CN1850721A - 2-substituted cubic-phase zirconium tungstate solid solution temperature-sensitive dispersion compensation porcelain body and preparing method therefor - Google Patents
2-substituted cubic-phase zirconium tungstate solid solution temperature-sensitive dispersion compensation porcelain body and preparing method therefor Download PDFInfo
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- CN1850721A CN1850721A CN 200610087416 CN200610087416A CN1850721A CN 1850721 A CN1850721 A CN 1850721A CN 200610087416 CN200610087416 CN 200610087416 CN 200610087416 A CN200610087416 A CN 200610087416A CN 1850721 A CN1850721 A CN 1850721A
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Abstract
This invention relates to one kind of disubstituted cube zirconium tungstate solid solution temperature sensitive dispersion compensation thermal shrinking ceramic body and its preparation method. Binding sol-gel method and high temperature solid phase method are used in this invention to make solid solution ceramic, its chemical formula is (Zr1-xAx)(W2-yMoy)O8-delta, and A equals to Yb,Er,Dy,Eu,Ce,Ga,Mn,Cu,Zn etc. X equals to 0-0.1, y equals to 0-1.3, delta equals to 0-0.1. The ceramic body with basic structure cube phase ZrW208 has linear thermal shrinking character of isotropy, good damp resistance character, its thermal lag character is low, thermoshock resistance is good, which can be used as no heat source temperature sensitive dispersion compensation compact ceramic basal body of Prague optical grating of adjustable minus thermal expansion coefficient.Its preparation technique is simple, manufacturing condition is easy to control, and material thermal shrinking and other physical property can be controlled by adjusting its components.
Description
Technical field
The present invention relates to class thermal contraction ceramic body and preparation method thereof, particularly relate to from two wolframic acid zircon ceramic bodies and preparation method thereof that replace of the temperature range internal linear thermal contraction of room temperature to 600 ℃.Adopt method provided by the invention can prepare thermal contraction ceramic body a series of densifications and that porosity is controlled within the specific limits.It can be used as the ceramic bases of the no thermal source temperature-sensitive dispersion compensation bragg grating device of optical filter, belongs to electronic device material or photoelectric device material technology field.
Background technology
(Fiber Bragg Grating is present best narrow band optical filter FBG) to bragg grating, almost is applied to each field of modern photoelectricity communication and precision optical instrument.Elimination is FBG peak reflectance wavelength (λ under Working environment
B) temperature-sensitive dispersion be one of gordian technique that improves all kinds of optical filter spectroscopical effeciencies.The research of no thermal source control temperature-sensitive dispersion compensation is based on the peak reflectance wavelength (λ of FBG
B) carry out with grating cycle (Λ) following relation: λ
B=2n Λ.λ
BWith drift (the Δ λ of applied stress (ε) with temperature variation (Δ T)
B) be: Δ λ
B=2n Λ (A ε+B Δ T); A wherein, B are respectively the relevant parameters of photoelastic tensor sum thermal expansivity with optical fiber.As seen the peak reflectance wavelength of FBG is all very responsive to temperature and stress.(A.K. Jia Dekarui according to the literature, publication number CN141309A), FBG under the tension force is assembled on the ceramic bases with thermal contraction character, make expansion mismatch coefficient between fiber grating and the thermal contraction substrate in the 4ppm-7ppm scope, will apply 120psi/ ℃ stress to fiber grating, the requirement that this can satisfy compensation FBG peak reflectance wavelength temperature-sensitive dispersion, the spectroscopical effeciency that greatly improves FBG is with stable.
At present, the ceramic bases that is applied to not have the thermal source temperature-sensitive dispersion compensation mainly is beta-eucryptite P series glass-pottery (NipponTakahiro et al, Patent No:WO2005012964), but because beta-eucryptite has anisotropic crystalline structure, heat-shock resistance is poor, be easy to generate tiny crack in the course of processing, reduced the thermal cycling stability of material and, also must bring complicacy and expensive to preparation technology to the wet fastness of wet environment.Prepared ZrW from usefulness such as A.W.Sleight co-precipitation-precursor thermal decomposition method
2O
8(Sleight A.W., US patent, 1996, No.5514360) and in depth disclosed cube-ZrW
2O
8In very wide temperature range (0.3-1050K), have bigger isotropic negative expansion coefficient (Mary T.A., Evans J.S.O., Sleight A.W., Vogt T., Science, Vol.272,1996, P90) since, Fleming (Fleming et al, US patent, 5694503) and Wen Huiling etc. (Wen Huiling etc., publication number CN 1406905A) proposed with cube-ZrW
2O
8There is not the ceramic bases of thermal source temperature-sensitive dispersion compensation FBG device with the compound preparation of material of positive thermal expansivity (as aluminum oxide, silicon oxide, zirconium white, magnesium oxide, calcium oxide or yttrium oxide), but substrate is cracked owing to matching of the matrix material coefficient of expansion, make the thermal expansion curve sluggishness of pottery, moisture resistance descends.Merkel (G.A.Merkel, US patent 9909888) uses the little materials A of negative thermal expansion coefficient
2P
2WO
12(A:Zr, Hf) and ZrW
2O
8Compound, though overcome the problems referred to above, because material is by multiple thing phase composite, technology is still very complicated, and from 0-70 ℃, FBG centre wavelength with the variation of temperature rate greater than desired value 2pm/ ℃.The hole waits on the sunny side (hole face south etc., publication number CN 1382663A) with doping ZrW
2O
8Sosoloid is that main crystalline phase is coated in the negative expansion microcrystalline coating on the quartz glass substrate, but thermal expansivity only reaches-0.3ppm/K--2.0ppm/K, and the linear relationship of material heat-shrinkable is bad, fails to satisfy the requirement of FBG temperature-sensitive dispersion compensation.
