CN1222491C - Preparation of zirconium tungstate ceramic body products thereby and optical fiber grating temperature compensator - Google Patents
Preparation of zirconium tungstate ceramic body products thereby and optical fiber grating temperature compensator Download PDFInfo
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- CN1222491C CN1222491C CN 01123642 CN01123642A CN1222491C CN 1222491 C CN1222491 C CN 1222491C CN 01123642 CN01123642 CN 01123642 CN 01123642 A CN01123642 A CN 01123642A CN 1222491 C CN1222491 C CN 1222491C
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Abstract
The present invention relates to a method for preparing zirconium tungstate (ZrW2O8) ceramic bodies. Raw material miropowder containing Zr compounds and W compounds is treated by reaction sintering to be prepared into zirconium tungstate ceramic bodies by the reaction sintering method, wherein zirconium tungstate monocrystal powder is added as a raw material reaction crystal seed, which has the advantages of effectively reducing technology steps, shortening the processing time, reducing the sintering temperature, reducing the production cost and simultaneously preparing uniform zirconium tungstate ceramic bodies. Additionally, the method of the present invention can further adjust the thermal expansion coefficient by means of the formation of the second phase inside the zirconium tungstate ceramic bodies so as to provide modified zirconium tungstate ceramic bodies. The present invention also relates to an application of the modified zirconium tungstate ceramic bodies to provide the temperature compensating device of a fiber bragg grating (FBG).
Description
Technical field
The present invention relates to wolframic acid zircon ceramic body preparation, wolframic acid zircon ceramic body and this application of wolframic acid zircon ceramic body in the FBG temperature-compensating device behind the upgrading are provided.
Background technology
Fiber grating (Fiber Bragg Grating, FBG) be widely used in making in the various element at high-density divided duplexing equipment networking (DWDM) for example fiber grating-stabilized LASER Light Source and be used in multiplexer, de-multiplexer and increase/subtract various DWDM devices in the wave filter.Yet when practical application, envrionment temperature rises and will exert an influence to FBG.Because width and specific refractory power determine catoptrical mid-frequency between the grid of FBG, therefore, all must be very accurate in design and manufacturing.And when ambient temperature rose, optical fibre refractivity changed thereupon, made fiber optic wavelength become big and the centre wavelength value at off-design center; Thereby need avoid this kind situation to take place.
For in response to above-mentioned problem, United States Patent (USP) the 5th, 042 discloses in No. 898 and has adopted the bimetal structure with different coefficients of expansion, as the FBG temperature-compensating device, to solve the influence of envrionment temperature to FBG.Other relevant document has: the Applied Optics. that the people showed such as No. the 08/539th, 473, U.S. patent application case and G.W.Yoffe, and Vol.34 (30), p.6859,1995.But prior art still has and is difficult for reaching predetermined tolerance range, structure comparatively complexity, manufacturing difficulty and the higher shortcoming of cost.Therefore, provide a kind of and make easily, simple and have the FBG temperature-compensating device of good temperature compensation effect still to belong to an important topic in this field.Wherein, the use of negative thermal expansion coefficient material is exactly a kind of method wherein.
Most of material presents the phenomenon of rising-heat contracting-cold when temperature change, but has the minority material to present the phenomenon of contraction when temperature rises.Wherein, the wolframic acid zirconium is exactly the iso negative expansion material that is well known, and its temperature range is between 0.3 to 1050K.This kind material is synthesized (J.Am.Ceram.Soc., 42[11] 570,1959) by people such as J.Graham first in nineteen fifty-nine, and is found it in nineteen sixty-eight and has negative expansion (J.Am.Ceram.Sco., 51[4] 227,1986).
