agent synthesis of ternary lamellar compound, it is preferable that add in mixture The amount for entering metal powder is specific as follows:
When addition metal powder fluxing agent be Al powder, need to be added the metal Al powder of the mixture weight ratio 5~15%；
When addition metal powder fluxing agent be Pb powder, need to be added the metal Pb powder of the mixture weight ratio 15~30%；
When addition metal powder fluxing agent be Zn powder, need to be added the metal Zn powder of the mixture weight ratio 5~15%.
The method as described above for using metal powder fluxing agent synthesis of ternary lamellar compound, it is preferable that when the metal of addition Powder fluxing agent is Al powder, and 700~1000 DEG C are warming up under inert protective atmosphere, keeps the temperature 3~5h or 7-11h；Preferably, lazy Property protective atmosphere under be warming up to 700~900 DEG C and keep the temperature 4~5h or 7-11h；
When addition metal powder fluxing agent be Pb powder, be put into quartz ampoule after tabletting, by the stone under inert protective atmosphere English pipe is warming up to 600~900 DEG C and keeps the temperature 15~22h；Preferably, 700~900 DEG C are warming up to and keeps the temperature 15~20h；
When addition metal powder fluxing agent be Zn powder, be warming up under inert protective atmosphere 700~1000 DEG C and keep the temperature 3~ 5h；Preferably, it is warming up to 700~900 DEG C under inert protective atmosphere and keeps the temperature 4~5h.
The method as described above for using metal powder fluxing agent synthesis of ternary lamellar compound, it is preferable that the TiH2Powder, nothing Sizing B powder and hexagonal AlN powder are put into reactor the process that is mixed evenly are as follows: in TiH2Powder, unformed B powder, hexagonal AlN powder are mixed It closes and is added in stirring after dehydrated alcohol is mixed evenly, naturally dry；
Preferably, after 5~30h of dehydrated alcohol mixing is added, naturally dry.
The method as described above for using metal powder fluxing agent synthesis of ternary lamellar compound, it is preferable that dehydrated alcohol adds Enter amount and must satisfy the dehydrated alcohol liquid level and flood completely to exceed TiH2Powder, unformed B powder and the mixed material of hexagonal AlN powder；
Preferably, the additional amount of dehydrated alcohol, which must satisfy the dehydrated alcohol liquid level and flood completely, exceeds TiH2Powder, nothing are fixed Type B powder and the mixed 1~5mm of material of hexagonal AlN powder.
The method as described above for using metal powder fluxing agent synthesis of ternary lamellar compound, it is preferable that the TiH2Powder, institute State the molar ratio TiH of three kinds of raw materials of unformed B powder and the hexagonal AlN powder2: B:BN=(2.5~3.5): (0.7~1.3): (0.7~1.3).
The method as described above for using metal powder fluxing agent synthesis of ternary lamellar compound, it is preferable that the TiH2Powder, institute State the molar ratio TiH of three kinds of raw materials of unformed B powder and the hexagonal AlN powder2: B:BN=(2.5~3): (1~1.3): (1~ 1.3)；
Preferably, the TiH2The molar ratio TiH of three kinds of powder, the unformed B powder and the hexagonal AlN powder raw materials2: B:BN =3:1:1.
The method as described above for using metal powder fluxing agent synthesis of ternary lamellar compound, it is preferable that protect gas in inertia It is heated up under atmosphere with the rate with 5~10 DEG C/min；
Preferably, it is heated up under inert protective atmosphere with the rate with 6~8 DEG C/min.
The method as described above for using metal powder fluxing agent synthesis of ternary lamellar compound, it is preferable that the inertia protection Inert gas under atmosphere is argon gas or nitrogen；
Preferably, the inert gas is argon gas.
The method as described above for using metal powder fluxing agent synthesis of ternary lamellar compound, it is preferable that the dilute hydrochloric acid Concentration is 10-20%；
Preferably, the time that the sample impregnates in the dilute hydrochloric acid is 24~96h.
Compared with the immediate prior art, technical solution provided by the invention has following excellent effect:
1, Ti can be greatly reduced in synthetic method provided by the invention3B2The synthesis temperature of N, the synthetic method are simply easily grasped Make, is suitble to industrial scale production, reduces production cost.
2, in the present invention using addition Al powder fluxing agent, successfully by Ti3B2N synthesis temperature is reduced to 700~1000 DEG C, Using addition Pb powder fluxing agent, successfully by Ti3B2N synthesis temperature is reduced to 600~900 DEG C, using addition Zn powder fluxing agent, Succeed Ti3B2N synthesis temperature is reduced to 700~1000 DEG C；Therefore these three metal powders can be in technical solution of the present invention It is substantially reduced Ti3B2The synthesis temperature of N, it is particularly significant for practical application.
Detailed description of the invention
Fig. 1 Ti3B2The theoretical XRD spectrum of N compound.
The Ti that specific embodiment 1 is prepared using Al fluxing agent in Fig. 2 present invention3B2The XRD spectrum of N sample.
The XRD spectrum of reference examples 1 in Fig. 3 present invention.
The Ti that specific embodiment 2 is prepared using Pb fluxing agent in Fig. 4 present invention3B2The XRD spectrum of N sample.
The XRD spectrum of reference examples 2 in Fig. 5 present invention.
