CN100497259C - Laser synthetic method for negative expansion coefficient material - Google Patents
Laser synthetic method for negative expansion coefficient material Download PDFInfo
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- CN100497259C CN100497259C CNB2006101070238A CN200610107023A CN100497259C CN 100497259 C CN100497259 C CN 100497259C CN B2006101070238 A CNB2006101070238 A CN B2006101070238A CN 200610107023 A CN200610107023 A CN 200610107023A CN 100497259 C CN100497259 C CN 100497259C
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Abstract
The laser synthesis process of negative thermal expansion coefficient material belongs to the field of laser technology application. Under the direct heating of laser beam, the raw materials for the negative thermal expansion coefficient material are reacted in a laser bath and solidified fast. The laser is CO2 gas laser or Nd:YAG solid laser of laser wavelength 10.6 micron or 1.06 micron, power density of 0.2-1.5 kW/sq cm and laser scanning speed of 0.2-12 mm/s. The negative thermal expansion coefficient material is ZrW2O8, HfW2O8, Zr1-xHfxW2O8 with x in 0-1.0, Zr1-xHfxMo2O8 with x in 0-1.0, ZrMo2-xWxO8 with x in 0-2.0 or HfMo2-xWxO8 with x in 0-2.0. The present invention has the features of fast synthesis speed, low cost, no pollution and being suitable for continuous production.
Description
Technical field
The invention belongs to laser application technique and field of material synthesis technology, particularly a kind of laser synthesis method of minus thermal-expansion coefficient.
Background technology
As thermal source, material composition (or in laser molten pool) reaction under lasing generates novel material and rapid solidification to laser synthetic materials technology with the laser beam of high-energy-density.Most materials all have the character of expanding with heat and contract with cold, and this thermal stresses (or thermal shock wave) that produces of expanding with heat and contract with cold often is the major cause that device fatigue, degradation, inefficacy even fracture takes place and comes off.At aerospace field, no matter be the baptism that function or structured material all are faced with thermal stresses (or thermal shock wave), spacecraft is shined upon when space flight, and the temperature difference of its back and sunny side is up to 300 ℃.This just requires the coefficient of thermal expansion of material little, and structural distortion is little, and distortion will cause the pointing accuracy variation as antenna with antenna holder, and gain descends.The head of retrievable satellite and spacecraft, owing to be acted upon by temperature changes, if the material coefficient of expansion of solar heat protection housing (or thermal insulation tile) and load housing does not match, generation intensive temperature is handed over seasonable getting through the earth's atmosphere, thermal-protective shell cognition cracks or causes thermal insulation tile to come off, destruction until part is scrapped, and its loss is imponderable, even the consequence of bringing on a disaster property.A large amount of components and parts of the guidance of guided missile, communication and transmission system, and precise parts such as the inner and outer ring of the active clearance control technology of high-performance aircraft engine, intake valve, turbine engine, wear ring all have strict requirement to coefficient of thermal expansion.At microelectronic, the material that preparation is complementary with the silicon coefficient of thermal expansion acquires a special sense, as circuit card, microelectronic packaging material, not only have high electroconductibility but also can and silicon the lead etc. of same coefficient of thermal expansion is arranged.In the key equipment lithography machine that large-scale integrated circuit is produced, the thermal distortion of thermal lensing effect and strut member is the major cause that causes the lithographic accuracy variation.At optics and optical communication field, ultralow coefficient of thermal expansion material can be used for the collimation of visual telescope, laser and opticfiber communication cable.Material coefficient of thermal expansion is the basic place that causes optical fiber Bragg raster and the drift of optical fiber laser centre wavelength.All optical elements of present superpower laser and outer light path thereof all need the water coolant of big flow to cool off, otherwise can cause that resonator cavity distortion, mirror coating come off, lens heat effect even burst.If can will bring into play enormous function in fields such as aerospace, microelectronics, laser technology and high-accuracy mechanical key parts with negative thermal expansion coefficient material and the positive compound material of making the zero thermal expansion coefficient of coefficient of expansion material.In addition, also has wide application prospect at medical bio pottery (gum filler, artificial skelecton) and aspects such as household electrical appliance, kitchen tools.
