CN101824556A - Method for producing ferrovanadium nitride by adopting self-propagating high temperature synthesis process - Google Patents
Method for producing ferrovanadium nitride by adopting self-propagating high temperature synthesis process Download PDFInfo
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Abstract
The invention relates to a method for producing ferrovanadium nitride by adopting a self-propagating high temperature synthesis process, which comprises the following steps of: firstly, crushing ferrovanadium in grinding equipment; drying and then charging the crushed ferrovanadium into a crucible in bulk; placing the crucible into a high-pressure synthesizer and filling 6-12MPa of nitrogen; starting an igniting device and igniting the raw materials to carry out synthetic reaction; automatically sustaining combustion synthesis reaction; and cooling and taking out the combusted and synthesized ferrovanadium nitride in the nitrogen and crushing into blocks, wherein the ferrovanadium and the nitrogen are used as raw materials. The method for synthesizing and producing the ferrovanadium nitride does not need additional energy sources, has no pollution, high synthesis speed, energy saving, environmental protection and high efficiency and is a hi-tech production process which is worthy of popularization.
Description
Technical field
The invention belongs to the production method of self propagating high temperature synthetic (claiming that also burning is synthetic) nitrided iron alloy, mainly be applicable to the production of ferrovanadium nitride.
Background technology
China is maximum in the world Iron and Steel Production state, also is maximum in the world steel consumption state.But what use was maximum in steel is low carbon-structural steel, accounts for the 70%[" steel vanadium titanium " 2005,26 (3): 7 of steel usage quantity], the intensity that therefore improves straight carbon steel is to promote China's Iron And Steel Industry technical progress, carries out the important directions that iron structure is adjusted.The method of its solution is the research and extension that strengthens microalloyed steel.Microalloying is meant and adds carbonitride forming elements such as micro-niobium, vanadium, titanium again that on the basis of former alloy generally its add-on is 0.02～0.20%.After adding the carbonitride forming element, in the heating and cooling process of steel processing, by the dissolving of this element in steel with separate out the mechanical property of behavior and play a role steel.Its strengthening mechanism mainly is that crystal grain thinning is strengthened and precipitation strength.These two kinds of schedule of reinforcements surpass 70% to the contribution of the yield strength of steel, have demonstrated fully the advantage of micro alloying element at technology, economic aspect.Adopt v n micro alloying, do not need to add again other valuable alloying element, under general hot-rolled condition, just can obtain the high-strength steel that yield strength is 550～600Mpa level, therefore in Products Development such as the isometric material of high strength cast iron and steel plate (band), slab, heavy wall shaped steel, weldless steel tube, CSP, obtain application widely.
In microalloyed steel, the microalloying of vanadium occupies critical role.According to statistics, the trade mark of chemical ingredients has 186 as can be known in various countries' microalloyed steel, the steel grade that wherein contains vanadium accounts for 158, contains 9 of niobium steel grades, 14 [" steel vanadium titaniums " 2000 of the compound steel grade of vanadium niobium, 21 (3): 29-33], and all have been included in the microalloying steel grade trade mark in the national standard in China, and the steel grade that contains vanadium has 139, contains 37 of niobium steel grades, 14 of rare earth steel grades [" steel vanadium titanium " 2000,21 (3): 1-10].This shows that in microalloyed steel, containing vanadium steel is leading kind, this is the same with ordinary steel because contain the rolling technology of vanadium steel, need not add special working condition.China is vanadium resource big country, and vanadium goods output occupies the third place in the world, and the microalloyed steel of development vanadium is with the obvious advantage.At present, China is in the Infrastructure stage of greatly developing, construction with material still based on straight carbon steel, and developed countries adopts the ratio of low (little) steel alloy to reach 40～50%, practical application shows, adopts the comparable straight carbon steel of low (little) steel alloy to save 20～30% steel, therefore, enlarge the application of low (little) steel alloy, the application that particularly enlarges the microalloyed steel of vanadium acquire a special sense [" microalloying knowledge lecture " " middle letter metal company " 2000: 83].