The Ti that specific embodiment 3 is prepared using Zn fluxing agent in Fig. 6 present invention3B2The XRD spectrum of N sample.
The XRD spectrum of reference examples 3 in Fig. 7 present invention.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation Example is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general Logical technical staff's every other embodiment obtained, shall fall within the protection scope of the present invention.
The present invention will be described in detail below with reference to the accompanying drawings and embodiments.It should be noted that in the feelings not conflicted Under condition, the feature in embodiment and embodiment in the present invention be can be combined with each other.
Specific embodiments of the present invention provide a kind of method using metal powder fluxing agent synthesis of ternary lamellar compound, should Ternary layered compound is Ti3B2N synthesizes Ti3B2The method of N includes:
The first step, first by TiH2Mixture is mixed evenly to obtain in powder, unformed B powder and hexagonal AlN powder.
TiH2Powder, unformed B powder and hexagonal AlN powder are put into reactor the process that is mixed evenly are as follows: in TiH2Powder, nothing are fixed Type B powder, hexagonal AlN powder add after dehydrated alcohol is mixed evenly in being mixed, naturally dry；Preferably, it is added anhydrous After 5~30h is mixed in ethyl alcohol, naturally dry
The additional amount of dehydrated alcohol, which must satisfy the dehydrated alcohol liquid level and flood completely, exceeds TiH2Powder, unformed B powder and The mixed material of hexagonal AlN powder；Preferably, the additional amount of dehydrated alcohol must satisfy the dehydrated alcohol liquid level and flood height completely Cross TiH2Powder, unformed B powder and the mixed 1~5mm of material of hexagonal AlN powder (such as 1.5mm, 2mm, 2.5mm, 3mm, 3.5mm, 4mm、4.5mm、4.8mm)。
TiH2The molar ratio TiH of three kinds of powder, the unformed B powder and the hexagonal AlN powder raw materials2: B:BN=(2.5~ 3.5) (such as 2.6,2.7,2.8,2.9,3,3.1,3.2,3.3,3.4): (0.7~1.3) (such as 0.7,0.9,1.0,1.1, 1.15,1.2,1.25,1.26,1.27): (0.7~1.3) (such as 0.7,0.9,1.0,1.1,1.15,1.2,1.25,1.26, 1.27).Preferably, TiH2The molar ratio TiH of three kinds of powder, the unformed B powder and the hexagonal AlN powder raw materials2: B:BN=(2.5 ~3) (such as 2.65,2.75,2.85,2.95): (1~1.3) (such as 1.1,1.15,1.2,1.25,1.26,1.27): (1~ 1.3) (such as 1.1,1.15,1.2,1.25,1.26,1.27)；More preferably, the TiH2Powder, the unformed B powder and described The molar ratio TiH of three kinds of raw materials of hexagonal AlN powder2: B:BN=3:1:1.
Second step is then added metal powder in mixture and as fluxing agent and is uniformly mixed, tabletting, and protects in inertia It is warming up to set temperature and held for some time under atmosphere, obtains sample.
In the present invention, metal powder fluxing agent is Al powder, Pb powder or Zn powder.
When the metal powder fluxing agent of addition is Al powder, 700~1000 DEG C (such as 750 are warming up under inert protective atmosphere ℃、760℃、780℃、800℃、820℃、840℃、860℃、880℃、900℃、920℃、940℃、960℃、980℃、 990 DEG C) and keep the temperature 2~12h (such as 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h、10h、10.5h、11h、11.5h)。
When addition metal powder fluxing agent be Pb powder, be put into quartz ampoule after tabletting, by the stone under inert protective atmosphere English pipe is warming up to 600~900 DEG C of (such as 650 DEG C, 660 DEG C, 680 DEG C, 700 DEG C, 720 DEG C, 740 DEG C, 760 DEG C, 780 DEG C, 800 DEG C, 820 DEG C, 840 DEG C, 860 DEG C, 880 DEG C, 890 DEG C) and keep the temperature 12~for 24 hours (such as 13h, 13.5h, 14h, 14.5h, 15h, 15.5h、16h、16.5h、17h、17.5h、18h、18.5h、19h、19.5h、20h、21h、22h、23h)。
When the metal powder fluxing agent of addition is Zn powder, 700~1000 DEG C (such as 750 are warming up under inert protective atmosphere ℃、760℃、780℃、800℃、820℃、840℃、860℃、880℃、900℃、920℃、940℃、960℃、980℃、 990 DEG C), it keeps the temperature 1~6h such as (1.5h, 1.8h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 5.8h).
Further preferably, when the metal powder fluxing agent of addition be Al powder, be warming up to 700~1000 under inert protective atmosphere DEG C (such as 750 DEG C, 760 DEG C, 780 DEG C, 800 DEG C, 820 DEG C, 840 DEG C, 860 DEG C, 880 DEG C, 900 DEG C, 920 DEG C, 940 DEG C, 960 DEG C, 980 DEG C, 990 DEG C), keep the temperature 3~5h or 7-11h；Preferably, be warming up under inert protective atmosphere 700~900 DEG C (such as 750 DEG C, 760 DEG C, 780 DEG C, 800 DEG C, 820 DEG C, 840 DEG C, 860 DEG C, 870 DEG C, 900 DEG C) and keep the temperature 4~5h or 7-11h.