The synthetic method of minus thermal-expansion coefficient mainly contains: (i) solid reaction process, most in the world at present study group adopt this method.Choosing suitable raw material mixes-grinds-briquetting-sintering-cooling fast, and repeatedly repeat this process, and liquid nitrogen is generally selected in cooling for use, and refrigerative in water is also arranged, and raw material generally selects for use oxide compound (as ZrO
2And WO
3) or salt (as Zircosol ZN and ammonium metawolframate).The shortcoming of this method is: 1. because ZrW
2O
8Stable phase has determined that 1150-1257 ℃ of very narrow temperature range its sintering needs to carry out under corresponding high temperature, preparation process generally needs 3-5 days time just can finish; 2. ZrW
2O
8Be decomposed into ZrO at 770-1050 ℃
2And WO
3So, must put into liquid nitrogen at once after normally coming out of the stove and cool off, decompose to reduce in the process of cooling; 3. WO
3A large amount of volatilizations in long-time sintering process can cause chemistry to compare mismatch.In order to address this problem, the major measure of taking at present is to cover one deck WO on the sintering blank
3, or in the quartz peace bubble of sealing sintering or blank is clipped in sintering between two blocks of platinum plates.The Evans of Britain De Lamu university professor study group put into quartzy peace bubble 1473K sintering 14 hours with raw material, cooled with liquid nitrogen, and the sample purity that obtains has only 72%, and all the other 28% are ZrO
2And WO
3(ii) liquid phase synthesizing method comprises hydrothermal method, coprecipitation method, combustion method, sol-gel method, spraying drying sintering process, precursor method (using earlier the chemosynthesis presoma, again through dehydration, sintering) etc.This method adopts salt compounds more, is raw material as Zircosol ZN and ammonium metawolframate etc., reaction in solvent (often need add acids reagent).The liquid phase synthesizing method reaction mechanism also is not clear and definite especially, its advantage is the product purity height, and synthesis temperature is low, but the waste liquid of preparation process, waste gas are obvious, as combustion method is to be fuel with urea etc., and liquid reactants heating flame in hot stove is produced large quantity of exhaust gas.Because ZrMo
2O
8A plurality of thermodynamically stable phases and MoO are arranged
3High volatile volatile, be difficult to solid reaction process syntheticly, generally adopt precursor process synthetic.
Summary of the invention
The object of the invention is to provide a kind of laser synthesis method of minus thermal-expansion coefficient.
For reaching above-mentioned purpose, the present invention adopts following technical scheme: laser synthetic method for negative expansion coefficient material, can generate the raw material composition of negative expansion coefficient material with the laser beam direct heating, and it is reacted and rapid solidification in laser molten pool.
Select CO for use
2Gas laser or Nd:YAG solid statelaser, optical maser wavelength 10.6 μ m or 1.06 μ m, power density 0.2-1.5kW/cm
2, beam flying speed 0.2-12mm/s.
Minus thermal-expansion coefficient is ZrW
2O
8, used raw material composition is ZrO
2And WO
3, ZrO
2With WO
3Mol ratio be 1:2-2.5.
Minus thermal-expansion coefficient is HfW
2O
8, used raw material composition is HfO
2And WO
3, HfO
2With WO
3Mol ratio be 1:2-2.5.
Minus thermal-expansion coefficient is Zr
1-xH
fXW
2O
8, 0＜x＜1.0, raw materials used composition is ZrO
2And HfO
2And WO
3, ZrO
2And HfO
2With WO
3Mol ratio is (ZrO
2+ HfO
2): WO
3=1:2-2.5.
Minus thermal-expansion coefficient is Zr
1-xHf
xMo
2O
8, 0＜x＜1.0, raw materials used composition is ZrO
2And HfO
2And MoO
3Or MoO
2Or Mo, ZrO
2And HfO
2With MoO
3Or MoO
2Or the Mo mol ratio is (ZrO
2+ HfO
2): MoO
3Or MoO
2Or Mo=1:2-2.5.
Minus thermal-expansion coefficient is ZrMo
2-xW
xO
8, 0＜x＜2.0, raw materials used composition is ZrO
2, WO
3And MoO
3Or MoO
2Or Mo, ZrO
2With WO
3And MoO
3Or MoO
2Or the Mo mol ratio is ZrO
2: (WO
3+ MoO
3Or MoO
2Or Mo)=1:2-2.5.
Minus thermal-expansion coefficient is HfMo
2-xW
xO
8, 0＜x＜2.0, raw materials used composition is HfO
2, WO
3And MoO
3Or MoO
2Or Mo, HfO
2With WO
3And MoO
3Or MoO
2Or the Mo mol ratio is HfO
2: (WO
3+ MoO
3Or MoO
2Or Mo)=1:2-2.5.
Concrete synthesis technique is: the raw material composition that can generate the negative expansion coefficient material, through ball milling or ground and mixed 60-120 minutes, with synchronous automatic powder feeding device mixed powder is directly sent into laser molten pool and react, or react with lf after with the mixing raw material briquetting with tabletting machine.The laser synthesis technologic parameter is: optical maser wavelength 10.6 μ m or 1.06 μ m, power density 0.2-1.5kW/cm
2, beam flying speed 0.2-12mm/s.Promptly get described minus thermal-expansion coefficient block after solidifying.
Laser synthetic minus thermal-expansion coefficient is tested with Raman spectrum and XRD.
