CN1270857C - Method for synthesizing TiNi-TiN gradient material by laser-induction self-spreading under high temperature - Google Patents
Method for synthesizing TiNi-TiN gradient material by laser-induction self-spreading under high temperature Download PDFInfo
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- CN1270857C CN1270857C CN 200410051876 CN200410051876A CN1270857C CN 1270857 C CN1270857 C CN 1270857C CN 200410051876 CN200410051876 CN 200410051876 CN 200410051876 A CN200410051876 A CN 200410051876A CN 1270857 C CN1270857 C CN 1270857C
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Abstract
The present invention discloses a method for making a TiNi-TiN gradient material by self-propagating high-temperature synthesis induced by lasers, which comprises the following steps: (1)metal powders of Ti and Ni are weighed in the molar ratio of 1 to 1 and then are evenly mixed; (2) the mixed powders of Ti and Ni are pressed into a cylindrical test sample; during the pressing process, the pressure maintaining time is from 1 to 4 minutes, and the pressing pressure is from 20 to 50KN; (3) the test sample is treated by heat preservation for 1 to 3 hours at the temperature of 80 to 150DEGC to remove water and part of gases; (4) after the test sample is put on a test sample table of a reaction container, the cover of the container is closed, and then, nitrogen with the flow quantity of 5 to 10 L/min is led into the container; after the nitrogen is filled more than 2 minutes, CO2 and Nd: YAG lasers are used for ignition to induce a self-propagating high-temperature synthesis reaction.
Description
Technical field
The present invention relates to the method for the synthetic TiNi-TiN functionally gradient material (FGM) of a kind of laser-induced self-propagating reaction high temperature, specifically be a kind of with laser as the igniting thermal source, induce Ti-Ni and Ti-N
2Self-propagating reaction takes place in two individual system simultaneously, the method for disposable synthetic TiNi-TiN functionally gradient material (FGM).
Background technology
The conventional method of preparation TiNi alloy mainly contains fusion casting, powder metallurgic method and reduction-diffusion process.What fusion casting was used is block raw material, and composition is difficult to accurate control during melting, easily produces segregation, often will handle the performance of improving ingot casting by repeatedly melting and high-temperature homogenization, so cost is very high; Powder metallurgic method is produced the TiNi alloy needs long high temperature sintering, time-consuming, energy consumption is big.And production process is difficult to accurate control, causes the sintered blank oxygen content to increase easily, and working plasticity is poor; Reduction-diffusion process is to react with reducing agent calcium grain, titanium dioxide and nickel powder to prepare the TiNi alloy, and cost height, post processing burden is heavy, and to the requirement of material and technological parameter also than higher.
Behind the synthetic TiNi alloy, the method that obtains the TiN overcoat at the TiNi alloy surface has vapour deposition process, plasma spraying method, and the N ion is inculcated method, triniding etc.The complex process that these methods have, what have is with high costs, and once finishes the synthetic of TiNi-TiN, also can't realize.
Summary of the invention
The objective of the invention is to shortcoming, provide a kind of laser of using, induce Ti-Ni and Ti-N as the igniting thermal source at the prior art existence
2Self-propagating reaction takes place in two individual system simultaneously, the method for disposable synthetic TiNi-TiN functionally gradient material (FGM).
For achieving the above object, the present invention has taked following technical scheme:
The method of the synthetic TiNi-TiN functionally gradient material (FGM) of laser-induced self-propagating reaction high temperature comprises the steps:
1, is to take by weighing Ti, Ni metal dust at 1: 1 in molar ratio, and mixes;
The purity of Ti powder 〉=99.0%, fineness are 200～300 orders; The purity of Ni 〉=99.5%, fineness are 200～300 orders;
2, Ti, Ni mixed-powder are pressed into cylindric sample, pressurize is 1～4 minute in the pressing process, preferred 2～3 minutes; Pressing pressure is 20～50KN;
3, sample is incubated 1～3 hour down at 80～150 ℃, removes moisture and portion gas;
Preferred temperature is 90～110 ℃, and optimum temperature is 100 ℃; Temperature retention time the best is 2 hours;
4, after sample being placed on the sample bench of reaction vessel, the closed container lid feeds nitrogen with the flow of 5～10L/min, behind inflationtime 〉=2 minute, uses CO
2With the Nd:YAG laser ignition, induce the self propagating high temperature synthetic reaction.