When addition metal powder fluxing agent be Pb powder, be put into quartz ampoule after tabletting, by the stone under inert protective atmosphere English pipe is warming up to 600~900 DEG C of (such as 650 DEG C, 660 DEG C, 680 DEG C, 700 DEG C, 720 DEG C, 740 DEG C, 760 DEG C, 780 DEG C, 800 DEG C, 820 DEG C, 840 DEG C, 860 DEG C, 880 DEG C, 890 DEG C) and keep the temperature 15~22h；Preferably, be warming up to 700~900 DEG C (such as 750 DEG C, 760 DEG C, 780 DEG C, 800 DEG C, 820 DEG C, 840 DEG C, 860 DEG C, 870 DEG C, 900 DEG C) and keep the temperature 15~20h.
When the metal powder fluxing agent of addition is Zn powder, 700~1000 DEG C (such as 750 are warming up under inert protective atmosphere ℃、760℃、780℃、800℃、820℃、840℃、860℃、880℃、900℃、920℃、940℃、960℃、980℃、 990 DEG C) and keep the temperature 3~5h；Preferably, 700~900 DEG C of (such as 750 DEG C, 760 DEG C, 780 are warming up under inert protective atmosphere DEG C, 800 DEG C, 820 DEG C, 840 DEG C, 860 DEG C, 870 DEG C, 900 DEG C) and keep the temperature 4~5h.
When addition metal powder fluxing agent be Al powder, need to be added the metal Al powder of the mixture weight ratio 5~15%；When The metal powder fluxing agent of addition is Pb powder, need to be added the mixture weight ratio 15~30% (such as 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%) metal Pb powder；When the gold of addition Category powder fluxing agent is Zn powder, need to be added the mixture weight ratio 5~15% (such as 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%) metal Zn powder.
In the present invention, under inert protective atmosphere with 5~10 DEG C/min (such as 5.5 DEG C/min, 6 DEG C/min, 6.5 DEG C/min, 7 DEG C/min, 7.5 DEG C/min, 8 DEG C/min, 8.5 DEG C/min, 9 DEG C/min, 9.5 DEG C/min) rate heat up； Preferably, under inert protective atmosphere with 6~8 DEG C/min (such as 6.2 DEG C/min, 6.5 DEG C/min, 7.3 DEG C/min, 7.6 DEG C/min, 7.8 DEG C/min) rate heat up.
In the present invention, the inert gas under inert protective atmosphere is argon gas or nitrogen；Preferably, the inert gas is Argon gas.
Third step, finally under inert protective atmosphere, after sample cooled to room temperature, then using dilute hydrochloric acid removing sample In remaining metal powder fluxing agent, obtain Ti3B2N。
Wherein the concentration of dilute hydrochloric acid be 10-20% (such as 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%)；Preferably, the time that the sample impregnates in the dilute hydrochloric acid be 24~96h (such as 26h, 27h, 28h, 29h,30h,35h,40h,45h,50h,55h,60h,65h,70h,75h,80h,85h,90h,95h).Specific soaking time depends on In the content of Gold Samples category powder, this is not limited by the present invention.
To sum up, the present invention synthesizes Ti using Al, Pb and Zn fluxing agent3B2The method of N: TiH is pressed2Powder, unformed B powder, The molar ratio TiH of three kinds of raw materials of hexagonal AlN powder2: B:BN=(2.5~3.5): (0.7~1.3): (0.7~1.3) weighs TiH2 Powder, unformed B powder and hexagonal AlN powder；By weighed TiH2Powder, unformed B powder, hexagonal AlN powder mix, and addition metal powder, which is used as, to be helped Flux is uniformly mixed, tabletting, after then heating up and keep the temperature under inert protective atmosphere；After the reaction was completed, in inert protective atmosphere Under, sample cooled to room temperature；Remaining metal powder in sample is removed using dilute hydrochloric acid, obtains Ti3B2N。
In synthetic method of the present invention, using addition Al powder fluxing agent, successfully by Ti3B2N synthesis temperature is reduced to 700 ~1000 DEG C.Using addition Pb powder fluxing agent, successfully by Ti3B2N synthesis temperature is reduced to 600~900 DEG C.Using addition Zn Powder fluxing agent, successfully by Ti3B2N synthesis temperature is reduced to 700~1000 DEG C.Technical solution of the present invention can be successfully by synthesis The main reason for temperature reduces are as follows: at a lower temperature, melted using lower melting-point fluxing agent, there is liquid in this way Under environment, the diffusion for participating in the raw material of solid phase reaction can be promoted, so as to start to react at a lower temperature.It specifically refers to:
I.e. the present invention selects the reason of Al powder fluxing agent: 1) Al fusing point is 660 DEG C low；2) although Al and B has Binary-phase chemical combination Object AlB12In the presence of, but its synthesis temperature needs 1000 DEG C or more；Al and N is with the presence of Binary-phase compound AlN, but its synthesis temperature Need 1200 DEG C or more；The ternary compound of Al-B-N is not present simultaneously.Therefore making fluxing agent using lower melting-point Al powder can have Effect reduces synthesis temperature.