By ZrO
2And WO
3Phasor (J.Am.Ceram.Soc., 50[4] 211,1967) in as can be known, ZrO
2And WO
3Generate ZrW 1105 ℃ of reactions
2O
8, in the time of 1257 ℃, begin fusion; Generating ZrW
2O
8After, if temperature slowly descends when reaching 1105 ℃ ZrW
2O
8Can be separated into ZrO again
2With WO
3, ZrW
2O
8Only about 150 ℃ of the scope of stable existence, so desire uses down the mode that then needs with quenching with ZrW in low temperature it
2O
8Remain the state of metastable phasing (metasable phase).Yet, the ZrW of meta existence at room temperature
2O
8In temperature-rise period, when reaching about 770 ℃ (1050K), temperature begins to be decomposed into ZrO
2With WO
3When temperature reaches about 1105 ℃, synthesize ZrW again
2O
8
Generally speaking, the manufacturing process of ceramic body is to generate ceramic powder with solid state reaction or chemical synthesis earlier, reshaping sintering after again the gained powder being ground.Specifically, promptly make the ceramic powder of pure phase earlier, again with this powder sintering densification.And in relevant research, wolframic acid zircon ceramic body roughly adopts above-mentioned prepared in one of two ways.
Early stage technology with solid state reaction prepare ceramic powder, sintering is with preparation wolframic acid zircon ceramic body again, for example, people such as Yamamura in Solid State Comm., in 114,453, the 2000 disclosed methods, earlier with the ZrO of metering
2And WO
3After the powder single shaft is molded, calcined about 12 hours down in 1200 ℃, carry out the solid state reaction of raw material, form the wolframic acid zirconium, quick cooling is to room temperature immediately, wolframic acid zirconium small cake (pellets) grind into powder of gained, again with the extrusion forming of wolframic acid zircon ceramic powder,, in liquid nitrogen, cool off immediately again with densification in 1200 ℃ of following sintering 12 hours, can obtain the wolframic acid zircon ceramic body of single phase.But prepared the common needs of wolframic acid zircon ceramic body tens of hours with this solid-state sintering, can generate the wolframic acid zircon ceramic body of pure phase.And its shortcoming is: if wolframic acid zirconium powder end particle diameter is inappropriate or mix inhomogeneously, then is difficult to obtain the wolframic acid zircon ceramic body of even pure phase, and then influences the suitability of wolframic acid zircon ceramic body.
Generate wolframic acid zirconium powder end with respect to solid state reaction, people such as Sleight then proposed in 1996 with the synthetic pure phase wolframic acid zirconium of chemical method, pertinent literature such as Science, 272,90,1996, Annu.Rev.Mater.Sci., 28,29,1998, J.Solid State Chem., 139,424,1998 and United States Patent (USP) the 5th, 514, No. 360, all list in herein for your guidance.The synthetic wolframic acid zirconium of so-called chemical method is that heating contains Zr and W ion solution earlier, treat solution loss evaporation after, get a throw out, can obtain containing ZrO through thermal treatment again
2And WO
3Or ZrW
2O
8Mixture, grind again afterwards, this mix powder of thermal treatment more at last can obtain the wolframic acid zirconium of single phase.Verified, chemical synthesis can provide control powder granule size and the effective ways that mix.Yet, its must use solvent with the pH value of adjusting solution with acquisition Zr
4+With W
6+Throw out, and need in addition the step of heat treatment precipitation thing, so preparation time is tediously long and loaded down with trivial details.
This case the contriver be surprised to find that, when preparing wolframic acid zircon ceramic body with reaction sintering, add wolframic acid zirconium monocrystal generates wolframic acid zirconium crystal grain as reaction crystal seed in containing the Zr compound in the raw material micro mist of W compound with containing, can reduce preparation process effectively, shorten the treatment time, reduce production costs, make uniform wolframic acid zircon ceramic body simultaneously.In addition, by in wolframic acid zircon ceramic body, forming second phase that is different from the wolframic acid zirconium, the ceramic body of the required coefficient of expansion of tool can be provided effectively, thereby needed temperature compensation effect is provided in the FBG temperature-compensating device.
Summary of the invention
The invention relates to a kind of method for preparing wolframic acid zircon ceramic body, it comprises
(a) will contain Zr compound and the raw material micro mist and the wolframic acid zirconium monocrystal that contain the W compound, ground and mixed is even;
(b) in said mixture, add a binding agent, form a slurry;
(c) with after the oven dry of this slurry again dry-pressing become base substrate; And
(d) this base substrate of sintering is to make said wolframic acid zircon ceramic body.