Because orderly cube of phase α-ZrW
2O
8(thermal expansivity: α=-8.8 * 10
-6K
-1, 0-400K) to unordered cube of phase β-ZrW
2O
8(thermal expansivity: α=-4.9 * 10
-6K
-1, 430-950K) (Cora Lind, Angus P.Wilkinson, ZhongboHu et al, Chem.Mater., 1998,10, crystal conversion temperature P2335) (J.S.O.Evans, T.A.Mary about 160 ℃, T.Vogt, M.A.Subramanian, and A.W.Sleight, Chem.Mater., 1996,8, cube P2809) ,-ZrW
2O
8Linear percent thermal shrinkage near phase transition temperature, change, be unfavorable for that the thermal cycling of material in comprising 160 ℃ temperature range use; And orderly cube of phase γ-ZrMo
2O
8(thermal expansivity: α=-6.9 * 10
-6K
-1) to unordered cube of phase ZrMo
2O
8(thermal expansivity: α=-5.0 * 10
-6K
-1) the crystal conversion temperature-73 ℃ (Simon Allen and J.S.O.Evans, Physical Review B, 2003,68, therefore 13401-3), form ZrW
2-yMo
yO
8-δSosoloid help reducing cube phase order-disorder crystal conversion temperature (Zhao Xinhua, Chin.J.Chem., 2000,18 (4), 571-575), improve the linear relationship of stupalith heat-shrinkable.J.S.O.Evans etc. have reported cube-ZrWMoO
8Alpha-beta crystal conversion temperature be reduced to-3 ℃ (J.S.O.Evans, P.A.Hanson, R.M.Ibberson, N.Duan, U.Kameswari and A.W.Sleight, J.Am.Chem.Soc., 2000,122, P8695).Cube β-ZrWMoO in-3 ℃ to 600 ℃ the temperature range
8Linear shrinkage, and its coefficient of expansion is-4--7 * 10
-6/ ℃, do not need to go again just can satisfy the requirement of FBG temperature-sensitive dispersion compensation with just the expansible material is compound.
Human combustion methods such as U.Kameswari, again 1200 ℃ the calcining 30s methods prepare a cube phase ZrWMoO
8(U.Kameswari, A.W.Sleight, J.S.O.Evans, International Journal of Inorganic Materials, 2 (2000), P334), but the bad control of reaction process generates dephasign easily.Since oxide compound easier distillation when high temperature of molybdenum, commonplace preparation cube phase ZrWMoO
8Method be earlier preparation precursor, cube phase β-ZrWMoO of thermolysis precursor preparation at a lower temperature again
8The method for preparing precursor at present report the preparation precursor (C.Closman that refluxes in strongly acidic solution such as C.Closman arranged, A.W.Sleight, J.C.Haygarth, Journal of Solid State Chemistry, Vol.139, P425,1998) and human acid vapour Hydrothermal Preparation precursor (Deng Xuebin etc., Chinese Journal of Inorganic Chemistry, Vol.21 such as Deng Xuebin, 2005, P1358).Because Zr and Mo solubleness in strongly acidic solution are bigger, (the Zr of the rich Mo of method for preparing
1-xA
x) (W
2-yMo
y) O
8-δSosoloid causes the component deviation stoichiometric ratio easily, produces the second phase compound, makes complex process.With cube phase (Zr that makes
1-xA
x) (W
2-yMo
y) O
8-δAfter sosoloid is dry-pressing formed, also will make blank Densification, and gained ceramic body compactness is bad by means of the high-temperature calcination second time.
The present invention has prepared monophasic cube of (Zr with a kind of novel method
1-xA
x) (W
2-yMo
y) O
8-δ(A comprises Yb, Er, Dy, Eu, Ce, Ga, Mn, Cu, Zn; X=0-0.1; Y=0-1.3; δ: 0-0.1) solid solution ceramic is preparing Mo replacement cube ZrW with high-temperature sintering process
2O
8The sosoloid aspect has obtained breakthrough.The present invention makes co-precipitation with so-called " wet-chemical-high-temperature sintering process " by sol-gel method, and is again that the presoma of gained after the co-precipitation thermal treatment is dry-pressing formed, and high-temperature calcination base substrate has then prepared the pure phase cube (Zr of even compact
1-xA
x) (W
2-yMo
y) O
8-δ(A comprises Yb, Er, Dy, Eu, Ce, Ga, Mn, Cu, Zn; X=0-0.1; Y=0-1.3; δ: 0-0.1) solid solution ceramic.Because presoma and ceramic body are isomerism compound (Zr
1-xA
x) (W
2-yMo
y) O
8-δOr its mixture, so the high temperature sintering base substrate just impels presoma to a cube phase (Zr
1-xA
x) (W
2-yMo
y) O
8-δThe transformation of crystal formation is and directly with oxide compound preparation (Zr
1-xA
x) (W
2-yMo
y) O
8-δCompare, it reduces greatly to the requirement in temperature of reaction and reaction times, has avoided the volatilization of molybdenum, tungsten oxide effectively, has reduced preparation process, has shortened the treatment time, has reduced production cost.In addition, replace Zr ionic dopant ion A, can improve compactness, heat-shock resistance and the moisture resistance of ceramic body effectively by in the preparation presoma, adding other; By regulating the mol ratio of tungsten, molybdenum in the presoma, can regulate, control the coefficient of expansion of ceramic body effectively, thereby realize the controllability of tungsten acid zircon ceramic volume coefficient.
