WO2018236297A1 - Structure composite - Google Patents

Structure composite Download PDF

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Publication number
WO2018236297A1
WO2018236297A1 PCT/TR2017/050279 TR2017050279W WO2018236297A1 WO 2018236297 A1 WO2018236297 A1 WO 2018236297A1 TR 2017050279 W TR2017050279 W TR 2017050279W WO 2018236297 A1 WO2018236297 A1 WO 2018236297A1
Authority
WO
WIPO (PCT)
Prior art keywords
composite structure
structure according
panel
zirconia
toughening composition
Prior art date
Application number
PCT/TR2017/050279
Other languages
English (en)
Inventor
Ismail Özgür ÖZER
Original Assignee
Anadolu Üniversitesi Rektörlügü
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Anadolu Üniversitesi Rektörlügü filed Critical Anadolu Üniversitesi Rektörlügü
Priority to PCT/TR2017/050279 priority Critical patent/WO2018236297A1/fr
Priority to PCT/TR2017/050733 priority patent/WO2018236313A1/fr
Publication of WO2018236297A1 publication Critical patent/WO2018236297A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/87—Ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
    • C04B41/5031—Alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
    • C04B41/5037—Clay, Kaolin
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
    • C04B41/5042—Zirconium oxides or zirconates; Hafnium oxides or hafnates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
    • C04B41/5057—Carbides
    • C04B41/5059—Silicon carbide
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04M—TELEPHONIC COMMUNICATION
    • H04M1/00—Substation equipment, e.g. for use by subscribers
    • H04M1/02—Constructional features of telephone sets
    • H04M1/18—Telephone sets specially adapted for use in ships, mines, or other places exposed to adverse environment
    • H04M1/185—Improving the rigidity of the casing or resistance to shocks
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
    • C04B2111/00405—Materials with a gradually increasing or decreasing concentration of ingredients or property from one layer to another
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/80—Optical properties, e.g. transparency or reflexibility
    • C04B2111/805—Transparent material

