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WO1999044953A1 - Materiau vitrocerame fritte particulierement approprie en tant que revetement et systeme structural - Google Patents

Materiau vitrocerame fritte particulierement approprie en tant que revetement et systeme structural Download PDF

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Publication number
WO1999044953A1
WO1999044953A1 PCT/EP1999/001323 EP9901323W WO9944953A1 WO 1999044953 A1 WO1999044953 A1 WO 1999044953A1 EP 9901323 W EP9901323 W EP 9901323W WO 9944953 A1 WO9944953 A1 WO 9944953A1
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Prior art keywords
glass
ceramic
powder
glassy
grinding
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PCT/EP1999/001323
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English (en)
Inventor
Ferruccio Giuliani
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Priority to AU31426/99A priority Critical patent/AU3142699A/en
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Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent

Definitions

  • the present invention relates to a sintered glass- ceramic material particularly suitable as a cladding and structural system.
  • the present invention relates to sintered glass-ceramic materials and composite materials with a glass-ceramic matrix, suitable for the cladding of structural elements and tiles of the ceramic type.
  • the starting material for producing the materials according to the invention is glass, i.e., an inorganic material which is amorphous due to the random arrangement of its structural units. This characteristic is made evident by the fact that in glass there is no exact melting point, which is instead typical of crystalline solids.
  • the basic structural unit is constituted by oxides, among which silicon oxide is the main component.
  • Glass-ceramic materials also known as glass-ceramics, are polycrystalline solid materials of the inorganic type which contain a residual amorphous phase.
  • the first techniques for preparing these materials were perfected by Corning Glass Works Limited in the USA and date back to 1947. These techniques entailed the transformation of a glassy material having a siliceous base into a polycrystalline ceramic material by providing a controlled thermal pretreatment for the nucleation of the glassy phase, followed by a so-called growth step.
  • glass-ceramic materials provide for suitable thermal treatments of glassy masses at a controlled temperature, usually in the presence of nucleating agents which facilitate the formation of the crystalline phase.
  • the present invention arises from the observation that there is strong market demand for new ceramic products suitable for cladding or structural application which meet the requirement of combining in a single product high functional properties with sophisticated aesthetic qualities.
  • the aim of the present invention is to provide sintered glass-ceramic materials, particularly suitable as cladding and structural systems, which have, together with high surface hardness, good resistance to abrasion and are also compatible with the main types of particulates and fibers used in the production of composites.
  • An object of the present invention is to provide a method for producing sintered glass-ceramic materials whose execution uses technologies employed in the manufacture of ceramic tiles, allowing low production costs.
  • Another object is to provide a sintered glass-ceramic material which can be easily obtained starting from easily commercially available raw materials, has low porosity and high chemical durability, such as to make it particularly suitable as a cladding or structural material for ceramic tiles.
  • a cladding and structural system which comprises a sintered ternary composition of Si0 2 , L_-.°2 and Zr0 2 having an Si0 2 /Li0 2 molar ratio between 70/30 and 78/22 and a Zr0 2 content of less than 13.04 mol%.
  • said material has a Zr0 2 content of 11.1 mol% or less.
  • a method for preparing sintered glass-ceramic materials particularly suitable as cladding and structural systems comprises the steps of: a) preparing a frit starting from a composition comprising Si0 2 , Li0 2 and Zr0 2 which advantageously has an Si0 2 /Li0 2 molar ratio between 70/30 and 78/22 and a Zr0 2 content preferably of less than 13.04 mol%, more preferably less than 11.1 mol%; b) breaking up the resulting frit to obtain a glassy powder; c) pressing the resulting glassy powder into a compacted sample; d) subjecting the resulting compacted sample to a heat treatment for sintering.
  • the raw materials suitable to form the frit constituted by lithium carbonate, zirconium silicate and quartz, are easily commercially available at low cost in highly pure form (purity >99.5%).
  • Si0 2 , Li0 2 and Zr0 2 in which the Si0 2 /Li0 2 molar ratio is between 70/30 and 78/22 and in which the Zr0 2 content is 4
  • substantially spherical particles with an average diameter of preferably less than 45 ⁇ m, are obtained.
  • the ground particles are then melted to form an amorphous glassy mass which is cooled suddenly with water or by contact with cold steel plates.