The synthetic tungsten acid of so-called wet-chemical-high-temperature sintering process zircon ceramic body, be will contain zirconium earlier, tungsten mixes stirring with the soluble salt of elements such as molybdenum, co-precipitation oven dry with gained, thermal treatment obtains presoma again, with presoma grinding, dry-pressing formed, high-temperature heat treatment again obtains the pure phase (Zr of single cubic crystalline structure at last
1-xA
x) (W
2-yMo
y) O
8-δCeramic body.With A.W.Sleight (USpatent, 1996, No.5514360) preparation heat-shrinkage material AW
2O
8(A=Zr Hf) compares, and the introducing of molybdenum has caused tripartite phase or contained tripartite phase (Zr
1-xA
x) (W
2-yMo
y) O
8-δThe formation of the presoma of (specifically deciding on the content of molybdenum and the temperature of processing co-precipitation) has reduced preparation cube phase (Zr to a great extent
1-xA
x) (W
2-yMo
y) O
8-δThe temperature of reaction and the reaction times of pottery, especially, a series of cube β-Zr have been made from-3 ℃ to the thermal contraction of 600 ℃ of temperature range internal linear by adjusting the tungsten ratio
1-xA
x-WMoO
8(A comprises Yb to ceramic body, Er, Dy, Eu, Ce, Ga, Mn, Cu, Zn; X=0-0.1), and its coefficient of expansion be-4--7 * 10
-6/ ℃.
Summary of the invention
The invention relates to the 2-substituted cubic-phase zirconium tungstate solid solution temperature-sensitive dispersion compensation porcelain body of a class along with temperature rising volume or dimensions shrink, especially from the preparation method of the temperature range internal linear thermal contraction ceramic body of room temperature to 600 ℃, comprise following concrete steps:
(1) preparation presoma: with tetravalence Zr ionically-soluble salt, the acid of sexavalence W, Mo, ammonium salt and the relevant metal oxide or the soluble metallic salt that dissolve in nitric acid, hydrochloric acid are raw material, mixing the back by stoichiometric ratio or non-stoichiometric constantly stirs, form co-precipitation, with co-precipitation oven dry, porphyrize, thermal treatment makes presoma;
(2) dry-pressing formed: coat lubricant at the inwall of stainless steel mould and make releasing agent, this lubricant can be for example vegetables oil or the organic grease of other easy volatile of organic grease.Take by weighing the presoma of an amount of porphyrize, put into stainless steel mould, dry-pressing becomes base substrate;
(3) high temperature sintering densification: base substrate is placed on thermal treatment in the platinum crucible, cover the platinum lid again, putting into the retort furnace that heats in advance is incubated, insulation between 910-1200 ℃, preferably 920-1150 ℃ of insulation, soaking time is 0.5-10 hour, preferred 1-3 hour, take out rapidly then, in air, cool off, obtain high fine and close thermal contraction ceramic body (Zr
1-xA
x) (W
2-yMo
y) O
8-δ(A comprises Yb, Er, and Dy, Eu, Ce, Ga, Mn, Cu, Zn, x=0.1, y=0-1.3, δ=0-0.1).
Preparation in accordance with the present invention, presoma change into a cube phase (Zr
1-xA
x) (W
2-yMo
y) O
8-δThe densification of ceramic body and base substrate is finished in same heat treatment step, thereby obtains needed fine and close tungsten acid zircon ceramic body.Because presoma is not the simple mixtures of zirconium white, Tungsten oxide 99.999 and molybdenum oxide etc., but contains tripartite phase (Zr
1-xA
x) (W
2-yMo
y) O
8-δCompound or amorphous mixture (specifically decide) on the content of molybdenum and the temperature of handling precursor, from three parts's phase or amorphous (Zr
1-xA
x) (W
2-yMo
y) O
8-δTo a cube phase (Zr
1-xA
x) (W
2-yMo
y) O
8-δConversion with directly with oxide compound preparation (Zr
1-xA
x) (W
2-yMo
y) O
8-δCompare, this conversion obviously reduces the requirement in temperature of reaction and reaction times, and the volatilization of molybdenum, tungsten oxide when having avoided high-temperature calcination has effectively guaranteed the stoichiometric relation of each element in the product.
Preparation in accordance with the present invention, the crystalline structure of presoma is relevant with the ratio of tungsten, as shown in Fig. 2 X-ray diffraction.Its crystalline structure also is subjected to the used Temperature Influence of calcined co-precipitation simultaneously, and as when calcining tungsten ratio is 1: 1 co-precipitation between 250-500 ℃, the gained presoma is unformed mixture; When calcining tungsten ratio was 1: 1 co-precipitation between 500-900 ℃, the gained presoma was the compound of tripartite phase.
Preparation in accordance with the present invention, used zirconates, tungsten salt and molybdenum salt, can be and anyly be applicable to that calcining and decomposing is the salt of corresponding oxide between 300-900 ℃, can be selected from Zircosol ZN, zirconium oxychloride, zirconium hydroxide, zirconium carbonate, ammonium tungstate, ammonium molybdate, wolframic acid, molybdic acid etc., preferred solubility Zircosol ZN, zirconium oxychloride, ammonium tungstate and ammonium molybdate; The A ion can derive from solubility nitrate, muriate, carbonate and dissolve in the metal oxide of acid such as hydrochloric acid, nitric acid.