Compared with the prior art, the present invention has following beneficial effect:
(1) Ti-Ni and Ti-N
2Two individual system react simultaneously, and interact, can disposable synthetic TiNi-TiN functionally gradient material (FGM), simplify building-up process;
(2) a large amount of holes are contained in product inside, and porosity is up to 50%;
(3) course of reaction does not rapidly and efficiently have Ti, the Ni pure element exists mutually in the product;
(4) contactless, pollution-free, easy to control, heating of LASER HEATING mode and cooldown rate height are easy to obtain the structure of non-equilibrium phase and many defectives, have peculiar advantage for synthetic some functional material;
(5) laser power is easily surveyed, and its energy that specifically is added on the reactant is easy to calculate, and is convenient to carry out thermodynamics and dynamic analysis;
(6) the self propagating high temperature synthetic technology have energy-conservation, efficient, product purity advantages of higher, and can produce material with super performance.
Description of drawings
Fig. 1 is the preparation flow figure of TiNi-TiN functionally gradient material (FGM);
Fig. 2 is the reaction vessel schematic diagram;
Fig. 3 is the X-ray diffraction spectrum of product;
Fig. 4 (a) is the SEM photo (* 3000) of product;
Fig. 4 (b) is the SEM photo (* 5000) of product;
The specific embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1
The raw material that the present invention adopts is Ti powder and Ni powder, and its key property is as shown in table 1.
The characteristic of table 1 Ti powder and Ni powder
| Purity | Atomic weight | Granularity | The place of production | |
| Titanium valve | 99.0％ | 47.88 | 200 orders | Prompt chemical reagent Co., Ltd is moistened in Shanghai |
| Nickel powder | 99.5％ | 58.71 | 300 orders | Last sea otter sunrise development in science and technology Co., Ltd |
(2), calculate the mass percent of Ti, Ni in the mixed-powder with 1: 1 mol ratio preparation Ti, Ni metal dust:
Tiwt％1∶1＝47.88/(47.88+58.71)×100％＝44.92％ (1)
Niwt％1∶1＝58.71/(47.88+58.71)×100％＝55.08％ (2)
According to result of calculation, be that the electronic balance of 0.01g takes by weighing an amount of Ti, Ni powder with precision, then with mixing powder machine (fineness: 30～300 orders, rotating speed: 24000r/min) with its mixing.Each start one minute is started shooting when the cup temperature of waiting to mix the powder machine is reduced to room temperature once more, three times so repeatedly, it is mixed.
(3) (model: WE-30, Guangzhou testing machine factory produce, and 300KN) Ti, Ni mixed-powder (3.4g) are pressed into the cylindric sample that diameter is 15mm, and pressurize is 1 minute in the pressing process, in order to avoid sample deformation or cracking with universal testing machine.The pressing pressure that adopts in the experimentation is respectively 25KN, 30KN, 35KN, 40KN, 45KN, 50KN.
(4) for reducing the influence of extraneous factor, improve the quality of self-propagating reaction product, before experiment, should dry sample, remove moisture and portion gas.The equipment that is adopted is electric drying oven with forced convection (temperature fluctuation: ± 1 ℃, temperature control scope: room temperature～300 ℃), 80 ℃ of insulations 1 hour down.
(5) self-propagating reaction carries out in reaction vessel (Fig. 2), sample is placed on the sample bench behind the appropriate location, the closed container lid, feed certain flow (5L/m) nitrogen (99.999%, 13.6MPa).
At this, nitrogen double as protective gas and reacting gas.After inflation a period of time (4m), use CO
2(Pmax=1500W) and Nd:YAG (Pmax=700W) laser ignition, inducing the self propagating high temperature synthetic reaction, is the stopwatch record duration of ignition, combustion-supporting time and reaction time of 0.01 second with precision, from observation window observing response phenomenon.
Embodiment 2
The raw material that the present invention adopts is Ti powder and Ni powder, and its key property is as shown in table 1.
The characteristic of table 1 Ti powder and Ni powder
| Purity | Atomic weight | Granularity | The place of production | |
| Titanium valve | 99.0％ | 47.88 | 250 orders | Prompt chemical reagent Co., Ltd is moistened in Shanghai |
| Nickel powder | 99.5％ | 58.71 | 250 orders | Last sea otter sunrise development in science and technology Co., Ltd |
(2), calculate the mass percent of Ti, Ni in the mixed-powder with 1: 1 mol ratio preparation Ti, Ni metal dust:
Tiwt％1∶1＝47.88/(47.88+58.71)×100％＝44.92％ (1)
Niwt％1∶1＝58.71/(47.88+58.71)×100％＝55.08％ (2)
According to result of calculation, be that the electronic balance of 0.01g takes by weighing an amount of Ti, Ni powder with precision, then with mixing powder machine (fineness: 30～300 orders, rotating speed: 24000r/min) with its mixing.Each start one minute is started shooting when the cup temperature of waiting to mix the powder machine is reduced to room temperature once more, three times so repeatedly, it is mixed.