Definitions

  • the present invention relates to a composite structure and a method for preparation thereof.
  • the present invention relates to a composite structure with enhanced mechanical durability.
  • the present invention further proposes a device including such composite structure.
  • Glass-based materials provide a more appealing interface and enhanced user experience on cover glasses, lenses or other transparent parts of everyday use devices, when compared to their polymer-based counterparts. Therefore, glass- based materials are generally preferred over polymer-based materials in panel- formed parts requiring optical transparency, when they are employed on devices including touchscreens, watch lenses or optical lenses such as those used in eyewear.
  • Tempered glass is widely used for approaching the extent of mechanical strength sought in daily use of such devices.
  • residual stress on outer surfaces of tempered glass is usually higher than that at glass before tempering.
  • Chemical processing is usually preferred instead of thermal processing in order to avoid optical heterogeneities when inspected under polarized light due to residual stresses and low thickness values of the panels, which are usually below 1.5 millimeters.
  • Hardness values of glass panels obtained by chemical tempering are usually between 6 GPa (gigapascals) and 6.5 GPa. These hardness levels suffice to protect the panel surfaces against scratching by metallic articles such as coins or keys. Yet, harder materials such as quartz can still easily scratch such surfaces. With regard to this issue, it is important to know that occurrence of scratches are not merely a cosmetic issue, but it also dramatically decreases the mechanical strength of such panel bodies made of tempered glass.
  • Fine scratches with a depth of between 30 and 40 micrometers can release the residual stress and accordingly result in disruption in integrity of tempered glass bodies even at small impacts. Such deformations not only cause economic losses, but also sharp edges appear around fractured areas of chemically tempered glass bodies unlike those appear at thermally tempered ones, which potentially jeopardize the health safety.
  • Sapphire monolithic crystal alumina
  • sapphire monolithic crystal alumina
  • Sapphire provides high hardness values of up to 22 GPa dependent to the cutting direction, and thus it is almost impossible to scratch its surfaces in daily use.
  • Sapphire has an elastic modulus of around 345 GPa, which is much higher than that of tempered glass: 70 to 75 GPa. This high elastic modulus causes load localization at impacts.
  • any micro-error in the sapphire crystal render it more prone to failure upon impacts when compared to tempered glass, even though the toughness of sapphire (about 2.3 MPa-m 1/2 ) is higher than that of tempered glass (0.65 to 0.70 MPa-m 1/2 ).
  • sapphire in panel bodies corresponds to about ten folds higher material costs when compared to tempered glass panel bodies. Sophisticated production process of sapphire is also an important barrier for achieving supply capacity levels required to satisfy the needs of e.g. the smartphone market.
  • a secondary phase can be placed on opaque ceramics in order to improve engineering properties, such as strength and toughness thereof. Crack deflection, crack bridging, and transformation toughening can be achieved to an extent dependent on the secondary phase material in order to improve the toughness of the obtained composite and enhance the performance thereof against impacts when compared to the ceramics alone. But use of such secondary phase on transparent ceramics decreases the transparency to an unacceptable extent in case where the material used as secondary phase has a different refractive index in its microstructure, thus causes light scattering and minimizes optical transparency. This phenomenon decreases the optical homogeneity throughout the panel bodies transparency of which are important. Therefore, microstructural design options are limited in transparent ceramics. For instance, achievement of crystal log raphica I and morphological orientation in anisotropic structures such as alumina provides only limited control on both optical and mechanical properties thereof.
  • Primary object of the present invention is to eliminate the above-mentioned shortcomings in the prior art.
  • a further object of the present invention is to provide an impact resistant and scratch resistant composite structure.
  • a further object of the present invention is to provide a device with an essentially transparent screen or cover having high impact resistance and scratch resistance with low cost and high production capacity.
  • the present invention proposes a composite structure comprising an essentially transparent ceramic part in form of a panel, the part being partly provided with a toughening composition which includes one or more component selected from Zirconia, alumina, Silicon carbide, and mullite, wherein the toughening composition is provided on one or more edge portions (10) of the composite structure (100).
  • the present invention further proposes a device including such composite structure.
  • Figure 1 schematically represents front view (of an outer surface) of an embodiment of the composite structure according to the present invention, which comprises a part provided with a toughened edge portion completely surrounding a transparent central portion which is still available upon partial toughening.
  • Figure 2 schematically represents front view (of an outer surface) of another embodiment of the composite structure according to the present invention, which comprises a part provided with toughened discrete edge portions at some of the edges of the part, wherein a transparent central portion is still available upon partial toughening.
  • Figure 3 represents an exemplary embodiment according to the present invention, wherein the composite structure has curved edge portions.
  • transparent ceramics which have an elastic modulus of about 275 GPa for transparent spinel ceramics and about 320 GPa for transparent aluminium oxynitride
  • opaque ceramics can be provided with enhanced impact resistance via microstructural design techniques, availability of the same is rather limited for transparent ceramics.
  • the present invention proposes a composite structure (100) comprising a transparent ceramic panel which is partly provided with a toughening composition including one or more material in the form of particles or whiskers.
  • the composition includes one or more component selected from Zirconia (Zirconium dioxide, Zr0 2 ), alumina, Silicon carbide (SiC) (e.g. in the form of whiskers), and mullite.
  • the component is preferably Zirconia.
  • the stabile phase of Zirconia at room temperature is monoclinic. Yet, mixing (or here: doping) with one or more of the Yttria, ceria (Cerium (IV) oxide), calcium oxide, magnesium oxide or constraining the Zirconia particles into a different matrix can semi -stabilize the high temperature (1200-2377°C) tetragonal phase at room temperature.
  • Zirconia shows a volumetric expansion in an extent of about 3% to 5% during the phase transition between tetragonal and monoclinic phases.
  • Such Zirconia which is kept in a semi-stable status at room temperature can show a tetragonal- monoclinic phase transition by being released via a crack propagation within its microstructure.
  • panel-shaped bodies such as screens, touchscreens, watch dial covers or lenses used in eyewear; especially edge portions thereof where such bodies are attached (e.g. secured, fixed, fitted or glued) to main frame of a device to be provided with such body.