U.S. strategic mineral company carried out applying of VN alloy technological development and patented product VN alloy thereof at the steel industry of China in 1998, more domestic steel mills have carried out application test in producing the production of HRB400 grade reinforcing steel, domestic research unit and some big steel mills have carried out big quantity research to adding VN alloy in the steel to the influence and the strengthening mechanism of steel mechanics performance, the result shows: the nitrogen in the VN alloy as the alloying element of cheapness after vanadium adds in the steel, it is better not only can to produce performance, more stable HRB400MpaIII level Twisted Steel and V-N steel, the add-on that simultaneously can also save the 30-40% vanadium greatly reduces steel product cost.American side declares, but the U.S. is the country of unique commercial production VN alloy, but this technology unofficial biography not.Domestic enterprise is through after the tackling key problem test, the VN alloy that can be mass-produced at present, but at present the output of China's vanadium-nitrogen alloy product not satisfy steel such as domestic production high strength cast iron required.We adopted self propagating high temperature synthetic technology development and produce ferrovanadium nitride since 2003, and some big steel mills are successfully applied to the production of V-N steel at home, and result of use quite or be better than U.S.'s VN alloy.
When being USSR (Union of Soviet Socialist Republics) academy of sciences chemical physics place exploration rocket solid fuel in 1967, the self propagating high temperature synthetic technology finds, its composition principle is that the outside minute quantity energy that is provided is provided earlier, bring out high heat-producing chemical reaction, to form the combustion wave of reaction leading edge, after this building-up reactions is brought out the continuation chemical reaction of contiguous material again under the support of self heat release, finish up to whole material reactions.The advantage of self propagating high temperature synthetic technology is energy-conservation (building-up process does not need external energy), efficient (resultant velocity is exceedingly fast), environmental protection (discharge of building-up process contamination-free), high-quality (stable components, purity height).The self propagating high temperature synthetic technology is the hi-tech in current synthetic field, and during " eight or five ", national 863 Program has been set up " self propagating high temperature synthetic technology research project " [" powder metallurgy technology ", 1992,10 (3): 223].At the end of the eighties in last century, the many units of China have carried out the research of this respect.
Self propagating high temperature synthesizes need not external heat source in building-up process, so possibility that focuses on discussing its reaction of calculation of thermodynamics, it is the basis that Combination Process of SHS is discussed, and this building-up reactions adiabatic combustion temperature (Tad) that directly calculates according to the thermodynamics formula, be again to characterize burning synthetic important parameter, all significant for theoretical investigation of self propagating high temperature synthetic and application.The prediction Combination Process of SHS realizes that the most reliable method of possibility is to calculate the adiabatic combustion temperature of given mixed system, and it is a qualitative foundation of judging that can combustion synthesis reaction self-be kept.Some general experience criterions of proposition such as self propagating high temperature synthesis technique originator Merzhanov [" burning synthetic " 1999:P.56]: when having only Tad＞1800K, the self propagating high temperature building-up reactions could continue to carry out certainly.Nitrogenize for the vanadium iron raw material, mainly be to calculate adiabatic combustion temperature by the reaction of vanadium and nitrogen, the adiabatic combustion temperature of vanadium nitrogen compound building-up reactions is 3500K, even its adiabatic combustion temperature of 50 vanadium iron also proposes the requirement of Tad＞1800K empirical value near Merzhanov etc.
Summary of the invention
Technical problem solved by the invention is that with various trade mark vanadium iron and high pure nitrogen be raw material, adopt the self propagating high temperature synthesis technique to produce ferrovanadium nitride, and make the result of use of this product in steel-making quite or be better than the VN alloy that current domestic each steel mill uses.