The present invention is in the laser building-up process of minus thermal-expansion coefficient, and the high temperature that utilizes laser to produce reacts described raw material in laser molten pool, thereby generates the material ZrW with negative expansion coefficient
2O
8, HfW
2O
8, Zr
1-xHf
xW
2O
8(0＜x＜1.0), Zr
1-xHf
xMo
2O
8(0＜x＜1.0), ZrMo
2-xW
xO
8(0＜x＜2.0), HfMo
2-xW
xO
8(0＜x＜2.0), and become solid material by the laser rapid solidification.Because the synthetic rapid solidification of laser has effectively been avoided the decomposition of minus thermal-expansion coefficient in process of cooling, and the minus thermal-expansion coefficient that at high temperature generates can be remained effectively.Laser is synthetic can to carry out continuously, is suitable for continuous batch production.Laser is synthetic to belong to green synthesis techniques, does not need to add other chemical ingredients, free from environmental pollution.The laser rapid solidification belongs to nature and cools off fast, do not need to use liquid nitrogen and water cooling, both saved cost, can save the subsequent disposal and the liquid phase synthetic liquid waste disposal of sample again, the exhaust emission and the solid reaction process WO in long-time high-temperature sintering process that have also avoided combustion method to bring simultaneously
3And MO
3A large amount of volatilizations.The laser resultant velocity is fast, in seconds can finish the preparation of several cubic centimetres of samples.So the synthetic minus thermal-expansion coefficient of laser has fast, low-cost, pollution-free, suitable quantity-produced characteristics.
Description of drawings
Fig. 1 (A), Fig. 1 (B) are respectively the synthetic minus thermal-expansion coefficient ZrW of laser
2O
8The XRD of γ phase, α phase (laser synthesis technologic parameter: the 5kW CO that Wuhan unity laser company produces
2Laser apparatus, wavelength 10.6 μ m, power density 1.03KW/cm
2, beam flying speed 6mm/s; The XRD testing tool is the D/max-2550 PC X-ray diffractometer of Japanese company of science);
Fig. 2 (A) is the synthetic minus thermal-expansion coefficient ZrW of laser
2O
8Raman spectrum (laser synthesis technologic parameter: the 5kW CO that Wuhan unity laser company produces
2Laser apparatus, wavelength 10.6 μ m, power density 1.03kW/cm
2, beam flying speed 6mm/s; The Raman spectrum testing tool is the MR-2000 type micro-Raman spectroscopy of Britain Renishaw company, and excitation wavelength is 633nm);
Fig. 2 (B) is the synthetic minus thermal-expansion coefficient ZrW of laser
2O
8Raman spectrum (laser synthesis technologic parameter: the 5kWCO that Wuhan unity laser company produces
2Laser apparatus, wavelength 10.6 μ m, power density 0.2kW/cm
2, beam flying speed 0.2mm/s; The Raman spectrum testing tool is the MR-2000 type micro-Raman spectroscopy of Britain Renishaw company, and excitation wavelength is 633nm);
Fig. 2 (C) is the synthetic minus thermal-expansion coefficient ZrW of laser
2O
8Raman spectrum (laser synthesis technologic parameter: the 5kW CO that Wuhan unity laser company produces
2Laser apparatus, wavelength 10.6 μ m, power density 1.5kW/cm
2, beam flying speed 12mm/s; The Raman spectrum testing tool is the MR-2000 type micro-Raman spectroscopy of Britain Renishaw company, and excitation wavelength is 633nm);
Fig. 3 is the synthetic minus thermal-expansion coefficient HfW of laser
2O
8XRD (laser synthesis technologic parameter: the 5kW CO that Wuhan unity laser company produces
2Laser apparatus, wavelength 10.6 μ m, power density 1.03KW/cm
2, beam flying speed 3mm/s; The XRD testing tool is the D/max-2550 PC X-ray diffractometer of Japanese company of science);
Fig. 4 (A) is the synthetic minus thermal-expansion coefficient HfW of laser
2O
8Raman spectrum (laser synthesis technologic parameter: the 5kW CO that Wuhan unity laser company produces
2Laser apparatus, wavelength 10.6 μ m, power density 1.02kW/cm
2, beam flying speed 4mm/s; The Raman spectrum testing tool is the MR-2000 type micro-Raman spectroscopy of Britain Renishaw company, and excitation wavelength is 633nm);
Fig. 4 (B) is the synthetic minus thermal-expansion coefficient HfW of laser
2O
8Raman spectrum (laser synthesis technologic parameter: the 5kW CO that Wuhan unity laser company produces
