CN101347042B - Acoustic matching material, ultrasonic vibrator, and ultrasonic flowmeter - Google Patents
Acoustic matching material, ultrasonic vibrator, and ultrasonic flowmeter Download PDFInfo
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- CN101347042B CN101347042B CN2007800009095A CN200780000909A CN101347042B CN 101347042 B CN101347042 B CN 101347042B CN 2007800009095 A CN2007800009095 A CN 2007800009095A CN 200780000909 A CN200780000909 A CN 200780000909A CN 101347042 B CN101347042 B CN 101347042B
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- G—PHYSICS
- G10—MUSICAL INSTRUMENTS; ACOUSTICS
- G10K—SOUND-PRODUCING DEVICES; METHODS OR DEVICES FOR PROTECTING AGAINST, OR FOR DAMPING, NOISE OR OTHER ACOUSTIC WAVES IN GENERAL; ACOUSTICS NOT OTHERWISE PROVIDED FOR
- G10K11/00—Methods or devices for transmitting, conducting or directing sound in general; Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
- G10K11/02—Mechanical acoustic impedances; Impedance matching, e.g. by horns; Acoustic resonators
Abstract
This invention provides an acoustic matching material comprising a dry gel produced by polymerizing a monomer comprising a polymerizable organosilicon compound, the polymerizable organosilicon compound comprising a nonhydrolyzable organic group being bonded directly to silicon. This acoustic matching material can be used as an acoustic matching layer (2) in an ultrasonic vibrator (1).Even when a piezoelectric material (3) or a case connected to the acoustic matching layer (2) is stretched, the acoustic matching layer follows the stretching of the piezoelectric material (3) or case and is stretched. Accordingly, the acoustic matching material can be stably operated over a wide temperature range and can be used over a long period of time.
Description
Technical field
The present invention relates to be used for send ultrasonic wave and be received in hyperacoustic acoustic matching body of propagating in the fluid, the ultrasonic vibrator that uses said acoustic matching body and the ultrasonic flowmeter that uses said ultrasonic vibrator at fluid (particularly gas).
Background technology
Piezoelectric 51 changes into mechanical oscillation with the signal of telecommunication.This mechanical oscillation transmit in the air inlet body as ultrasonic wave through acoustic matching layer 55.For the said vibration that produces in the piezoelectric 51 is transmitted in the air inlet body effectively, need to consider acoustic impedance.
The acoustic impedance Z of material is by the velocity of sound (C) and density (ρ) definition, suc as formula (10).
Z＝ρ×C (10)
Acoustic impedance Z as the piezoelectric 51 of vibration generating apparatus
PBe 30 * 10
6Kg/ (m
2S).On the other hand, as the gas of the hyperacoustic radiation medium about 400kg/ (m of acoustic impedance of air for example
2S).As stated, the acoustic impedance of piezoelectric 51 and air is actually different.
When the acoustic impedance of piezoelectric and radiation medium not simultaneously, ultrasonic wave is easy to reflection at the interface betwixt.When ultrasonic reflections, because therefore airborne hyperacoustic weak strength exists ultrasonic wave can not be sent to the problem of predetermine one effectively.
In order to address this problem, to use acoustic matching layer (being also referred to as the acoustic matching parts), and between piezoelectric and radiation medium, form.Form the acoustic matching parts, make the acoustic impedance Z of parts
MSatisfy following formula (11), guarantee that thus ultrasonic wave has effect spread to advance in the radiation medium.
Z
M＝(Z
p×Z
A)
(1/2) (11)
Optimum value is about 11 * 10
4Kg/ (m
2S).Be appreciated that from formula (11) acoustic matching layer need be a solid, and have the low-density and the low velocity of sound.Desiccant gel is often as the material that satisfies these requirements.The method of making this desiccant gel for example is disclosed in Japan Patent and openly speciallys permit the communique spy and open among the No.2005-8424.Japan Patent is openly speciallyyed permit the communique spy and is driven the ultrasonic vibrator that No.2002-262394 discloses the use dry silica gel.
Disclosure of the Invention
Invent problem to be solved
In the ultrasonic vibrator of structure shown in Figure 16, housing 53 is formed by metal material such as stainless steel.Stainless thermal coefficient of expansion for example is about 17.8ppm/ ℃, and is higher relatively.On the other hand, the thermal coefficient of expansion as the desiccant gel of acoustic matching layer 52 is several ppm/ ℃ or littler.Therefore, combine with housing 53 and housing 53 expands with the variation of ambient temperature or when shrinking, desiccant gel is not to expand with housing 53 identical modes or to shrink, because desiccant gel is not easy to expand or contraction when desiccant gel.The result makes desiccant gel break.Therefore, the fluctuation of service of ultrasonic vibrator.In addition, because the thermal coefficient of expansion of piezoelectric for example is 7.5ppm/ ℃, therefore identical problem appears also when desiccant gel combines with piezoelectric 51.
The objective of the invention is to address the above problem, and the acoustic matching body of the variations in temperature stably operable that is directed against environment for use that is formed by desiccant gel, the ultrasonic vibrator and the ultrasonic flowmeter of the said acoustic matching body of use are provided.
The mode of dealing with problems
For addressing the above problem, the present invention provides a kind of acoustic matching body, and it comprises the desiccant gel that contains the monomer formation of polymerizable organo-silicon compound through polymerization, and the said organo-silicon compound wherein organic group of non-hydrolysable directly combine with silicon.Contain desiccant gel that the monomer of this particular silicone compound forms than being suggested through polymerization as the conventional drying gel of acoustic matching body softness more.
Here, term " acoustic matching body " is used in reference to as acoustic matching layer and is introduced into the individual components before the ultrasonic vibrator etc., and it can be known as " acoustic matching layer " after introducing ultrasonic vibrator.That is, it is different that " acoustic matching body " and " acoustic matching layer " do not have on function, and whether their difference is to be introduced in ultrasonic vibrator etc.
Acoustic matching body of the present invention can be the single layer structure that is only formed by desiccant gel, perhaps can be the laminated construction that is formed by desiccant gel and another kind of porous body.The acoustic matching body of laminated construction is preferably formed by desiccant gel and ceramic porous article.
The present invention also provides a kind of ultrasonic vibrator that comprises piezoelectric and acoustic matching layer, and wherein said acoustic matching layer is an acoustic matching body of the present invention.
In addition, the present invention provides a kind of ultrasonic flowmeter that comprises ultrasonic vibrator, and said ultrasonic vibrator comprises piezoelectric and acoustic matching layer, is acoustic matching body of the present invention at acoustic matching layer described in the said vibrator.
The invention effect
Acoustic matching body of the present invention is characterized in that it is formed by desiccant gel, and said desiccant gel is formed by the monomer that contains the particular silicone hydride compounds and has a bigger flexibility.When this acoustic matching body and function was in ultrasonic vibrator, because housing expands with the variations in temperature of environment for use or shrinks, the acoustic matching body can expand or shrinks with housing, and this specific character can prevent the breakage of acoustic matching body so.Therefore, the ultrasonic vibrator that wherein uses acoustic matching body of the present invention and the voice traffic meter that comprises said ultrasonic vibrator can operations stably in wide temperature range, and can be safely and send and receive ultrasonic wave well.
Description of drawings
Fig. 1 is a cross-sectional view, schematically shows the embodiment of ultrasonic vibrator of the present invention.
Fig. 2 is a flow chart, and first method of acoustic matching body of the present invention is made in expression.
Fig. 3 is a sketch map, is illustrated in the molecule of making the organic silane compound that uses in the acoustic matching body of the present invention.
Fig. 4 is a sketch map, is illustrated in the molecule of making the silane compound that uses in the acoustic matching body of the present invention.
Fig. 5 (a) and Fig. 5 (b) are sketch mapes, respectively the gel rubber material in material preparation process and the gelation step in first method of expression manufacturing acoustic matching body of the present invention.
Fig. 6 (a), Fig. 6 (b) and Fig. 6 (c) are sketch mapes, are illustrated respectively in the gel rubber material in material preparation process, gelation step and the reconstruction step in second method of making acoustic matching body of the present invention.
Fig. 7 is a cross-sectional view, schematically shows the anchor clamps of the flexural strength of measuring the desiccant gel that constitutes acoustic matching body of the present invention.
Fig. 8 is the figure of the flexural strength measurement result of the expression desiccant gel that constitutes acoustic matching body of the present invention.
Fig. 9 is the sectional view of the another kind of embodiment of ultrasonic vibrator of the present invention.
Figure 10 is a flow chart, and expression is used for the method for the ultrasonic vibrator shown in the shop drawings 9.
Figure 11 is a cross-sectional view, representes an embodiment of acoustic matching body of the present invention.
Figure 12 is a flow chart, and expression is used to make the method for the ceramic porous article that constitutes acoustic matching body of the present invention.
Figure 13 is a sketch map, and third party's method of acoustic matching body of the present invention is made in expression.
Figure 14 is a cross-sectional view, schematically shows the part of the acoustic matching body of making according to method shown in Figure 13 of the present invention.
Figure 15 is a calcspar, representes the structure of ultrasonic flowmeter of the present invention.
Figure 16 is a cross-sectional view, schematically shows the prior art ultrasonic vibrator.