  • the frits are then broken up to yield a powdery glassy material with particles having an average diameter of preferably less than 100 ⁇ m; this material is then advantageously ground to provide a glassy powder whose granules have a diameter of preferably less than 2 mm.
  • the glassy powder produced by step b) is then subjected to a step for compaction by pressing with a conventional press, capable of developing pressures between 20 and 55 MPa.
  • a conventional press capable of developing pressures between 20 and 55 MPa.
  • suitable sintering of the samples from step c) of the process according to the invention is provided by means of two alternative heat treatments.
  • the first one entails raising the temperature with a single heating ramp with a temperature increase gradient of 25 to 35 °C/min until temperatures between 600 and 980 °C are reached; this is followed by an isothermal treatment until a high degree of sintering is reached.
  • the second treatment entails, as an alternative, the execution of a cycle with two heating ramps, both of which have a temperature increase gradient of 25 to 35 C/min, separated by an isothermal period at a temperature in the interval between 700 and 800 °C and followed by isothermal annealing at a temperature between 850 and 950 °C until a high degree of sintering is reached.
  • Sintered glass ceramics are used in conventional ceramics technology both as a protective cladding for ceramic tiles and as structural material in the manufacture of ceramic tiles.
  • Comparative analysis with gres has further shown that the glass-ceramics produced with the process according to the invention have higher functional and aesthetic qualities.
  • the characteristic milky coloring further allows to color them easily by adding inorganic pigments during the preparation of the frits, allowing further dry or wet applications in screen-printing and/or lithographic methods .
  • a process for producing decals particularly suitable for application to ceramic, glass and metal items comprises the steps of:
  • the decals produced according to this aspect of the invention are transferred onto items preferably made of ceramic, glass or metal by means of an annealing cycle (of the rapid or se irapid type).
  • said annealing cycle comprises a heat treatment at a temperature between 600 and 980°C, preferably at approximately 850°C, advantageously for a period of time between 5 and 15 minutes, preferably 10 minutes.
  • the starting glass-ceramic frit can be in the form of a granulate and/or flakes, colorless (neutral) or colored; in the latter case, coloring is provided by melting with colors or pigments.
  • the grinding step is advantageously performed in drum mills or cylindrical mills, preferably lined with high- density alumina and provided with alumina grinding media. Grinding can be performed dry or wet; in the latter case, the resulting barbotine is dried with drying processes, among which vertical or horizontal atomization and continuous drying on a belt are preferred.
  • the dried glass- ceramic material advantageously has a relative humidity of less than 0.5% by weight.
  • the present invention relates to the above-described glass-ceramic powder obtained from the above-described grinding step and also to the mixture of said powder with colors and pigments. The colors and pigments used during the coloring of 7
  • the ground product are of a type which is compatible with ceramic products, such as for example coloring oxides and ceramic colors.
  • the ceramic mix is applied to a suitable substrate for decals by means of screen-printing or lithographic techniques in predefined forms and in variable amounts in order to provide a decorative layer whose thickness is advantageously between 0.05 mm and 3 mm.
  • the decorative layer formed after the annealing cycle has a highly appreciable aesthetic effect and has class IV and V resistance to surface abrasion according to UNI EN 154 and IS 10545 standards.
  • the decorative layer also provides high impermeabilization of the treated (decorated) surface, such as to allow classification in class V for abraded surface stain resistance tests, according to the above-cited standards.
  • the decorated surface is also highly resistant to thermal shock.
  • a method for the direct application of grit or powder of glass-ceramic material according to the invention to items by screen-printing or lithography comprising the steps of: la) dry or wet grinding the glass-ceramic frit according to the invention to obtain a glass-ceramic grit or product which preferably has a residue of no more than 1% by weight at 15,000 mesh/cm 2 for wet grinding and a residue at 10,000 mesh/cm 2 for dry grinding, said wet- ground product being then dried, or, as an alternative, lb) granulating the glass-ceramic frit according to the invention to obtain a glass-ceramic grit,
  • the method according to the present aspect of the invention allows to provide, on the surface of the item, one or more layers based on sintered glass-ceramic material, which in addition to being highly resistant to wear and abrasions produces a decorative and chromatic effect which is highly appreciable from an aesthetic point of view.