Preparation in accordance with the present invention is at a cube phase sosoloid (Zr
1-xA
x) (W
2-yMo
y) O
8-δIn, the content y of Mo is from 0-1.3.When 0≤y≤1, high temperature sintering body preparation pure phase (Zr
1-xA
x) (W
2-yMo
y) O
8-δThe temperature of sosoloid reduces with the increase of y; When 1＜y≤1.3, high temperature sintering body preparation pure phase (Zr
1-xA
x) (W
2-yMo
y) O
8-δThe temperature of sosoloid raises with the increase of y; And when y＞1.3, be difficult to prepare pure phase (Zr by wet-chemical-high-temperature sintering process
1-xA
x) (W
2-yMo
y) O
8-δCeramic body.For making (the Zr that shrinks in normal temperature to 600 ℃ temperature range internal linear
1-xA
x) (W
2-yMo
y) O
8-δCeramic body, y should be selected between the 0.9-1.3.According to a cube phase γ-ZrMo
2O
8Transformation temperature be-73 ℃, cube phase ZrW
2O
8The crystal conversion temperature about 160 ℃ and cube phase ZrWMoO
8The crystal conversion temperature can know for-3 ℃, when 1＜y≤1.3, with the increase of y value, (Zr
1-xA
x) (W
2-yMo
y) O
8-δThe transformation temperature of ceramic body should compare ZrWMoO
8-3 ℃ lower, thereby the material yardstick is with the temperature linear shrinkage that raises in wideer temperature range.
Preparation in accordance with the present invention, when dry-pressing formed blank sintering was handled, its reaction sintering temperature was 910-1200 ℃, preferred 920-1150 ℃.The reaction sintering time is 0.5-10 hour, preferred 1-3 hour.Sintering time can shorten with the rising of sintering temperature; The temperature range of preparation pure phase doped ceramics body is subjected to the influence of tungsten ratio remarkable, and also the difference with dopant ion changes.
Preparation in accordance with the present invention, dry-pressing formed pressure do not play conclusive effect in the densification of ceramic body, so forming pressure is not to be the bigger the better, forming pressure is bigger, tangential pressure is also bigger, and base substrate is cracked easily in knockout course, causes blank forming bad.Used forming pressure is 1-30MPa, preferred 2-5MPa, and this compares with the forming pressure of other bibliographical information, greatly reduces the fine and close (Zr of preparation
1-xA
x) (W
2-yMo
y) O
8-δCeramic body is to the requirement of pressure, and do not need to add binding agent in moulding process, simplified operation steps, and the volatilization of having avoided binding agent is in the inner porous phenomenon that forms of ceramic body.
Preparation in accordance with the present invention, if need the preparation porous ceramic bodies, can be in proportion with some volatile solid-state organism, inorganics etc. and presoma mixed grinding, high temperature sintering prepares porous (Zr then
1-xA
x) (W
2-yMo
y) O
8-δCeramic body.So according to the inventive method, it is external to remove the preparation ceramic of compact, can also be as required, and the controllable within the specific limits porous ceramic matrices suitable of preparation porosity is as with Zr
0.99Yb
0.01WMoO
7.995The polyoxyethylene glycol mixed grinding of presoma and 10% (mass ratio), dry-pressing formed, it is 80.1% ceramic body that high-temperature calcination makes the sintering degree.
Preparation in accordance with the present invention, the coking property of solid solution ceramic, hardness, density are subjected to the influence of dopant ion A remarkable.Dopant ion A difference is to sosoloid (Zr
1-xA
x) (W
2-yMo
y) O
8-δThe influence of ceramic post sintering is also inequality.With Zr in the preparation in 1 hour of 1000 ℃ of sintering
0.99A
0.01WMoO
8-δ(A comprises Yb, Er, Dy, Eu, Ce, Ga, Mn, Cu, Zn; δ=0-0.01) is an example, has listed different dopant ions in Table 1 to solid solution ceramic Zr
0.99A
0.01WMoO
8-δThe influence of sintering degree.As can be seen, lanthanon is bigger to the sintering degree influence of ceramic body from table one.
Table one: different dopant ion sosoloid Zr
0.99A
0.01WMoO
8-δ(the sintering degree of the pottery of δ=0-0.01)
| A | Ce | Yb | Er | Eu | Dy | Ga | Mn | Zn | Cu | x＝0 | Yb(x＝0.04) |
| Density (g/cm 3) theoretical density (g/cm 3) sintering degree (%) | 3.81 4.34 87.8 | 3.80 4.35 87.4 | 3.78 4.34 87.1 | 3.67 4.34 84.6 | 3.61 4.35 83.0 | 3.51 4.34 80.9 | 3.44 4.34 80.8 | 3.21 4.34 74.0 | 3.25 4.34 74.9 | 3.28 4.34 75.6 | 4.04 4.37 92.4 |
Preparation in accordance with the present invention, prepared sosoloid ZrW
2-yMo
yO
8The crystal conversion temperature with the difference of y value difference.In table two, listed the sosoloid ZrW that measures with TMA
2-yMo
yO
8(y=0-1.3) Tao Ci crystal conversion temperature, the coefficient of expansion and preparation condition.Be lower than the sosoloid of room temperature (20 ℃) for phase transition temperature,, only list its coefficient of expansion because they shrink in the temperature range internal linear of measuring; And for the sosoloid of phase transition temperature apparently higher than room temperature (20 ℃), segmentation has provided their coefficient of expansion mutually mutually with β by α respectively.By table two data as can be known, sosoloid ZrW
2-yMo
yO
8The crystal conversion temperature reduce with the increase of y value, and in y 〉=0.9 o'clock, ZrW
2-yMo
yO
8Sosoloid in room temperature with a cube β-ZrW
2O
8Form exists, and the crystal conversion temperature of alpha-beta phase is lower than room temperature, ceramic body in the temperature range of room temperature to 600 ℃ with the increase in temperature linear shrinkage.It can also be seen that preparation ZrW by table two
2-yMo
yO
8The temperature of sosoloid is along with y departs from 1 and raise, and the preparation temperature scope is dwindled, the harshness that synthesis condition becomes; When y=1, can in 913-1000 ℃ of very wide temperature range, make pure phase ZrWMoO
8Sosoloid, the preparation condition of this gentleness provides possibility for producing the thermal contraction pottery in batches, and it is from-3 ℃ to 600 ℃ temperature range internal linear contraction, with a cube ZrW
2O
8Compare, have potential widely application.The relevant data of y=0 sample is also listed in figure three and the table two as a comparison, but the non-feature of the present invention of its preparation method place.