The letter or number explanation
1, the 50... ultrasonic vibrator; 2, the 52... acoustic matching layer; 3, the 51... piezoelectric; 4,4a, 4b, 54... bonded block; 5,6, the 55... electrode; 14... organic silane compound; 15... the organic group of non-hydrolysable; 16... silicon; 17... hydrolyzable organic group; 18... tetraalkoxysilane; 19... gel rubber material solution; 20... wet gel; 21... gel rubber material solution; 22... wet gel; 23... reconstituted solutions; 24... wet gel; 25... be used to measure the anchor clamps of flexural strength; 26... sample; 27... test desk; 28.. push strut; 31... ultrasonic vibrator; 32, the 53... housing; 33, the 34... electrode; 35... electric installation; 36... terminal board; 37, the 38... electrode terminal; 39... the insulated part of terminal board; 40... confined space; 41... ceramic matrix; 42... first porous body; 43... second porous body; 44... acoustic matching body; 45... hole; 61... mould; 62... container; 63... recess; 64... material solution; 65... ceramic matrix; 66... hole; 81... path; 82... ultrasonic vibrator A; 83... ultrasonic vibrator B; 84... dispensing device; 85... receiving system; 86... time set; 87... switching device shifter; 88... ultrasonic flowmeter; 89... computing unit.
Embodiment
Below, selectivity is with reference to description of drawings embodiment of the present invention.It should be noted, the invention is not restricted to embodiment of the present invention.
Use the example of the ultrasonic vibrator of acoustic matching body formation of the present invention to be shown in Fig. 1.In Fig. 1, the acoustic matching body is by Reference numeral 2 expression, and uses adhesive to be combined by the piezoelectric of bonded block 3 with conduct as combination 4, forms ultrasonic vibrator 1 thus.Electrode 5 respect to one another and 6 is formed on the piezoelectric 4.Conductive paste through heating silver or gold etc. also cures the formation electrode.Electrode 5 and 6 uses scolder or silver solder to be electrically connected with electrode cable 7 and 8.Below, the desiccant gel that constitutes the acoustic matching body is described, and is further specified the acoustic matching body of the composite construction that forms by desiccant gel and another kind of porous body.
(desiccant gel)
Acoustic matching body of the present invention comprises the desiccant gel that contains the monomer formation of polymerizable organo-silicon compound through polymerization; Said organo-silicon compound wherein the group of non-hydrolysable directly combine with silicon (below; For simplicity, this organo-silicon compound are called " first organo-silicon compound ").The polymerizable organo-silicon compound are a kind of compounds that generate the polymer that contains repetition Si-O key through hydrolysis and/or dehydration.The polymerizable organo-silicon compound silane compound that for example to be wherein hydrolyzable organic group combine with silicon, silanol, silicone compounds etc. with OH group.
Acoustic matching body of the present invention preferably contains the desiccant gel that contains the monomer formation of organic silane compound through polymerization, and the compound of wherein hydrolyzable organic group of said organic silane compound and non-hydrolysable directly combines with same silicon.Through the polymerization organosilicon hydride compounds and/or through polymerization organosilicon hydride compounds and another kind of compound, dry then, obtain desiccant gel.In this desiccant gel, the organic group of non-hydrolysable combines with the silicon that forms gel skeleton.According to thinking that this will guarantee flexibility.
Organic silane compound preferably contains two or more hydrolyzable organic groups.This is because in order to make the organic silane compound hydrolysis carrying out polymerization, thereby forms the skeleton that is made up of the Si-O key, requires two or more polymerizable moieties.Yet the organic silane compound with a hydrolyzable organic group can use with another kind of organic silane compound with two or more hydrolyzable organic groups and/or another kind of polymerizable compound.
Organic silane compound has the structure that Fig. 3 for example schematically shows.In the compound shown in Fig. 3 14, the organic group 15 of a non-hydrolysable directly combines with silicon 16, and three hydrolyzable organic groups 17 directly combine with silicon 16.The organic group of non-hydrolysable not through hydrolysis with another kind of organic silane compound polymerization.Hydrolyzable organic group through hydrolysis, then dehydration and with another kind of organic silane compound polymerization.The example of the compound shown in this figure is the organotrialkoxysilane that following formula (2) is explained.
Hydrolyzable organic group comprise carbon number be 1～4 alkoxyl, acetoxyl group ,-the oximido group of O-N=C-R (R ') representative ,-the alkene oxygen base of O-C (R)=C (R ') R representative, amino ,-aminooxy group of O-N (R) R ' representative and-N (R)-C (=O) amide group of R ' representative (in these formulas, R, R ' and R " be hydrogen or monovalence hydrocarbon independently) and halogen atom.
As the organic group of non-hydrolysable, the carbon number that has that can give an example is 1～8 replacement or unsubstituted monovalence alkyl.Particularly, that can give an example has an alkyl, like methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or octyl group; Cycloalkyl is like cyclopenta or cyclohexyl; Aralkyl is like 2-phenylethyl or 3-phenyl propyl; Aryl is like phenyl or tolyl; Thiazolinyl is like vinyl or pi-allyl; The substituted alkyl of halogen is like chloromethyl, γ-chloropropyl or 3,3,3-trifluoro propyl; Substituted alkyl, like γ-methacryloxypropyl, γ-glycidyl ether oxygen propyl, 3,4-epoxycyclohexyl ethyl or γ-sulfydryl propyl group.
That considers organic silane compound is easy to synthetic and availability, and the organic group of non-hydrolysable preferably carbon number is 1～4 alkyl or phenyl.From the viewpoint of the hardness excessive descent of the desiccant gel that prevents to obtain, the organic group of this non-hydrolysable is preferred.
More specifically, preferably, at least a compound in organic silane compound organic dialkoxy silicane that to be the organotrialkoxysilane that is selected from following formula (2) representative represent with following formula (3).
R
3Si(OR
2)
3 (2)
(R
5)
2Si(OR
4)
2 (3)
In formula (2) and (3), R
2And R
4In each be that carbon number is 1～4 alkyl.In formula (2), all R
2S is normally identical, but they can differ from one another.This situation also is applicable to the R in the formula (3)
4
R
3And R
5In each be that carbon number is 1～8 replacement or unsubstituted monovalence alkyl.Particularly, as the organic group of non-hydrolysable, the carbon number that has that can give an example is 1～8 monovalence hydrocarbon.Particularly, that can give an example has an alkyl, like methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or octyl group; Cycloalkyl is like cyclopenta or cyclohexyl; Aralkyl is like 2-phenylethyl or 3-phenyl propyl; Aryl is like phenyl or tolyl; Thiazolinyl is like vinyl or pi-allyl; The substituted alkyl of halogen is like chloromethyl, γ-chloropropyl or 3,3,3-trifluoro propyl; Substituted alkyl, like γ-methacryloxypropyl, γ-glycidyl ether oxygen propyl, 3,4-epoxycyclohexyl ethyl or γ-sulfydryl propyl group.R
3And R
5Be preferably carbon number and be 1～4 alkyl and phenyl.Its reason as stated.In formula (3), two R
5Normally identical, but they can differ from one another.
As the trialkoxy silane of formula (2), that can give an example has MTMS, MTES, methyl three isopropoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane and 3,3, a 3-trifluoro propyl trimethoxy silane.
As the dialkoxy silicane of formula (3), that can give an example has dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane and aminomethyl phenyl dimethoxy silane.
When the compound of formula (2) or (3) representative during by polymerization, the molecular weight after the polymerization is preferably 200 or bigger.When molecular weight is 200 or when bigger, can more guarantee with more effectively to make the gel that obtains softening.Molecular weight is generally 10000 or littler, and preferred 200～5000.If molecular weight less than 200, possibly be difficult to keep the shape of gel so.If the intensity of the desiccant gel that molecular weight greater than 5000, obtains so possibly reduce.
Selectively, acoustic matching body of the present invention can comprise the desiccant gel that forms through the following monomer of polymerization, and said monomer contains the silicone glycol of following formula (4) representative as first organo-silicon compound.This compound produces gives the remarkable result of the desiccant gel flexibility that obtains through this compound of polymerization.Therefore, the desiccant gel that contains the monomer formation of this compound through polymerization has flexibility, and when said desiccant gel is used as the acoustic matching body, performance and the identical effect of desiccant gel that forms through the above-mentioned organic silane compound of polymerization.
HO((R
6)
2SiO)
nH (4)
Formula (4) all has the OH group and comprises repetition-R at two ends
6)
2The silicone compounds of SiO-.Through dehydration and this compound of condensation reaction polymerizable at OH group place.In formula (4), R
6Be that carbon number is 1～4 alkyl.In formula (4), all R
6Usually identical, but they can differ from one another.Work as R
6When being methyl, the compound of formula (4) representative is a polydimethylsiloxanediols diols.
" n " is 2 or bigger integer, preferred 5～100.When " n " greater than 100 the time, tend to variation with other compatibilities that form the material of desiccant gels, thereby possibly cause shortcoming such as the inhomogeneities in the gel.When " n " less than 2 the time, the gel that obtains maybe be softening by fully.In addition, when the compound of formula (4) representative when the compound of formula (1) representative uses, easy controls reaction speed is because they tend to copolymerization (crosslinked).
The desiccant gel that contains in the acoustic matching body of the present invention can contain the desiccant gel that forms through the such monomer of polymerization, and said monomer contains the polymer of the partial hydrolysis of the compound of following formula (1) representative or the compound that formula (1) is represented except that first organo-silicon compound.
Si(OR
1)
4 (1)
The compound of formula (1) representative is a tetraalkoxysilane.Each R
1Be that carbon number is 1～8 replacement or unsubstituted monovalence alkyl.As R
1Example, that can give an example has top R
3And R
5The group of giving an example.Therefore, omit R here
1Example.With preferred R
3And R
5Similar, preferred R
1Be that carbon number is 1～4 alkyl or phenyl.In formula (1), four R
1Usually identical, but they can differ from one another.
The compound of formula (1) representative has the structure that schematically shows like Fig. 4.As shown in Figure 4, in tetraalkoxysilane 18, only there is hydrolyzable organic group 17 to combine with silicon 15.More specifically, the example of the compound of formula (1) representative comprises tetramethoxy-silicane and tetraethoxysilane.