The method according to this invention, the chemical reaction of raw material micro mist and the sintering densification of base substrate are to finish in same heat treatment step, that is, in same heat treatment step, reach the process that reaction generates wolframic acid zirconium and blank sintering densification, thereby obtain needed wolframic acid zircon ceramic body.Adopt method of the present invention, can reduce preparation process effectively, shorten the treatment time, reduce production costs, and make the good wolframic acid zircon ceramic body of uniformity coefficient.
Method of the present invention also can further be finely tuned the thermal expansivity of wolframic acid zircon ceramic body.Wherein, contain the Zr compound and contain in the raw material micro mist of W compound Zr by control to the ratio of W, with residual ZrO in wolframic acid zircon ceramic body
2Or WO
3And form second phase, adjust thermal expansivity thus to required value.Perhaps, select an additive for use, be added in the raw material micro mist and in wolframic acid zircon ceramic body, forming equally distributed second behind the sintering mutually or emptying aperture, to adjust thermal expansivity.
The invention still further relates to the FBG temperature-compensating device that comprises the prepared substrate of wolframic acid zircon ceramic body of the present invention, it can lay the adhesive coating of a positive coefficient of expansion in addition in substrate; Or install a low-expansion material additional between optical fiber and wolframic acid zircon ceramic substrate; Or install a setting device additional, reach the purpose of control FBG centre wavelength.
Description of drawings
Fig. 1 is a kind of vertical view that comprises according to the FBG temperature-compensating device of wolframic acid zircon ceramic substrate of the present invention, and this compensation system comprises the adhesive coating of a positive coefficient of expansion in addition;
Fig. 2 is that another kind comprises the vertical view according to the FBG temperature-compensating device of wolframic acid zircon ceramic substrate of the present invention, and this compensation system comprises a low-expansion material in addition; And
Fig. 3 is that another kind comprises the sectional view according to the FBG temperature-compensating device of wolframic acid zircon ceramic substrate of the present invention, and this compensation system comprises a setting device in addition.
Fig. 4 shows the curve of the wolframic acid zircon ceramic body shown in the embodiment 1 to 5 with the temperature movement situation.
The explanation of symbol among the figure:
10,20 and 30 expressions, one FBG temperature-compensating device;
11 expressions, one wolframic acid zircon ceramic substrate;
12 expressions, one adhesive coating;
13 expressions, one optical fiber;
14 expressions, one fiber grating;
15 expressions, 1 epoxide adhesive point;
21 expressions, one wolframic acid zircon ceramic substrate;
23 expressions, one optical fiber;
24 expressions, one fiber grating;
25 expressions, 1 epoxide adhesive point;
26 expressions, one low thermal coefficient of expansion material;
301 and 302 expression arms;
31 expressions, one wolframic acid zircon ceramic substrate;
33 expressions, one optical fiber;
34 expressions, one fiber grating;
35 expressions, 1 epoxide adhesive point;
37 expressions, one counterscrew;
371 expressions, one dextrorotation screw thread;
372 expressions, one derotation screw thread; And
38 expressions, one depression.
The invention provides a kind of method for preparing wolframic acid zircon ceramic body, the method comprises:
(a) will contain Zr compound and the raw material micro mist and the wolframic acid zirconium monocrystal that contain the W compound, Ground and mixed is even;
(b) in said mixture, add a binding agent, form a slurry;
(c) with after the oven dry of this slurry again dry-pressing become base substrate; And
(d) this base substrate of sintering is to make said wolframic acid zircon ceramic body.
In the methods of the invention, the employed Zr of containing compound and contain the W compound, can be any containing the Zr compound and containing the W compound of reaction sintering that be applicable to, can be selected from oxide, sulfate, carbonate, nitrate, acetate, sulfide, hydroxide, tungsten, the wolframic acid (H of Zr and W2WO
4) and composition thereof etc., preferably adopt its oxide, i.e. ZrO2With WO3。
According to the inventive method, with the base substrate of dry-pressing, when carrying out the reaction-sintered processing, its reaction Sintering temperature is typically between 1105 ℃ to 1257 ℃, is preferably 1150 ℃ to 1200 ℃. Reaction is burnt The knot time is typically 1 to 10 hour, is preferably 3 to 8 hours, more preferably 4 to 6 hours. Generally speaking, sintering temperature is more high, and required sintering time is more short.