Technical scheme of the present invention is: a kind of method that adopts the self propagating high temperature synthesis technique to produce ferrovanadium nitride, raw material is vanadium iron and nitrogen, at first that the raw material vanadium iron is broken in abrasive blast equipment, in bulk in crucible behind the vanadium iron raw material drying that fragmentation is good, place crucible in the high pressure synthesizer and charge into the nitrogen of 6-12Mpa, the starting ignition device raw material that ignites carries out building-up reactions, and combustion synthesis reaction is from continuing to carry out, burning synthetic ferrovanadium nitride cools off the back and takes out in nitrogen, be broken into piece.
Wherein: for the vanadiumcontent massfraction greater than 58% vanadium iron raw material; oxidized in shattering process for preventing vanadium iron; shattering process need adopt nitrogen or protection of inert gas raw material, and nitrogen in the abrasive blast equipment or rare gas element gas content reach the massfraction more than 98% that accounts for total mass.
When the massfraction of vanadium in the vanadium iron greater than 60% the time, the inert diluent that needs to add the massfraction that accounts for total mass and be 0-20% is to reduce synthesis temperature.
This inert diluent is the broken powder of ferrovanadium nitride.
The size composition of raw material vanadium iron fragmentation is: the massfraction that 40～100 orders account for total mass is that massfraction that 0～15%, 100～200 orders account for total mass is that the massfraction that 40～50%,＜200 orders account for total mass is 40～60%.
When nitrogen pressure drops to 5.5～6.0Mpa in the high pressure synthesizer, need ftercompction in high pressure vessel, promptly feed nitrogen and make pressure maintain 6～12Mpa.
The raw material vanadium iron is 50 vanadium iron, 60 vanadium iron or 80 vanadium iron.
Bake out temperature is 50～70 ℃, and drying time is 2～4 hours.
Beneficial effect of the present invention is: adopt self propagating high temperature synthetic ferrovanadium nitride product performance to be better than VN alloy, show that the rate of recovery of vanadium is higher than VN alloy, the steel mechanics performance undulating quantity dwindles greatly, and the steel over-all properties is more stable.Utilize method of the present invention to can be used as the ferrovanadium nitride that a kind of general production technique is used to produce the various content of vanadium trades mark.50 vanadium iron, 60 vanadium iron or 80 vanadium iron that adopt present commercial production are that the various trade mark ferrovanadium nitrides of raw material production all can be achieved success.
In addition, adopt the synthetic ferrovanadium nitride of producing of self propagating high temperature of the present invention, need not external energy, pollution-free, resultant velocity is fast, and energy-saving and environmental protection, efficient are a kind of hi-tech production technique that is worthy to be popularized.
The ferrovanadium nitride product of producing is used in enterprises such as Xinxin Vanadium Titanium Co., Ltd., Chengde City, capital Steel stock Co., Ltd, Tangshan Iron ﹠ Steel Co., Ltd., successfully produce qualified HRB400 level (III level), HRB500 level (IV level), English and mark 460 grade high-strength Twisted Steels, these products show that undulating quantity dwindles greatly on the steel mechanics performance, quality product is more stable, than using vanadium iron to save vanadium 20～40%, than using VN alloy to save vanadium 4～7%.
Description of drawings
Fig. 1 produces the FB(flow block) of the method for ferrovanadium nitride for the present invention adopts the self propagating high temperature synthesis technique.
Embodiment
Below the principle of at first self propagating high temperature synthesis technique of the present invention being produced the method for ferrovanadium nitride is carried out brief description.