I.e. the present invention selects the reason of Pb powder fluxing agent: 1) Pb fusing point is 327 DEG C low；2) simultaneously there is no Pb-B, Pb-N, The binary or ternary compound of Pb-B-N.Therefore synthesis temperature can be effectively reduced by making fluxing agent using lower melting-point Pb powder.
I.e. the present invention selects the reason of Zn powder fluxing agent: 1) Zn fusing point is 419 DEG C low；2) simultaneously there is no Zn-B, Zn-N, The binary or ternary compound of Zn-B-N.Therefore synthesis temperature can be effectively reduced by making fluxing agent using lower melting-point Zn powder.
Therefore the present invention can be substantially reduced Ti3B2The synthesis temperature of N, it is particularly significant for practical application.
Zn powder, TiH in following embodiment2Powder, unformed B powder and hexagonal AlN powder are commercial product, purity 99.9% More than.
Embodiment 1
Ti is synthesized using Al fluxing agent the present embodiment provides a kind of3B2The method of N synthesizes Ti3B2The method of N includes as follows Step:
1) TiH is weighed respectively2Powder, unformed B powder and hexagonal AlN powder, it is spare；
And TiH2The molar ratio TiH of three kinds of powder, unformed B powder and hexagonal AlN powder raw materials2: B:BN=3:1:1；
2) by TiH weighed in step 1)2Powder, unformed B powder and hexagonal AlN powder are put into container and are mixed evenly, and obtain Mixture；
TiH2Powder, unformed B powder and hexagonal AlN powder are put into container the process that is mixed evenly are as follows: in TiH2It is powder, unformed After adding dehydrated alcohol mixing 18h in B powder, the mixing of hexagonal AlN powder, naturally dry.Wherein, dehydrated alcohol plus Enter amount and must satisfy the dehydrated alcohol liquid level and flood completely to exceed TiH2Powder, unformed B powder and the mixed material of hexagonal AlN powder 3mm。
3) the metal Al powder of the mixture weight ratio 10% is added into the mixture in step 2) as fluxing agent, in Ma It is uniformly mixed in Nao mortar, tabletting (pressure in tableting processes must be in 5MPa) is cold-pressed into biscuit block；Biscuit block is placed in Then tube furnace is warming up to 900 DEG C under inert protective atmosphere with the rate of 10 DEG C/min, keep the temperature 3h.
4) sample is obtained after the completion of step 3)；Under inert protective atmosphere, after sample cooled to room temperature；Sample is set It is to impregnate to remove remaining Al in sample in 15% dilute hydrochloric acid in concentration, the time of immersion is 48h, is diluted with distilled water, is filtered Centrifugation, can obtain Ti3B2N black sample.
Ti manufactured in the present embodiment3B2The XRD spectrum of N product is shown in Fig. 2.Due to Ti3B2N is a kind of newly synthesized substance, because It is not yet included in this X-ray diffraction standard card valut.Using crystal XRD spectra simulation softward poudrix, Ti can be obtained3B2The reason of N By XRD spectrum, Fig. 1 is seen.Fig. 1 and Fig. 2 are compared, it may be determined that main phase is Ti in synthetic sample3B2N compound.Meanwhile sample Also contain a small amount of miscellaneous phase (TiN, JCPDS card number: 38-1420 in product；TiB2, JCPDS card number: 35-0741).
Embodiment 2
Ti is synthesized using Al fluxing agent the present embodiment provides a kind of3B2The method of N synthesizes Ti3B2The method of N includes as follows Step:
1) TiH is weighed respectively2Powder, unformed B powder and hexagonal AlN powder, it is spare；
And TiH2The molar ratio TiH of three kinds of powder, unformed B powder and hexagonal AlN powder raw materials2: B:BN=3.5:0.7:1；
2) by TiH weighed in step 1)2Powder, unformed B powder and hexagonal AlN powder are put into container and are mixed evenly, and obtain Mixture；
TiH2Powder, unformed B powder and hexagonal AlN powder are put into container the process that is mixed evenly are as follows: in TiH2It is powder, unformed After adding dehydrated alcohol mixing 30h in B powder, the mixing of hexagonal AlN powder, naturally dry.The additional amount of dehydrated alcohol must It the dehydrated alcohol liquid level must be met floods completely and exceed TiH2Powder, unformed B powder and the mixed material 2mm of hexagonal AlN powder.
3) the metal Al powder of the mixture weight ratio 15% is added into the mixture in step 2) as fluxing agent, in Ma It is uniformly mixed in Nao mortar, tabletting (pressure in tableting processes must be in 3MPa) is cold-pressed into biscuit block；Biscuit block is placed in Then tube furnace is warming up to 700 DEG C under inert protective atmosphere with the rate of 6 DEG C/min, keep the temperature 4h.
4) sample is obtained after the completion of step 3)；Under inert protective atmosphere, after sample cooled to room temperature；Sample is set It is to impregnate to remove remaining Al in sample in 15% dilute hydrochloric acid in concentration, the time of immersion is 30h, is diluted with distilled water, is filtered Centrifugation, can obtain Ti3B2N black sample.
The XRD spectrum of product manufactured in the present embodiment is not shown.The present embodiment contains Ti3B2N、TiB2With tri- kinds of phases of TiN, And Ti in the sample of embodiment synthesis3B2The content of N is similar in embodiment 1.