2Laser apparatus, wavelength 10.6 μ m, power density 0.2kW/cm
2, beam flying speed 0.2mm/s; The Raman spectrum testing tool is the MR-2000 type micro-Raman spectroscopy of Britain Renishaw company, and excitation wavelength is 633nm);
Fig. 4 (C) is the synthetic minus thermal-expansion coefficient HfW of laser
2O
8Raman spectrum (laser synthesis technologic parameter: the 5kW CO that Wuhan unity laser company produces
2Laser apparatus, wavelength 10.6 μ m, power density 1.5kW/cm
2, beam flying speed 12mm/s; The Raman spectrum testing tool is the MR-2000 type micro-Raman spectroscopy of Britain Renishaw company, and excitation wavelength is 633nm);
Fig. 5 is the synthetic minus thermal-expansion coefficient Zr of laser
0.6Hf
0.4W
2O
8XRD (laser synthesis technologic parameter: the 5kW CO that Wuhan unity laser company produces
2Laser apparatus, wavelength 10.6 μ m, power density 0.94kW/cm
2, beam flying speed 6mm/s; The XRD testing tool is the D/max-2550PCX x ray diffractometer x of Japanese company of science);
Fig. 6 (A) is the synthetic minus thermal-expansion coefficient Zr of laser
0.6Hf
0.4W
2O
8Raman spectrum (laser synthesis technologic parameter: the 5kW CO that Wuhan unity laser company produces
2Laser apparatus, wavelength 10.6 μ m, power density 0.94kW/cm
2, beam flying speed 6mm/s; The Raman spectrum testing tool is the MR-2000 type micro-Raman spectroscopy of Britain Renishaw company, and excitation wavelength is 633nm);
Fig. 6 (B) is the synthetic minus thermal-expansion coefficient Zr of laser
0.8Hf
0.2W
2O
8Raman spectrum (laser synthesis technologic parameter: the 5kW CO that Wuhan unity laser company produces
2Laser apparatus, wavelength 10.6 μ m, power density 1.5kW/cm
2, beam flying speed 12mm/s; The Raman spectrum testing tool is the MR-2000 type micro-Raman spectroscopy of Britain Renishaw company, and excitation wavelength is 633nm);
Fig. 6 (C) is the synthetic minus thermal-expansion coefficient Zr of laser
0.5Hf
0.5W
2O
8Raman spectrum (laser synthesis technologic parameter: the 5kW CO that Wuhan unity laser company produces
2Laser apparatus, wavelength 10.6 μ m, power density 0.2kW/cm
2, beam flying speed 0.2mm/s; The Raman spectrum testing tool is the MR-2000 type micro-Raman spectroscopy of Britain Renishaw company, and excitation wavelength is 633nm);
Fig. 7 is the synthetic minus thermal-expansion coefficient ZrW of laser
1.2Mo
0.8O
8XRD (laser synthesis technologic parameter: the 5kW CO that Wuhan unity laser company produces
2Laser apparatus, wavelength 10.6 μ m, power density 1.5kW/cm
2, beam flying speed 12mm/s; The XRD testing tool is the D/max-2550 PC X-ray diffractometer of Japanese company of science);
Fig. 8 (A) is the synthetic minus thermal-expansion coefficient ZrW of laser
1.2Mo
0.8O
8Raman spectrum (laser synthesis technologic parameter: the 5kW CO that Wuhan unity laser company produces
2Laser apparatus, wavelength 10.6 μ m, power density 1.5kW/cm
2, beam flying speed 12mm/s; The Raman spectrum testing tool is the MR-2000 type micro-Raman spectroscopy of Britain Renishaw company, and excitation wavelength is 633nm);
Fig. 8 (B) is the synthetic minus thermal-expansion coefficient ZrW of laser
1.2Mo
0.8O
8Raman spectrum (laser synthesis technologic parameter: the 5kW CO that Wuhan unity laser company produces
2Laser apparatus, wavelength 10.6 μ m, power density 1.02kW/cm
2, beam flying speed 4mm/s; The Raman spectrum testing tool is the MR-2000 type micro-Raman spectroscopy of Britain Renishaw company, and excitation wavelength is 633nm);
Fig. 8 (C) is the synthetic minus thermal-expansion coefficient ZrW of laser
1.6Mo
0.4O
8Raman spectrum (laser synthesis technologic parameter: the 5kW CO that Wuhan unity laser company produces
2Laser apparatus, wavelength 10.6 μ m, power density 0.2kW/cm
2, beam flying speed 0.2mm/s; The Raman spectrum testing tool is the MR-2000 type micro-Raman spectroscopy of Britain Renishaw company, and excitation wavelength is 633nm);
Fig. 9 is the synthetic minus thermal-expansion coefficient HfW of laser
1.2Mo
0.8O
8XRD (laser synthesis technologic parameter: the 5kW CO that Wuhan unity laser company produces
2Laser apparatus, wavelength 10.6 μ m, power density 0.35kW/cm
2, beam flying speed 4mm/s; The XRD testing tool is the D/max-2550 PC X-ray diffractometer of Japanese company of science);