Table two: ZrW
2-yMo
yO
8Alpha-beta phase crystal conversion temperature, the coefficient of expansion and the preparation condition of solid solution ceramic
| y | Transformation temperature (℃) | The coefficient of expansion (* 10 -6/℃) | |
| 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 | 152 143 128 110 96 82 54 42 29 | α＝-10.6(25-120℃) α＝-6.0(160-300℃) α＝-10.9(22-110℃) α＝-5.8(155-300℃) α＝-11.9(25-110℃) α＝-5.7(155-300℃) α＝-12.7(30-90℃) α＝-5.7(120-300℃) α＝-13.3(25-75℃) α＝-5.7(110-300℃) α＝-5.7(100-300℃) α＝-5.6(90-300℃) α＝-5.6(60-300℃) α＝-5.7(50-300℃) α＝-5.7(30-300℃) α＝-5.6(30-300℃) α＝-5.6(30-300℃) α＝-5.6(30-300℃) α＝-5.4(20-300℃) | 1200℃2h，1160℃6h 1150℃1h 1150℃1h 1100℃1h 1100℃1h 1150℃1h 1050℃1h 1000℃1h 1000℃1h 1000℃1h 913-1000℃1h 1000℃1h 980℃1h 980℃1h |
Preparation in accordance with the present invention is with prepared negative expansion Zr
0.96Yb
0.04WMoO
7.98Solid solution ceramic takes out soak 120h in deionized water after, the forward and backward quality of weighing ceramic body immersion respectively, the water-intake rate of pottery only be 2.8% and immersion back ceramic surface do not find tiny crack.Measure the heat stagnation curve of the forward and backward ceramic body of immersion respectively, find that wet environment is little to the heat stagnation influence of ceramic body, ceramic moisture resistance is good.
Preparation in accordance with the present invention is with prepared negative expansion Zr
0.96Yb
0.04WMoO
7.988Solid solution ceramic is placed on and carries out cycle heat treatment in the retort furnace, the heat-shock resistance of observation pottery.Tiny crack does not appear in ceramic surface after the cycle heat treatment, measures the heat stagnation curve of the forward and backward ceramic body of cycle heat treatment respectively, finds that cycle heat treatment is little to the heat stagnation influence of ceramic body, and the ceramic body heat-shock resistance is good.
Preparation in accordance with the present invention is with prepared negative expansion solid solution ceramic Zr
0.99A
0.01WMoO
8-δ(A=Zn, Yb) compound with FBG, measure respectively bare optical fibers and bare optical gratings and compound after fiber grating from 20-70 ℃ with the raise drift of its centre wavelength of temperature.After the result showed that fiber grating and prepared negative expansion ceramic body are compound, its temperature-sensitive dispersion obviously reduced.Select negative thermal expansion coefficient suitable ceramic body and FBG compound, can further reduce its temperature-sensitive dispersion.
Description of drawings
Fig. 1 is with synthesis of cubic phase β-ZrWMoO according to the present invention
8Outline flowchart for example.
Fig. 2 is according to the embodiment of the invention 1 prepared ZrW
2-yMo
yO
8(y=0-2.0) the powder x-ray diffraction characteristic spectrum of presoma.
ZrW
2-yMo
yO
8(y=0-2.0) powder x-ray diffraction of presoma shows, when 0≤y≤0.3, presoma is amorphous substance or tripartite phase ZrW
2-yMo
yO
8Mixture with amorphous substance; When y 〉=0.4, presoma is mainly with the ZrW of tripartite phase
2-yMo
yO
8Exist.
Fig. 3 is according to 1 prepared cube of ZrW of the embodiment of the invention
2-yMo
yO
8(y=0-1.5) powder X-ray of sosoloid-ray ray diffraction characteristic spectrum.
Cube ZrW
2-yMo
yO
8(y=0-1.5) powder x-ray diffraction shows, when 0≤y≤0.8, and sosoloid (Zr
1-xA
x) (W
2-yMo
y) O
8-δIn room temperature with a cube phase α-ZrW
2O
8Form exists; When 0.9≤y≤1.3, sosoloid (Zr
1-xA
x) (W
2-yMo
y) O
8-δIn room temperature with a cube phase β-ZrW
2O
8Form exist; And when y＞1.3, have the diffraction peak of impurity to occur among the figure.
Fig. 4 is according to 1 prepared cube of ZrW of the embodiment of the invention
1.9Mo
0.1O
8The temperature variant graphic representation of the dimensional change of ceramic body.
As can be seen from the figure sample has a weight break point about 143 ℃, and this weight break point is ZrW
1.9Mo
0.1O
8The α-βXiang Bian temperature spot, the sample coefficient of expansion is listed in the table two before and after the turnover.
Fig. 5 is according to the embodiment of the invention 2 prepared ceramic body Zr
0.96Yb
0.04WMoO
7.98The X-ray diffraction characteristic spectrum of indexing.