Reference examples 1
This reference examples difference from example 1 is that: Al fluxing agent is not added.The same embodiment of other synthesis steps 1。
The XRD spectrum of the product of this reference examples preparation is shown in Fig. 3.From figure 3, it can be seen that the comparative example and embodiment 1 its Its condition is identical, but in the case where being added without Al fluxing agent, comparative example can not obtain Ti3B2N phase.
Embodiment 3
Ti is synthesized using Pb fluxing agent the present embodiment provides a kind of3B2The method of N synthesizes Ti3B2The method of N includes as follows Step:
1) TiH is weighed respectively2Powder, unformed B powder and hexagonal AlN powder, it is spare；
And TiH2The molar ratio TiH of three kinds of powder, unformed B powder and hexagonal AlN powder raw materials2: B:BN=3:1:1；
2) by TiH weighed in step 1)2Powder, unformed B powder and hexagonal AlN powder are put into container and are mixed evenly, and obtain Mixture；
TiH2Powder, unformed B powder and hexagonal AlN powder are put into container the process that is mixed evenly are as follows: in TiH2It is powder, unformed After adding dehydrated alcohol mixing 18h in B powder, the mixing of hexagonal AlN powder, naturally dry.Wherein, dehydrated alcohol plus Enter amount and must satisfy the dehydrated alcohol liquid level and flood completely to exceed TiH2Powder, unformed B powder and the mixed material of hexagonal AlN powder 3mm。
3) the metal Pb powder of the mixture weight ratio 20% is added into the mixture in step 2) as fluxing agent, in Ma It is uniformly mixed in Nao mortar, tabletting (pressure in tableting processes must be in 5MPa) is cold-pressed into biscuit block；Biscuit block is placed in In quartz ampoule, vacuumizes and be filled with Ar gas, sealed silica envelope；The quartz ampoule is warming up to 800 DEG C with the rate of 10 DEG C/min, heat preservation 18h。
4) sample is obtained after the completion of step 3)；After sample is with furnace cooled to room temperature；It is 15% that sample, which is placed in concentration, It is impregnated in dilute hydrochloric acid and removes remaining Pb in sample, the time of immersion is 48h, is diluted, filter centrifugation, can be obtained with distilled water Ti3B2N black sample.
Ti manufactured in the present embodiment3B2The XRD spectrum of N product is shown in Fig. 4.Due to Ti3B2N is a kind of newly synthesized substance, because It is not yet included in this X-ray diffraction standard card valut.Using crystal XRD spectra simulation softward poudrix, Ti can be obtained3B2The reason of N By XRD spectrum, Fig. 1 is seen.Fig. 1 and Fig. 4 are compared, it may be determined that main phase is Ti in synthetic sample3B2N compound.Meanwhile sample Also contain a small amount of miscellaneous phase (TiN, JCPDS card number: 38-1420 in product；TiB2, JCPDS card number: 35-0741).
Embodiment 4
Ti is synthesized using Pb fluxing agent the present embodiment provides a kind of3B2The method of N synthesizes Ti3B2The method of N includes as follows Step:
1) TiH is weighed respectively2Powder, unformed B powder and hexagonal AlN powder, it is spare；
And TiH2The molar ratio TiH of three kinds of powder, unformed B powder and hexagonal AlN powder raw materials2: B:BN=3:0.8:0.8；
2) by TiH weighed in step 1)2Powder, unformed B powder and hexagonal AlN powder are put into container and are mixed evenly, and obtain Mixture；
TiH2Powder, unformed B powder and hexagonal AlN powder are put into container the process that is mixed evenly are as follows: in TiH2It is powder, unformed After adding dehydrated alcohol mixing 25h in B powder, the mixing of hexagonal AlN powder, naturally dry.The additional amount of dehydrated alcohol must It the dehydrated alcohol liquid level must be met floods completely and exceed TiH2Powder, unformed B powder and the mixed material 4mm of hexagonal AlN powder.
3) the metal Pb powder of the mixture weight ratio 20% is added into the mixture in step 2) as fluxing agent, in Ma It is uniformly mixed in Nao mortar, tabletting (pressure in tableting processes must be in 8MPa) is cold-pressed into biscuit block；Biscuit block is placed in In quartz ampoule, vacuumizes and be filled with Ar gas, sealed silica envelope；The quartz ampoule is warming up to 800 DEG C with the rate of 8 DEG C/min, heat preservation 17h。
4) sample is obtained after the completion of step 3)；After sample is with furnace cooled to room temperature；It is 12% that sample, which is placed in concentration, It is impregnated in dilute hydrochloric acid and removes remaining Pb in sample, the time of immersion is 40h, is diluted, filter centrifugation, can be obtained with distilled water Ti3B2N black sample.
The XRD spectrum of product manufactured in the present embodiment is not shown.The present embodiment contains Ti3B2N、TiB2With tri- kinds of phases of TiN, And Ti in the sample of embodiment synthesis3B2The content of N is similar in embodiment 3.
Reference examples 2
This reference examples and embodiment 3 the difference is that: Pb fluxing agent is not added, does not carry out salt acid soak.Its His synthesis step is the same as embodiment 3.
The XRD spectrum of the product of this reference examples preparation is shown in Fig. 5.From fig. 5, it can be seen that the comparative example and embodiment 3 its Its condition is identical, but in the case where being added without Pb fluxing agent, comparative example can not obtain Ti3B2N phase.