The raw material that the present invention produces the method use of ferrovanadium nitride can be 50 vanadium iron (FeV50), 60 vanadium iron (FeV60) or 80 vanadium iron (FeV80) and high pure nitrogen (N
2), mainly calculating adiabatic combustion temperature by the reaction of V and N, the adiabatic combustion temperature of vanadium nitrogen compound building-up reactions is 3500K, the condition that as seen adopts the self propagating high temperature synthetic technology to synthesize ferrovanadium nitride can satisfy the requirement of Tad＞1800K.Though the synthetic heat of FeV50 is on the low side, but the adiabatic combustion temperature of synthetic system can satisfy by the change to combustion conditions, as change the quality etc. of the granularity of raw material, initial synthesis temperature, unit volume internal heat generation material, to improve or to reduce adiabatic combustion temperature within the specific limits.In addition, the solubleness of nitrogen in refractory metal is big, and the volume heat is emitted in dissolving can keep burning synthetic [" burning is synthetic " 1999:P.124].For the nitrogenize of some refractory metals, the propelling of combustion wave is the result who forms sosoloid, and nitrogenize is the result of afterfire fully.After so-called afterfire was meant that combustion wave passes through, still the long period was in quite high temperature, continuation reaction and structural transformation to sample.Vanadium also is a refractory metal, and its synthesis temperature that takes fire is lower than the adiabatic combustion temperature in the calculating, but belongs to the category of stable burning.Secondly, can see that from the phase equilibrium diagram of Fe and V a phase change zone is arranged near the FeV50 composition, studies show that the existence of phase change zone can improve 3 times [" burning is synthetic " 1999:P.124] of building-up reactions speed, it is synthetic that this helps the FeV50 nitrogenize.Among standard GB/T4139-2004, the V content of FeV50 is 48.0～55.0%, and the V content of FeV60 is 58.0～65.0%, and the V content of FeV80 is 78.0～82.0% (above-mentioned percentage ratio is all massfraction).If can synthesize ferrovanadium nitride to the FeV50 of 48.0%V, just can synthesize ferrovanadium nitride to V content 82.0% with all interior vanadium iron raw materials, and make the self propagating high temperature synthesis technique become the common processes that synthesizes ferrovanadium nitride.Because the increase of vanadium iron weight alloy after nitrogenize, the content of vanadium in the sintetics is 42.0～72.0%, and nitrogen content is 9.0～17.0%, and the also corresponding decline of other foreign matter content in the vanadium iron raw material more helps satisfying the steel-making demand.
The synthetic infiltration burning synthetic system that belongs to of ferrovanadium nitride, Gu-solid/liquid/gas reactions occupies critical role, is that gas-permeable is gone into chemical transformation and the structural transformation process that takes place in the porous medium.In the infiltration of ferrovanadium nitride is synthetic, a kind of reactant is porous medium (vanadium iron in bulk), another kind of reactant is gaseous oxidant (nitrogen), nitrogen is reagent, it is again carrier, the material transfer in its participation reaction and the transmission of heat, the power of nitrogen infiltration is the interior nitrogen of high-pressure system and the nitrogen pressure reduction in building-up reactions interval, the big more then nitrogen gas stream of pressure reduction is big more.When naturally osmotic was synthetic, the supply of nitrogen was determined by chemical reaction itself.If gas and metal reaction are fast, in fact the gaseous tension of reaction zone can be reduced to zero, and extraneous gas then is easy to be penetrated into reaction zone; If gas and metal reaction are slow, gas-permeable is just few to reaction zone.Because nitrogen is the gas of participating in building-up reactions, constantly is consumed in building-up process, nitrogen gas pressure constantly descends, so the osmotic engine of nitrogen constantly reduces.Another important factor of nitrogen infiltration is the osmotic resistance of nitrogen, and the factor that influences osmotic resistance is as follows:
1, powder size, size composition and granularity shape promptly form relevant with the passage in hole;
2, relevant with the material amount of distance of permeating and adding, material amount distance big more or infiltration is long more, and the resistance of infiltration is big more;
3, relevant with the volume increase of synthetic product, the volume of general synthetic product is greater than the volume of metal, so the passage of nitrogen infiltration diminishes, the resistance of infiltration increases;
4, relevant with the sintering situation of synthetic material, sintetics is finer and close, and the resistance of infiltration is big more;
5,, as metal pool occurs and can stop up gas passage because of effect capillaceous with whether metal pool to occur relevant.