The disappearance of 310 diffraction peaks indicates that sample is with a cube phase β-ZrW among the figure
2O
8Form exist.
Fig. 6 is according to the embodiment of the invention 2 prepared ceramic body Zr
0.96Yb
0.04WMoO
7.98The temperature variant graphic representation of dimensional change.
As can be seen from Figure 6, Zr
0.96Yb
0.04WMoO
7.98Ceramic body shrinks from the temperature range internal linear of room temperature to 600 ℃, and its coefficient of expansion is-4.5 * 10
-6/ ℃.
Fig. 7 is according to the embodiment of the invention 2 prepared ceramic body Zr
0.96Yb
0.04WMoO
7.98The heat stagnation curve.
As can be seen from Figure 7, curve sample size in the different process of the cooling that heats up is very little in same temperature difference, the interpret sample dimensional change is very sensitive with variation of temperature, thereby can avoid producing the thermal stresses that causes owing to temperature variation, thereby the tiny crack of having avoided temperature variation to cause in sample interior.
Fig. 8 is prepared ceramic body Zr according to the present invention
0.96Yb
0.04WMoO
7.98Carry out the heat stagnation curve of moisture resistance experiment preceding (a), back (b).
Fig. 9 is prepared ceramic body Zr according to the present invention
0.96Yb
0.04WMoO
7.98The heat stagnation curve of (a), back (b) before the cycle heat treatment.
Figure 10 changes temperature variant curve according to the part ceramic body sample size that the embodiment of the invention 5 makes.
Be followed successively by Ga, the Er that mixes 1% mole, the sample curve of Yb, Cu among the figure from top to bottom.As seen from the figure, the ion A difference, little to the influence of the thermal expansion of ceramic body, its coefficient of expansion is between-5.2--5.6 * 10
-6/ ℃ between, but can improve the coking property of material.
Figure 11 is the Zr that fiber grating and embodiment 5 make
0.99Zn
0.01WMoO
7.99The compound forward and backward drift curve of ceramic body with temperature rising fiber grating centre wavelength.
As can be seen from the figure, fiber grating and this ceramic body compound after wherein the drift that raises of cardiac wave personal attendant temperature obviously reduce.
Synthetic method of the present invention weak point consuming time, the product purity height, gained ceramic body compactness is good, and porosity is may command within the specific limits, is easy to grasp.Now further specify the method that the present invention prepares tungsten acid zircon ceramic body, be familiar with this operator and can finish these embodiment easily with the following example.
Embodiment
Stoichiometric ratio according to molecular formula is added to ammonium paratungstate in the three-necked bottle that fills the 20ml deionized water, stirs; Zirconium oxychloride and ammonium molybdate are dissolved in respectively in the 30ml deionized water, are added drop-wise to simultaneously in the secondary tungsten acid ammonium solution, continue to stir several hrs with constant pressure funnel.With the co-precipitation oven dry, porphyrize, calcining obtained presoma in 3 hours under 600 ℃, took out presoma and ground, and the characteristic X-ray diffraction of gained presoma is as shown in Figure 2.Take by weighing about 0.6g presoma and put into the stainless steel mould that coats lubricant, earlier with the pressure of 2MPa, behind the several minutes again the pressure single shaft dry-pressing with 4MPa become base substrate.Earlier base substrate is placed in the platinum crucible 600 ℃ of calcinings 0.1 hour, remove the aqueous vapor, lubricant etc. of its absorption, cover with another platinum crucible, be placed in the retort furnace that heats in advance, 920-1150 ℃ temperature range insulation 1 hour, taking-up immediately places air to cool off, and obtains fine and close ZrW
2-yMo
yO
8Ceramic body, the powder x-ray diffraction characteristic spectrum of gained pottery as shown in Figure 3.ZrW
2-yMo
yO
8The transformation temperature of ceramic body, the coefficient of expansion and preparation condition are listed in the table two.The dimensional change of sample with variation of temperature as shown in Figure 4 during y=0.1.The relevant data of y=0 sample is also listed in figure three and the table two as a comparison, but the non-feature of the present invention of its preparation method place.
Embodiment 2 Zr
0.96Yb
0.04WMoO
7.98The preparation of ceramic body
The adding of 5.2095g ammonium paratungstate is filled in the three-necked bottle of 20ml deionized water, stir; Take by weighing 0.1576g Yb
2O
3Put into 5ml concentrated nitric acid heating for dissolving; 6.1273g zirconium oxychloride and 3.5466g ammonium molybdate are dissolved in respectively in the 30ml deionized water, are added drop-wise to simultaneously in the secondary tungsten acid ammonium solution, again with the Yb (NO for preparing with constant pressure funnel
3)
3Be added drop-wise in the co-precipitation, continue to stir several hrs.With the co-precipitation oven dry, porphyrize, calcining made presoma in 3 hours under 600 ℃.Presoma take out is ground, takes by weighing about 0.6g and put into the stainless steel mould that coats lubricant, the pressure of usefulness 2MPa earlier, behind the several minutes again the pressure single shaft dry-pressing with 4MPa become base substrate.Earlier base substrate is placed in the platinum crucible, 600 ℃ of calcinings 0.1 hour, remove the aqueous vapor, releasing agent etc. of its absorption, then base substrate is covered with another platinum crucible, be placed in the retort furnace that heats in advance, insulation is 1 hour in 930-1000 ℃ temperature range, takes out immediately to place air to cool off.Present case is taken at 1000 ℃ of insulations 1 hour, and the powder X-ray ray feature diffracting spectrum of gained pottery as shown in Figure 5.Be raised to the 300 ℃ thermal expansions of measuring ceramic bodies with the temperature rise rate of 3 ℃/min from 25 ℃ with thermomechanical analyzer (TMA), its coefficient of expansion is-4.5 * 10
-6/ ℃, as shown in Figure 6.Temperature rise rate with 3 ℃/min is raised to 300 ℃ of test condition mensuration ceramic body heat stagnations that drop to 50 ℃ again with identical speed from 25 ℃, its heat stagnation curve as shown in Figure 7, two curves are quite similar, heat up, only be 10ppm in the cooling various process at same temperature sample size maximum difference, the interpret sample dimensional change is very sensitive with variation of temperature, thereby has avoided in the inner thermal stresses that is caused by temperature variation that produces of pottery.