Embodiment 5
Ti is synthesized using Zn fluxing agent the present embodiment provides a kind of3B2The method of N synthesizes Ti3B2The method of N includes as follows Step:
1) TiH is weighed respectively2Powder, unformed B powder and hexagonal AlN powder, it is spare；
And TiH2The molar ratio TiH of three kinds of powder, unformed B powder and hexagonal AlN powder raw materials2: B:BN=3:1:1；
2) by TiH weighed in step 1)2Powder, unformed B powder and hexagonal AlN powder are put into container and are mixed evenly, and obtain Mixture；
TiH2Powder, unformed B powder and hexagonal AlN powder are put into container the process that is mixed evenly are as follows: in TiH2It is powder, unformed After adding dehydrated alcohol mixing 18h in B powder, the mixing of hexagonal AlN powder, naturally dry.Wherein, dehydrated alcohol plus Enter amount and must satisfy the dehydrated alcohol liquid level and flood completely to exceed TiH2Powder, unformed B powder and the mixed material of hexagonal AlN powder 3mm。
3) the metal Zn powder of the mixture weight ratio 10% is added into the mixture in step 2) as fluxing agent, in Ma It is uniformly mixed in Nao mortar, tabletting (pressure in tableting processes must be in 5MPa) is cold-pressed into biscuit block；Biscuit block is placed in Then tube furnace is warming up to 900 DEG C under inert protective atmosphere with the rate of 10 DEG C/min, keep the temperature 3h.
4) sample is obtained after the completion of step 3)；Under inert protective atmosphere, after sample cooled to room temperature；Sample is set It is to impregnate to remove remaining Zn in sample in 15% dilute hydrochloric acid in concentration, the time of immersion is 48h, is diluted with distilled water, is filtered Centrifugation, can obtain Ti3B2N black sample.
Ti manufactured in the present embodiment3B2The XRD spectrum of N product is shown in Fig. 6.Due to Ti3B2N is a kind of newly synthesized substance, because It is not yet included in this X-ray diffraction standard card valut.Using crystal XRD spectra simulation softward poudrix, Ti can be obtained3B2The reason of N By XRD spectrum, Fig. 1 is seen.Fig. 1 and Fig. 6 are compared, it may be determined that main phase is Ti in synthetic sample3B2N compound.Meanwhile sample Also contain a small amount of miscellaneous phase (TiN, JCPDS card number: 38-1420 in product；TiB2, JCPDS card number: 35-0741).
Embodiment 6
Ti is synthesized using Zn fluxing agent the present embodiment provides a kind of3B2The method of N synthesizes Ti3B2The method of N includes as follows Step:
1) TiH is weighed respectively2Powder, unformed B powder and hexagonal AlN powder, it is spare；
And TiH2The molar ratio TiH of three kinds of powder, unformed B powder and hexagonal AlN powder raw materials2: B:BN=2.5:1:1.3；
2) by TiH weighed in step 1)2Powder, unformed B powder and hexagonal AlN powder are put into container and are mixed evenly, and obtain Mixture；
TiH2Powder, unformed B powder and hexagonal AlN powder are put into container the process that is mixed evenly are as follows: in TiH2It is powder, unformed After adding dehydrated alcohol mixing 10h in B powder, the mixing of hexagonal AlN powder, naturally dry.The additional amount of dehydrated alcohol must It the dehydrated alcohol liquid level must be met floods completely and exceed TiH2Powder, unformed B powder and the mixed material 5mm of hexagonal AlN powder.
3) the metal Zn powder of the mixture weight ratio 12% is added into the mixture in step 2) as fluxing agent, in Ma It is uniformly mixed in Nao mortar, tabletting (pressure in tableting processes must be in 4MPa) is cold-pressed into biscuit block；Biscuit block is placed in Then tube furnace is warming up to 850 DEG C under inert protective atmosphere with the rate of 7 DEG C/min, keep the temperature 4.5h.
4) sample is obtained after the completion of step 3)；Under inert protective atmosphere, after sample cooled to room temperature；Sample is set It is to impregnate to remove remaining Zn in sample in 16% dilute hydrochloric acid in concentration, the time of immersion is 80h, is diluted with distilled water, is filtered Centrifugation, can obtain Ti3B2N black sample.
The XRD spectrum of product manufactured in the present embodiment is not shown.The present embodiment contains Ti3B2N、TiB2With tri- kinds of phases of TiN, And Ti in the sample of embodiment synthesis3B2The content of N is similar in embodiment 5.
Reference examples 3
This reference examples and embodiment 5 the difference is that: Zn fluxing agent is not added.The same embodiment of other synthesis steps 5。
The XRD spectrum of the product of this reference examples preparation is shown in Fig. 7.From figure 7 it can be seen that the comparative example and embodiment 5 its Its condition is identical, but in the case where being added without Zn fluxing agent, comparative example can not obtain Ti3B2N phase.
In conclusion the present invention has the following technical effect that
1, Ti can be greatly reduced in synthetic method provided by the invention3B2The synthesis temperature of N, the synthetic method are simply easily grasped Make, is suitble to industrial scale production, reduces production cost.