Figure 10 (A) is the synthetic minus thermal-expansion coefficient HfW of laser
1.6Mo
0.6O
8Raman spectrum (laser synthesis technologic parameter: the 5kW CO that Wuhan unity laser company produces
2Laser apparatus, wavelength 10.6 μ m, power density 0.35kW/cm
2, beam flying speed 4mm/s; The Raman spectrum testing tool is the MR-2000 type micro-Raman spectroscopy of Britain Renishaw company, and excitation wavelength is 633nm);
Figure 10 (B) is the synthetic minus thermal-expansion coefficient HfW of laser
1.6Mo
0.6O
8Raman spectrum (laser synthesis technologic parameter: the 5kW CO that Wuhan unity laser company produces
2Laser apparatus, wavelength 10.6 μ m, power density 1.5kW/cm
2, beam flying speed 12mm/s; The Raman spectrum testing tool is the MR-2000 type micro-Raman spectroscopy of Britain Renishaw company, and excitation wavelength is 633nm);
Figure 10 (C) is the synthetic minus thermal-expansion coefficient HfW of laser
1.6Mo
0.6O
8Raman spectrum (laser synthesis technologic parameter: the 5kW CO that Wuhan unity laser company produces
2Laser apparatus, wavelength 10.6 μ m, power density 0.2kW/cm
2, beam flying speed 0.2mm/s; The Raman spectrum testing tool is the MR-2000 type micro-Raman spectroscopy of Britain Renishaw company, and excitation wavelength is 633nm).
Embodiment
1:2 takes by weighing ZrO in molar ratio
2With WO
3, mixed, grind 90 minutes, with batch briquetting, carry out laser then and synthesize.The laser synthesis technologic parameter is: optical maser wavelength 10.6 μ m, power density 1.03kW/cm
2, beam flying speed 6mm/s.The laser synthetic materials is even green block, and macro morphology is smooth, smooth.Corresponding X-ray diffraction and Raman spectrum are seen accompanying drawing 1 (A), (B), Fig. 2 (A), (B), (C).
XRD analysis by with＜FindIt,＜PCPDFWIN, XRD database comparison such as " Search-Match " finishes (following identical).The X-ray diffraction material phase analysis shows laser synthetic materials ZrW
2O
8Being mainly γ phase (Figure 1A), is the γ ZrW mutually of P212121, ICSD card number 56566 with spacer
2O
8XRD fit like a glove.After 200 ℃ of annealing, ZrW
2O
8Becoming the α phase mutually by γ, is the α ZrW mutually of P213, ICSD card number 56565 with spacer
2O
8XRD fit like a glove.
Minus thermal-expansion coefficient involved in the present invention is by WO
4Or MoO
4Tetrahedron and ZrO
6Or HfO
6The octahedra skeleton construction of forming, wherein WO
4Or MoO
4Three Sauerstoffatoms and ZrO are arranged in the tetrahedron
6Or HfO
6Octahedra public, have the very Raman spectrum of feature, so Raman spectrum also can be used as the important means of its structural characterization.Fig. 2 is laser synthetic ZrW
2O
8The feature Raman spectrum.Principal character is at 920-1034cm
-1Between v appears
1(WO
4) the Raman mould, at 600-910cm
1Between v appears
3(WO
4) the Raman mould, at 330-440cm
-1Between v appears
4(WO
4) the Raman mould, at 310cm
-1" lattice+translation+swing " Raman mould below appears, the position of these Raman moulds and bibliographical information (J.Phys.:Condens.Mater 13:11573,2001) in full accord.ZrW
2O
8The another one feature of Raman spectrum be between 440-600, not have the Raman mould, and raw material ZrO
2At 475cm
-1Near very strong Raman mould is arranged, raw materials used ZrO
2At 755cm
-1More than and WO
3At 810cm
-1More than there is not the Raman mould.Therefore, according to these features 810cm particularly
-1Below whether there is the Raman mould ZrW to occur to determine whether to have generated
2O
8, according to 475cm
-1Whether the Raman mould occurs and the strong and weak purity that can judge the generation sample.
Analytical procedure is identical in the following embodiment.
Embodiment 2: laser synthesizes minus thermal-expansion coefficient ZrW
2O
8:
1:2 takes by weighing ZrO in molar ratio
2With WO
3, mixed, grind 90 minutes, with batch briquetting, carry out laser then and synthesize.The laser synthesis technologic parameter is: optical maser wavelength 10.6 μ m, power density 0.2kW/cm
2, beam flying speed 0.2mm/s.The laser synthetic materials is even green block, and macro morphology is smooth, smooth.Corresponding Raman spectrum is seen accompanying drawing 2 (B).
