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US3388001A - Method of making piezoelectric layers by flame spraying - Google Patents

Method of making piezoelectric layers by flame spraying Download PDF

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US3388001A
US3388001A US468609A US46860965A US3388001A US 3388001 A US3388001 A US 3388001A US 468609 A US468609 A US 468609A US 46860965 A US46860965 A US 46860965A US 3388001 A US3388001 A US 3388001A
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Prior art keywords
piezoelectric
flame spraying
substrate
flame
titauate
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US468609A
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Blum Seymour
Mountvala Adi
Mckinley Robert
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IIT Research Institute
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IIT Research Institute
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/51Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on compounds of actinides
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/50Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00Piezoelectric or electrostrictive devices
    • H10N30/01Manufacture or treatment
    • H10N30/07Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
    • H10N30/074Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00Piezoelectric or electrostrictive devices
    • H10N30/80Constructional details
    • H10N30/85Piezoelectric or electrostrictive active materials
    • H10N30/853Ceramic compositions
    • H10N30/8536Alkaline earth metal based oxides, e.g. barium titanates

Definitions

  • the present invention relates to a method of making piezoelectric layers and more especially relates to a flame spraying process whereby such layers or coatings may be readily and conveniently made.
  • a primary object of our invention is to provide a flame spraying method of making thin piezoelectric layers, films or coatings.
  • a more specific object of our invention is to provide a flame spraying method of making piezoelectric barium titauate multicrystalline coatings.
  • Another object of our invention is to provide an improved flame spraying method of forming piezoelectric thin films wherein the material being so sprayed is impinged upon a heated substrate and the cooling rate of the coating so controlled as to prevent or deter conversion of the sprayed material from a piezoelectric to a nonpiezoelectric crystal structure.
  • flame spraying as used in the present specification and claims is meant the passage of particulate materials through a continuous flame generating device such as an oxyacetylene torch, oxyhydrogen torch or a plasma flame unit and the deposition of said materials as an adherent, coherent coating upon the substrate being so treated.
  • a continuous flame generating device such as an oxyacetylene torch, oxyhydrogen torch or a plasma flame unit and the deposition of said materials as an adherent, coherent coating upon the substrate being so treated.
  • Such flame generating members are well known.
  • the present process represents an improvement over the flame spraying techniques disclosed in US. Patent 2,904,449.
  • Our invention is based upon our discovery that by flame spraying for example barium titauate (BaTiO onto a heated substrate that we can maintain the piezoelectric properties of the material.
  • Barium titauate BaTiO onto a heated substrate that we can maintain the piezoelectric properties of the material.
  • Mere flame spraying of such materials upon a chilled substrate destroys the piezoelectric properties of the sprayed layer.
  • flame spraying onto a heated substrate we are able to maintain such desirable piezoelectric properties.
  • This feature is a controlled cooling rate phenomenon whereby one controls crystallographic transformation.
  • EXAMPLE 1 Particulate barium titauate of a particle size ranging from 44 to microns was passed through a oxyhydrogen flame onto an Inconel substrate.
  • the gun to substrate distance was maintained at from 2 to 3 inches and we used a gas ratio of 55 cubic feet per hour oxygen to 100 cubic feet per hour hydrogen.
  • the Inconel was in disc form, inch thick and was maintained at a temperature of from 1100 F. to 1300 F. while the barium titauate was being deposited thereon.
  • an essential feature of our invention is the flame spraying of crystal structure material which can easily be converted under controlled conditions to avoid the formation of the high temperature crystal structure.
  • the flame spraying of crystal structure material which can easily be converted under controlled conditions to avoid the formation of the high temperature crystal structure.
  • the deposited barium titauate was found to be porous and did not adhere well to the substrate and at approximately 14 grams per minute reduced barium titauate was formed.
  • a range of from 20 to 35 grams per minute can be employed to make the present piezoelectric coatings.
  • our process is applicable for the deposition of titanates, niobates, vanadates and zirconates characterized by a perovskite crystallographic structure and to the solid solutions of such materials.
  • examples of such materials are barium titauate, potassium titauate, sodium tantalate, potassium niobate, lead titauate, lithium tantalate, lithium niobate, cadmium niobate and lead zirconate titanates.
  • These materials are flame sprayed onto a heated substrate maintained at such a temperature to prevent rapid chilling of the impinging particles with the resulting formation of a non-piezoelectric crystal structure.
  • the substrate material employed must be capable of withstanding the particular heating involved.
  • the method of making a layer of piezoelectric material upon a substrate which comprises the steps of: flame spraying an oxygen containing material of perovskite structure onto a heated substrate while maintaining said substrate at a temperature whereby said material is not chilled in a non-piezoelectric crystal phase and permitting the resulting layer to cool.
  • the method of making a multicrystalline piezoelectric layer upon a substrate which comprises the steps of: flame spraying particles of a material selected from the group consisting of titanates, tantalates, niobates and zirconates which material is characterized by a relatively low temperature piezoelectric structure and a relatively high temperature non-piezoelectric structure onto a heated substrate while maintaining said substrate during spraying at such an elevated temperature whereby said particles upon impingement and deposition are not chilled in the high temperature, non-piezoelectric structure, and then permitting said layer to cool.
  • a material selected from the group consisting of titanates, tantalates, niobates and zirconates which material is characterized by a relatively low temperature piezoelectric structure and a relatively high temperature non-piezoelectric structure onto a heated substrate while maintaining said substrate during spraying at such an elevated temperature whereby said particles upon impingement and deposition are not chilled in the high temperature, non-piezoelectric structure, and then permitting said layer to cool.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Composite Materials (AREA)
  • Coating By Spraying Or Casting (AREA)