Embodiment 3 moisture resistances
Three ceramic bodies that embodiment 2 is made soaked in deionized water 120 hours, took out, and with paper water were blotted, and according to soaking forward and backward quality, calculating the ceramic body water-intake rate is 2.8%.Soaking the back ceramic body does not have tiny crack to occur, and shows that the ceramic body moisture resistance is good.Be raised to 300 ℃ with the temperature rise rate of 3 ℃/min from 25 ℃ with TMA and drop to 50 ℃ with identical speed again, measure the thermal expansion and the heat stagnation (Fig. 8 a, b are respectively thermal expansion and the heat stagnation curve that soaks forward and backward ceramic body) of soaking forward and backward ceramic body respectively, its coefficient of expansion is respectively-4.2 * 10
-6/ ℃ and-4.5 * 10
-6/ ℃.
Embodiment 4 heat-shock resistances
Ceramic body temperature rise rate with 1 ℃/min in retort furnace that embodiment 2 is made is raised to 200 ℃ from 30 ℃, reduce to 40 ℃ with identical speed again, so circulation is 20 times, but in the actually operating because the uncontrollability of temperature-fall period, actual temperature-fall period can not move by setup program, stove only cools to 75 ℃ of temperature-rise periods that just begin a new round again, causes ceramic body through with temperature rising expansion curve one " platform " that slowly changes being arranged after the cycle heat treatment between 60-80 ℃.But do not find tiny crack after the cycle heat treatment in the ceramic body, the ceramic body heat-shock resistance is good.Be raised to 300 ℃ with the temperature rise rate of 3 ℃/min from 25 ℃ with TMA and drop to 50 ℃ with identical speed again, measure the thermal expansion and the heat stagnation (Fig. 9 a, b are respectively the thermal expansion and the heat stagnation curve of the forward and backward ceramic body of cycle heat treatment) of the forward and backward ceramic body of cycle heat treatment respectively, its coefficient of expansion is respectively-4.5 * 10
-6/ ℃ and-4.2 * 10
-6/ ℃ (100-300 ℃).
The porosity that embodiment 5 regulates ceramic body
The ceramic body preparation method is with embodiment 2.Respectively with 1% mole A (A=Yb, Er, Dy, Eu, Ce, Ga, Mn, Cu Zn) replaces Yb, has prepared Zr
0.99A
0.01WMoO
8-δ(A=Yb, Er, Dy, Eu, Ce, Ga, Mn, Cu, Zn; X=0.01; The solid solution ceramic of δ=0-0.01).With the size of TMA mensuration ceramic body, calculate its volume, according to ρ
Actual=m/V calculates the actual density of ceramic body; With the ceramic body porphyrize of preparation, add SiO
2Mark in doing is measured ceramic unit cell parameters with X-ray diffraction, according to
(unit cell volume of V sample, the molar mass of M sample) calculates the theoretical density of sample; The sintering degree
According to porosity=1-sintering degree, conversion can obtain the porosity of ceramic body.The density of this embodiment gained ceramic body, theoretical density and sintering degree are listed in the table one.From table one and Figure 10 as can be seen, the introducing of dopant ion A can improve the coking property of pottery, and is but little to the hot expansion property influence of ceramic body, and its coefficient of expansion is between-5.2--5.6 * 10
-6/ ℃ between; Dopant ion A difference is also different to the coking property influence of pottery.
With Zr
0.99Zn
0.01WMoO
7.99Solid solution ceramic and fiber grating are compound, measure the drift of the compound forward and backward fiber grating centre wavelength of bare optical fibers and bare optical gratings and ceramic body respectively, and the drift curve as shown in figure 11.Experiment shows that this ceramic body and FBG can significantly reduce the temperature-sensitive dispersion of FBG centre wavelength after compound.
Claims (10)
1. a class is about the 2-substituted cubic-phase zirconium tungstate solid solution temperature-sensitive dispersion compensation porcelain body along with temperature rising volume or dimensions shrink, especially from the preparation method of the temperature range internal linear thermal contraction ceramic body of room temperature to 600 ℃, it is characterized in that comprising following concrete steps:
(1) preparation presoma: with tetravalence Zr ionically-soluble salt, the acid of sexavalence W, Mo, ammonium salt and the relevant metal oxide or the soluble metallic salt that dissolve in nitric acid, hydrochloric acid are raw material, by stoichiometric ratio or non-metering than continuous stirring the after mixing, form co-precipitation, with co-precipitation oven dry, porphyrize, thermal treatment makes presoma again;
(2) dry-pressing formed: coat lubricant at the inwall of stainless steel mould and make releasing agent, take by weighing the presoma of an amount of porphyrize, put into stainless steel mould, dry-pressing becomes base substrate;
(3) high temperature sintering densification: base substrate is placed on thermal treatment in the platinum crucible, covers the platinum lid again, put into the retort furnace that heats in advance and be incubated, take out rapidly then, in air, cool off, obtain densification and even high fine and close thermal contraction ceramic body (Zr
1-xA
x) (W
2-yMO
y) O
8-δ(A comprises Yb, Er, Dy, Eu, Ce, Ga, Mn, Cu, Zn; X=0-0.1, y=0-1.3, δ=0-0.1).
