Patent Application
20170203998
This application claims the benefit of priority under 35 U.S.C. §119 of French Patent Application Serial No. 1154213, filed on May 16, 2011, the content of which is relied upon and incorporated herein by reference in its entirety.
The present disclosure relates to glass-ceramics of the lithium aluminosilicate type, having a dark color and containing a solid solution of β-quartz as the predominant crystalline phase. The disclosure also relates to articles made from such glass-ceramics, precursor glasses for such glass-ceramics, and methods for obtaining such glass-ceramics and related articles.
Applicant is a manufacturer of glass-ceramic products intended for the home market, such as cooktops, fire proof doors and windows, stove and oven windows, fireplace inserts, etc. They have been producing millions of lithium aluminosilicate glass-ceramic cooktops for the last 20 years. They have notably produced plates such as described in U.S. Pat. No. 5,070,045 and more particularly such plates of a glass-ceramic containing a solid solution of β-quartz as the predominant crystalline phase, colored with vanadium oxide (V2O5), and marketed under the brand Kerablack®. These plates have characteristic properties and notably a coefficient of thermal expansion close to zero (in order to withstand thermal shocks) associated with a specific optical transmission curve. Said specific optical transmission curve for a thickness of 4 mm is such that the integrated optical transmission TV, in the visible range (between 380 and 780 nm, as measured with the illuminant D65, the observer at 2°) is between 0.8 and 2%, advantageously between 1 and 1.7%. One therefore has 0.8≦Tv≦2%, advantageously 1%≦Tv≦1.7%. If the integrated optical transmission is greater than 2%, the heating elements, laid out under the plate, are not concealed when they are out of operation and if said integrated optical transmission is less than 0.8%, said heating elements in operation are not visible (safety problem).
The optical transmission at 625 nm is greater than 3.5%, advantageously greater than 4% (T625>3.5%, advantageously T625>4%). With this, it is possible to see red displays (the most commonly used color) laid out under the plate. The optical transmission at 950 nm (near infrared) is between 50 and 70% (50%≦T950≦70%). With this it is possible to use conventional electronic control buttons, emitting and receiving at this wavelength. The infrared optical transmission at 1,600 nm is between 65 and 75% (65%≦T1600≦75%). If said infrared optical transmission is less than 65%, the heating performances of the plate are not satisfactory and if said infrared optical transmission is greater than 75%, said heating performances are excessive and may induce dangerous heating of materials placed in proximity to the plate.
The plates of this type give entire satisfaction. However, their composition contains arsenic oxide (arsenic oxide involved as a fining agent during the step for melting the vitrifiable load of raw materials used. One skilled in the art is aware of the three successive steps applied for obtaining glass-ceramic articles: melting and fining of a vitrifiable load of raw materials and then shaping, and then a crystallization heat treatment (also called ceramming treatment) and, for obvious reasons of protection of the environment, it is desired to avoid the use of this toxic compound. It is incidentally noted that the U.S. Pat. No. 5,070,045 mentions arsenic oxide and antimony oxide as conventional fining agents. As both of these products are toxic, the use of either one is desirably avoided. Applicant therefore desired to develop novel performing plates, having the same optical transmission properties (functional properties: see above) as Kerablack® plates, but free of arsenic oxide (and of antimony oxide) in their composition.
Tin oxide (SnO2) has been recommended for many years as a fining agent, instead and in place of arsenic oxide (and/or antimony oxide). This substitution is however not totally neutral.
On the one hand, tin oxide is a less performing fining agent than arsenic oxide. Thus, in absolute terms, it should be involved in a relatively large amount, which is not without posing problems, more particularly of devitrification. Thus, various alternatives were proposed according to the prior art for obtaining highly performing fining and notably applying fining with said tin oxide at a higher temperature (see EP 1 313 675), and using fining auxiliaries such as fluorine, bromine, manganese oxide and/or cerium oxide together with said tin oxide (see WO 2007/03566, WO 2007/03567 and WO 2007/065910, respectively).