  • edge portions of touchscreens of smartphones are generally opaque and this does not prevent such devices from being completely useful.
  • the panel according to the present invention is also suitable to be employed in transparent armors or other applications requiring transparency in several portions of a panel.
  • Yttria stabilized Zirconia having a refractive index of about 2.15 at a wavelength of 600 nm, causes severe scattering in Mg-spinel which shows a refractive index of about 1.71 at the same wavelength, and therefore renders the matrix (portions of Mg-spinel toughened by Yttria stabilized Zirconia) essentially opaque.
  • Mean particle diameter (or particle size) of the component in the toughening composition is preferably within the range between 10 nanometers and 10 micrometers. This particle diameter is observed to provide better performance especially in the case where the component comprises Zirconia.
  • the toughening composition is preferably provided on one or more edge portions (10) of the ceramic panel as shown in Fig. 2.
  • the composite structure is partially toughened by application of the toughening composition to the edge portions of the ceramic panel (to form the composite structure).
  • the edge portions essentially serve for securing the composite structure onto a main frame where optical transparency is not sought. Therefore optical opacity potentially brought by the toughening does not affect the optical performance of the transparent ceramic panel.
  • a device comprising the composite structure according to the present invention, which is for instance a screen covering a display (such as LCD) at its central portions and attached to a frame of the display at its edge portions
  • the central portions of the composite structure are not provided with the toughening composition for maintaining the transparency and transmittance of the ceramic matrix; and the linear transmittance in these central portions is at least 50% at 1 mm of panel thickness and 600 nm of wavelength.
  • Hardness in the central portions is mainly higher than 12 GPa, which is essentially sufficient against daily mechanical factors such as impacts on the surface at the central portions, or frictions by metallic articles such as keys or coins.
  • the toughness is higher than 1.5 MPa.m 1 2 , where in the edge portions of the composite structure which are provided with the toughening composition (i.e. partially toughened), toughness values higher than 3 MPa.m 1/2 is available with the composite structure according to the present invention.
  • the composite structure is rendered durable against impacts at its edge portions and/or its corners.
  • Zirconia provided onto the transparent ceramic provides reinforcement of said ceramic against collision-induced deformation.
  • Zirconia is preferably stabilized with one or more further component selected from the list consisting of Yttria (Yttrium (III) oxide, Y 2 0 3 ) or oxides of Calcium, Magnesium, Scandium, and Cerium.
  • the further component preferably comprises Yttria.
  • the further component content in such toughening composition is preferably within the range between 1% and 15% (mol/mol) and more preferably within the range between 2% and 4% (mol/mol) with respect to the molar concentration of Zirconia in the toughening composition, and the further component is preferably Yttria.
  • the mean particle diameter (or particle size) of Zirconia in the toughening composition is preferably within the range between 10 nanometers and 10 micrometers
  • the further component content in said toughening composition is within the range between 2% and 4% (mol/mol) with respect to the molar concentration of Zirconia.
  • the further component is preferably Yttria.
  • the Zirconia content in the toughened portions (where transparency is not sought and essentially not available upon the partial toughening) of the transparent ceramic composite panel body is preferably within the range between 0.1% and 50% (v/v), more preferably 3% and 15% (v/v), and even more preferably between 8% and 12% (v/v) with respect to the total volume of said toughened portion.
  • all of the edge portions surrounding the panel body is provided with the reinforcement (toughened) as exemplified in the Fig. 1. This enhances the toughness around the panel body and thus enables a maximized protection of the panel body against disintegration by maintaining it essentially transparent, by application of the reinforcement on the zones where transparency is not essential.
  • the (reinforced or toughened) edge portion (10) of the panel is in form of a strip treated with the toughening composition, said strip having a width (W) which corresponds to a distance of an untreated central portion (11) from an edge of the panel. Said width (W, W) being less than one fifth of the distance (D, D 7 ) between the center (C) of an outer surface of the panel and the corresponding edge (12, 12 7 ), preferably less than one tenth of the distance (D, D 7 ) between the center (C) and the said corresponding edge (12, 12').
  • the edge portions (10) of the composite structure can be curved so that the outer (or front) surface of the composite structure most prone to receive the mechanical contacts from outside is essentially convex.
  • An exemplary drawing according to this embodiment is shown in Fig.3.
  • the edge portions (10) of the composite structure can be essentially flat and central portions of the composite structure can be concave.
  • direct impacts can be mostly received by the toughened/reinforced edge portions of the front surface of the panel instead of the central portions thereof, resulting in an even higher durability to the panel.
  • Transparency and transmittance of the composite panel structure is at least partly compromised on the zones provided with said toughening composition, but the remaining (non-toughened) portions of the panel remain essentially transparent.
  • the transparent ceramics is Mg-spinel
  • actual linear transmittance is around 80% for panel thickness of 1 mm and wavelength of 600 nm.
  • the high-hardness transparent ceramics based composite structure according to the present invention overcomes both the impact-related body disintegration tendency and scratch-related surface vulnerabilities under conditions expected to be encountered in daily use of end-user portable devices. Thanks to the available hardness values between about 15 GPa and 22 GPa, screens or transparent cover panels of such devices cannot be even scratched by everyday hard materials e.g. which form sand or gravel.
  • the partially toughened transparent ceramic based composite panel body structure according to the present invention provides enhanced fracture resistance against impacts from their corners or edges (e.g. in case of dropping) when compared to non-reinforced ceramics, tempered glasses and sapphire.
  • concentration of the component in the toughening composition is preferably gradient throughout the edge portions (10) of the part, so that the concentration of the component in the toughening composition is higher in vicinity of an edge (12) when compared to another zone of the edge portion (10) in vicinity of a central portion of the part.
  • This embodiment is easier to produce when compared to another embodiment in which the toughened edge portions (10) are provided with the toughening composition with a uniform concentration of the component.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Signal Processing (AREA)
  • Aiming, Guidance, Guns With A Light Source, Armor, Camouflage, And Targets (AREA)