2. the method for claim 1, it is characterized in that described raw material is to mix with stoichiometric ratio or non-stoichiometric, preferably mix that these raw materials pass through 300-900 ℃ of calcining with stoichiometric ratio, preferably, can remove other composition that does not contain in the sosoloid 500-800 ℃ of calcining.
3. the method for claim 1, it is characterized in that described presoma is by calcined co-precipitation in 500-900 ℃ temperature range, soaking time is to make in 0.5-10 hour, preferred calcined co-precipitation in 600-800 ℃ temperature range, and soaking time is 2-5 hour.
4. the method for claim 1 is characterized in that described presoma is not the simple mixtures of zirconium white, Tungsten oxide 99.999 and molybdenum oxide etc., but one with the three parts mutually or amorphous (Zr
1-xA
x) (W
2-yMo
y) O
8-δBe the compound or the mixture of basic structure, and the thing of presoma ratio of tungsten when feeding intake is relevant, also relevant with the temperature of calcined co-precipitation.
5. the method for claim 1 is characterized in that described dry-pressing formedly, and used pressure is 1-30MPa, preferred 2-5Mpa; Be the furtherance type, can in presoma, drip suitable quantity of water or other easy volatile liquid pressing blank.
6. the method for claim 1, the insulation scope that it is characterized in that described preparation thermal contraction ceramic body between 910-1200 ℃, preferred 920-1150 ℃; Temperature range is difference with the difference of tungsten two element ratios, doping A ionic kind and content; Soaking time is between 0.5-10 hour, preferred 1-3 hour.
7. method according to claim 1, the transformation temperature that it is characterized in that described thermal contraction ceramic body reduces with the increase of molybdenum content, when the y value was 0.9-1.3, its transformation temperature was reduced to below the room temperature, and ceramic body shrinks in the temperature range internal linear of room temperature to 600 ℃; The coefficient of expansion of ceramic body is difference with the difference of A ionic species, content and tungsten ratio.
8. thermal contraction ceramic body as claimed in claim 7, it is characterized in that the A ion can be for+2 ,+3 or+4 valency atoms metals, A comprises Yb, Er, Dy, Eu, Ce, Ga, Mn, Cu, Zn, A ionic kind, content can influence physicalies such as the sintering degree, the coefficient of expansion of ceramic body.
9. thermal contraction ceramic body as claimed in claim 1, it is characterized in that in presoma, to mix the volatile solid matter that is heated, in the inner porous that forms of pottery, and control the porosity of ceramic body behind the sintering by the content of control easy volatile material, thus the physicals of regulating ceramic body.
10. thermal contraction ceramic body as claimed in claim 1, it is characterized in that ceramic body and bragg grating are compound after, bragg grating centre wavelength significantly reduces with the drift that temperature raises.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101993245A (en) * | 2010-09-27 | 2011-03-30 | 北京师范大学 | Isotropic thermal contraction tungstate solid solution and preparation method thereof |
| CN102434853A (en) * | 2011-10-25 | 2012-05-02 | 深圳市光峰光电技术有限公司 | Optical wavelength conversion piece, preparation method thereof and light source using optical wavelength conversion piece |
| WO2019042033A1 (en) * | 2017-08-30 | 2019-03-07 | 京东方科技集团股份有限公司 | Negative thermal expansion material, negative thermal expansion thin film and preparation method therefor |
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| JP3601525B2 (en) * | 2001-07-12 | 2004-12-15 | 松下電器産業株式会社 | Zero thermal expansion material and applied parts using it |
| CN1159258C (en) * | 2002-06-03 | 2004-07-28 | 上海交通大学 | Multi-element negative-expansion tungstate layer coated on microcrystal ceramics and its preparing process |
| WO2004063120A1 (en) * | 2003-01-14 | 2004-07-29 | Matsushita Electric Industrial Co., Ltd. | Low thermal expansion material |
| CN1238303C (en) * | 2004-07-01 | 2006-01-25 | 上海交通大学 | Negative thermal-expansion coefficient adjustable laminated ceramic matrix composite and preparing method thereof |
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| CN101993245A (en) * | 2010-09-27 | 2011-03-30 | 北京师范大学 | Isotropic thermal contraction tungstate solid solution and preparation method thereof |
| CN102434853A (en) * | 2011-10-25 | 2012-05-02 | 深圳市光峰光电技术有限公司 | Optical wavelength conversion piece, preparation method thereof and light source using optical wavelength conversion piece |
| CN102434853B (en) * | 2011-10-25 | 2016-03-16 | 深圳市光峰光电技术有限公司 | Optical wavelength conversion chip, its preparation method and use the light source of this optical wavelength conversion chip |
| WO2019042033A1 (en) * | 2017-08-30 | 2019-03-07 | 京东方科技集团股份有限公司 | Negative thermal expansion material, negative thermal expansion thin film and preparation method therefor |
| US11396454B2 (en) | 2017-08-30 | 2022-07-26 | Ordos Yuansheng Optoelectronics Co., Ltd. | Negative thermal expansion material, negative thermal expansion film and preparation method thereof |
| CN110591706A (en) * | 2019-09-12 | 2019-12-20 | 天津大学 | Rare earth ion doped cubic phase zirconium tungstate up-conversion nanocrystal and preparation method thereof |
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