When preparation pure phase wolframic acid zircon ceramic body, the binding agent that the inventive method adopts is selected from tradition Organic binder bond, for example United States Patent (USP) the 5th, 694, disclosed binding agent in No. 503. In other words, The kind of binding agent and consumption are not key point of the present invention, and haveing the knack of this skill person can be optionally And select suitable binding agent kind and consumption, thereby implement method of the present invention.
The method according to this invention adds wolframic acid zirconium monocrystal to generate ZrW as containing the Zr compound and containing the reaction of W compounds solid state in the raw material micro mist2O
8Crystal seed, can effectively reduce reaction Temperature and time, and improved the uniformity of ceramic body, thus complemented the conventional solid-state sintering process not Easily make the shortcoming of even wolframic acid zircon ceramic body. The consumption of said wolframic acid zirconium monocrystal is not heavy Want, just add too much, its effect does not promote thereupon, so considers based on economic factor, and is general Adopt 0.1 to 5 % by weight, in the gross weight of raw material micro mist, be preferably 0.5 to 2 % by weight. Although ZrW in the base substrate2O
8Crystal seed can be decomposed into ZrO when in the process that heats up, reaching 770 ℃2With WO3, but when persistently overheating then again original place (in situ) generate ZrW2O
8, this autochthonous ZrW2O
8Reaction still can be prior to the generation of raw material solid-state reaction, thereby continue as solid-state anti-Seasonable crystal seed, and the uniformity of raising base substrate.
With regard to the demand in the FBG encapsulation, the thermal expansivity of ceramic substrate has the needs of its adjustment.The general purpose that adopts the mode that forms a matrix material (composite) or porous ceramic body (porous ceramic) to reach the fine setting thermal expansivity more.
Contain the method for wolframic acid zirconium composite material thermal expansivity about fine setting, people such as Holzer (J.Mater.Res., 14,3,780,1999) once add the wolframic acid zirconium of 50 to 60 volume % in the copper, form Cu/ZrW
2O
8Metal composite (metal matrix composites), observe it and change mutually and the variation of thermal expansivity.In addition, United States Patent (USP) the 5th, 694 discloses the oxide compound such as the Al that add other in wolframic acid zirconium powder end for No. 503
2O
3, positive coefficient of expansion material such as MgO and CaO, after heat treatment in wolframic acid zircon ceramic body, form second phase, thus the adjustable heat coefficient of expansion.
Because it is to adopt the reaction of raw material reaction thing and the method that sintering densification is finished in same heat treatment step that the present invention prepares wolframic acid zircon ceramic body, if as United States Patent (USP) the 5th, 694, the other interpolation of being instructed for No. 503 is different from the oxide compound that contains Zr and contain the W compound, then should add oxide compound might be before the reaction of raw material reaction thing generates the wolframic acid zirconium, react with the raw material reaction thing earlier, and then influence the generation of final product wolframic acid zirconium.
Therefore, the present invention further provides through adjusting the upgrading wolframic acid zircon ceramic body of thermal expansivity, it can be by the ratio of raw material reactant in the control entire reaction system, or sneak into the kind and the quantity of additive by control, form equally distributed second in the wolframic acid zircon ceramic body after burning till mutually or emptying aperture and reaching.
In the methods of the invention, control contains the Zr compound and contains that Zr is to form residual ZrO behind the reaction sintering in wolframic acid zircon ceramic body to the purpose of W ratio in the raw material micro mist of W compound
2Or WO
3Second phase, avoid containing the Zr compound and containing the oxide compound of W compound and raw material reaction thing and react and influence the formation of wolframic acid zirconium because of interpolation is different from; Also or avoid in wolframic acid zircon ceramic body, excessive because of skewness or particle, because of causing the material internal stress concentration, variation of temperature make wolframic acid zircon ceramic body produce microfracture in use.