In a word, when burning was synthetic, along with the prolongation in reaction times, the osmotic engine of nitrogen constantly reduced, and the resistance of infiltration constantly increases.When the infiltration rate of nitrogen drops to a certain degree, the variation of combustion mode will appear, and successively burning and two kinds of patterns of surface combustion promptly appear.Successively burning is that nitrogen is penetrated into sample interior from the outside by hole, and combustion wave one deck connects one deck ground and advances in entire sample, obtains macroscopic view products of combustion uniformly, and this is the synthetic desirable result of burning.Surface combustion is the surface that reaction only occurs in sample, and materials inside does not react.
Merzhanov etc. propose the criterion [" burning is synthetic " 1999:P.118] of two kinds of combustion modes of a difference:
∏＝Tp/Tr＝Um·d/Kp·P2
In the formula:
∏-nondimensional judgement parameter;
Tp, Tr-are the characteristic time of infiltration and chemical reaction (burning);
The Um-quality combustion speed; The Kp-permeability coefficient;
The D-sample diameter; The P-pressure of ambient gas;
When ∏＜1, infiltration rate is greater than chemical reaction rate, and gas reaches the burning aspect if having time, forms burning successively.
When ∏＞1, infiltration rate is less than chemical reaction rate, the not free burning aspect that reaches of gas, and burning is only limited to upper layer.
This shows, improve gaseous tension P or coefficient of permeability K
p, reduce sample diameter size d or add thinner etc., can make surface combustion transfer burning successively to, obtain needed synthetic product.In ferrovanadium nitride is produced, when nitrogen gas pressure drops to certain value, can carry out smoothly in order to make building-up reactions, need ftercompction in high-pressure system (as increasing nitrogen); When the content of vanadium in the synthetic material is high, add a certain amount of inert diluent (can adopt the broken powder of ferrovanadium nitride) to reduce temperature and to stop the appearance of melting metal layer.
Self propagating high temperature synthesis technique of the present invention is produced the method for ferrovanadium nitride, and the chemical energy that utilizes the material building-up reactions to emit carries out the synthetic of novel material, does not need in the synthetic process from the outside restock energy.
See also shown in Figure 1ly, the step of method that self propagating high temperature synthesis technique of the present invention is produced ferrovanadium nitride is as follows:
1, at first that the raw material vanadium iron is broken in abrasive blast equipment;
2, in bulk in crucible behind the vanadium iron raw material drying that fragmentation is good;
3, with crucible as in the high pressure synthesizer and charge into the nitrogen of 6-12Mpa;
4, the starting ignition device raw material that ignites carries out building-up reactions;
5, burning synthetic ferrovanadium nitride cools off the back taking-up in nitrogen, is broken into piece.
According to above-mentioned steps, can obtain required ferrovanadium nitride.Utilize method of the present invention to can be used as the ferrovanadium nitride that a kind of general production technique is used to produce the various content of vanadium trades mark.50 vanadium iron, 60 vanadium iron or 80 vanadium iron that adopt present commercial production are that the various trade mark ferrovanadium nitrides of raw material production all can be achieved success.The composition of the ferrovanadium nitride product of its production sees Table 1.
The composition of table 1 part ferrovanadium nitride product
In addition, adopt the synthetic ferrovanadium nitride of producing of self propagating high temperature of the present invention, need not external energy, pollution-free, resultant velocity is fast, and energy-saving and environmental protection, efficient are a kind of hi-tech production technique that is worthy to be popularized.
The ferrovanadium nitride product of producing is used in enterprises such as Xinxin Vanadium Titanium Co., Ltd., Chengde City, capital Steel stock Co., Ltd, Tangshan Iron ﹠ Steel Co., Ltd., successfully producing qualified HRB400 level (III level), HRB500 level (IV level), English marks 460 these products of grade high-strength Twisted Steel and shows that the steel mechanics performance undulating quantity dwindles greatly, quality product is more stable, than using vanadium iron to save vanadium 20～40%, save vanadium 4～7% than using VN alloy.