2, in the present invention using addition Al powder fluxing agent, successfully by Ti3B2N synthesis temperature is reduced to 700~1000 DEG C, Using addition Pb powder fluxing agent, successfully by Ti3B2N synthesis temperature is reduced to 600~900 DEG C, using addition Zn powder fluxing agent, Succeed Ti3B2N synthesis temperature is reduced to 700~1000 DEG C；Therefore these three metal powders can be in technical solution of the present invention It is substantially reduced Ti3B2The synthesis temperature of N, it is particularly significant for practical application.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Mind and principle within, any modification, equivalent replacement, improvement and so on, accompanying claims protection scope of the present invention it It is interior.

Claims (10)

1.一种采用金属粉助熔剂合成三元层状化合物的方法，其特征在于，所述三元层状化合物为Ti3B2N，合成所述Ti3B2N的方法包括：1. A method for synthesizing a ternary layered compound using a metal powder flux, wherein the ternary layered compound is Ti 3 B 2 N, and the method for synthesizing the Ti 3 B 2 N comprises: 首先将TiH2粉、无定型B粉和六方BN粉混合搅拌均匀得混合料；接着在混合料中加入金属粉作为助熔剂并混合均匀，压片，并在惰性保护气氛下升温到设定温度并保温一定时间，得样品；最后在惰性保护气氛下，样品自然冷却至室温后，再采用稀盐酸除去样品中残留的金属粉助熔剂，得Ti3B2N；Firstly, the TiH 2 powder, amorphous B powder and hexagonal BN powder are mixed and stirred evenly to obtain a mixture; then metal powder is added as a flux in the mixture and mixed evenly, pressed into tablets, and heated to a set temperature under an inert protective atmosphere And keep for a certain period of time to obtain the sample; finally, under the inert protective atmosphere, after the sample is naturally cooled to room temperature, dilute hydrochloric acid is used to remove the residual metal powder flux in the sample to obtain Ti 3 B 2 N; 所述金属粉助熔剂为Al粉、Pb粉或者Zn粉；The metal powder flux is Al powder, Pb powder or Zn powder; 当加入的金属粉助熔剂为Al粉，在惰性保护气氛下升温到700～1000℃并保温2～12h；When the added metal powder flux is Al powder, the temperature is raised to 700～1000℃ in an inert protective atmosphere and kept for 2～12h; 当加入的金属粉助熔剂为Pb粉，压片后放入石英管中，在惰性保护气氛下将该石英管升温至600～900℃并保温12～24h；When the added metal powder flux is Pb powder, it is put into a quartz tube after tableting, and the quartz tube is heated to 600-900°C under an inert protective atmosphere and kept for 12-24 hours; 当加入的金属粉助熔剂为Zn粉，在惰性保护气氛下升温到700～1000℃，保温1～6h。When the added metal powder flux is Zn powder, the temperature is raised to 700-1000 ℃ under an inert protective atmosphere, and the temperature is kept for 1-6 hours. 2.如权利要求1所述的采用金属粉助熔剂合成三元层状化合物的方法，其特征在于，在混合料中加入金属粉的量具体如下：2. the method that adopts metal powder flux to synthesize ternary layered compound as claimed in claim 1 is characterized in that, the amount that adds metal powder in the mixture is specifically as follows: 当加入的金属粉助熔剂为Al粉，需要加入该混合料重量比5～15％的金属Al粉；When the added metal powder flux is Al powder, it is necessary to add metal Al powder with a weight ratio of 5 to 15% of the mixture; 当加入的金属粉助熔剂为Pb粉，需要加入该混合料重量比15～30％的金属Pb粉；When the added metal powder flux is Pb powder, it is necessary to add metal Pb powder with a weight ratio of 15 to 30% of the mixture; 当加入的金属粉助熔剂为Zn粉，需要加入该混合料重量比5～15％的金属Zn粉。When the added metal powder flux is Zn powder, it is necessary to add metal Zn powder with a weight ratio of 5 to 15% of the mixture. 3.如权利要求1所述的采用金属粉助熔剂合成三元层状化合物的方法，其特征在于，3. the method that adopts metal powder flux to synthesize ternary layered compound as claimed in claim 1 is characterized in that, 当加入的金属粉助熔剂为Al粉，在惰性保护气氛下升温到700～1000℃，保温3～5h或7-11h；优选地，在惰性保护气氛下升温至700～900℃并保温4～5h或7-11h；When the added metal powder flux is Al powder, the temperature is raised to 700-1000 ℃ under an inert protective atmosphere, and the temperature is kept for 3-5 h or 7-11 h; 5h or 7-11h; 当加入的金属粉助熔剂为Pb粉，压片后放入石英管中，在惰性保护气氛下将该石英管升温至600～900℃并保温15～22h；优选地，升温至700～900℃并保温15～20h；When the added metal powder flux is Pb powder, it is put into a quartz tube after tableting, and the quartz tube is heated to 600-900°C under an inert protective atmosphere and kept for 15-22 hours; preferably, the temperature is raised to 700-900°C And keep warm for 15-20h; 当加入的金属粉助熔剂为Zn粉，在惰性保护气氛下升温到700～1000℃并保温3～5h；优选地，在惰性保护气氛下升温至700～900℃并保温4～5h。