In the methods of the invention, in the raw material micro mist, add inorganic tackiness agent, can through after the high-temperature heat treatment in wolframic acid zircon ceramic body residual equally distributed second phase, but note that the oxide compound that forms after the thermal treatment can be to ZrO
2And WO
3Reactive system exerts an influence.Wherein, this mineral binder bond can be water glass (Na
2OnSiO
2), it can form residual Na in wolframic acid zircon ceramic body after thermal treatment
2O and SiO
2Second phase, reach and adjust the purpose of thermal expansivity to required value.
Wherein, residual ZrO
2Or WO
3And/or the consumption of inorganic tackiness agent, be and to get by known computation schema derivation, as Introduction to Ceramics, Chap.12,2
NdEd., Wiley, NewYork, 1976 and No. the 5th, 694,503, United States Patent (USP) disclosed.But it is not the place of the technology of the present invention feature.
Except that forming the matrix material ceramic body, but also mat forms the purpose that the porous ceramic body reaches its thermal expansivity of adjustment.The method for preparing the porous ceramic body is quite a lot of, generally is to adopt to add the organic binder bond that can form emptying aperture after thermal treatment in ceramic body.But mat adds organic binder bond in the raw material micro mist in the methods of the invention, through form second phase of the emptying aperture that is evenly distributed behind the sintering in wolframic acid zircon ceramic body, makes its thermal expansivity reach required value.The direct solidification method of preferred employing, as J.European Ceramic Soc., 18,131,1998 disclose, this technology is ceramic and organic binder bond to be added water mix under room temperature, solidifies more than pouring this slurry into be warming up to binding agent in the mould gelatinization temperature, is dried and obtains a biscuit of ceramics.Biscuit of ceramics will can obtain the ceramic body of a porous matter again through thermal treatment behind this organic binder bond removal and the sintering.In the present invention, this organic binder bond is preferably selected from the group that is made up of starch and methylcellulose gum.
According to the present invention, through the upgrading wolframic acid zircon ceramic body of fine setting thermal expansivity, also can replace according to measuring containing the Zr compound and containing the W compound of ratio, with formation second additives mixed mutually with wolframic acid zirconium powder end by direct, carry out sintering densification again, to reach the purpose of fine setting.
, be made up of mutually with second of residue first of wolframic acid zirconium matrix through upgrading wolframic acid zircon ceramic body according to of the present invention, wherein second by being selected from ZrO
2, WO
3, Na
2O+SiO
2, emptying aperture or its combination etc. forms.
The invention still further relates to the FBG temperature-compensating device of substrate with upgrading wolframic acid zircon ceramic body of the present invention, existing according to following examples, illustrated.
Fig. 1 is a kind of fiber grating temperature compensator 10 of the present invention, it comprises according to wolframic acid zircon ceramic substrate 11 of the present invention, substrate 11 can be laid positive coefficient of expansion adhesive coating 12 (being layed in the substrate two sides at this), and optical fiber 13 mat epoxide adhesive points 15 are fixed on the two ends of substrate 11.Wherein, the stage casing of optical fiber 13 has the read-write grating and becomes a fiber grating 14.The use of uniting of mat wolframic acid zircon ceramic substrate 11 and adhesive coating 12 can further be adjusted this compensation system 10 again to required thermal expansivity.
Fig. 2 is the another kind of fiber grating temperature compensator 20 of the present invention, and it comprises according to a wolframic acid zircon ceramic substrate 21 of the present invention and a low-expansion material 26.Wherein, optical fiber 23 mat epoxide adhesive points 25 are fixed on substrate 21 two ends.The stage casing of optical fiber 23 has the read-write grating, and becomes a fiber grating 24.Low-expansion material 26 shops place between substrate 21 and the optical fiber 23.Low-expansion material 26 is meant that thermal expansivity is lower than stainless material, preferably is lower than stainless 1/10 or lower material, can select quartz or invar (invar) etc. for use, and its shape does not have specific limited.The use of uniting of mat wolframic acid zircon ceramic substrate 21 and low-expansion material 26 can further be adjusted the centre wavelength of fiber grating 24, again to adapt to the needs of specification adjustment joint.