Produce in the method for ferrovanadium nitride at employing self propagating high temperature synthesis technique of the present invention, there is main Points to pay close attention to, the one, for the vanadiumcontent massfraction greater than 58% vanadium iron raw material, oxidized in shattering process for preventing vanadium iron, adopt nitrogen or protection of inert gas raw material in shattering process, nitrogen in the abrasive blast equipment or rare gas element gas content reach the massfraction more than 98% that accounts for total mass; When the massfraction of vanadium in the vanadium iron greater than 60% the time, the temperature for reducing when synthetic is to prevent the appearance of molten metal, needing to add the massfraction that accounts for total mass is the inert diluent of 0-20%, carries out fragmentation again.This inert diluent is the broken powder of ferrovanadium nitride.
The 2nd, the size composition of the fragmentation of raw material vanadium iron can be preferably: the massfraction that 40～100 orders account for total mass is that massfraction that 0～15%, 100～200 orders account for total mass is that the massfraction that 40～50%,＜200 orders account for total mass is 40～60%.
The 3rd, in reaction process, when nitrogen pressure drops to 5.5～6.0Mpa in the high pressure synthesizer, need ftercompction in high pressure vessel, promptly feed nitrogen and make pressure maintain 6～12Mpa.
With several groups of specific embodiments the present invention is described below:
As follows with different trade mark vanadium iron raw material production ferrovanadium nitride implementation steps: that the vanadium iron raw material is undertaken just mixing by the inert diluent that certain (is a collection of as 5 tons or 10 tons) in batches adds massfraction 0～20%, be crushed to the size composition of regulation again, promptly 40～100 orders account for 0～15%, 100～200 orders account for 40～50%, and＜200 orders account for 40～60% (above percentage ratio is all massfraction).Mixed uniformly raw material is placed in the baking oven 50～70 ℃ of bakings 2～4 hours down, reinstall the high pressure synthesizer that crucible places 85～100 liters, airtight, vacuumize, send nitrogen; Nitrogen pressure before the synthetic beginning is controlled at 6～12Mpa, adopt the ignite building-up reactions of synthetic material one end of lighter for ignition, in building-up process, when nitrogen pressure drops to 5.5～6.0Mpa, then ftercompction in synthesizer, under the situation that no external thermal source replenishes, the nitrogenize building-up reactions goes on from keeping like this, synthesizes up to nitrogenize to finish.The synthetic product is crushed to the specified dimension lumpiness after cooling off in nitrogen.The typical production composite traces sees Table 2:
Table 2 is produced the composite traces table
As mentioned above, the invention provides a kind of method that adopts the self propagating high temperature synthesis technique to produce ferrovanadium nitride, the application of patent of invention is offered in the whence in accordance with the law; Yet, above implementation and graphic shown in, be one of preferred embodiment of the present invention, be not to limit to the present invention with this, be with, approximate with structure of the present invention, device, feature etc. such as, identical person all should belong to of the present invention founding within purpose and the claim.
Claims (8)
1. method that adopts the self propagating high temperature synthesis technique to produce ferrovanadium nitride is characterized in that:
Raw material is vanadium iron and nitrogen, at first that the raw material vanadium iron is broken in abrasive blast equipment, in bulk in crucible behind the vanadium iron raw material drying that fragmentation is good, place crucible in the high pressure synthesizer and charge into the nitrogen of 6-12Mpa, the starting ignition device raw material that ignites carries out building-up reactions, combustion synthesis reaction takes out after continue to carry out, burning synthetic ferrovanadium nitride cools off in nitrogen, is broken into piece.
2. employing self propagating high temperature synthesis technique as claimed in claim 1 is produced the method for ferrovanadium nitride; it is characterized in that: for the vanadiumcontent massfraction greater than 58% vanadium iron raw material; oxidized in shattering process for preventing vanadium iron; shattering process need adopt nitrogen or protection of inert gas raw material, and nitrogen in the abrasive blast equipment or rare gas element gas content reach the massfraction more than 98% that accounts for total mass.