Description

United States Patent 3,388,001 METHOD 0F MAKHJG PIEZOELECTRIC LAYERS BY FLAME SPRAYING Seymour Blum, Giencoe, Adi Mountvala, Chicago, and
Robert McKinley, Broadview, 111., assignors to IIT Research Institute, Chicago, 111., a nonprofit corporation of lllinois No Drawing. Filed June 30, 1965, Ser. No. 468,609 4 Claims. (Cl. 117-213) The present invention relates to a method of making piezoelectric layers and more especially relates to a flame spraying process whereby such layers or coatings may be readily and conveniently made.
Accordingly a primary object of our invention is to provide a flame spraying method of making thin piezoelectric layers, films or coatings.
A more specific object of our invention is to provide a flame spraying method of making piezoelectric barium titauate multicrystalline coatings.
Another object of our invention is to provide an improved flame spraying method of forming piezoelectric thin films wherein the material being so sprayed is impinged upon a heated substrate and the cooling rate of the coating so controlled as to prevent or deter conversion of the sprayed material from a piezoelectric to a nonpiezoelectric crystal structure.
These and other objects, features and advantages of our invention will become apparent to those skilled in this art from the following detailed disclosure thereof.
As is well known to those skilled in this art, it has been most difficult to prepare thin piezoelectric coatings of perovskite type structures by known techniques. In distinction to such problems we have discovered that by the flame spraying of particulate materials as herein taught, that such films may be readily fabricated.
By the term flame spraying as used in the present specification and claims is meant the passage of particulate materials through a continuous flame generating device such as an oxyacetylene torch, oxyhydrogen torch or a plasma flame unit and the deposition of said materials as an adherent, coherent coating upon the substrate being so treated. Such flame generating members are well known. Generally speaking the present process represents an improvement over the flame spraying techniques disclosed in US. Patent 2,904,449.
Our invention is based upon our discovery that by flame spraying for example barium titauate (BaTiO onto a heated substrate that we can maintain the piezoelectric properties of the material. Mere flame spraying of such materials upon a chilled substrate destroys the piezoelectric properties of the sprayed layer. On the other hand by flame spraying onto a heated substrate we are able to maintain such desirable piezoelectric properties. This feature is a controlled cooling rate phenomenon whereby one controls crystallographic transformation.
Before proceeding further in a discussion of our process reference should first be had to an example thereof:
EXAMPLE 1 Particulate barium titauate of a particle size ranging from 44 to microns was passed through a oxyhydrogen flame onto an Inconel substrate. The gun to substrate distance was maintained at from 2 to 3 inches and we used a gas ratio of 55 cubic feet per hour oxygen to 100 cubic feet per hour hydrogen. The Inconel was in disc form, inch thick and was maintained at a temperature of from 1100 F. to 1300 F. while the barium titauate was being deposited thereon. We determined that the thin, dense layer of barium titauate was p1ezoelectr1c.
3,388,001 Patented June 11, 1968 ICC It is known that barium titauate at room temperature exists in the tetragonal crystal form. At temperatures of approximately 126 C. the tetragonal form converts to the cubic and at temperatures of approximately 1400 C. the latter in turn converts to the hexagonal crystalline structure. It is the tetragonal form which is piezoelectric. If one merely flame sprays barium titauate onto a chilled substrate in their passage through the flame the barium titauate particles are converted to the hexagonal crystalline form, a non-piezoelectric embodiment. Conversion of the hexagonal to the cubic is most sluggish and for practical purposes can be said to be almost non-existent. On the other hand the intermediate temperature cubic structure readily reverts to the piezoelectric tetragonal. Accordingly an essential feature of our invention is the flame spraying of crystal structure material which can easily be converted under controlled conditions to avoid the formation of the high temperature crystal structure. We have found that by the avoidance of the quenching of the barium titauate, for example, in the high temperature hexagonal form and that is by flame spraying onto a heated substrate, that We can maintain the piezoelectric qualities of the material being sprayed. After the flame spraying onto the heated substrate the material may be air-cooled and while in layer form it reverts to the piezoelectric tetragonal structure.
In addition to using a heated substrate in the carrying out of our process we have also found that it is important to control the particle feed rate into the flame. 1f the feed rate is too low the particles become very hot thus increasing the probability of obtaining reduced BaTiO a material which is non-piezoelectric. If on the other hand the feed rate is too high the temperature of the particles in the flame would be too low and a dense coating would not be obtained. Both reduced barium titauate and reduced but porous BaTiO layer do not have the desirable piezoelectric properties we wish to provide. Preferably we use a deposition rate of approximately 23 grams per minute in order to make the desired new coatings of this invention. At 40 grams per minute the deposited barium titauate was found to be porous and did not adhere well to the substrate and at approximately 14 grams per minute reduced barium titauate was formed. A range of from 20 to 35 grams per minute can be employed to make the present piezoelectric coatings.
Even more specifically, our process is applicable for the deposition of titanates, niobates, vanadates and zirconates characterized by a perovskite crystallographic structure and to the solid solutions of such materials. Examples of such materials are barium titauate, potassium titauate, sodium tantalate, potassium niobate, lead titauate, lithium tantalate, lithium niobate, cadmium niobate and lead zirconate titanates. These materials are flame sprayed onto a heated substrate maintained at such a temperature to prevent rapid chilling of the impinging particles with the resulting formation of a non-piezoelectric crystal structure. Obviously the substrate material employed must be capable of withstanding the particular heating involved.
It will be understood that various modifications and variations may be effected without departing from the spirit or scope of the novel concepts of our invention.
We claim as our invention:
1. The method of making a layer of piezoelectric material upon a substrate which comprises the steps of: flame spraying an oxygen containing material of perovskite structure onto a heated substrate while maintaining said substrate at a temperature whereby said material is not chilled in a non-piezoelectric crystal phase and permitting the resulting layer to cool.
2. The method of making a multicrystalline piezoelectric layer upon a substrate which comprises the steps of: flame spraying particles of a material selected from the group consisting of titanates, tantalates, niobates and zirconates which material is characterized by a relatively low temperature piezoelectric structure and a relatively high temperature non-piezoelectric structure onto a heated substrate while maintaining said substrate during spraying at such an elevated temperature whereby said particles upon impingement and deposition are not chilled in the high temperature, non-piezoelectric structure, and then permitting said layer to cool.
3. The method as defined in claim 2 wherein said material being flame sprayed is barium titanate.
4. The method as defined in claim 2 wherein said ma- 15 terial being flame sprayed is a lead titanate zirconate.
4 References Cited UNITED STATES PATENTS 2,904,449 9/1959 Bradstreet 117-46 3,246,114 5/1966 Matuay 219-76 FOREIGN PATENTS 345 ,65 3 2/ 1920 Germany.
OTHER REFERENCES 10 Metco Bulletin 10F 1M, August 1963, Powders for Flame Spraying, 1963, 2 pages.
RALPH S. KENDALL, Primary Examiner.
ALFRED L. LEAVITT, Examiner.
A. GOLIAN, Assistant Examiner.