Fig. 3 is another fiber grating temperature compensator 30 of the present invention, and it comprises the screw rod 37 according to a wolframic acid zircon ceramic substrate 31 of the present invention and a manual setting device, forms depression 38 and two arms 301 and 302 on substrate 31 end faces.Screw rod 37 with dextrorotation screw thread 371 and derotation screw thread 372 can stride across depression 38 along the longitudinal direction of substrate 31, and wherein this dextrorotation screw thread 371 and derotation screw thread 372 are to be incorporated into respectively on arm 301 and 302.33 mat epoxide of optical fiber adhesive point 35 is fixed on two arms 301 and 302, and the stage casing of optical fiber 33 has the read-write grating and becomes a fiber grating 34.Mode according to this, when manual rotary screw 37 on a direction, then screw rod 37 promptly orders about arm 301 and moves closer to arm 302 gradually.When with the manual rotary screw 37 of other direction, then screw rod 37 orders about arm 302 and moves away from arm 301 gradually.Because having the optical fiber 33 of fiber grating 34 is to be fixed on two arms 301 and 302, therefore, can manually controls the length of fiber grating and adjust its centre wavelength by screw rod 37.
Now further specifying the present invention with the following example and prepare the method for wolframic acid zircon ceramic body and novel wolframic acid zircon ceramic body, yet should be noted that these embodiment implement the present invention for those who familiarize themselves with the technology, is not in order to restriction protection scope of the present invention.
The preparation of wolframic acid zircon ceramic substrate---do not add wolframic acid zirconium monocrystal
With ZrO
2Micro mist and WO
3Micro mist carries out proportioning with 1: 2 mol ratio, and adding organic binder bond, grind and mixing with deionized water, the slurry that mixes is in 105 ℃ of oven dry down, powder 25 after oven dry gram is pressed into 60 millimeters * 35 millimeters tabular green compact with dry pressing, in 1200 ℃ of following reaction sinterings 6 hours, place the air quenching immediately, can obtain the ZrW of single phase
2O
8Ceramic body.The Coefficient of Thermal Expansion value that records wolframic acid zircon ceramic body-40 ℃ to 80 ℃ the time with the low temperature modification thermal dilatometer is-10.02 * 10
-6K
-1, this ceramic body with the situation of temperature movement shown in the curve d of Fig. 4.Grind wolframic acid zircon ceramic substrate two sides smooth and reach after the desired thickness, needed size is to encapsulate when cutting into encapsulation with diamond cutter again.
Embodiment 2
The preparation of wolframic acid zircon ceramic substrate---add wolframic acid zirconium monocrystal
With ZrO
2Micro mist and WO
3Micro mist carries out proportioning with 1: 2 mol ratio, and the wolframic acid zirconium monocrystal that adds 1.0 weight % generates the crystal seed of wolframic acid zirconium crystal grain during as reaction sintering, and these raw materials with the deionized water ground and mixed, and are added organic binder bond and mix oven dry thereafter.Get mixed raw materials powder 25 gram and be pressed into 60 millimeters * 35 millimeters tabular green compact,, place the air quenching immediately, obtain the ZrW of single phase in 1150 ℃ of following reaction sinterings 4 hours with dry pressing
2O
8Ceramic body, sintering temperature and sintering time obviously reduce.The thermal expansivity of this ceramic body is-10.85 * 10
-6K
-1, its with the situation of temperature movement shown in the curve e of Fig. 4.Grind wolframic acid zircon ceramic substrate two sides smooth and reach after the desired thickness, needed size is to encapsulate when cutting into encapsulation with diamond cutter again.
Embodiment 3
The thermal expansivity of fine setting wolframic acid zircon ceramic substrate---adopt non-metering ZrO
2With WO
3
ZrO with 10.4 grams
2The WO of micro mist and 31.6 grams
3Micro mist is with the deionized water ground and mixed, and the adding organic binder bond, this slurry is dried down in 105 ℃ again, and preparation after the oven dry and procedure of processing are identical with embodiment 1, and the thermal expansivity of gained ceramic body is-9.51 * 10
-6K
-1, its with the situation of temperature movement shown in the curve c of Fig. 4.