Abstract

La présente invention concerne une structure composite (100) comprenant une partie en céramique essentiellement transparente sous la forme d'un panneau, la partie étant partiellement pourvue d'une composition de renforcement qui comprend un ou plusieurs composants choisis parmi la zircone, l'alumine, le carbure de silicium et la mullite, la composition de renforcement étant disposée sur une ou plusieurs parties de bord (10) de la structure composite (100). L'invention concerne en outre un dispositif comprenant une telle structure composite.
PCT/TR2017/050279 2017-06-20 2017-06-20 Structure composite WO2018236297A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/TR2017/050279 WO2018236297A1 (fr) 2017-06-20 2017-06-20 Structure composite
PCT/TR2017/050733 WO2018236313A1 (fr) 2017-06-20 2017-12-29 Lame céramique transparente et outil de coupe comportant cette lame

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/TR2017/050279 WO2018236297A1 (fr) 2017-06-20 2017-06-20 Structure composite

Publications (1)

Publication Number Publication Date
WO2018236297A1 true WO2018236297A1 (fr) 2018-12-27

Family

ID=60120118

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/TR2017/050279 WO2018236297A1 (fr) 2017-06-20 2017-06-20 Structure composite

Country Status (1)

Country Link
WO (1) WO2018236297A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150183179A1 (en) * 2013-12-31 2015-07-02 Saint-Gobain Ceramics & Plastics, Inc. Article comprising a transparent body including a layer of a ceramic material and a method of forming the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150183179A1 (en) * 2013-12-31 2015-07-02 Saint-Gobain Ceramics & Plastics, Inc. Article comprising a transparent body including a layer of a ceramic material and a method of forming the same

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