The desiccant gel that the monomer of the tetraalkoxysilane through containing formula (1) representative except that first organo-silicon compound obtains has intensity and flexibility simultaneously.Therefore; Use the acoustic matching body surface of this desiccant gel to reveal durability, and more be not easy to break, because matching body can be with by bonded block (for example; Housing) expansion or the contraction that cause owing to the variations in temperature of environment for use change, and the intensity of matching body self is high.
In this case, carry out aggregation processing simultaneously through the polymer that makes first organo-silicon compound and tetraalkoxysilane or its partial hydrolysis and can obtain desiccant gel.Perhaps, can make desiccant gel through polymerization first organo-silicon compound in the presence of wet gel, wherein said wet gel forms through the polymer or the tetraalkoxysilane of the partial hydrolysis of polymerization tetraalkoxysilane.The flexibility that this gel that forms by this way has the intensity brought because of tetraalkoxysilane and brings because of first organo-silicon compound, and obtain the ultrasonic vibrator and the ultrasonic wave sending and receiving device of stable operation in very wide temperature range.
The monomer of 0.01wt%～10wt% of total amount that preferably accounts for the polymer of tetraalkoxysilane and tetraalkoxysilane partial hydrolysis through the amount of first organo-silicon compound wherein forms contained desiccant gel in the acoustic matching body of the present invention.This monomer generates respectively the desiccant gel of the excellent specific property that shows because of first organo-silicon compound and tetraalkoxysilane.In the ban the polymerization tetraalkoxysilane, then during polymerization first organo-silicon compound, preferably use first organo-silicon compound of this ratio.
The contained desiccant gel of acoustic matching body of the present invention can contain the desiccant gel that forms through the such monomer of polymerization; Said monomer also contains at least a compound of following formula (5) and (6) representative and the copolymer of the compound that following formula (7) is represented except that containing first organo-silicon compound.
CH
2＝CR
10(COOR
11) (5)
CH
2＝CR
12(COOR
13) (6)
CH
2＝CR
14(COOR
15) (7)
In formula (5)～(7), R
10, R
12And R
14In each be hydrogen atom or methyl.In formula (5), R
11Be that carbon number is 1～9 replacement or unsubstituted monovalence hydrocarbon.In formula (6), R
13It is the group that is selected from epoxide group, glycidyl and contains at least a alkyl (for example, γ-glycidyl ether oxygen propyl) in these groups.
In formula (7), R
15It is the alkyl that contains the silicyl of alkoxysilyl or halogenation.More specifically, R
15Be selected from trimethoxy-silylpropyl, dimethoxy-methyl silicyl propyl group, mono methoxy dimetylsilyl propyl group, triethoxysilylpropyltetrasulfide, diethoxymethyl silicyl propyl group, ethyoxyl dimetylsilyl propyl group, silicochloroform base propyl group, dichloromethyl silicyl propyl group, Chlorodimethyl silicyl propyl group, chlorine dimethoxy silicyl propyl group and dichloro methoxyl group silicyl propyl group.
Through polymerization CH
2=C, the compound of formula (5) or (6) representative and the compound of formula (7) representative form copolymer.This copolymer generates the polymer that contains repetition Si-O at silicyl place and the copolymer or first polymerizable organosilicon compound.
For in the compound of formula (5)～(7) representatives each, can use the compound of two kinds or more kinds of types.The copolymer (four types) that in other words, can use two types compound representing by two types compound of formula (5) representative and formula (7) to form.
The monomer of the copolymer of the compound of representing when at least a compound and the formula (7) that contain formula (5) and (6) representative can obtain having the more desiccant gel of high flexibility during by polymerization.Therefore, said desiccant gel be easier to along with by bonded block owing to expansion or the contraction that the variations in temperature of environment for use causes changes.Especially, the compound of formula (5) representative can more effectively make gel softening.In addition, contain the desiccant gel that the monomer of the copolymer of these compounds forms through polymerization and have higher adhesiveness, therefore use the acoustic matching body of desiccant gel to be difficult to from being peeled off, and can stably operate by bonded block for different substrate materials.Especially, the compound of formula (6) representative can more effectively improve the adhesiveness to base material.
Preferred its density of desiccant gel that contains the monomer formation of first organo-silicon compound through polymerization is 0.15g/cm
3～1.00g/cm
3, the average pore size of measuring through the BJH method of using nitrogen adsorption method is 2mm～40nm.In addition, according to application, select the size and dimension of acoustic matching body of the present invention.For example, when the acoustic matching body and function was made the acoustic matching layer in the ultrasonic vibrator, it can be the disc-shape of the about 5mm of diameter～about 20mm, the about 0.4mm of thickness～about 1.5mm.
Above-mentioned desiccant gel can constitute the acoustic matching body individually, or can constitute complex with another kind of porous material, makes complex constitute the acoustic matching body.Because fracture is tended in the end of desiccant gel, therefore said desiccant gel preferably forms composite construction with another kind of porous material, makes the end of gel be protected.The porous material that constitutes complex with this desiccant gel is ceramic porous article preferably.In addition, thus complex has that its center dant is formed in the ceramic porous article, desiccant gel places the structure that makes in the recess that the marginal portion of desiccant gel is protected.
For example, the present invention provides a kind of acoustic matching body that comprises first porous body and second porous body, wherein:
First porous body is the ceramic porous article that comprises the ceramic particle that constitutes ceramic matrix, and wherein said ceramic matrix limits a plurality of holes,
In said ceramic matrix, form between ceramic particle the space and
Said second porous body is the desiccant gel that contains the monomer formation of first organo-silicon compound through polymerization.
In this acoustic matching body, second porous body has improved the coupling of the acoustic impedance of its acoustic impedance and gas, and first porous body is used to protect second porous body.In addition, except the hole that is limited by ceramic matrix, first porous body has space between the ceramic particle that in ceramic matrix, forms.In other words, the structure of this ceramic porous article has many spaces, has high strength as a whole, and therefore, its density is low.In addition, the skeleton of ceramic matrix can linear extension and is produced the zigzag channel that ultrasonic wave is used, because there is space between hole and ceramic particle.This has reduced hyperacoustic propagation velocity.Therefore, said first porous body has the characteristic of the low-density and the low velocity of sound, and it is had obvious improved ultrasonic wave propagation characteristic as in the ultrasonic vibrator of acoustic matching layer.
Here, " hole " refers to viewed gap when the microscope of about 20 times of amplifications (for example, by means of) observed the ceramic matrix that is made up of ceramic particle on macroscopic view." space between ceramic particle " refers to the short space that forms between each particle of ceramic matrix constituting refer to that particularly diameter is not more than the aperture of 10 μ m.Perhaps, can think that " hole " is the space that ceramic size foaming is formed according to following method, " space between ceramic particle " is no matter have or not foaming in pottery, to form.
In first porous body of the acoustic matching body of this composite construction, the size in preferred hole makes that aperture (hole dimension) central value of distribution is 10 μ m～500 μ m.When first porous body has the hole of this size and through make second porous body and first porous body integrated during with the formation complex with the material solution of second porous body dipping, promoted the dipping with material solution.
This ceramic matrix preferably contains the pottery of hard-to-sinter, but can not contain the pottery of hard-to-sinter.The pottery of hard-to-sinter preferably accounts for the 80vol% of ceramic matrix, more preferably accounts for the 90vol% of ceramic matrix, more preferably accounts for the 100vol% of ceramic matrix again.
Selectively; Material that can be through being mixed for forming ceramic matrix (for example; Aluminium oxide) and the hole form material; Then the hole is formed material and suppress, combine to form the material of ceramic matrix then and remove the sintering processes that the hole forms material, can make ceramic porous article with the mixtures of material that forms ceramic matrix.The hole forms material and is formed by the material of fusion in sintering processes or the material that in specific solvent, dissolves.It for example is the ball (fusion in sintering processes) or the iron ball (in sulfuric acid, dissolving) of acrylic compounds that the hole forms material.The material that forms ceramic matrix can be different from main material and the firm auxiliary material of main material are formed by main material that forms skeleton and size.Auxiliary material for example are glass.
In the acoustic matching body of this composite construction, the outer peripheral portion of second porous body is preferably surrounded by first porous body.That is, the profile of the surface direction of second porous body (that is, limiting the profile of the surface area of second porous body) preferably contacts with first porous body.Through this structure, can prevent the outward flange fracture of second porous body, the thickness of the acoustic matching body of this composite construction can be controlled in the surface of therefore placing through second porous body of polishing.
In the acoustic matching body of this composite construction, second porous body is preferably filled space between part or all of hole and the ceramic particle in first porous body.This allow second porous body and first porous body through the set effect strong the combination.
When the thermal coefficient of expansion of two kinds of different materials in the acoustic matching body that forms by two kinds of different materials not simultaneously, wherein a kind of material possibly rupture owing to the variations in temperature of environment for use.Because desiccant gel has flexibility in acoustic matching body of the present invention, and change along with the expansion of parts (porous body) on every side or contraction easily, thereby be difficult for rupturing, therefore this acoustic matching body can use easily in very wide temperature range.
Next, accompanying drawings is made the method for acoustic matching body of the present invention.
(first manufacturing approach)
Explanation manufacturing constitutes an embodiment of the desiccant gel method of acoustic matching body of the present invention below.Fig. 2 illustrates the flow chart of desiccant gel manufacturing step.In Fig. 2, the desiccant gel manufacturing step comprises material preparation process (step a), gelation step (step b), reconstruction step (step c), hydrophobization step (step d) and drying steps (step e).The operation of each step practical implementation shows the flow chart as mid portion among the figure.In addition, the material that uses in each step shows right side row in the drawings.Below, specify each step a～e.