If will add wolframic acid zirconium crystal seed further reduces sintering temperature and time, then change the ZrO that adopts 10.316 grams into
2The WO of micro mist, 31.284 grams
3The ZrW of micro mist and 0.4 gram
2O
8Micro mist is a raw material, and mixing step thereafter is same as described above.But because the interpolation of crystal seed, the tabular green compact of gained can be in 1150 ℃ of following reaction sinterings 4 hours, get final product a wolframic acid zircon ceramic body, sintering temperature and sintering time obviously reduce.The characteristic of gained ceramic body is same as described above.
Embodiment 4
The thermal expansivity of fine setting wolframic acid zircon ceramic substrate---add mineral binder bond
ZrO with 8.4 grams
2The WO of micro mist and 31.6 grams
3Micro mist is with the deionized water ground and mixed, and the water glass 2.1 that adds solid content 38.1 weight % restrains, mix the back in 105 ℃ of oven dry down, get raw material powder 25 grams after the oven dry are pressed into 60 millimeters * 35 millimeters with dry pressing tabular green compact, in 1150 ℃ of following reaction sinterings 6 hours, place the air quenching immediately, the thermal expansivity of gained ceramic body is-9.02 * 10
-6K
-1, its with the situation of temperature movement shown in the curve a of Fig. 4.Grind wolframic acid zircon ceramic substrate two sides smooth and reach after the desired thickness, needed size is to encapsulate when cutting into encapsulation with diamond cutter again.
Embodiment 5
The thermal expansivity of fine setting wolframic acid zircon ceramic substrate---add the organic binder bond that can form emptying aperture through thermal treatment
ZrO with 8.4 grams
2The WO of micro mist and 31.6 grams
3Micro mist is sneaked into the starch that is scattered in the water with deionized water ground and mixed 24 hours, forms the slurry of solid content 45 volume %.This slurry poured into be warming up to 80 ℃ in the model, and keep this temperature to make it in 1 hour to solidify.Made biscuit down in dry 12 hours in 120 ℃ again after the demoulding.The gained biscuit is warming up to 500 ℃ of following degreasings (debinder) earlier, in 1200 ℃ sintering temperature 5 hours, obtains porous matter wolframic acid zircon ceramic body again, and its thermal expansivity is-9.21 * 10
-6K
-1, this ceramic body with the situation of temperature movement shown in the curve b of Fig. 4.Grind wolframic acid zircon ceramic substrate two sides smooth and reach after the desired thickness, needed size is to encapsulate when cutting into encapsulation with diamond cutter again.
If will add wolframic acid zirconium crystal seed further reduces sintering temperature and time, then change the ZrO that adopts 8.316 grams into
2The WO of micro mist, 31.284 grams
3Micro mist and 0.4 ZrW
2O
8Micro mist is a raw material, and mixing step thereafter is same as described above, but because the interpolation of crystal seed, and the gained biscuit can be in 1160 ℃ of following reaction sinterings 3.5 hours, get final product porous matter wolframic acid zircon ceramic body, sintering temperature and sintering time obviously reduce.The characteristic of gained ceramic body is identical with above-mentioned way gained person.
Claims (17)
1, a kind of method for preparing wolframic acid zircon ceramic body, it comprises:
(a) will contain the Zr compound and to contain the raw material micro mist and the wolframic acid zirconium monocrystal ground and mixed of W compound even;
(b) in said mixture, add a binding agent, form a slurry;
(c) drying this slurry again, dry-pressing becomes base substrate; And
(d) this base substrate of sintering is to make said wolframic acid zircon ceramic body, wherein
In the gross weight of raw material micro mist, the addition of said wolframic acid zirconium monocrystal is 0.1 to 5 weight %.
2, according to the process of claim 1 wherein that the said Zr of containing compound is than mixing with metering with containing the W compound.
3, according to the process of claim 1 wherein that the said Zr of containing compound and W compound are than mixing with non-metering.
4, according to the process of claim 1 wherein the said Zr of containing compound with contain the W compound and be selected from its oxide compound, vitriol, carbonate, nitrate, acetate, sulfide and oxyhydroxide, tungsten, wolframic acid and composition thereof.