On the other hand, tin oxide is a more powerful reducing agent than arsenic oxide (and antimony oxide). Thus, its influence on the coloration (i.e. on the optical transmission properties) of the final glass-ceramic is different from that of arsenic oxide (and antimony oxide). One skilled in the art indeed is aware that tin and arsenic oxides (or even antimony oxides), in addition to their “first” function of a fining agent, are indirectly involved in the process for coloring the final glass-ceramic insofar that they reduce the vanadium oxide present during ceramming (the reduced forms of said vanadium oxide being responsible for coloration). This is perfectly explained in the teaching of patent application EP 1 313 675.
Providing glass-ceramic plates, without arsenic (or antimony) in their composition, obtained with efficient fining of the vitrifiable raw material (fining applied at a conventional fining temperature, generally between 1,600 and 1,700° C.) and exhibiting the same optical transmission curve as the plates of the prior art with arsenic (and/or antimony) in their composition (Kerablack® plates), was therefore the technical problem tackled by the inventors.
Of course, many documents of the prior art have already described glass-ceramics of the lithium aluminosilicate type, containing a solid solution of β-quartz as the predominant crystalline phase, colored with vanadium oxide and containing tin oxide (involved as a fining agent). Said documents do not however propose the glass-ceramics of the present disclosure, and meeting the specifications discussed above.
Japanese Patent Application Number 11-100229 is, to the knowledge of the Applicant, the first document of the prior art to have recommended the use of SnO2 (optionally in combination with chlorine: Cl) as a fining agent. This document mentions the presence of 0.1 to 2% by weight of SnO2 in the composition of glass-ceramics transmitting infrared; it expressly describes SnO2 contents from 0.7 to 1% by weight (in the absence of Cl) and from 0.9 to 1.9% by weight (in the presence of Cl). Such high contents raise concerns on devitrification problems. This document contains little teaching on the optical transmission curves of the described glass-ceramics, it does not contain any teaching on the control of said curves.
EP Patent Application 1 313 675, already mentioned above, also describes the use of SnO2 (used at maximum contents of 0.3% by weight in the examples) as a fining agent. Carrying out fining at a high temperature (1,975° C. for 1 hour) is recommended for obtaining glass-ceramics of good quality. Provision is made within the composition for the possible presence, in addition to that of V2O5, of other coloring agents such as chromium, manganese, iron, cobalt, nickel, copper, selenium and chlorine compounds. However, for optimizing the optical transmission of infrared, it is indicated in this document that it is hardly desirable to involve coloring agents in addition to V2O5, such coloring agents absorbing in the infrared.
Patent applications WO 2007/03566, WO 2007/03567 and WO 2007/065910 recommend, as indicated above, the presence of fining auxiliaries. The examples show said fining auxiliaries associated with 0.2% by weight of SnO2. The possible presence of the conventional coloring agents (in addition to V2O5) is mentioned. In these documents no teaching is found on the optical transmission curves of the described glass-ceramics.
Patent application WO 2008/056080 describes an original technique (floating) for obtaining glass-ceramic plates. It mentions the opportune use of SnO2 as a fining agent, as well as that of coloring agents (Fe2O3, Cr2O3, V2O5 . . . ). This document does not contain any teaching on optical transmission curves.
Patent application DE 10 2008 050 263 describes glass-ceramics, the composition of which is optimized with reference to transmission in the visible range (red, but also blue, green). The composition of said glass-ceramics contains SnO2 as a fining agent (less than 0.3% in the examples), V2O5 as a “main” coloring agent as well as optionally other coloring agents (chromium, manganese, cobalt, nickel, copper, selenium, rare earth and molybdenum compounds . . . ). It is also indicated in this document that the presence of these other coloring agents is detrimental to optical transmission in the infrared.
Patent application FR 2 946 042 describes plates having an optical transmission from 0.2 to 4% for at least one wavelength between 400 and 500 nm (blue). The described plates contain less than 0.3% by weight of SnO2 and V2O5 as a “main” coloring agent, as well as optionally other coloring agents such as Fe2O3, NiO, CuO and MnO. Advantageously they contain less than 25 ppm of chromium oxide.