Material preparation process (step a)
This step is to prepare the step of raw mix solution, wherein in this step, adds first organo-silicon compound, the water that makes compound hydrolysis, reaction dissolvent and catalyst as the material (gel rubber material) that forms the desiccant gel skeleton.In Fig. 2, in the example that illustrates, organic silane compound is as first organo-silicon compound.The example of organic silane compound as stated.The tetraalkoxysilane of giving an example out above in addition, can be used as gel rubber material.In addition, the copolymer that can add at least a compound of formula (5) and (6) representative and the compound that formula (7) is represented is as gel rubber material (monomer component), and organic silane compound.Selectively, can use the silicone glycol compound of formula (4) representative to replace organic silane compound.
First organo-silicon compound, the optional polymer that contains, to account for ratio overall before the polymerization (being that these compounds account for these compounds and the ratio of the total amount of the monomer of the compound represented derived from formula (1)) derived from the summation of the unreacted material of the copolymer of the compound of formula (5), (6) and (7) and these compounds unrestricted, but be preferably 0.01wt%～20wt%.When crossing derived from the concentration of the composition of these compounds when low, can not prevent breaking of desiccant gel, and if on base material, form desiccant gel, desiccant gel possibly strip down from base material so.On the other hand, if derived from the excessive concentration of the composition of these compounds, intensity decreases so, and in the drying of wet gel, can shrink.For those reasons, the concentration derived from the composition of these compounds was preferably 0.1wt%～10wt% before polymerization.Therefore, the material preparation process (in the step a), randomly use tetraalkoxysilane, make in the desiccant gel that obtains, derived from the concentration before these monomer component polymerizations in above-mentioned concentration range.
As catalyst, use general organic acid, general inorganic acid, general organic base or general inorganic base.As organic acid, that can give an example has acetate and a citric acid.As inorganic acid, that can give an example has sulfuric acid, hydrochloric acid and nitric acid.As organic base, that can give an example has a piperidines.As inorganic base, that can give an example has ammoniacal liquor.In addition, imines series catalysts such as piperidines can increase the bore dia in the desiccant gel.Therefore, the angle of the capillary force of the desiccant gel that obtains from reduction, this catalyst is preferred.
As solvent, can use water-miscible organic solvent, like lower alcohol, like methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol or diethylene glycol; The monoether of ethylene glycol or diethylene glycol or diether, lower ketones is like acetone; And rudimentary ether, like oxolane and 1, the 3-dioxolane.In addition, when the hydrolysis of passing through gel rubber material and polycondensation formation gel, in the material preparation process, add the required water of hydrolysis.
Solution preferably is prepared to and makes organic silane compound that its compound and same silicon of containing wherein hydrolyzable group and the non-hydrolysable of 10wt%～40wt% for example directly combine or by the silicone glycol of following formula (4) expression; With if when containing this compound, the tetraalkoxysilane of 0.01wt%～4.0wt% and the solvent of 60wt%～90wt%.
HO((R
6)
2SiO)
nH (4)
Mix mentioned component, carry out material and prepare.Fig. 5 (a) and Fig. 5 (b) be illustrated in organic silane compound when first organo-silicon compound before the polymerization with the sketch map of afterwards state.In Fig. 5 (a) and Fig. 5 (b), triangle (△) refers to the organic silane compound with non-hydrolysable organic group 15 14 shown in Fig. 3, and square () refers to the silane compound that only has hydrolyzable groups 17 18 shown in Fig. 4.Fig. 5 (a) expression wherein is dispersed with the gel rubber material solution 19 of these silane compounds, catalyst (figure does not show) and solvent.Make these silane compound hydrolysis through catalyst, and polymerization.Fig. 5 (b) illustrates the sketch map of the silane compound of polymerization.As shown in the figure, in gel rubber material solution 19, carry out polymerization and form wet gel 20, the dry then desiccant gel that forms.
Gelation step (step b)
In this step, through promoting hydrolytic polymerization in the mixture solution that catalyst is added to preparation, form the solid skeletal of gel, thereby generate the wet gel that contains solvent.In order to quicken gelation, randomly add catalyst, and improve the temperature of solution.The example of catalyst is pressed described in the material preparation process, therefore omits here.Catalyst can (step a) and gelation step (add in these two steps of step b) at the material preparation process.Selectively, the material preparation process ((can carry out simultaneously for step a) and gelation step by step b).Gelation step can be carried out under for example 20 ℃～70 ℃.
Reconstruction step (step c)
In this step, (part of the solid skeletal of the wet gel that forms in the step b) is decomposed, and forms new solid skeletal simultaneously in gelation step.Particularly, through add and mix reconstruct with material, reconstruct with catalyst, water with the solvent when needing, prepare the reconstruct material solution.The wet gel that in gelation step, forms is immersed in this solution.Through the processing time and the treatment temperature of this step, the density that can regulate desiccant gel.Processing time for example is 2 hours～50 hours, and treatment temperature for example is 40 ℃～80 ℃.
(gel rubber material described in the step b) and catalyst can be as the reconstruct material and the reconstruct catalyst that use in the reconstruction step in gelation step.Yet, reconstruct material and reconstruct catalyst needn't require with gelation step in the gel rubber material and the catalyst that use identical.The organic silane compound that the compound that the reconstruct material solution preferably is prepared to the wherein hydrolyzable group that contains 35wt%～80wt% and non-hydrolysable and same silicon directly combine or by following formula (4) if the silicone glycol of expression contains then contains the tetraalkoxysilane of 0.04wt%～8.0wt% and the solvent of 20wt%～60wt%.After strengthening gel skeleton, for stopping reaction, for example using, isopropyl alcohol replaces the reconstruct material solution that reaction is stopped.
HO((R
6)
2SiO)
nH (4)
Hydrophobization step (step d)
In this step, hydrophobizers is dissolved in hydrophobization solution and surface reaction in the solvent through making wherein, and (hydrophobic grouping is introduced on the wet gel surface that obtains in the step c) in reconstruction step.
As hydrophobizers, preferably use silylating agent, because it is reactive high.As silylating agent, that can give an example has silicon nitrogen silane compound, chlorosilane cpd, alkyl silane alcoholic compound and an alkylalkoxy silane compound.
In these silylating agents, silicon nitrogen silane compound, chlorosilane cpd and alkylalkoxy silane compound directly or through hydrolysis become corresponding alkyl silanol, and react with the silanol on the gel surface.When alkyl silanol was used as silylating agent, it in statu quo reacted with lip-deep silanol.
In these, consider high response and being easy to get property in the hydrophobization step, chlorosilane cpd and silicon nitrogen silane compound are preferred especially.Consider being easy to get property and can not produce that alkylalkoxy silane is a particularly suitable such as gases such as hydrogen chloride or ammonias.
More specifically; As the representative example of silylating agent, the pure and mild triethyl silicane alcohol of chlorosilane cpd such as trim,ethylchlorosilane, methyl trichlorosilane and dimethyldichlorosilane, silicon nitrogen silane compound such as HMDS, alkylalkoxy silane compound such as methoxytrimethylsilane, ethoxytrimethylsilane, dimethoxy dimethylsilane, dimethoxy trimethyl silane and di ethoxy di methyl-monosilane and silanol compound such as trimethyl silane is arranged.When using these compounds, alkyl silicyl such as trimethyl silyl are introduced into the surface of wet gel, thereby gel can be by hydrophobization.
Selectively, the silylating agent of fluoridizing can be used as hydrophobizers.When it was used, the hydrophobicity of gel strengthened and can carry out hydrophobization effectively by the utmost point.
Selectively, can be used as hydrophobizers such as alcohols such as ethanol, propyl alcohol, butanols, hexanol, enanthol, octanol, ethylene glycol or glycerine and such as carboxylic acids such as formic acid, acetate, propionic acid and butanedioic acids.Hydroxyl reaction on they and the gel surface forms ether or ester, thereby gel is by hydrophobization.Use in these hydrophobizers any reaction relatively slow.For this reason, use that any processing all requires at high temperature to carry out in these hydrophobizers (for example, 60 ℃～80 ℃).
The hydrophobization step is a kind of processing of the desiccant gel moisture absorption that prevents to obtain.Particularly, carry out the hydrophobization step through gel being put into silane coupled treatment fluid.Through using isopropyl alcohol to replace solution that hydrophobization reaction (silane treatment reaction) is stopped.
Drying steps (step e)
In this step, from removing up to the resulting wet gel of hydrophobization step and desolvate, thereby obtain desiccant gel through carrying out said step.As seasoning (1) natural seasoning and (2) special seasoning are arranged.
(1) natural seasoning is the seasoning of the most general and most convenient.This method is that a kind of wet gel that will contain solvent leaves standstill so that liquid solvent evaporation and the method that is removed.From the angle of cost, this seasoning is most preferred.From the angle of productivity ratio, the heat drying of heating wet gel and wherein the wet gel drying under reduced pressure that is in subatmospheric decompression state all should be included in the natural seasoning.The heating-up temperature of heat drying is not restricted to specified temp, as long as solvent can evaporate under this temperature.
When the density of gel is low and since with gel in the proportional capillary force of surface tension of solvent, gel is temporary transient in dry run shrinks and possibly break.For this reason, the solvent of in drying steps, the removing hydrocarbon system solvent that preferably surface tension under boiling point is low, hexane, pentane or its mixture are because inexpensive but preferred especially.On the other hand, from the viewpoint of fail safe, preferably from gel, remove mixed solvent such as alcohols such as isopropyl alcohol, ethanol or butanols or water and organic solvent.For those reasons, the solvent of giving an example above preferably using replaces being used to form the solvent of wet gel, then wet gel is carried out dried.Can reduce the stress in the dry run like this, and make wet gel can resist breaking in the drying.
(2) as special seasoning two kinds of method-supercritical dryings and freeze-drying are arranged.Because solvent is removed as supercriticality rather than through liquid state in supercritical drying, therefore can not produce the capillary force that forms liquid-vapor interface.For this reason, wet gel is difficult to break in drying.As being used for dry supercritical fluid, that can give an example has water, a pure and mild carbon dioxide.It is harmless under minimum temperature, arriving supercritical carbon dioxide, and under multiple situation, uses.