Claims (1)

1. THE METHOD OF MAKING A LAYER OF PIEZOELECTRIC MATERIAL UPON A SUBSTRATE WHICH COMPRISES THE STEPS OF: FLAME SPRAYING AN OXYGEN CONTAINING MATERIAL OF PEROVSKITE STRUCTURE ONTO A HEATED SUBSTATE WHILE MAINTAINING SAID SUBSTRATE AT A TEMPERATURE WHEREBY SAID MATERIAL IS NOT CHILLED IN A NON-PIEZOELECTRIC CYRSTAL PHASE AND PERMITTING THE RESULTING LAYER TO COOL.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3487238A (en) * 1967-07-27 1969-12-30 Gulton Ind Inc Ceramic transducer elements and accelerometers utilizing same
US3617376A (en) * 1967-03-16 1971-11-02 North American Rockwell Antisublimation coating and method for thermoelectric materials

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE345653C (en) * 1919-11-25 1922-03-27 Nicolaus Meurer Device for executing cover layers made of enamel, glass, quartz, hard metal and the like, which are produced by means of spraying onto heat-resistant workpieces and are connected to the latter by welding. like
US2904449A (en) * 1955-07-26 1959-09-15 Armour Res Found Method and compositions for flame spraying
US3246114A (en) * 1959-12-14 1966-04-12 Matvay Leo Process for plasma flame formation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE345653C (en) * 1919-11-25 1922-03-27 Nicolaus Meurer Device for executing cover layers made of enamel, glass, quartz, hard metal and the like, which are produced by means of spraying onto heat-resistant workpieces and are connected to the latter by welding. like
US2904449A (en) * 1955-07-26 1959-09-15 Armour Res Found Method and compositions for flame spraying
US3246114A (en) * 1959-12-14 1966-04-12 Matvay Leo Process for plasma flame formation

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617376A (en) * 1967-03-16 1971-11-02 North American Rockwell Antisublimation coating and method for thermoelectric materials
US3487238A (en) * 1967-07-27 1969-12-30 Gulton Ind Inc Ceramic transducer elements and accelerometers utilizing same

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