Patent application WO 2010/137000 also describes glass-ceramic plates transmitting blue light. These plates, which may contain As2O3 or SnO2 as a fining agent, contain a specific combination of vanadium oxide (V2O5) and cobalt oxide (CoO). They may also contain other coloring agents (NiO, only in a small amount) but advantageously they only contain V2O5 and CoO.
Patent application PCT/EP2011/050830 discloses an optimization of the base composition of the glass-ceramic with reference to its mechanical stability and aging properties notably. It does not contain any teaching on the optical transmission properties and their control.
Patent application FR 1 056 406 teaches the benefit of controlling the chemical oxygen demand (COD) of a lithium aluminosilicate glass with the purpose of optimizing its fining.
In such a context, the inventors have therefore elaborated glass-ceramics, free of arsenic (and of antimony), having an optimized optical transmission curve with reference to their use, more particularly as cooktops. They are thus able to propose substitutes for the existing Kerablack® plates. Their disclosure is based on an original association, within the composition of glass-ceramics, of SnO2 (which provides the fining agent function and then the reducing agent function, said reducing agent participating in the final coloration of the product) and of coloring species (V2O5+Fe2O3+Cr2O3). This is explained hereafter.
According to a first embodiment, the present disclosure relates to glass-ceramics of the lithium aluminosilicate (LAS) type. They contain Li2O, Al2O3 and SiO2 as essential constituents of the β-quartz solid solution. They contain a β-quartz solid solution as the predominant crystalline phase where said β-quartz solid solution accounts for more than 80% by weight of the total crystalline phase (of the crystallized fraction), and have the same or substantially the same optical transmission curve as the glass-ceramic of the Kerablack® plates. Further, they have the optical transmission characteristics hereafter, for a thickness of 4 mm of 0.8%≦TV≦2%, advantageously 1%≦TV≦1.7%, T625>3.5%, advantageously T625>4%, 50%≦T950≦70%, and 65%≦T1600≦75%.
These are glass-ceramics of dark color, most particularly suitable for use as cooktops.
In a characteristic way, the composition of these glass-ceramics, expressed as percentages by weight of oxides, contains:
Said composition therefore contains SnO2 as a fining agent. The fining is all the more easier to apply and all the more performing since the amount of SnO2 present is significant. However it should be kept in mind that any devitrification should be minimized or even avoided and the influence of said SnO2 on the optical transmission should be controlled (i.e. on the coloration). In fact SnO2 is capable of reducing the vanadium and the iron present during ceramming. An SnO2 content from 0.3. to 0.6% by weight may be used. Such a content is advantageously greater than 0.3% by weight (greater than the SnO2 content of many glass-ceramics of the prior art). Preferably, the disclosed glass-ceramics contain more than 0.36% and up to 0.5% by weight of SnO2. More preferably, they contain from 0.35 to 0.45% by weight of SnO2. A content of 0.4% by weight or close to 0.4% by weight (0.40±0.03) is strongly recommended.
The disclosed glass-ceramics contain neither any As2O3, nor any Sb2O3 or only contain traces of at least one of these toxic compounds, SnO2 being present instead of and in place of these conventional fining agents. If traces of at least one of these compounds are present, this is as a contaminating product, this is a priori due to the presence of recycled materials of the cullet type (stemming from old glass-ceramics, fined with these compounds) in the vitrifiable load of raw materials. In any case, only traces of these toxic compounds are likely to be present: As2O3+Sb2O3<500 ppm.
V2O5 is therefore the main coloring agent of the glass-ceramics. Indeed, V2O5, in the presence of SnO2, significantly darkens the glass during its ceramming (see above). V2O5 is responsible for absorption mainly below 700 nm and it is possible in its presence to retain sufficiently high transmission at 950 nm and in the infrared. An amount of V2O5 between 0.025 and 0.045% (between 250 and 450 ppm) has proved to be adequate.