(3) (model: WE-30, Guangzhou testing machine factory produce, and 300KN) Ti, Ni mixed-powder (3.4g) are pressed into the cylindric sample that diameter is 15mm, and pressurize is 4 minutes in the pressing process, in order to avoid sample deformation or cracking with universal testing machine.The pressing pressure that adopts in the experimentation is respectively 25KN, 30KN, 35KN, 40KN, 45KN, 50KN.
(4) for reducing the influence of extraneous factor, improve the quality of self-propagating reaction product, before experiment, should dry sample, remove moisture and portion gas.The equipment that is adopted is electric drying oven with forced convection (temperature fluctuation: ± 1 ℃, temperature control scope: room temperature～300 ℃), 150 ℃ of insulations 3 hours down.
(5) self-propagating reaction carries out in reaction vessel (Fig. 2), sample is placed on the sample bench behind the appropriate location, the closed container lid, feed certain flow (10L/m) nitrogen (99.999%, 13.6MPa).
At this, nitrogen double as protective gas and reacting gas.After inflation a period of time (4m), use CO
2(Pmax=1500W) and Nd:YAG (Pmax=700W) laser ignition, inducing the self propagating high temperature synthetic reaction, is the stopwatch record duration of ignition, combustion-supporting time and reaction time of 0.01 second with precision, from observation window observing response phenomenon.
Embodiment 3
The raw material that the present invention adopts is Ti powder and Ni powder, and its key property is as shown in table 1.
The characteristic of table 1 Ti powder and Ni powder
| Purity | Atomic weight | Granularity | The place of production | |
| Titanium valve | 99.0％ | 47.88 | 300 orders | Prompt chemical reagent Co., Ltd is moistened in Shanghai |
| Nickel powder | 99.5％ | 58.71 | 200 orders | Last sea otter sunrise development in science and technology Co., Ltd |
(2), calculate the mass percent of Ti, Ni in the mixed-powder with 1: 1 mol ratio preparation Ti, Ni metal dust:
Tiwt％1∶1＝47.88/(47.88+58.71)×100％＝44.92％ (1)
Niwt％1∶1＝58.71/(47.88+58.71)×100％＝55.08％ (2)
According to result of calculation, be that the electronic balance of 0.01g takes by weighing an amount of Ti, Ni powder with precision, then with mixing powder machine (fineness: 30～300 orders, rotating speed: 24000r/min) with its mixing.Each start one minute is started shooting when the cup temperature of waiting to mix the powder machine is reduced to room temperature once more, three times so repeatedly, it is mixed.
(3) (model: WE-30, Guangzhou testing machine factory produce, and 300KN) Ti, Ni mixed-powder (3.4g) are pressed into the cylindric sample that diameter is 15mm, and pressurize is 2 minutes in the pressing process, in order to avoid sample deformation or cracking with universal testing machine.The pressing pressure that adopts in the experimentation is respectively 25KN, 30KN, 35KN, 40KN, 45KN, 50KN.
(4) for reducing the influence of extraneous factor, improve the quality of self-propagating reaction product, before experiment, should dry sample, remove moisture and portion gas.The equipment that is adopted is electric drying oven with forced convection (temperature fluctuation: ± 1 ℃, temperature control scope: room temperature～300 ℃), 100 ℃ of insulations two hours down.
(5) self-propagating reaction carries out in reaction vessel (Fig. 2), sample is placed on the sample bench behind the appropriate location, the closed container lid, feed certain flow (8L/m) nitrogen (99.999%, 13.6MPa).
At this, nitrogen double as protective gas and reacting gas.After inflation a period of time (4m), use CO
2(Pmax=1500W) and Nd:YAG (Pmax=700W) laser ignition, inducing the self propagating high temperature synthetic reaction, is the stopwatch record duration of ignition, combustion-supporting time and reaction time of 0.01 second with precision, from observation window observing response phenomenon.
(6) after reaction finishes, use phase composition, the observing response product microstructure of X-ray diffraction (XRD) technology, ESEM (SEM) technical Analysis product respectively, and use formula:
P＝(1-V1/V2)×100％ (3)
Calculate the voidage of product, wherein P is porosity (%), V
1Be the volume of sample before the self-propagating reaction, V
2Be the volume of sample behind the self-propagating reaction, the volume precision of sample is that the graduated cylinder of 0.1ml is measured (Archimedes's drainage).