Particularly, liquefied carbon dioxide is charged in the pressure vessel, and with the solvent in the wet gel of placing in the liquefied carbon dioxide displacement container.Next, pressure and temperature rises to more than the super critical point, thereby arrives supercriticality.Through keeping discharging carbon dioxide completion drying under the temperature conditions gradually.
Freeze-drying is that the solvent in a kind of wet gel is frozen and removes through distillation the seasoning desolvate.In these methods, solvent does not experience liquid state, in gel, does not produce liquid-vapor interface, does not therefore produce capillary force.For this reason, can suppress the contraction of gel in the drying.
The solvent that freeze-drying is used is the very high solvent of vapour pressure under solidifying point preferably.The example of solvent comprises the tert-butyl alcohol, glycerine, cyclohexane, cyclohexanol, paraxylene, benzene and phenol.In these, the tert-butyl alcohol and cyclohexane are because the steam pressure under fusing point is very high but preferred especially.
Through being used in the solvent in the solvent exchange wet gel that vapour pressure is high under the solidifying point earlier, can more effectively carry out freeze-drying.In addition, the solvent that in gelation, uses originally has high vapour pressure under solidifying point be preferred.This is because can make effectively through omitting solvent exchange.
Drying can be carried out after the hydrophobization step, perhaps can before the hydrophobization step, carry out.When the hydrophobization step is carried out after drying steps, through making the steam rather than the solution of desiccant gel contact hydrophobizers, the surface of hydrophobic grouping being introduced desiccant gel.Therefore, this method can reduce the quantity of solvent of use.
Above-mentioned hydrophobizers can be as the hydrophobizers of using in the hydrophobization step of after drying steps, carrying out.Chlorosilane cpd such as trim,ethylchlorosilane or dimethyldichlorosilane are because high response but most preferred.In addition, during hydrophobizers outside using chlorosilane cpd, what use can gaseous state be introduced is effective such as catalyst such as ammonia or hydrogen chloride.
In addition, when in gas phase, carrying out hydrophobization, the temperature in the time of can improving hydrophobization, and do not receive the restriction of solvent and hydrophobizers boiling point.Therefore, the hydrophobization in the gas phase is effective for accelerated reaction.In addition, when wet gel was film or powder, the steam of hydrophobizers penetrated easily.When gel is film, can advantageously reduce quantity of solvent.
The acoustic matching body that contains the desiccant gel of making in the above described manner has flexibility.For this reason, even as being expanded owing to variations in temperature or shrink by the piezoelectric of bonded block, the acoustic matching body with flexibility also can expand along with the expansion of piezoelectric or contraction or shrink, thereby can prevent breaking of acoustic matching body itself.Can make ultrasonic vibrator of the present invention shown in Figure 1 operation stably in very wide temperature range like this.
(second manufacturing approach)
Explanation manufacturing constitutes the another kind of embodiment of the desiccant gel method of acoustic matching body of the present invention below.Fig. 6 (a)～Fig. 6 (c) is a sketch map, shows material preparation process, gelation step and reconstruction step when organic silane compound is used as first organo-silicon compound in this embodiment respectively.The implication of △ and and the implication of each Reference numeral such as Fig. 5 are said.(the gel rubber material solution 21 in the step a), the silane compound 18 that wherein only hydrolyzable organic group combines with silicon is dispersed in wherein Fig. 6 (a) expression material preparation process.Make this solution carry out gelation step (step b), and carry out gelation.
Shown in Fig. 6 (b); Be added in gelation step reconstituted solutions 23 (in the wet gel 22 that forms in the step b); Be hydrolyzed then, said reconstituted solutions 23 wherein have non-hydrolysable organic group 15 organic silane compound 14 and only to have an organic silane compound 18 of hydrolyzable organic group 17 mixed and disperse.Consequently, through hydrolysis and polymerization (crosslinked), obtain wet gel 24.(organic silane compound, catalyst and the solvent that uses in step a) and the reconstruction step (c) therefore omits the explanation to them by described in first manufacturing approach to the material preparation process.In addition, by carrying out hydrophobization step and drying steps with the said identical mode of first manufacturing approach.
The acoustic matching body that contains the desiccant gel of with good grounds this manufacturing approach formation has flexibility.In addition; Compare with first manufacturing approach; This manufacturing approach is used organic silane compound in reconstruction step, make stably to make desiccant gel within a short period of time, and the desiccant gel that obtains has the structure of relative higher modulus of elasticity and flexibility.
(the 3rd manufacturing approach)
The embodiment of the method for the acoustic matching body of making the composite construction that is formed by above-mentioned specific desiccant gel and ceramic porous article is described below.
In Figure 11, provide the acoustic matching body of the composite construction of making according to this embodiment.Acoustic matching body 44 shown in Figure 11 is that for example diameter is that 10.8mm and thickness are the disc-shape of 1.8mm, and comprising the ceramic porous article as first porous body 42, desiccant gel is filled in the recess that forms in first porous body 42 as second porous body 43.
In Figure 11, first porous body 42 is a kind of comprising as the ceramic matrix 41 of skeleton with by the structure in the hole 45 of ceramic matrix 41 qualifications.As stated, in ceramic matrix 41, form space between ceramic particle.The embodiment of the method for this ceramic matrix is made in explanation below.Figure 12 illustrates the flow chart of ceramic matrix manufacturing step.
Manufacturing step roughly is divided into to be prepared mixed slurry (steps A), prepare to contain slurry (step B), forming step (step C), drying steps (step D), degreasing and the sintering step (step e) of bubble and cuts off step (step F).The operation of each step practical implementation shows the flow chart as right side among the figure.In addition, the material that uses in each step is presented at the middle row of figure.
Steps A comprises mixing/pulverising step; Wherein for example mix and pulverize, obtain mixed slurry as the ceramic powders (for example, carborundum and glass) of feed material and water (wherein mixed organic solvents) when needed through ball mill; With the froth breaking step, the mixed slurry that wherein obtains is by froth breaking.Ceramic powders contains the ceramic powders of at least a hard-to-sinter.The ceramic powders of said hard-to-sinter can be a carborundum for example.Froth breaking can carry out in the glove box of filling nitrogen.For this reason, before the froth breaking step, outgas and the nitrogen replacement step.
Step B is a foaming step, wherein in nitrogen atmosphere, surfactant (blowing agent) and gelling agent is added in the mixed slurry, and mixes them with mixer.In this step, speed, mixing time and the temperature of the kind of surfactant, the kind of ceramic powders, mixer is the size of the bubble (that is the hole that, in ceramic porous article, is limited by ceramic matrix) that contains of decision and the parameter of distribution.Therefore, these parameters must suitably be selected, thereby obtain required hole.This step is an important step for definite loose structure.
Step C shifts the ceramic size that contains bubble that obtains in the mould of arbitrary shape, gelation then, the step of formation gel porous former.Through being placed, slurry carried out gelation in tens of minutes in the mould of sealing.
For from mould, taking out the gel porous former and removing moisture and the part organic principle carries out step D.Owing to will be solid (curing), therefore be easy to handle by hand-held gel porous former.Selectively, part mould wall that can be through sliding mould exposes at least one surface in upper surface, lower surface and the side surface of gel porous former, thereby carries out step D.Like this, owing to must from mould, not take out the gel porous former, so the impaired possibility of gel porous former reduces.
Preferably carry out drying, decompose, move and assemble with the bubble that prevents to contain in the gel porous former.For example, the gel porous former preferably be not less than 20 ℃ be not more than under 30 ℃ the temperature slowly dry 48 hours or longer time.
Step e comprises defatting step; Wherein dry porous former is heated to removes the required temperature of excessive organic component contained in the formed body; And sintering step, said sintering step at high temperature carries out sintering (or roasting or calcining), makes ceramic powders combine to form matrix.Particularly, the temperature and time section of degreasing decides according to the kind and the amount of used organic component.For example, sintering can carry out under 400 ℃～700 ℃ 24 hours～48 hours, thereby burnt gelling agent.Sintering temperature decides according to the ceramic powders (that is the ceramic powders of glass or hard-to-sinter) that uses.
For example, the glass that is lower than the carborundum fusing point when carborundum and fusing point is during as ceramic powders, and sintering is for example carrying out under 800 ℃.Sintering time can be for example 12 hours～48 hours.When use contains the ceramic powders of carborundum and glass, can think that a part of carborundum particle is bonded to each other through glass in this sintering processes, and most of carborundum particle is bonded to each other through oxygen.Selectively, can only use carborundum to be used as ceramic powders.In this case, sintering temperature can be 900 ℃～1350 ℃, and sintering time can be for example 12 hours～48 hours.
Step F is the sintered body that obtains (ceramic porous article) to be cut off become its step as the body required size of acoustic matching body.
The ceramic porous article of making in such a way is such structure, and said structure has such hole, and the central value of pore-size distribution is 10 μ m～500 μ m, and porosity is 60vol% at least, the about 0.4g/cm of apparent density
3～about 0.8g/cm
3In addition, in ceramic porous article, a plurality of holes are connected to form intercommunicating pore.
Shown in figure 11, wherein second porous body 43 (desiccant gel) places the complex in the recess that first porous body 42 (ceramic matrix) forms can be through method manufacturing shown in Figure 13.Figure 13 representes such state, and first porous body 42 that has the recess 63 of placing second porous body therein under the said state is placed in downwards on the mould 61 with recess 63, and they are placed in the container 62.Be used in material solution 64 filling containers 62 of a of step shown in Fig. 2 preparation, this step is said by first manufacturing approach.When mould 61 being immersed in this solution 64, solution 64 soaks into as the intercommunicating pore in first porous body 42 of ceramic porous article.Consequently, recess 63 is filled by solution 64.Next, keep this state to carry out the step b shown in Fig. 2.Here, the intercommunicating pore in first porous body 42 is through the perforate that is connected to form between connection between the connection between the hole that limits in the ceramic matrix, hole and the inter-particle voids and the inter-particle voids.