Embodiment 3: laser synthesizes minus thermal-expansion coefficient ZrW
2O
8:
1:2 takes by weighing ZrO in molar ratio
2With WO
3, mixed, grind 90 minutes, with batch briquetting, carry out laser then and synthesize.The laser synthesis technologic parameter is: optical maser wavelength 10.6 μ m, power density 1.5kW/cm
2, beam flying speed 12mm/s.The laser synthetic materials is even green block, and macro morphology is smooth, smooth.Corresponding X-ray diffraction and Raman spectrum are seen accompanying drawing 2 (C).
Embodiment 4: laser synthesizes minus thermal-expansion coefficient HfW
2O
8:
1:2 takes by weighing HfO in molar ratio
2With WO
3, mixed, grind 90 minutes, with batch briquetting, carry out laser then and synthesize.The laser synthesis technologic parameter is: optical maser wavelength 10.6 μ m, power density 1.02kW/cm
2, beam flying speed 4mm/s.The laser synthetic materials is even green block, and macro morphology is smooth, smooth.Corresponding X-ray diffraction and Raman spectrum are seen accompanying drawing 3, Fig. 4 (A).HfW in XRD spectrum and " Search-Match " database
2O
8XRD coincide (Pdf No.21-363).Raman spectrum is HfW
2O
8The feature Raman spectrum, analytical procedure is identical with embodiment 1.Raw material HfO
2Hale most graceful mould at 497cm
-1, in Fig. 4 and HfW
2O
8Character modules compare very a little less than, HfW is described
2O
8Generation and purity quite high.Raw material HfO
2At 780cm
-1More than there is not the Raman mould.
Embodiment 5: laser synthesizes minus thermal-expansion coefficient HfW
2O
8:
1:2 takes by weighing HfO in molar ratio
2With WO
3, mixed, grind 90 minutes, with batch briquetting, carry out laser then and synthesize.The laser synthesis technologic parameter is: optical maser wavelength 10.6 μ m, power density 0.2kW/cm
2, beam flying speed 0.2mm/s.The laser synthetic materials is even green block, and macro morphology is smooth, smooth.Corresponding Raman spectrum is seen accompanying drawing 4 (B).Raman spectrum is HfW
2O
8The feature Raman spectrum, analytical procedure is identical with embodiment 1.Raw material HfO
2Hale most graceful mould at 497cm
-1, in Fig. 4 (B), do not occur, HfW is described
2O
8Generation and purity quite high.Raw material HfO
2At 780cm
-1More than there is not the Raman mould.
Embodiment 6: laser synthesizes minus thermal-expansion coefficient HfW
2O
8:
1:2 takes by weighing HfO in molar ratio
2With WO
3, mixed, grind 90 minutes, with batch briquetting, carry out laser then and synthesize.The laser synthesis technologic parameter is: optical maser wavelength 10.6 μ m, power density 1.5kW/cm
2, beam flying speed 12mm/s.The laser synthetic materials is even green block, and macro morphology is smooth, smooth.Corresponding Raman spectrum is seen accompanying drawing 4 (C).Raman spectrum is HfW
2O
8The feature Raman spectrum, analytical procedure is identical with embodiment 1.Raw material HfO
2Hale most graceful mould at 497cm
-1, in Fig. 4 (C), do not occur, HfW is described
2O
8Generation and purity quite high.Raw material HfO
2At 780cm
-1More than there is not the Raman mould.
Embodiment 7: laser synthesizes minus thermal-expansion coefficient Zr
1-xHf
xW
2O
8:
0.6:0.4:2 takes by weighing ZrO in molar ratio
2, HfO
2With WO
3, mixed, grind 90 minutes, with batch briquetting, carry out laser then and synthesize.The laser synthesis technologic parameter is: optical maser wavelength 10.6 μ m, power density 0.94kW/cm
2, beam flying speed 6mm/s.The laser synthetic materials is even green block, and macro morphology is smooth, smooth.X-ray diffraction and Raman spectrum analysis show that the material that generates is Zr
0.6Hf
0.4W
2O
8Corresponding X-ray diffraction and Raman spectrum are seen accompanying drawing 5 and Fig. 6 (A).XRD spectrum and " FindIt " middle α ZrW mutually
2O
8XRD coincide (ICSD CCode56565) and " Search-Match " database in HfW
2O
8XRD coincide (Pdf No.21-363).Raman spectrum possesses ZrW
2O
8And HfW
2O
8The skeleton construction feature.