In the presence of SnO2 and of V2O5, it has proved to be delicate to obtain for the sought glass-ceramics, both the required integrated optical transmission (Tv) and the required optical transmission at 625 nm (T625). Indeed, insofar that the absorption due to vanadium is relatively high at this wavelength (625 nm), when an acceptable value is reached for the integrated optical transmission, the value of the optical transmission at 625 nm is too low and vice versa. Hence the non-obviousness of proposing SnO2-fined glass-ceramics with the sought transmission curve. It is in fact to the credit of the inventors of having found the suitable coloring agent, to be associated in an adequate amount (also suitable with reference to the other required criteria of T950 and T1600) with V2O5 in order to obtain the desired values of TV and of T625 (and this with unexceptional fining conditions). This coloring agent is chromium oxide (Cr2O3). It is suitable for providing the darkening agent function in the small wavelength of the visible range (400-600 nm) while retaining high transmission in the wavelengths between 600 and 800 nm. The desired result is therefore reached with the presence of Cr2O3 at a content from 0.01 to 0.04% by weight, in the composition of the glass-ceramics. Because of this presence in their composition, the glass-ceramics only show low transmission in the blue range. For a thickness of 4 mm, the glass-ceramics generally have an optical transmission at 450 nm of less than 0.1% (T450<0.1 N.
Iron oxide leads to absorption mainly in the infrared and its content should be of at least 500 ppm, advantageously at least 700 ppm in order to obtain the required transmission. If its content exceeds 1,500 ppm, absorption in the infrared is too high in the glass-ceramic but also in the initial glass, which makes it more difficult to be melted and fined. Advantageously, the iron oxide content is comprised between 700 and 1,200 ppm.
In the visible range, iron is also involved in the coloration process. It is noted here that its effect within the listed compositions may be compensated by that of the vanadium present. Thus, it was observed that at Fe2O3 contents greater than 0.09%, transmission in the visible range is slightly increased (probably at such Fe2O3 contents, SnO2 preferentially reduces Fe2O3 and more V2O5). Such lightening of the glass-ceramic may then be compensated by a greater V2O5 content (however remaining within the range indicated above).
Within the scope of the disclosed embodiments, it is not excluded that the composition of the glass-ceramics contains in a more or less significant amount, in addition to V2O5, Fe2O3 and Cr2O3, of at least one other coloring agent such as CoO, MnO2, NiO, CeO2. However, it is out of the question that the presence of said at least one other coloring agent have a significant influence on the targeted optical transmission curve. Attention should notably be paid to possible interactions, capable, even with low levels of coloring agents, of significantly modifying said optical transmission curve. Thus, CoO may a priori only be present in a very small amount insofar that this element strongly absorbs in the infrared and in a non-negligible way at 625 nm. According to a preferred alternative, the composition of the glass-ceramics does not contain any CoO, in any case it contains less than 200 ppm of the latter, advantageously less than 100 ppm.
According to another preferred alternative, the composition of the glass-ceramics does not contain any fining auxiliaries such as F and Br. It does not contain any F and Br except for inevitable traces. This is particularly advantageous considering the price and/or the toxicity of these compounds. Within the disclosed compositions, the presence of fining auxiliary(ies) is a priori unnecessary insofar that SnO2, present in the indicated amounts (≧0.3% by weight, advantageously >3% by weight) is highly effective as a fining agent.
The base composition of the glass-ceramics may vary to a great extent. By no means as a limitation, such a composition may be specified. In addition to SnO2, V2O5, Cr2O3 and Fe2O3 in the weight percentages specified above (with As2O3+Sb2O3<500 ppm), such a composition may contain, in the weight percentages indicated hereafter:
According to a preferred alternative, the glass-ceramics have a composition consisting of at least 98% by weight, advantageously at least 99% by weight, or even 100% by weight of SnO2, V2O5, Cr2O3, Fe2O3 (with As2O3+Sb2O3<500 ppm) and of the oxides listed below (in the amounts specified above).