  • the starting glass-ceramic material can be in the form of a granulate or flakes, colorless (neutral) or colored; in the latter case, coloring is provided by melting with colors or pigments.
  • the grinding step is performed in mills of the above-described type.
  • the colors or pigments used to color the glass-ceramic ground product or grit are of the type commonly used in the ceramics field. These colors/pigments are added in such an amount as to provide a coloring which is detectable by the human eye and is conveniently between 0.1% and 10% by weight with respect to the glass-ceramic material.
  • carriers, diluents and additives commonly used in screen-printing and/or lithographic application methods are added during mixing.
  • the present invention further relates to the ground product and to the grit made of glass-ceramic material, obtained during step 1) of the process, according to this last aspect of the invention, and to the mixture of said ground product or grit with colors or pigments according to step 2 ) of the process.
  • a process for producing items with a glass- ceramic base comprises the steps of:
  • a glass-ceramic powder which preferably has a residue of no more than 1% by weight at 15,000 mesh/cm 2 when wet grinding is performed, or a residue of no more than 1% by weight at 10,000 mesh/cm 2 when dry grinding is performed; 2) adding, if necessary, an amount of water to obtain a semifluid mix suitable to a forming process;
  • forming relates to a conventional forming process, preferably selected from casting, forming in the plastic state (plastic forming) and forming in the semi-dry state
  • step 1) of the process entails wet grinding, a barbotine which conveniently includes 30 to 40% water is 10
  • the barbotine obtained from wet grinding is poured to obtain a wet semifinished item which is dried and then annealed.
  • the resulting item is made of sintered glass-ceramic material .
  • the barbotine obtained from wet grinding is dried, for example by using vertical or horizontal atomizers.
  • the drying process provides a granulate which conveniently contains 4 to 6% water and preferably has an average particle size between 50 and 450 microns.
  • Said granulate can be worked with two operating methods .
  • the first method provides for molding in the semi-dry state (4-6% relative humidity), in which the granulate is pressed to obtain a semifinished item, for example a tile, plate or other shape.
  • the resulting semifinished item is then dried and annealed.
  • the second operating method entails subjecting the granulate, after adding water, to plastic forming by means of at least one drawing and cutting process; once the intended shape has been obtained, optionally by additional pressing, the item is dried. The dried item is then sent to the furnace for annealing.
  • step 1) of the process provides for dry grinding, a glass-ceramic powder is obtained to which water is added to provide a mix which is suitable for forming according to one of the following methods: casting, molding in the plastic state and molding in the semi-dry state. in particular, it has been found that by adding an 11
  • the added water contains fluidifiers, suspension promoters and additives which are suitable to give the mix the optimum physical characteristics for forming.
  • step 3 provides for plastic forming of the mix, a semifinished item is obtained which can be pressed or extruded.
  • the resulting semifinished item is then rolled, cut, optionally pressed and finished before being dried and annealed.
  • step 3 provides for the molding in the semi-dry state of the mix, a semifinished item having a specific shape is produced which can then be sent to the drying and annealing steps.
  • Items produced in accordance with this aspect of the invention have a high resistance to surface abrasion, in class V and higher according to UNI EN 154 and ISO 10545 standards; a deep abrasion resistance which meets the requirements of the UNI EN 176 standard; a high impermeabilization of the surface, such as to allow to classify them in class V in the abraded surface stain resistance test, according to the above-cited standards; and a high resistance to thermal shock.
  • the above- described techniques for applying the sintered glass- ceramic material to items are of a known type, as disclosed in EP 0 570 855, or are lithographic and screen-printing techniques used in the field of the working/decoration of ceramic items, such as for example those disclosed in EP 0 769 372 and EP 0 805 131.
  • the above-cited patents are assumed to be entirely included herein as reference.
  • the glassy systems that are suitable for producing the materials according to the invention were prepared by using, as raw materials, lithium carbonate (Li 2 C0 3 ), quartz 13
  • Si0 2 zirconium silicate
  • ZrSi0 4 zirconium silicate
  • the initial powders were homogenized by means of a mixer until compositions selected in terms of Si0 2 /Li0 2 ratio and zirconium oxide content were obtained, as listed in table 1.
  • the maximum allowed Zr0 2 was 13.04 mol% (over this content it has been found that regardless of the values of the Si0 2 /Li0 2 molar ratios, incomplete dissolution of ZrSi0 4 in the glassy structure was observed) .