Embodiment 8: laser synthesizes minus thermal-expansion coefficient Zr
1-xHf
xW
2O
8:
0.8:0.2:2 takes by weighing ZrO in molar ratio
2, HfO
2With WO
3, mixed, grind 90 minutes, with batch briquetting, carry out laser then and synthesize.The laser synthesis technologic parameter is: optical maser wavelength 10.6 μ m, power density 1.5kW/cm
2, beam flying speed 12mm/s.The laser synthetic materials is even green block, and macro morphology is smooth, smooth.Raman spectrum analysis shows that the material that generates is Zr
0.8Hf
0.2W
2O
8Corresponding Raman spectrum is seen accompanying drawing 6 (B).
Embodiment 9: laser synthesizes minus thermal-expansion coefficient Zr
1-xHf
xW
2O
8:
0.5:0.5:2 takes by weighing ZrO in molar ratio
2, HfO
2With WO
3, mixed, grind 90 minutes, with batch briquetting, carry out laser then and synthesize.The laser synthesis technologic parameter is: optical maser wavelength 10.6 μ m, power density 0.2kW/cm
2, beam flying speed 0.2mm/s.The laser synthetic materials is even green block, and macro morphology is smooth, smooth.Raman spectrum analysis shows that the material that generates is Zr
0.5Hf
0.5W
2O
8Corresponding Raman spectrum is seen accompanying drawing 6 (C).
Embodiment 10: laser synthesizes minus thermal-expansion coefficient ZrW
1-xMo
xO
8:
1:1.2:0.8 takes by weighing ZrO in molar ratio
2, WO
3With MoO
3, mixed, grind 90 minutes, with batch briquetting, carry out laser then and synthesize.The laser synthesis technologic parameter is: optical maser wavelength 10.6 μ m, power density 1.5kW/cm
2, beam flying speed 12mm/s.The laser synthetic materials is even green block, and macro morphology is smooth, smooth.X-ray diffraction and Raman spectrum analysis show that the material that generates is ZrW
1.2Mo
0.8O
8Corresponding X-ray diffraction and Raman spectrum are seen accompanying drawing 7 and Fig. 8 (A).XRD spectrum and " FindIt " middle α ZrW mutually
2O
8XRD coincide (ICSD CCode 56565) and " Search-Match " database in ZrMo
2O
8XRD coincide (Pdf No.38-1496).Raman spectrum possesses ZrW
2O
8And ZrMo
2O
8The skeleton construction feature.
Embodiment 11: laser synthesizes minus thermal-expansion coefficient ZrW
1.4Mo
0.6O
8:
1:1.4:0.7 takes by weighing ZrO in molar ratio
2, WO
3With MoO
3, mixed, grind 90 minutes, with batch briquetting, carry out laser then and synthesize.The laser synthesis technologic parameter is: optical maser wavelength 10.6 μ m, power density 1.02kW/cm
2, beam flying speed 4mm/s.The laser synthetic materials is even green block, and macro morphology is smooth, smooth.Raman spectrum analysis shows that the material that generates is ZrW
1.4Mo
0.6O
8Corresponding Raman spectrum is seen accompanying drawing 8 (B).Raman spectrum possesses ZrW
2O
8And ZrMo
2O
8The skeleton construction feature.
Embodiment 12: laser synthesizes minus thermal-expansion coefficient ZrW
1-xMo
xO
8:
1:1.6:0.6 takes by weighing ZrO in molar ratio
2, WO
3With MoO
3, mixed, grind 90 minutes, with batch briquetting, carry out laser then and synthesize.The laser synthesis technologic parameter is: optical maser wavelength 10.6 μ m, power density 0.2kW/cm
2, beam flying speed 0.2mm/s.The laser synthetic materials is even green block, and macro morphology is smooth, smooth.Raman spectrum analysis shows that the material that generates is ZrW
1.4Mo
0.6O
8Corresponding Raman spectrum is seen accompanying drawing 8 (C).Raman spectrum possesses ZrW
2O
8And ZrMo
2O
8The skeleton construction feature.
Embodiment 13: laser synthesizes minus thermal-expansion coefficient HfW
1-xMo
xO
8:
1:1.6:0.6 takes by weighing HfO in molar ratio
2, WO
3With MoO
3, mixed, grind 60-120 minutes, with batch briquetting, carry out laser then and synthesize.The laser synthesis technologic parameter is: optical maser wavelength 10.6 μ m, power density 0.35kW/cm
2, beam flying speed 4mm/s.The laser synthetic materials is even green block.X-ray diffraction and Raman spectrum analysis show that the material that generates is HfW
1.2Mo
0.8O
8Corresponding X-ray diffraction and Raman spectrum are seen accompanying drawing 9 and Figure 10 (A).HfW in XRD spectrum and " Search-Match " database
2O
8Coincide HfMo in (Pdf No.21-363) and " FindIt " of XRD
2O
8XRD coincide (ICSD CCode27029).Raman spectrum possesses HfW
2O
8And HfMo
2O
8The skeleton construction feature.