5, according to the method for claim 4, the wherein said Zr of containing compound is ZrO
2, and the said W of containing compound is WO
3
6, method according to claim 1, wherein in the gross weight of raw material micro mist, the addition of said wolframic acid zirconium monocrystal is 0.5 to 2 weight %.
7, according to the process of claim 1 wherein that said binding agent is an organic binder bond.
8, according to the process of claim 1 wherein that said binding agent is a mineral binder bond, it is forming equally distributed second phase in wolframic acid zircon ceramic body after thermal treatment.
9, method according to Claim 8, wherein said mineral binder bond is a water glass.
10, according to the process of claim 1 wherein that said binding agent is the organic binder bond that after heat treatment forms emptying aperture in wolframic acid zircon ceramic body.
11, according to the method for claim 10, wherein said organic binder bond is selected from starch and methylcellulose gum.
12, according to the method for claim 11, the gelatinization temperature that is warming up to said organic binder bond in step (c) after wherein earlier pouring into said slurry in the model solidifies, obtain a biscuit of ceramics after, through thermal treatment said organic binder bond is removed again.
13, according to the process of claim 1 wherein that said sintering temperature is between 1105 to 1257 ℃.
14, method according to claim 13, wherein said sintering temperature are between 1150 to 1200 ℃.
15, method according to claim 1, wherein said sintering time are in 10 hours between 1.
16, method according to claim 15, wherein said sintering time are between 3 to 8 hours.
17, according to the method for claim 16, wherein said sintering time is between 4 to 6 hours.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01123642 CN1222491C (en) | 2001-08-24 | 2001-08-24 | Preparation of zirconium tungstate ceramic body products thereby and optical fiber grating temperature compensator |
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| CN 01123642 CN1222491C (en) | 2001-08-24 | 2001-08-24 | Preparation of zirconium tungstate ceramic body products thereby and optical fiber grating temperature compensator |
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| CN1406905A CN1406905A (en) | 2003-04-02 |
| CN1222491C true CN1222491C (en) | 2005-10-12 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583551A (en) * | 2012-03-02 | 2012-07-18 | 河北联合大学 | Design synthesis of zirconium tungstate ultra-long nanometer wires |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301347C (en) * | 2005-01-25 | 2007-02-21 | 北京科技大学 | Preparation of single-crystal of thermal negative expanding material ZrW2O8 |
| JP4997433B2 (en) * | 2006-03-13 | 2012-08-08 | 学校法人東京理科大学 | Method for producing zirconium tungstate-magnesium tungstate composite |
| CN100425537C (en) * | 2006-09-08 | 2008-10-15 | 郑州大学 | Synthesis method of zirconium tungstate with minus thermal-expansion coefficient |
| CN105919874A (en) * | 2016-06-01 | 2016-09-07 | 合肥丰瑞隆生物科技有限公司 | Pine mushroom mud mask and preparation method thereof |
| CN110128138A (en) * | 2019-05-22 | 2019-08-16 | 无锡必创传感科技有限公司 | The preparation method and fiber grating temperature compensator of ceramic substrate |
| CN111847515B (en) * | 2020-06-30 | 2022-06-03 | 福建工程学院 | Preparation method of zirconium tungstate |
| CN113372107B (en) * | 2021-07-08 | 2023-01-31 | 铜陵四拓智能装备科技有限公司 | Preparation process of low-thermal-expansion composite material |
| CN114322816A (en) * | 2021-12-31 | 2022-04-12 | 中国空气动力研究与发展中心超高速空气动力研究所 | Mounting glue and application thereof in optical fiber sensor |
-
2001
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583551A (en) * | 2012-03-02 | 2012-07-18 | 河北联合大学 | Design synthesis of zirconium tungstate ultra-long nanometer wires |
| CN102583551B (en) * | 2012-03-02 | 2014-10-01 | 河北联合大学 | Design synthesis of zirconium tungstate ultra-long nanometer wires |
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| Publication number | Publication date |
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| CN1406905A (en) | 2003-04-02 |
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