3. employing self propagating high temperature synthesis technique as claimed in claim 1 or 2 is produced the method for ferrovanadium nitride, it is characterized in that: when the massfraction of vanadium in the vanadium iron greater than 60% the time, the inert diluent that needs to add the massfraction that accounts for total mass and be 0-20% is to reduce synthesis temperature.
4. employing self propagating high temperature synthesis technique as claimed in claim 3 is produced the method for ferrovanadium nitride, it is characterized in that: this inert diluent is the broken powder of ferrovanadium nitride.
5. employing self propagating high temperature synthesis technique as claimed in claim 1 or 2 is produced the method for ferrovanadium nitride, it is characterized in that: the size composition of raw material vanadium iron fragmentation is: the massfraction that 40～100 orders account for total mass is 0～15%, the massfraction that 100～200 orders account for total mass is that the massfraction that 40～50%,＜200 orders account for total mass is 40～60%.
6. employing self propagating high temperature synthesis technique as claimed in claim 1 or 2 is produced the method for ferrovanadium nitride, it is characterized in that: when nitrogen pressure drops to 5.5～6.0Mpa in the high pressure synthesizer, need ftercompction in high pressure vessel, promptly feed nitrogen and make pressure maintain 6～12Mpa.
7. employing self propagating high temperature synthesis technique as claimed in claim 1 is produced the method for ferrovanadium nitride, and it is characterized in that: the raw material vanadium iron is 50 vanadium iron, 60 vanadium iron or 80 vanadium iron.
8. employing self propagating high temperature synthesis technique as claimed in claim 1 is produced the method for ferrovanadium nitride, and it is characterized in that: bake out temperature is 50～70 ℃, and drying time is 2～4 hours.
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| CN103866175B (en) * | 2014-02-24 | 2015-12-09 | 承德金科科技开发有限责任公司 | FeV65N13 ferrovanadium nitride and synthetic method thereof |
| CN103866175A (en) * | 2014-02-24 | 2014-06-18 | 承德金科科技开发有限责任公司 | Ferrous vanadium nitride (FeV65N13) and synthetic method thereof |
| CN103834849B (en) * | 2014-03-07 | 2016-08-24 | 承德锦科科技股份有限公司 | FeV45N10 ferrovanadium nitride and burning synthesis method thereof |
| CN103834849A (en) * | 2014-03-07 | 2014-06-04 | 承德金科科技开发有限责任公司 | FeV45N10 ferric vanadium nitrate and combustion synthesis method thereof |
| CN104878236A (en) * | 2015-06-17 | 2015-09-02 | 韶关市晟茂冶金材料有限公司 | High-density vanadium-nitrogen alloy and preparation method thereof |
| CN105002386A (en) * | 2015-09-06 | 2015-10-28 | 湖南众鑫新材料科技股份有限公司 | Process capable of producing high-purity vanadium-nitrogen alloy on a large scale |
| CN105063398A (en) * | 2015-09-06 | 2015-11-18 | 湖南众鑫新材料科技股份有限公司 | Technique for preparing high-nitrogen vanadium-nitrogen alloy |
| CN105087994A (en) * | 2015-09-06 | 2015-11-25 | 湖南众鑫新材料科技股份有限公司 | Method for preparing high-nitrogen high-purity vanadium-nitrogen alloy |
| CN105002386B (en) * | 2015-09-06 | 2017-06-16 | 湖南众鑫新材料科技股份有限公司 | It is a kind of can the high-purity VN alloy of large-scale production technique |
| CN107904425A (en) * | 2017-11-27 | 2018-04-13 | 攀钢集团钒钛资源股份有限公司 | The preparation method of ferrovanadium nitride |
| CN111206172A (en) * | 2020-03-09 | 2020-05-29 | 承德锦科科技股份有限公司 | Nitrided ferrocolumbium alloy and preparation method and application thereof |
| CN111206172B (en) * | 2020-03-09 | 2021-09-14 | 承德锦科科技股份有限公司 | Nitrided ferrocolumbium alloy and preparation method and application thereof |
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