Figure 14 is the enlarged drawing that first porous body 42 places the part on the mould 61 shown in Figure 13.Because the recess 63 that forms in first porous body 42 is soaked into the solution of intercommunicating pore in the porous body 42 and is full of, so gel also is formed on the intercommunicating pore interior (this gel finally is used to form second porous body (desiccant gel 43)) of first porous body.The gel that in recess 63, forms also contacts with mould 61.In Figure 14, only show hole 66 that ceramic matrix 65 limits and the intercommunicating pore that forms by these holes, but should be noted that, intercommunicating pore is formed between hole 66 and ceramic particle between the space and between ceramic particle between the space.
Owing to carry out reconstruction step as step c to keep this structure; Therefore the mixed solution of initiate organic silane compound, water, ammoniacal liquor and ethanol is also through the gel in the hole 66 that is formed on first porous body 43; Arrive the gel that in recess 63, forms then, to strengthen in recess 63 and the gel skeleton in hole 66.Then, carry out step up to steps d to keep this structure.
Solution that in each step, uses and solvent arrive recess 63 through the gel that in the hole 66 of first porous body 42, forms.In other words, the solution through the gels that form in the hole 66 etc. has strengthened the gel skeleton of formation recess 63 in or the reaction of in gel, carrying out is stopped.Therefore, the hole 66 in first porous body 42 is too small, and its shortcoming is, solution can not soak into fully and almost can not arrive the gel 43 that in recess 63, forms.When the hole in first porous body 42 66 was excessive, ultrasonic wave was propagated and is obstructed.For this reason, first porous body 42 is preferably by such formation, makes that promptly the central value of pore-size distribution in the hole 66 that ceramic matrix limits is 100 μ m～500 μ m.The size in the hole 66 in the preparation process of the slurry that contains bubble in adjustment first porous body 42, this step is the step C shown in Figure 12.
According to wherein making that through flooding required material desiccant gel passes through to form the method as the desiccant gel of second porous body the formed intercommunicating pores such as hole that the matrix as the ceramic porous article of first porous body limits, can use the confined space that forms by recess that forms in first porous body and die surface to carry out step up to the drying steps that obtains second porous body.Consequently, in the process that forms second porous body, be difficult for forming the crack in the gel.In other words, when making desiccant gel according to the manufacturing approach shown in Fig. 2, its shortcoming is, because gel surface is exposed, therefore is easy in gel, form the crack.Yet this manufacturing approach can prevent the desiccant gel cracking, is not vulnerable to stress because will become that part of of second porous body by the protection of first porous body.In addition, owing to form down second porous body contact, so when die surface when being level and smooth with mould shown in figure 14, its surface dead smooth that also becomes.
Make the outer rim of second porous body 43 contact through second porous body 43 is set, thereby make the edge of second porous body 43 receive the protection of first porous body 42 with first porous body 42.Therefore, because the use of this composite construction has prevented breaking of second porous body, 43 edges effectively,, can easily make the thickness D of second porous body 43 reach desired thickness therefore through for example grinding the surface of second porous body 43.For example, second porous body 43 forms following shape in first porous body 42 of the about 10.8mm of diameter: the about 8mm of diameter, thickness 0.15mm～0.4mm.
(measurement of flexural strength)
Fig. 7 representes to be used to measure the cross-sectional view of anchor clamps of the flexural strength of desiccant gel.According to first manufacturing approach, use the material shown in the table 1, catalyst and seasoning to make desiccant gel.In addition, for comparing purpose, only use tetraalkoxysilane compounds (that is tetraethoxysilane) to make desiccant gel.Desiccant gel is manufactured into the cylindrical of diameter 10mm and thickness 1.5mm.Through regulating the processing time of reconstruction step, has the multiple gel of different densities for each sample manufacturing.
Table 1
The desiccant gel that obtains 26 is placed on the test desk 27 in order to the anchor clamps 25 of measuring flexural strength,, measure flexural strength then with constant speed vertical moving push strut 28.Fig. 8 representes the measurement result of the flexural strength of desiccant gel.
Transverse axis among Fig. 8 shows the density of desiccant gel sample, and the longitudinal axis shows the modulus of elasticity of calculating from the flexural strength of desiccant gel sample.In Fig. 8; The desiccant gel sample that dotted line 29 expression only uses tetraalkoxysilane compounds (sample 2) to make, solid line 30 expressions are given the desiccant gel sample (sample 1) of its flexibility through using wherein the organic group of non-hydrolysable with the organo-silicon compound that silicon directly combines.Under equal densities, sample 1 has lower modulus of elasticity than sample 2, has higher flexibility than sample 2.If expanded with variations in temperature or shrink by bonded block, so this flexibility can make the silicon dioxide desiccant gel along with being changed by the expansion of bonded block or contraction.Therefore, wherein the acoustic matching body is that the ultrasonic vibrator of the desiccant gel of sample 1 has the effect that prevents that desiccant gel self from breaking, and can in very wide temperature range, operate.
Can form the desiccant gel in the acoustic matching body of the present invention of sample 1 representative, make modulus of elasticity satisfy following formula (1), create conditions although this depends on.
E＝K·e
AD (1)
Wherein E is a modulus of elasticity, and K is 20～55 constant (or coefficient), and A is 4～5.5 constant (or coefficient), and D is the density of desiccant gel.
On the other hand, the modulus of elasticity of the desiccant gel of sample 2 representative satisfies following formula (2), in gel, only have organo-silicon compound that hydrolyzable organic group combines with silicon as monomer by polymerization.Therefore, the modulus of elasticity of this desiccant gel is greater than the desiccant gel that under any density, contains in the acoustic matching body of the present invention, and has low flexibility.
E＝K′·e
A′D (2)
Wherein E is a modulus of elasticity, and K ' is 60～100 constant (or coefficient), and A ' is 5.5～7 constant (or coefficient), and D is the density of desiccant gel.
(ultrasonic vibrator)
Fig. 9 representes to have the cross-sectional view of embodiment of the ultrasonic vibrator of the present invention 31 of housing, and Figure 10 representes the flow chart making of ultrasonic vibrator 31.The manufacturing process of ultrasonic vibrator 31 is described below.Step (i) is the step that forms acoustic matching layer 2, and of first to the 3rd manufacturing approach, therefore omits the explanation to it.Step (ii) be on the surface of the electrode 33 that forms through roasting silver on its surface with have as on by the top cover outer surface of the cylindrical metal housing 32 that top cover is arranged of bonded block, print step as the adhesive of bonded block 4a and 4b.The not special restriction of printing process, needing only through this printing process can be silk-screen, intaglio printing or transfer printing with the predetermined thickness printing binder.In addition, there is the cylindrical metal housing of top cover to be formed by one of these metals of metal plated by for example iron, brass, copper, aluminium, stainless steel or its alloy or its surface.
Step (iii) in, the terminal board 36 that is attached with the cylindrical metal housing that top cover is arranged of piezoelectric 3 harmony matching blocks 2 and wherein inserts electric installation 35 is connected by welding to together.Terminal board 36 is provided with electrode terminal 37 and 38.These terminals are through insulated part 39 mutually insulateds of terminal board.Through constituting electric installation 35, and be electrically connected with electrode 34 and electrode terminal 38 such as elastomer such as silicon rubber, butadiene rubber or artificial rubber and electric conductor.Electrode 33, as being electrically connected by the cylinder shell that top cover is arranged of bonded block and electrode terminal 37.
When terminal board 36 is welded to the cylindrical metal housing, inert gas is injected the inside of the confined space 40 that is formed by cylindrical metal housing with top cover and terminal board 36, thereby accomplish ultrasonic vibrator 31.Inert gas for example is helium or nitrogen, and not special restriction, only otherwise react with silver electrode.The time have in welding that inert gas injecting can make the piezoelectric 3 that is provided with silver electrode isolate with external environment condition in the cylinder shell of top cover, be electrically connected steady in a long-termly, and guaranteeing long-term reliability thereby make.
As the ultrasonic vibrator 31 of above-mentioned structure in, acoustic matching layer contains the desiccant gel that forms through polymerization particular silicone compound (particularly organic silane compound or silicone glycol compound), and has flexibility.Therefore,, can prevent that acoustic matching layer is destroyed, because it can be along with this expansion or contraction and expands or shrink if housing 32 expands with variations in temperature or shrinks.Ultrasonic vibrator of the present invention 31 with this acoustic matching layer can stably be operated in wide temperature range, therefore can use for a long time.
(ultrasonic wave sends and receiving equipment)
Comprise that with reference to Figure 15 explanation containing acoustic matching body of the present invention sends and receiving equipment as the ultrasonic wave of the ultrasonic vibrator of acoustic matching layer.Figure 15 is a circuit block diagram, shows that the ultrasonic wave of the present invention that is introduced in the flowmeter 88 that is used for measuring fluid flow sends and receiving system.Ultrasonic vibrator " A " 82 and ultrasonic vibrator " B " 83 place fluid passage 81.Ultrasonic vibrator " A " and " B " are configured such that the signal that angled
sends between ultrasonic wave propagation and the fluid passage is sent to ultrasonic vibrator " A " 81 and ultrasonic vibrator " B " 83 from dispensing device 84.In addition, the signal of ultrasonic vibrator reception is sent to receiving system 85.Select to send or receive through switching device shifter 87.When switching device shifter 87 was selected being connected of ultrasonic vibrator " A " 82 and dispensing device 84, ultrasonic vibrator " B " 83 was connected to receiving system 85.