When the added metal powder flux is Zn powder, the temperature is raised to 700-1000°C under an inert protective atmosphere and kept for 3-5 hours; preferably, the temperature is raised to 700-900°C under an inert protective atmosphere and kept for 4-5 hours. 4.如权利要求1所述的采用金属粉助熔剂合成三元层状化合物的方法，其特征在于，所述TiH2粉、无定型B粉和六方BN粉放入反应器中混合搅拌均匀过程为：在TiH2粉、无定型B粉、六方BN粉混合搅拌中再加入无水乙醇混合搅拌均匀后，自然晾干；4. the method for synthesizing ternary layered compound using metal powder flux as claimed in claim 1 , is characterized in that, described TiH powder, amorphous B powder and hexagonal BN powder are put into the reactor and mix and stir evenly process It is as follows: add anhydrous ethanol in the mixing and stirring of TiH 2 powder, amorphous B powder and hexagonal BN powder, mix and stir evenly, and then dry it naturally; 优选地，加入无水乙醇混合搅拌5～30h后，自然晾干。Preferably, after adding anhydrous ethanol, mixing and stirring for 5-30 hours, it is naturally air-dried. 5.如权利要求4所述的采用金属粉助熔剂合成三元层状化合物的方法，其特征在于，无水乙醇的加入量必须满足该无水乙醇液面完全淹没高过TiH2粉、无定型B粉和六方BN粉混合后的物料；5. the method for synthesizing ternary layered compound using metal powder flux as claimed in claim 4, is characterized in that, the add-on of absolute ethanol must satisfy that this absolute ethanol liquid level is completely submerged higher than TiH 2 powder, no The material mixed with the stereotyped B powder and the hexagonal BN powder; 优选地，无水乙醇的加入量必须满足该无水乙醇液面完全淹没高过TiH2粉、无定型B粉和六方BN粉混合后的物料1～5mm。Preferably, the amount of anhydrous ethanol added must be such that the liquid level of the anhydrous ethanol completely submerges 1-5 mm higher than the mixed material of TiH 2 powder, amorphous B powder and hexagonal BN powder. 6.如权利要求1所述的采用金属粉助熔剂合成三元层状化合物的方法，其特征在于，所述TiH2粉、所述无定型B粉和所述六方BN粉三种原料的摩尔比TiH2：B：BN＝(2.5～3.5)：(0.7～1.3)：(0.7～1.3)。6. the method for synthesizing ternary layered compound using metal powder flux as claimed in claim 1, is characterized in that, the mole of three kinds of raw materials of described TiH powder, described amorphous B powder and described hexagonal BN powder Ratio TiH 2 :B:BN=(2.5-3.5):(0.7-1.3):(0.7-1.3). 7.如权利要求6所述的采用金属粉助熔剂合成三元层状化合物的方法，其特征在于，所述TiH2粉、所述无定型B粉和所述六方BN粉三种原料的摩尔比TiH2：B：BN＝(2.5～3)：(1～1.3)：(1～1.3)；7. the method for synthesizing ternary layered compound using metal powder flux as claimed in claim 6, is characterized in that, described TiH 2 powder, described amorphous B powder and described hexagonal BN powder three kinds of moles of raw materials Ratio TiH 2 :B:BN=(2.5～3):(1～1.3):(1～1.3); 优选地，所述TiH2粉、所述无定型B粉和所述六方BN粉三种原料的摩尔比TiH2：B：BN＝3：1：1。Preferably, the molar ratio of the three raw materials of the TiH 2 powder, the amorphous B powder and the hexagonal BN powder is TiH 2 :B:BN=3:1:1. 8.如权利要求1所述的采用金属粉助熔剂合成三元层状化合物的方法，其特征在于，在惰性保护气氛下以以5～10℃/min的速率进行升温；8. The method for synthesizing a ternary layered compound using a metal powder flux as claimed in claim 1, wherein the temperature is increased at a rate of 5 to 10°C/min under an inert protective atmosphere; 优选地，在惰性保护气氛下以以6～8℃/min的速率进行升温。Preferably, the temperature rises at a rate of 6-8°C/min under an inert protective atmosphere. 9.如权利要求1所述的采用金属粉助熔剂合成三元层状化合物的方法，其特征在于，所述惰性保护气氛下的惰性气体为氩气或氮气；9. The method for synthesizing a ternary layered compound using a metal powder flux as claimed in claim 1, wherein the inert gas under the inert protective atmosphere is argon or nitrogen; 优选地，所述惰性气体为氩气。Preferably, the inert gas is argon. 10.如权利要求1所述的采用金属粉助熔剂合成三元层状化合物的方法，其特征在于，所述稀盐酸的浓度为10-20％；10. The method for synthesizing a ternary layered compound using a metal powder flux as claimed in claim 1, wherein the concentration of the dilute hydrochloric acid is 10-20%; 优选地，所述样品在所述稀盐酸中浸泡的时间为24～96h。Preferably, the soaking time of the sample in the dilute hydrochloric acid is 24-96 hours.
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田灿鑫等: "电弧离子镀制备TiBN 纳米复合涂层", 《表面技术》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110256083A (en) * 2019-07-29 2019-09-20 河南理工大学 One kind is with TiH2For the Ti of titanium source2AlN ceramic powder and preparation method thereof

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