By X-ray diffraction figure (Fig. 3, CO
2Laser instrument, 300W, 30KN, 10L/S, the combustion-supporting time: 2S) as can be known, product is by TiN, TiNi, Ti
2Ni and Ni
3Ti four constitutes mutually, and the diffraction maximum of no Ti, Ni pure element phase occurs.
This shows: although only there are several seconds in Ti powder and the Ni powder reaction time in the SHS process, compare insignificantly with the powder diffusion-sintering method that reaches several hours to tens hours, the combination reaction between element powders is carried out very fully.The TiN that the TiNi alloy surface forms is favourable to improving its surface property.Having of TiN is beneficial to the release that suppresses poisonous Ni ion, significantly improves TiNi corrosion resistance of alloy and bio-compatible performance, and helps improving TiNi hardness of alloy and wearability.
Composition, the Tissue distribution of product are even, the microstructure photo (backscattered electron image) of Fig. 4 product.
In Fig. 4, there are black, white, three kinds of zones that color is different of ash, represent three kinds of different tissues respectively.Be not difficult to find out that from figure three kinds of distributions that are organized in the product are all compared evenly, this illustrates that mixed powder has been realized the purpose of homogenising substantially in the sample preparatory stage.
Claims (5)
1, the method for the synthetic TiNi-TiN functionally gradient material (FGM) of laser-induced self-propagating reaction high temperature is characterized in that comprising the steps:
(1) is to take by weighing Ti, Ni metal dust at 1: 1 in molar ratio, and mixes;
Wherein, the purity of Ti powder 〉=99.0%, fineness is 200～300 orders; The purity of Ni 〉=99.5%, fineness are 200～300 orders;
(2) Ti, Ni mixed-powder are pressed into cylindric sample, pressurize is 1～4 minute in the pressing process, and pressing pressure is 20～50KN;
(3) sample is incubated 1～3 hour down at 80～150 ℃, removes moisture and portion gas;
(4) after sample being placed on the sample bench of reaction vessel, the closed container lid feeds nitrogen with the flow of 5～10L/min, behind inflationtime 〉=2 minute, uses CO
2With the Nd:YAG laser ignition, induce the self propagating high temperature synthetic reaction.
2, the method for the synthetic TiNi-TiN functionally gradient material (FGM) of laser-induced self-propagating reaction high temperature according to claim 1 is characterized in that the dwell time in the step 2 is 2～3 minutes.
3, the method for the synthetic TiNi-TiN functionally gradient material (FGM) of laser-induced self-propagating reaction high temperature according to claim 1 is characterized in that the temperature in the step 3 is 90～110 ℃.
4, the method for the synthetic TiNi-TiN functionally gradient material (FGM) of laser-induced self-propagating reaction high temperature according to claim 3 is characterized in that the temperature in the step 3 is 100 ℃.
5, the method for the synthetic TiNi-TiN functionally gradient material (FGM) of laser-induced self-propagating reaction high temperature according to claim 1 is characterized in that the temperature retention time in the step 3 is 2 hours.
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| CN101906631B (en) * | 2010-08-17 | 2011-12-07 | 华东理工大学 | Method for quickly preparing Ti3Al/TiN composite coating |
| CN102825253A (en) * | 2012-08-27 | 2012-12-19 | 长春理工大学 | Laser ignition and combustion extrusion synthesis method of Al-Ti-C powder metallurgy part |
| CN106384779B (en) * | 2016-03-06 | 2019-05-24 | 武汉理工大学 | A method of being that one step of starting material is supper-fast from simple substance powder prepares thermo-electric device |
| CN106673670A (en) * | 2016-12-30 | 2017-05-17 | 烟台同立高科新材料股份有限公司 | Preparation method of high-purity silicon nitride powder |
| CN108690967B (en) * | 2018-05-04 | 2020-07-28 | 深圳市中科摩方科技有限公司 | Nickel-titanium alloy medical instrument with surface coating and coating preparation method |
| CN114505478A (en) * | 2020-11-16 | 2022-05-17 | 中国科学院上海硅酸盐研究所 | TiN-Ni gradient functional material and preparation method and application thereof |
| CN114686724A (en) * | 2022-03-11 | 2022-07-01 | 华南理工大学 | Composite material with shape memory function and SLM (Selective laser melting) preparation method thereof |
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