Shown in figure 15, when fluid from the left side of figure when flowing to the right side, the ultrasonic wave that ultrasonic vibrator " A " 82 sends arrives ultrasonic vibrator " B " 83 behind propagation time T1.On the contrary, the ultrasonic wave of ultrasonic vibrator " B " 83 transmissions arrives ultrasonic vibrator " A " 82 behind propagation time T2.Here, because fluid flow direction is the extremely right side, a left side, therefore set up T1＜T2.Measure these time T 1 and T2 through time set 86.This time relates to flow rate of fluid.Because from the flow of the long-pending Fluid Computation of flow velocity and passage sections, therefore through can be in the hope of flow from the flow velocity of T1 and T2 mensuration.Computing unit 89 is confirmed flow velocity based on the data of time set 86.
As stated, the present invention provides following acoustic matching body, ultrasonic vibrator and ultrasonic flowmeter.
As first pattern, the present invention provides a kind of acoustic matching body, and it comprises the desiccant gel that the monomer of the polymerizable organo-silicon compound that the organic group that contains first non-hydrolysable wherein through polymerization and silicon directly combine forms.
As second pattern, the present invention provides the acoustic matching body according to first pattern, and it is made up of said desiccant gel and another kind of porous body.
As three-mode, the present invention provides the acoustic matching body according to first or second pattern, and wherein said another kind of porous body is a ceramic porous article.
As four-mode; The present invention provides according to first to each acoustic matching body of three-mode, and wherein said polymerizable organo-silicon compound are organic silane compounds that organic group and the same silicon of wherein hydrolyzable organic group and non-hydrolysable directly combines.
As the 5th pattern, the present invention provides according to each acoustic matching body of first to fourth pattern, and wherein said monomer also contains the polymer of partial hydrolysis of compound of compound or formula (1) representative of following formula (1) representative,
Si(OR
1)
4 (1)
Each R wherein
1Be that carbon number is 1～8 replacement or unsubstituted monovalence alkyl.
As the 6th pattern; The present invention provides the acoustic matching body according to the 5th pattern; Wherein the polymer of the partial hydrolysis of the compound of compound through gathering (1) representative or formula (1) representative obtains wet gel, and the said polymerizable organo-silicon compound of polymerization form said desiccant gel in the presence of wet gel then.
As the 7th pattern; The present invention provides the acoustic matching body according to the 5th or the 6th pattern; Wherein pass through the polymer sum by the partial hydrolysis of the compound of representing with respect to the compound and the formula (1) of formula (1) representative, polymerizable organo-silicon compound amount is that the monomer of 0.1wt%～10wt% forms said desiccant gel.
As the 8th pattern, the present invention provides according to each acoustic matching body of first to the 7th pattern, and wherein said polymerizable organo-silicon compound are at least a compounds of following formula (2) and (3) representative,
R
3Si(OR
2)
3 (2)
(R
5)
2Si(OR
4)
2 (3)
R wherein
2And R
4In each be that carbon number is 1～4 alkyl, R
3And R
5In each be that carbon number is 1～8 replacement or unsubstituted monovalence alkyl.
As the 9th pattern, the present invention provides the acoustic matching body according to the 8th pattern, and wherein at least a compound through gathering (2) and (3) representative makes that molecular weight is 200 or more greatly to form said desiccant gel.
As the tenth pattern, the present invention provides according to each acoustic matching body of first to the 8th pattern, and the compound that wherein contains following formula (4) representative through polymerization forms said desiccant gel as the monomer of said polymerizable organo-silicon compound,
HO((R
6)
2SiO)
nH (4)
R wherein
6Be that carbon number is 1～4 alkyl, n is 2 or bigger integer.
As the 11 pattern, the present invention provides the acoustic matching body according to first to the tenth pattern, and wherein said monomer also comprises at least a compound of following formula (5) and (6) representative and the copolymer of the compound that following formula (7) is represented,
CH
2＝CR
10(COOR
11) (5)
CH
2＝CR
12(COOR
13) (6)
CH
2＝CR
14(COOR
15) (7)
R wherein
10, R
12And R
14In each hydrogen atom or methyl naturally, R
11Be that carbon number is 1～9 replacement or unsubstituted monovalence hydrocarbon, R
13Be the group that is selected from epoxide group, glycidyl and contains at least a alkyl (for example, γ-glycidyl ether oxygen propyl) in these groups, and R
15It is the alkyl that contains the silicyl of alkoxysilyl or halogenation.
As the tenth two modes, the present invention provides according to each acoustic matching body of the first to the 11 pattern, and the modulus of elasticity of wherein said desiccant gel satisfies following formula (1),
E＝K·e
AD (1)
Wherein E is a modulus of elasticity, and K is 20～55 constant (or coefficient), and A is 4～5.5 constant (or coefficient), and D is the density of desiccant gel.
As the tenth three-mode, the present invention provides a kind of ultrasonic vibrator that comprises piezoelectric and acoustic matching layer, and wherein said acoustic matching layer is by forming according to each acoustic matching body of first to the tenth two modes.
As the tenth four-mode, the present invention provides a kind of ultrasonic flowmeter, and it comprises:
The path that fluid to be determined flows;
A pair of ultrasonic vibrator according to the tenth three-mode; And
Be used to measure the time set of the ultrasonic propagation time between ultrasonic vibrator.
Industrial applicibility
As stated; Acoustic matching body of the present invention comprises the desiccant gel with flexibility; And have desiccant gel and be not easy to breakage, even housing expansion or contraction and desiccant gel are also along with the expansion of housing or contraction and change as the ultrasonic vibrator of acoustic matching layer.Therefore; Have the ultrasonic vibrator of acoustic matching body of the present invention can be in wide temperature range operation stably, and be suitable for as industrial or home-use ultrasonic gas flowmeter, the flow that is used to measure natural-gas or compressed petroleum gas (for example; Gas meter) with as water factory's flowmeter.
Claims (27)
1. acoustic matching body, it comprises through polymerization and contains the desiccant gel that the monomer of polymerizable organo-silicon compound forms, the organic group of non-hydrolysable directly combines with silicon in the said polymerizable organo-silicon compound,
Wherein said monomer also comprises at least a compound of formula (5) and (6) representative and the copolymer of the compound that formula (7) is represented,
CH
2＝CR
10(COOR
11) (5)
CH
2＝CR
12(COOR
13) (6)
CH
2＝CR
14(COOR
15) (7)
R wherein
10, R
12And R
14Each is hydrogen atom or methyl naturally, R
11Be that carbon number is 1～9 replacement or unsubstituted monovalence hydrocarbyl group, R
13Be be selected from epoxide group, glycidyl and contain epoxide group and glycidyl in the group of at least a alkyl, and R
15Be the alkyl that contains the silicyl of alkoxysilyl or halogenation,
The modulus of elasticity of wherein said desiccant gel satisfies following formula (1),
E＝K·e
AD (1)
Wherein E is a modulus of elasticity, and K is 20～55 constant, and A is 4～5.5 constant, and D is the density of desiccant gel,
Wherein term " acoustic matching body " is used in reference to as acoustic matching layer and is introduced into ultrasonic vibrator individual components before, and it is known as " acoustic matching layer " after introducing ultrasonic vibrator.
2. acoustic matching body according to claim 1, wherein said alkyl is γ-glycidyl ether oxygen propyl.
3. acoustic matching body according to claim 1, it is made up of said desiccant gel and another kind of porous body.
4. acoustic matching body according to claim 3, wherein said another kind of porous body is a ceramic porous article.
5. acoustic matching body according to claim 1, wherein said polymerizable organo-silicon compound are organic silane compounds that organic group and the same silicon of wherein hydrolyzable organic group and non-hydrolysable directly combines.
6. acoustic matching body according to claim 1, wherein said monomer also contain the polymer of the partial hydrolysis of the compound of formula (1) representative or the compound that formula (1) is represented,
Si(OR
1)
4 (1)
Each R wherein
1Be that carbon number is 1～8 replacement or unsubstituted monovalence alkyl.
7. acoustic matching body according to claim 6; Wherein form said desiccant gel through such monomer; The polymer sum of the partial hydrolysis of the compound of representing with respect to the compound and the formula (1) of formula (1) representative in the said monomer, the amount of polymerizable organo-silicon compound is 0.1wt%～10wt%.
8. acoustic matching body according to claim 5, wherein said organic silane compound are at least a in the compound of formula (2) and (3) representative,
R
3Si(OR
2)
3 (2)
(R
5)
2Si(OR
4)
2 (3)
R wherein
2And R
4Each naturally carbon number be 1～4 alkyl, R
3And R
5Each naturally carbon number be 1～8 replacement or unsubstituted monovalence alkyl.
9. acoustic matching body according to claim 8, wherein at least a compound through gathering (2) and (3) representative makes that molecular weight is 200 or bigger, thereby forms said desiccant gel.
10. acoustic matching body according to claim 1, the compound that wherein contains formula (4) representative through polymerization forms said desiccant gel as the monomer of said polymerizable organo-silicon compound,
HO((R
6)
2SiO)
nH (4)
R wherein
6Be that carbon number is 1～4 alkyl, n is 2 or bigger integer.
11. a method of making the described acoustic matching body of claim 1, it comprises that the method through may further comprise the steps forms desiccant gel:
The monomer that contains such polymerizable organo-silicon compound through polymerization forms wet gel, and the organic group of non-hydrolysable directly combines with silicon in the said polymerizable organo-silicon compound; And
Dry said wet gel.
12. a method of making the described acoustic matching body of claim 1, it comprises that the method through comprising following steps forms wet gel:
The monomer of polymer of partial hydrolysis of compound that comprises compound or formula (1) representative of formula (1) representative through polymerization forms first wet gel,
Si(OR
1)
4 (1)
Each R wherein
1Be that carbon number is 1～8 replacement or unsubstituted monovalence alkyl,
The monomer that contains such polymerizable organo-silicon compound through polymerization in first wet gel forms second wet gel, and the organic group of non-hydrolysable directly combines with silicon in the said polymerizable organo-silicon compound; And
Dry said second wet gel.