Embodiment 14: laser synthesizes minus thermal-expansion coefficient HfW
1-xMo
xO
8:
1:1.6:0.8 takes by weighing HfO in molar ratio
2, WO
3With MoO
3, mixed, grind 60-120 minutes, with batch briquetting, carry out laser then and synthesize.The laser synthesis technologic parameter is: optical maser wavelength 10.6 μ m, power density 1.5kW/cm
2, beam flying speed 12mm/s.The laser synthetic materials is even green block.Raman spectrum analysis shows that the material that generates is HfW
1.2Mo
0.8O
8Corresponding Raman spectrum is seen accompanying drawing 10 (B).Raman spectrum possesses HfW
2O
8And HfMo
2O
8The skeleton construction feature.
Embodiment 15: laser synthesizes minus thermal-expansion coefficient HfW
1-xMo
xO
8:
1:1.6:0.6 takes by weighing HfO in molar ratio
2, WO
3With MoO
3, mixed, grind 60-120 minutes, with batch briquetting, carry out laser then and synthesize.The laser synthesis technologic parameter is: optical maser wavelength 10.6 μ m, power density 0.2kW/cm
2, beam flying speed 0.2mm/s.The laser synthetic materials is even green block.Raman spectrum analysis shows that the material that generates is HfW
1.2Mo
0.8O
8Corresponding Raman spectrum is seen accompanying drawing 10 (C).Raman spectrum possesses HfW
2O
8And HfMo
2O
8The skeleton construction feature.
Claims (8)
1, laser synthetic method for negative expansion coefficient material is characterized in that, can generate the raw material composition of negative expansion coefficient material with the laser beam direct heating, it is reacted and rapid solidification in laser molten pool.
2, laser synthetic method for negative expansion coefficient material as claimed in claim 1 is characterized in that, selects CO for use
2Gas laser or Nd:YAG solid statelaser, optical maser wavelength 10.6 μ m or 1.06 μ m, power density 0.2-1.5kW/cm
2, beam flying speed 0.2-12mm/s.
3, laser synthetic method for negative expansion coefficient material as claimed in claim 2 is characterized in that, minus thermal-expansion coefficient is ZrW
2O
8, used raw material composition is ZrO
2And WO
3, ZrO
2With WO
3Mol ratio be 1:2-2.5.
4, laser synthetic method for negative expansion coefficient material as claimed in claim 2 is characterized in that, minus thermal-expansion coefficient is HfW
2O
8, used raw material composition is HfO
2And WO
3, HfO
2With WO
3Mol ratio be 1:2-2.5.
5, laser synthetic method for negative expansion coefficient material as claimed in claim 2 is characterized in that, minus thermal-expansion coefficient is Zr
1-xHf
xW
2O
8, 0＜x＜1.0, raw materials used composition is ZrO
2And HfO
2And WO
3, ZrO
2And HfO
2With WO
3Mol ratio is (ZrO
2+ HfO
2): WO
3=1:2-2.5.
6, laser synthetic method for negative expansion coefficient material as claimed in claim 2 is characterized in that, minus thermal-expansion coefficient is Zr
1-xHf
xMo
2O
8, 0＜x＜1.0, raw materials used composition is ZrO
2And HfO
2And MoO
3Or MoO
2Or Mo, ZrO
2And HfO
2With MoO
3Or MoO
2Or the Mo mol ratio is (ZrO
2+ HfO
2): MoO
3Or MoO
2Or Mo=1:2-2.5.
7, laser synthetic method for negative expansion coefficient material as claimed in claim 2 is characterized in that, minus thermal-expansion coefficient is ZrMo
2-xW
xO
8, 0＜x＜2.0, raw materials used composition is ZrO
2, WO
3And MoO
3Or MoO
2Or Mo, ZrO
2With WO
3And MoO
3Or MoO
2Or the Mo mol ratio is ZrO
2: (WO
3+ MoO
3Or MoO
2Or Mo)=1:2-2.5.
8, laser synthetic method for negative expansion coefficient material as claimed in claim 2 is characterized in that, minus thermal-expansion coefficient is HfMo
2-xW
xO
8, 0＜x＜2.0, raw materials used composition is HfO
2, WO
3And MoO
3Or MoO
2Or Mo, HfO
2With WO
3And MoO
3Or MoO
2Or the Mo mol ratio is HfO
2: (WO
3+ MoO
3Or MoO
2Or Mo)=1:2-2.5.
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| CN102584330B (en) * | 2012-02-29 | 2013-12-11 | 郑州大学 | Laser preparation method of lanthanum molybdate based oxygen ion conductor |
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| 陶瓷材料的激光合成工艺研究. 曾祥斌.电子元件与材料，第14卷第5期. 1995 * |
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