  • the initial material used is constituted by raw materials which are commonly commercially available and are currently used in the preparation of ceramic enamels.
  • Table 1 below lists the chemical compositions, in mol%, of the vitreous systems that have been found to be particularly suitable for forming the frits of step a) of the process according to the invention.
  • the glassy system was divided into 10-g samples, which were cooled, dried and dry-ground in a mill for approximately 40 minutes.
  • the result was a powder constituted by substantially spherical particles with a diameter of less than 20 ⁇ m for X-ray diffraction on powders (XRD), differential thermal analysis (DTA) , FT-IR spectroscopy and for the preparation of the specimens to be subjected to preliminary sintering tests.
  • XRD X-ray diffraction on powders
  • DTA differential thermal analysis
  • FT-IR spectroscopy FT-IR spectroscopy
  • the initial step of the method according to the invention consists in preparing the frits, which allow to obtain a glassy powder which, compacted by pressing, can be subjected to a suitable sintering treatment.
  • compositions have been found to crystallize easily and to be accordingly also particularly suitable for obtaining glass-ceramic and/or composite materials even with rather bland heat cycles.
  • compositions according to the invention were prepared starting from lithium carbonate (Li 2 C0 3 ), zirconium silicate ( ZrSi0 4 ) and quartz (SiC> 2 ); these starting components had a high purity (>99.5%) and an average particle diameter of less than 45 ⁇ m.
  • Table 2 below lists the percentages by weight of the constituent oxides of the raw materials used in the preferred compositions.
  • An amount equal to 2 kg for each selected composition was subjected to dry mixing in a ball mill and then transferred to a gas-fired furnace, where they melted at a temperature of approximately 1500 °C after a heat cycle lasting 7 hours.
  • the resulting glassy system was then cooled suddenly by casting into water.
  • the glassy powder was advantageously subjected to wet grinding in a discontinuous rotary cylindrical mill in the presence of grinding media made of sintered alumina, using barbotines with a density of 1.6 g/cm .
  • the suspension was dried in a stove at 110 C until a constant weight was reached.
  • the powders were then disaggregated in a ceramic vessel and then humidified, adding water in an amount equal to 6% by weight, without introducing any binder in the resulting mix. 19
  • step b The powders, granulated as described in step b), were then compacted uniaxially by using a press capable of developing a working pressure of 40 MPa (400 bar).
  • the pressed and stove-dried samples were then subjected to the thermal treatment for sintering, which was performed by annealing in a gradient furnace in an oxidizing atmosphere at temperatures between 600 and 980 °C, more preferably between 750 and 800 °C.
  • the samples 20 were then subjected to the thermal treatment for sintering, which was performed by annealing in a gradient furnace in an oxidizing atmosphere at temperatures between 600 and 980 °C, more preferably between 750 and 800 °C.
  • glass ceramics according to the invention Comparison between the properties of glass ceramics according to the invention and those of some ceramic-type materials of the prior art.
  • the glass-ceramic materials sintered with the process according to the invention have improved characteristic properties when compared with materials of the prior art.
  • the modulus of rupture of the glass- ceramic material was found to be 3 times higher than for a porcelainized gres. This characteristic is of particular value if the glass-ceramic materials according to the 21
  • Deep abrasion value 34 34 35 J609+36 142+1 - (120-150) (mm3)
  • the glassy system used in the present invention reaches, at temperatures in the range between 750-800 °C and when performing heat cycles with a total duration of 40 minutes, densification above 90% without the onset of shape distortions in the material.
  • total crystallinity at 900 °C is close to values between 50 and 55% by weight, rising to 60% at 950 °C; it has been found that an excessive growth of the particles occurs at the latter temperature, consequently forming secondary porosity which degrades the degree of densification of the material.
  • composition designated earlier as D4 has a microstructure which is characterized by crystals which are slightly finer than those of composition A6.
  • the glass-ceramic materials according to the invention have mechanical properties which are optimized at 900 °C.
  • This temperature is an intermediate value between the temperatures of 750-800 °C at which the maximum degree of densification is reached and the temperatures of 900-950 C at which complete crystallization occurs.
  • compositions A6 , B4, D4 have shown values of the modulus of rupture of more than 160 MPa, a Vickers hardness of 24
  • the properties of the glass-ceramic materials according to the invention have values which are typical of advanced ceramics although they are produced with heat treatment methods which are typical of conventional ceramics.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