13. a method of making the described acoustic matching body of claim 1 comprises:
(1) form first porous body through the method that may further comprise the steps:
In first mould, make the ceramic size gelatine that contains bubble that comprises at least a ceramic powders, form gel porous former with one or more recesses;
Make gel porous former drying and degreasing; And
The said gel porous former of sintering; And
(2) in one or more recesses, form second porous body through the method that may further comprise the steps:
In another mould, place first porous body;
In said another mould, add the material solution that comprises the monomer that contains such polymerizable organo-silicon compound, the organic group of non-hydrolysable directly combines with silicon in the said polymerizable organo-silicon compound, thereby floods first porous body with said material solution; And
The said monomer of polymerization forms wet gel, and
Dry said wet gel.
14. ultrasonic vibrator that comprises piezoelectric and acoustic matching layer; Wherein said acoustic matching layer is formed by the described acoustic matching body of claim 1; Said acoustic matching body comprises the desiccant gel that contains the monomer formation of polymerizable organo-silicon compound through polymerization, and the organic group of non-hydrolysable directly combines with silicon in the said polymerizable organo-silicon compound.
15. ultrasonic vibrator according to claim 14, wherein said acoustic matching body is made up of said desiccant gel and another kind of porous body.
16. ultrasonic vibrator according to claim 15, wherein said another kind of porous body is a ceramic porous article.
17. ultrasonic vibrator according to claim 14, wherein said polymerizable organo-silicon compound are organic silane compounds that organic group and the same silicon of wherein hydrolyzable organic group and non-hydrolysable directly combines.
18. ultrasonic vibrator according to claim 14, wherein said monomer also contain the polymer of the partial hydrolysis of the compound of formula (1) representative or the compound that formula (1) is represented,
Si(OR
1)
4 (1)
Each R wherein
1Be that carbon number is 1～8 replacement or unsubstituted monovalence alkyl.
19. ultrasonic vibrator according to claim 18; Wherein the polymer of the partial hydrolysis of the compound of compound through gathering (1) representative or formula (1) representative obtains wet gel, then said polymerizable organo-silicon compound of polymerization and form said desiccant gel in the presence of wet gel.
20. ultrasonic vibrator according to claim 18; Wherein form said desiccant gel through such monomer; The polymer sum of the partial hydrolysis of the compound of representing with respect to the compound and the formula (1) of formula (1) representative in the said monomer, the amount of polymerizable organo-silicon compound is 0.1wt%～10wt%.
21. ultrasonic vibrator according to claim 17, wherein said organic silane compound are at least a in the compound of formula (2) and (3) representative,
R
3Si(OR
2)
3 (2)
(R
5)
2Si(OR
4)
2 (3)
R wherein
2And R
4Each naturally carbon number be 1～4 alkyl, R
3And R
5Each naturally carbon number be 1～8 replacement or unsubstituted monovalence alkyl.
22. ultrasonic vibrator according to claim 21, wherein at least a compound through gathering (2) and (3) representative makes that molecular weight is 200 or bigger, thereby forms said desiccant gel.
23. ultrasonic vibrator according to claim 14, the compound that wherein contains formula (4) representative through polymerization forms said desiccant gel as the monomer of said polymerizable organo-silicon compound,
HO((R
6)
2SiO)
nH (4)
R wherein
6Be that carbon number is 1～4 alkyl, n is 2 or bigger integer.
24. ultrasonic vibrator according to claim 14, wherein said monomer also comprise at least a compound of formula (5) and (6) representative and the copolymer of the compound that formula (7) is represented,
CH
2＝CR
10(COOR
11) (5)
CH
2＝CR
12(COOR
13) (6)
CH
2＝CR
14(COOR
15) (7)
R wherein
10, R
12And R
14Each is hydrogen atom or methyl naturally, R
11Be that carbon number is 1～9 replacement or unsubstituted monovalence hydrocarbyl group, R
13Be be selected from epoxide group, glycidyl and contain epoxide group and glycidyl in the group of at least a alkyl, and R
15It is the alkyl that contains the silicyl of alkoxysilyl or halogenation.
25. ultrasonic vibrator according to claim 24, wherein said alkyl is γ-glycidyl ether oxygen propyl.
26. ultrasonic vibrator according to claim 14, the modulus of elasticity of wherein said desiccant gel satisfy following formula (1),
E＝K·e
AD (1)
Wherein E is a modulus of elasticity, and K is 20～55 constant, and A is 4～5.5 constant, and D is the density of desiccant gel.
27. a ultrasonic flowmeter, it comprises:
Treat the flow passage of fluid measured;
A pair of according to each described ultrasonic vibrator among the claim 14-26; And
Be used to measure the time set of the ultrasonic propagation time between ultrasonic vibrator.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006063808A JP4873966B2 (en) | 2006-03-09 | 2006-03-09 | Ultrasonic transducer |
| JP063808/2006 | 2006-03-09 | ||
| PCT/JP2007/054023 WO2007102424A1 (en) | 2006-03-09 | 2007-03-02 | Acoustic matching material, ultrasonic vibrator, and ultrasonic flowmeter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101347042A CN101347042A (en) | 2009-01-14 |
| CN101347042B true CN101347042B (en) | 2012-10-31 |
Family
ID=38474855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800009095A Expired - Fee Related CN101347042B (en) | 2006-03-09 | 2007-03-02 | Acoustic matching material, ultrasonic vibrator, and ultrasonic flowmeter |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1993321A4 (en) |
| JP (1) | JP4873966B2 (en) |
| CN (1) | CN101347042B (en) |
| TW (1) | TW200740533A (en) |
| WO (1) | WO2007102424A1 (en) |
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| JP5075665B2 (en) * | 2008-02-18 | 2012-11-21 | 株式会社東芝 | Two-dimensional array ultrasonic probe |
| JP5705386B1 (en) * | 2013-07-26 | 2015-04-22 | オリンパスメディカルシステムズ株式会社 | Ultrasonic vibrator and method for manufacturing ultrasonic vibrator |
| CN105758940A (en) * | 2014-12-15 | 2016-07-13 | 郑经伟 | Preserved egg internal quality nondestructive detecting and grading method |
| CN105170437A (en) * | 2015-09-25 | 2015-12-23 | 无锡市博阳超声电器有限公司 | Pressure-resistant and shock-resistant ultrasonic transducer |
| JP7108816B2 (en) * | 2017-06-30 | 2022-07-29 | パナソニックＩｐマネジメント株式会社 | Acoustic matching layer |
| JP7441044B2 (en) * | 2017-11-21 | 2024-02-29 | 日東電工株式会社 | piezoelectric speaker |
| CN116208895A (en) * | 2017-11-21 | 2023-06-02 | 日东电工株式会社 | Piezoelectric loudspeaker |
| CN108543689B (en) * | 2018-04-17 | 2020-04-17 | 陕西师范大学 | Broadband air-dielectric ultrasonic transducer with phononic crystal matching and radiation composite structure |
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| JPH07310050A (en) * | 1994-05-17 | 1995-11-28 | Nippon Synthetic Chem Ind Co Ltd:The | Film-forming agent and its production and fogged glass using the same and its production |
| JP3611796B2 (en) * | 2001-02-28 | 2005-01-19 | 松下電器産業株式会社 | Ultrasonic transducer, manufacturing method of ultrasonic transducer, and ultrasonic flowmeter |
| JP2003284191A (en) * | 2002-03-22 | 2003-10-03 | Matsushita Electric Ind Co Ltd | Acoustic matching member, manufacturing method therefor, ultrasonic wave transceiver employing the same, and ultrasonic wave flowmeter |
| JP2005008424A (en) * | 2002-07-10 | 2005-01-13 | Matsushita Electric Ind Co Ltd | Porous body and its production method |
| JP4231329B2 (en) * | 2003-04-25 | 2009-02-25 | パナソニック株式会社 | Molded body containing dried gel and method for producing the same |
| JP4321239B2 (en) * | 2003-11-27 | 2009-08-26 | パナソニック株式会社 | Method for manufacturing ultrasonic transducer |
| JP2005350519A (en) * | 2004-06-08 | 2005-12-22 | Matsushita Electric Ind Co Ltd | Porous material and method for producing the same |
| JP2006023099A (en) * | 2004-07-06 | 2006-01-26 | Matsushita Electric Ind Co Ltd | Acoustic matching layer, ultrasonic transducer using it, and ultrasonic flow measuring apparatus having ultrasonic transducer |
-
2006
- 2006-03-09 JP JP2006063808A patent/JP4873966B2/en not_active Expired - Fee Related
-
2007
- 2007-03-02 EP EP07737671A patent/EP1993321A4/en not_active Withdrawn
- 2007-03-02 WO PCT/JP2007/054023 patent/WO2007102424A1/en active Application Filing
- 2007-03-02 CN CN2007800009095A patent/CN101347042B/en not_active Expired - Fee Related
- 2007-03-07 TW TW096107835A patent/TW200740533A/en unknown
Non-Patent Citations (3)
| Title |
|---|
| JP特开2004-323752A 2004.11.18 |
| JP特开2005-350519A 2005.12.22 |
| JP特开2006-23099A 2006.01.26 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007243640A (en) | 2007-09-20 |
| EP1993321A4 (en) | 2010-12-29 |
| TW200740533A (en) | 2007-11-01 |
| CN101347042A (en) | 2009-01-14 |
| EP1993321A1 (en) | 2008-11-19 |
| JP4873966B2 (en) | 2012-02-08 |
| WO2007102424A1 (en) | 2007-09-13 |
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