They have the same optical transmission curve as the glass-ceramic of the Kerablack® products while being free of any toxic fining agent (SnO2 being involved instead of and in place of the arsenic oxide). It was seen that SnO2 is a less effective fining agent than arsenic oxide but it is involved at relatively consequent levels (between 0.3 and 0.6% by weight) in the composition of the disclosed glass-ceramics. Moreover it is quite possible to use for the glass-ceramics a less viscous base glass (or having a lower high temperature viscosity) than that of the Kerablack® products, in order to facilitate melting and therefore fining. The combination of coloring agents V2O5+Cr2O3+Fe2O3 is quite compatible with such a base glass.
Said combination of coloring agents V2O5+Cr2O3+Fe2O3 is capable of containing high Cr2O3 and Fe2O3 contents. Thus, low cost raw materials are suitable insofar as iron and chromium are ordinary impurities of such low cost natural raw materials. This is particularly advantageous.
Moreover it is known that β-quartz glass-ceramics colored with vanadium oxide tend to darken during heat treatments subsequent to their ceramming treatment. The material may undergo such heat treatments during its use for example as a material making up cooktops. The disclosed glass-ceramics exhibit darkening during these heat treatments which is not more significant than that of Kerablack® glass-ceramics.
The glass-ceramics according to the disclosed embodiments therefore are particularly interesting substitutes for said Kerablack® glass-ceramics.
According to a second embodiment, the disclosure relates to articles at least partly consisting of a glass-ceramic as described above. Said articles advantageously consist in totality of a glass-ceramic as disclosed herein. Said articles advantageously consist of a cooktop, a cooking utensil or a microwave oven part. They very advantageously consist in a cooktop or a cooking utensil.
According to a third embodiment, the present disclosure relates to lithium aluminosilicate glasses, precursors of the disclosed glass-ceramics as described above. Said glasses have the weight composition of glass-ceramics as explained above. Incidentally, it may be noted that said precursor glasses advantageously have an optical transmission, for any wavelength comprised between 1,000 and 2,500 nm, of more than 60% for a thickness of 3 mm. Their melting and fining are then facilitated.
According to further embodiments, the present disclosure relates also to a method for elaborating a glass-ceramic as described above, and to a method for elaborating an article at least partly consisting of a glass-ceramic as described above.
Conventionally, said method for elaborating a glass-ceramic comprises the heat treatment of a vitrifiable load of raw materials, under conditions which successively ensure melting, fining and then ceramming.
In a characteristic way, said load has a composition with which it is possible to obtain a glass-ceramic as described above. In a characteristic way, said load is a precursor of a glass or of a glass-ceramic, advantageously having the base composition specified above, and containing, in any case, the amounts of SnO2, V2O5, Cr2O3, Fe2O3 and optionally As2O3+Sb2O3, as indicated above.
Conventionally, said method for elaborating an article successively comprises melting of a vitrifiable load of raw materials, said load containing SnO2 as a fining agent; followed by the fining of the obtained molten glass; cooling of the obtained fined molten glass and simultaneously, its shaping to the desired shape for the targeted article; and ceramming of said shaped glass.
In a characteristic way, said load has a composition with which it is possible to obtain a glass-ceramic as described above. In a characteristic way, said load is the precursor of a glass and of a glass-ceramic, advantageously having the base composition specified above, and containing in any case, the amounts of SnO2, V2O5, Cr2O3, Fe2O3 and optionally of As2O3+Sb2O3, as indicated above.
When carrying out either one of the methods above, the load has advantageously an optical transmission for any wavelength comprised between a 1,000 and 2,500 nm, of more than 60%, for a thickness of 3 mm. As indicated above, the melting and fining operations are thereby facilitated.
It is now suggested to illustrate various embodiments by the examples hereafter.
In order to produce batches of 1 kg of precursor glass, the raw materials have been mixed carefully in the proportions (proportions expressed as weight percentages of oxides) copied into the first portion of Table 1 hereafter (Tables 1-a, 1-b and 1-c).