Cette invention porte sur un matériau vitrocérame fritté particulièrement adapté pour être utilisé en tant que revêtement et système structural, ce matériau comprenant une composition ternaire frittée de SiO2, LiO2 et de ZrO2 dont le rapport molaire SiO2/LiO2 se situe entre 70/30 et 78/22 et dont la teneur en ZrO2 est inférieure à 13,04 moles %. Le matériau vitrocérame de cette invention est utilisé dans le domaine classique de la céramique et dans les domaines de la sérigraphie et de la lithographie.
PCT/EP1999/001323 1998-03-02 1999-03-01 Materiau vitrocerame fritte particulierement approprie en tant que revetement et systeme structural Ceased WO1999044953A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU31426/99A AU3142699A (en) 1998-03-02 1999-03-01 Sintered glass-ceramic material particularly suitable as a cladding and structural system

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI980414 IT1298323B1 (it) 1998-03-02 1998-03-02 Materiale vetroceramico sinterizzato, particolarmente idoneo come sistema di rivestimento e di supporto
ITMI98A000414 1998-03-02

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WO1999044953A1 true WO1999044953A1 (fr) 1999-09-10

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IT (1) IT1298323B1 (fr)
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10206665A1 (de) * 2002-02-01 2003-09-04 Schott Glas Verfahren zum Erschmelzen von anorganischen nichtmetallischen Werkstoffen aus einem Gemenge von vorgegebenen Rohstoffen, das Gemenge dieser Rohstoffe und vobehandelter amorpher Rohstoff dieses Gemenges
RU2611809C2 (ru) * 2012-05-11 2017-03-01 Ивоклар Вивадент Аг Предварительно спеченная заготовка для дентального применения
US9757217B2 (en) 2012-05-11 2017-09-12 Ivoclar Vivadent Ag Pre-sintered blank for dental purposes

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
A. P NOVAES DE OLIVEIRA ET AL.: "Properties of glasses belonging to the Li2O-ZrO2-SiO2 system", PHYSICS AND CHEMISTRY OF GLASSES., vol. 39, no. 4, August 1998 (1998-08-01), SOCIETY OF GLASS TECHNOLOGY. SHEFFIELD., GB, pages 213 - 221, XP002108892, ISSN: 0031-9090 *
CHEKHOVSKII V G ET AL: "CRYSTALLIZATION OF LITHIUM ZIRCONIUM SILICATE GLASSES", SOVIET JOURNAL OF GLASS PHYSICS AND CHEMISTRY, vol. 15, no. 3, 1 May 1989 (1989-05-01), pages 265 - 272, XP000121248, ISSN: 0360-5043 *
CHEMICAL ABSTRACTS, vol. 70, no. 12, 24 March 1969, Columbus, Ohio, US; abstract no. 50081, E. M. MILYUKOV: "Crystallization and structure of lithium zirconium silicate glasses" XP002108893 *
NOVAES DE OLIVEIRA ANTONIO PEDRO ET AL: "Physical properties of quenched glasses in the Li2O-ZrO2-SiO2 system", J AM CERAM SOC;JOURNAL OF THE AMERICAN CERAMIC SOCIETY APR 1996 AMERICAN CERAMIC SOC, WESTERVILLE, OH, USA, vol. 79, no. 4, April 1996 (1996-04-01), pages 1092 - 1094, XP002108890 *
OLIVEIRA DE A P N ET AL: "SINTERING AND CRYSTALLIZATION OF A GLASS POWDER IN THE LI2O-ZRO2- SIO2 SYSTEM", JOURNAL OF THE AMERICAN CERAMIC SOCIETY, vol. 81, no. 3, 1 March 1998 (1998-03-01), pages 777 - 780, XP000738310, ISSN: 0002-7820 *
P. QUINTANA ET AL.: "Preliminary Study of the System Li2O-ZrO2-SiO2", TRANSACTIONS OF THE BRITISH CERAMIC SOCIETY., vol. 80, no. 3, 1981, BRITISH CERAMIC SOCIETY. STOKE-ON-TRENT., GB, pages 91 - 96, XP002108891 *
ZH. PRIKL. KHIM., vol. 41, no. 12, 1968, Leningrad, pages 2614 - 2618 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10206665A1 (de) * 2002-02-01 2003-09-04 Schott Glas Verfahren zum Erschmelzen von anorganischen nichtmetallischen Werkstoffen aus einem Gemenge von vorgegebenen Rohstoffen, das Gemenge dieser Rohstoffe und vobehandelter amorpher Rohstoff dieses Gemenges
RU2611809C2 (ru) * 2012-05-11 2017-03-01 Ивоклар Вивадент Аг Предварительно спеченная заготовка для дентального применения
US9757217B2 (en) 2012-05-11 2017-09-12 Ivoclar Vivadent Ag Pre-sintered blank for dental purposes
US10206761B2 (en) 2012-05-11 2019-02-19 Ivoclar Vivadent Ag Pre-sintered blank for dental purposes
US10470854B2 (en) 2012-05-11 2019-11-12 Ivoclar Vivadent Ag Pre-sintered blank for dental purposes

Also Published As

Publication number Publication date
ITMI980414A1 (it) 1999-09-02
AU3142699A (en) 1999-09-20
IT1298323B1 (it) 1999-12-20

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