The mixtures are placed in platinum crucibles and melted at 1,650° C.
After melting, the glasses are rolled to a thickness of 5 mm and annealed at 650° C. for 1 hr.
Glass samples (in the form of plates of about 10 cm×10 cm) then undergo the following crystallization treatment: fast heating up to 650° C., heating from 650° C. to 820° C. at a heating rate of 5° C./min, heating from 820° C. to the maximum crystallization temperature, Tmax, at a heating rate of 15° C./min, maintaining said temperature Tmax for a period t and then cooling at the cooling rate of the oven.
The values of Tmax and t are indicated in the second part of Table 1.
The optical properties of the obtained glass-ceramic plates are measured on polished samples with a thickness of 4 mm. The illuminant D65 (observer at 2°) was used. The results are given in the third part of Table 1 hereafter: Tv is the integrated transmission in the visible range T450, T625, T950 and T1600 are the transmissions measured at 450, 625, 950 and 1,600 nm respectively.
For Example 4, the transmission of the precursor glass was measured under 3 mm and the minimum transmission value measured between 1,000 and 2,500 nm is the one indicated (Table 1b).
The Examples A, B, C, D, E and F do not belong to the invention. Example A corresponds to the Kerablack® glass-ceramic which contains arsenic. The compositions of Examples B to F do not contain adequate contents (in the sense of the disclosed materials) of V2O5 and/or Cr2O3 and/or SnO2 for obtaining the desired transmission.
For Example 1, Table 2 hereafter reports a few properties measured on the glass-ceramic, including the coefficient of thermal expansion (CTE), the percentage (by weight, based on the total crystallized fraction) and the average size of the crystals of the beta-quartz solid solution (% of beta-quartz and size of the crystals). X-ray diffraction analysis was carried out with a diffractometer operating with monochromatic radiation from a Cu cathode and having a fast multichannel linear detector (Real Time Multichannel Scaler RTMS).
Embodiments are also illustrated by the following examples, which have been carried out with melting of a vitrifiable mixture in an industrial furnace. In both cases, the glass was formed by rolling to a thickness of 4 mm, annealed and then cut out. A glass sample was then subject to the ceramming treatment described above. The optical properties were measured as described above.
In the case of Example 8, a sample of the obtained glass-ceramic was subject to ageing treatment for 100 h at 725° C. The integrated transmission, Tv, was measured before and after this ageing treatment on a polished sample with a thickness of 3 mm. The same data are indicated for the Kerablack® materials. It is seen that the glass-ceramic as disclosed herein does not lose more in transmission than Kerablack®.
A melting test with precursor glasses (of Example 10 according to embodiments and of Example G which does not belong to the invention) was conducted.
Both glasses, the composition of which is indicated in Table 4 hereafter, were melted. The compositions differ by their SnO2 content. The same raw materials were used for making both glasses.
After mixing, the raw materials required for obtaining 1 kg of glass were placed for melting (and fining) in platinum crucibles. The filled crucibles were introduced into an electric furnace pre-heated to 1400° C. Therein, they were subject to the melting cycle hereafter: rise in temperature from 1,400° C. to 1,600° C. within 2 hrs, rise in temperature from 1,600° C. to 1,630° C. within 1 hour, and maintaining 1,630° C. for 1 hour.
The crucibles were then taken out of the furnace and the molten glass was poured on a heated steel plate. It was then rolled to a thickness of 5 mm and annealed for 1 hr at 650° C.
Because of the short holding time at 1,630° C., the fining is incomplete. The number of bubbles in the plates was automatically counted by a camera coupled with an image analyzer.
The results are given in Table 4 hereafter, expressed in number of bubbles per cm3. They show that the glass containing an SnO2 content of 0.39% (Example 10) is better fined during this test than the one which only contains 0.29% of SnO2 (Example G).
| Number | Date | Country | Kind |
|---|---|---|---|
| 1154213 | May 2011 | FR | national |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 14117383 | Feb 2015 | US |
| Child | 15477649 | US |
